trs 432 companion cd-rom - publications - international atomic
TRANSCRIPT
TECHNICAL REPORTS SERIES No. 432 COMPANION CD-ROM
STANDARDIZED HIGH CURRENT SOLID TARGETS FOR CYCLOTRON
PRODUCTION OF DIAGNOSTIC AND THERAPEUTIC
RADIONUCLIDES
UNEDITED REPORTS OF THE PARTICIPANTS
OF THE THIRD RESEARCH COORDINATION MEETING
INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA, 2004
CONTENTS
Development of a high current solid target, a novel radiochemistry for Tl-201 and Pd-103 production
R. Strangis, C. Rocco, E. Guevara, G. Maslat, F. Corral, N. Gonzáles, R. Téramo, J. Lago, G. Casale
A plating/electrodissolution/recovery cycle for rhodium target material used for the industrial cyclotron production of palladium-103
P. van den Winkel, L. de Vis, R. Waegeneer, A. de Schrijver, H. Afarideh, M. Sadeghi, M. Haji Saeid
New technology for the industrial preparation of high quality Tl-203 cyclotron targets by constant current electroplating
P. van den Winkel, L. de Vis, M. de Vreese, R. Wageneer, A. de Schrijver, A. Arzumanov, N. Gorodiskaya, P. Zheltov
Cyclotron production of iodine-123 and Pd-103 Zhou Wei, Wang Yongxian, Zhang Chunfu
Production of diagnostic and therapeutic radionuclides S. Takács
High current Tl-203, Rh-103 targets preparation for cyclotron production of Tl-201 and Pd-103 radionuclides
A. Arzumanov, V. Berger, A. Borissenko, N. Gorodisskaya, I. Ilmatov, A. Knyazev, V. Koptev, S. Lyssukhin, A. Platov, G. Sychikov, D. Zheltov
Research and technological development for the production of Pd-103 at the U-120 cyclotron from Bucharest
P.M. Racolta, D. Dudu
An operated solid target device design for iodine-123(124) production L.M. Solin, V.A. Jakovlev, A.I. Baranov, A.A. Timofeev, D.A. Zubov
Standardized high solid targets for cyclotron production of diagnostic and therapeutic radionuclides
S. Al Jammaz, S. Al-Yanbawi, S. Melibari, Rahma
Useful concepts in solid state target technologies D.J. Schlyer, R.A. Ferrieri
DEVELOPMENT OF A HIGH CURRENT SOLID TARGET, A NOVEL
RADIOCHEMISTRY FOR TL-201 AND PD-103 PRODUCTION
R. STRANGIS, C. ROCCO, E. GUEVARA, G. MASLAT, F. CORRAL, N. GONZÁLES, R. TÉRAMO, J. LAGO, G. CASALE Cyclotron Facility, Ezeiza Atomic Centre, Comisión Nacional de Energía Atómica, Argentina
Abstract
Solid targets development aims to obtain large quantities of radionuclides from accelerators. P
201
PTl is the most used
radioisotope in nuclear medicine, which is produced in cyclotron. The scope of the research was to test another procedure of
Tl-201 production as an alternative of the precipitation and extraction method used at present. Utilization of ionic exchange
resins was studied. Pd-103 is increasingly used in brachytheraphy seeds. A high current solid target technique for cyclotron
irradiation of electroplated metals was developed to produce Tl-201 and Pd-103. The design of the solid target set up and
different procedures to obtain Pd-103 for seeds applications are presented.
1. INTRODUCTION
Tl-201 has wide utilization in cardiologic studies, renal, and in the last years as tumoural
cerebral detector. P
103PPd has been used in treatment of various cancers such as eye, brain, neck, uterus,
colon [1], but it is almost exclusively used for prostate cancer as the most common cancer and causing the highest death rate in men. These radionuclides are cyclotron-produced by irradiation of solid targets and the objective of this CRP is to develop procedures to obtain these targets.
2. DEVELOPMENT OF A NEW SOLID TARGET CARRIER
The solid target system installed in the Cyclotron Facility by Forschungszentrum Karlsruhe
(FZK), Germany, has the following characteristics: Tangent beam 7 P
oP, ISO-RABBIT pneumatic
transport system; welded system, Al body + Ag face, Irradiation surface of 23 mm × 80 mm. Problems after 160 P
203PTl irradiations:
• High cost: US$1800 • Recovery needed: High dose (Ag-105) 6 month of decay to reuse. • 30 Targets for a weekly routine production • AgP
+P ions are introduced with Tl-203. Pitting of the silver surface reduce the life.
• Cooling studies made by Prof. Van Den Winkel show that at 100 µA metallic thallium melts. • Ag+ traces are recovered with enriched Tl (same cationic group)
The proposed target has the following advantages:
• Screwed system, no weld needed. • Frontal face: 1mm Cu (not recycled) thickness • Two-pieces target. Al body (low dose, recycled) Cu face, (high dose, not recycled). • Low assembly dose. • 3-4 target body/weekly irradiation. • Low irradiation cost. • Allows Rh irradiation for P
103PPd production; better cooling.
1
FIG. 1. Ezeiza target.
TABLE I. DEFORMATION OF DIFFERENT CU SHEETS (MM)
Thickness Pressure 1 Kg/cm P
2P 3 Kg/cm P
2P
7 Kg/cm P
2P
1 mm - 0.02 0.04 1.5 mm - 0.01 0.02 2 mm - - 0.01
3. NEW CHROMATOGRAPHIC TL/PB SEPARATION FOR TL-201 CYCLOTRON PRODUCTION
3.1. Analytical methods
The distribution constants (Kd) of Tl P
+P, TlP
3+P and Pb P
2+P were determined for the cation exchange
resin BioRad AG-50W of different cross-linkages and particle sizes and different HCl and HNOB3B concentrations. To measure Tl tracer of P
201PTl, was used to detect Pb P
2+P tracer of P
210PPb was involved. The
concentrations of Tl measured in the Jarrell-Ash equipment by atomic emission (sensibility 1.0 ppm) at 3445 Å were correlated with Pb measured in the same equipment at 2170 Å (sensibility 0/01ppm).
2
The chromatographic separation was developed using preparative equipment constituted by a
peristaltic pump, a GILSON fractions collector coupled to a NaI (Tl) detector and a home made data acquisition system.
3.2. Determination of Kd
1,000 g of cationic resin in 50 ml acid solution was equilibrated with 250 mg of TlB2 BSO4 labeled
with P
201PTl. For the Pb P
2+ P, a solution of Pb (NOB3 B)B2B (concentration 0.1mg/ml) spiked with P
210PPb was used.
The P
201PTl P
3+P was obtained oxidizing the P
201PTl P
+P with a Cl B2 B generator (KMnO B4B + HCl) bubbling gently
during one minute and then heating in order to eliminate the residual ClB2 B. Table II shows the Kd values obtained with AG50Wx12, 200-400 mesh resin for different concentration of HCl and HNOB2.
TABLE II. KD RESULTS
[HNOB3 B] 0.1 M 0.25 M 0.5 M 1.0 M 2.0 M 5.0 M PbP
2+P
10P
4P
1420 183 35 8.5 7.2 Tl P
+P
173 91 41 22.3 9.9 7.6
[HCl] 0.1M 0.25 M TL P
+P
100 62 Tl P
3+P
80 53 PbP
2+P
10P
4P
3500
3.3. Optimization of the chromatographic Pb/Tl separation
Using a simulated target (700 mg of TlNO B3 B and 1mg of Pb (NO) B2 B labeled with P
201PTl and P
210PPb
respectively) in a low pressure chromatographic equipment, separations involving different types of columns, resin bulks, gradients and solvent flows were tried.
The optimal conditions for the separation are, as follows: • Type of Resin: AG50WX12 200-400 • Solvent: HNO B3B 0.1M • Resin bulk: 1,20 g • Flow: 1.3 ml / min • Temperature: ambient
In these conditions, a high ratio of Kd Pb P
+P/Tl P
+P in HNOB3 B 0.1M is found, allowing to keep Pb P
2+P
adsorbed on the column during quantitative elution of Tl P
+P.
3.4. Proposed method
The previous results allow to realize a new separation of 203Tl carrier from the carrier-free 201Pb after dissolution of the irradiated target in diluted HNO3 and adsorption on a small AG-50W X12 (200-400 merk) column. The P
203PTl is quantitatively eluted with 0,1 MHNO3 and 0,1 MHCl. Upon a 32
hrs decay period, the 201Tl is eluted with 0,1 MHCl. The flow diagram is represented in Fig. 3.
3
0
50
100
150
0 50 100 150 200 250 300 350 400 450
HCL 2MHNO .1M HCL .1M
PbTl
FIG. 2. Chromatogrammes.
FIG. 3. Method of cyclotron produced P
201PTl using chromatographic withholding in P
201PPb
column.
The solution obtained in the 203Tl recovery step is HNO3 0.1M, a medium allowing use as
such in the recovery step of 203Tl. The active residues from Pb obtained in the last step were used to study the percentage of Pb2+,
remaining on the column and by the isotopic relationship, the energy range to which was irradiated the target.
3.5. Target irradiation
The main production reaction is: P
203PTl (p, 3n) P
201PPb P
201PTl (t½=73hs)
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and the secondary reactions are: P
203PTl (p, n) P
203PPb (t½=52hs. )
P
203PTl(p,2n)P
202PPbP
202PTl(t½=12.2 d)
P
203PTl (p, 4n) P
200PPbP
200PTl(t½ = 26.1hs)
From the ALICE code and according to literature (8, 9) it follows that the optimum irradiation
range with H P
+P is 28 to 18Mev. This range minimizes the impurities produced by the secondary
reactions, in order to produce a final product according the pharmacopoeia regulations. A target thickness corresponding with such energy degradation was produced and sufficient
surface area for the power dissipation of the cyclotron beam (3 kw) was realized. For solid targets, the proton beam target angle equals 7 P
oP. The target area consists of an ellipse
(to 7 degree projection of a circle of 10 mm in diameter) of 80 * 10 mm with 700 mg of P
203PTl (98%),
electroplated in basic medium according Van den Winkel’s recommendations in a double window cube.
3.6. Tests in the cyclotron and results
The method was tested in the cyclotron of the Ezeiza Atomic Centre, distant 30 km from the
city of Buenos Aires. This cyclotron accelerates H P
+P up to 45 Mev with a current of 150 µA. Irradiation
with different currents were performed in order to evaluate the quality of the electrodeposited target layer and the final product. Using natural thallium facilitates the study of the adsorption of Pb since large quantities of P
203PPb are produced by the reaction:
P
205PTl (p, 3n) P
203PPb (t½=52hs)
The following yields (EOB corrected) were obtained: o Recovery of PbP
2+Pon column: 99.8%
o Yield of P
201PTl (respect to the theoretical): 95%
o Recovery of P
203PTl: 99.5%
The radionuclidic purity was determined by gamma spectrometry with HPGE detector coupled
to the multichannel Canberra series 4100; (EOB corrected): o P
201PTl (reference): 100%; P
200PTl: 1.0%; P
202PTl: 0.4%; P
201PPb: 6.10-3%; P
203PPb: 0.21%
o Radiochemical Purity: according to bibliography (7,8) obtaining: o P
201PTlP
+P: 100%; P
201PTlP
3+P: 0%
3.7. Conclusions
The method developed gives a good yield for the P
201PTl production. The quality control of the
P
201PTl obtained complies with the regulations of the current pharmacopoeia requirements; even for the
irradiation of natural thallium. The principal advantage of this method is that precipitation and/or extraction steps are avoided, steps that are difficult to do in hot cells.
The ion exchange chromatography proposed for the separation of nanomoles of Pb P
2+P from large
quantities of Tl P
+P, is simple and allows total automation of the entire process.
4. DIRECT PC P
201PTl PRODUCTION
In order to complete our radiochemical P
201PTl processing presented in this workshop, an
automated system was developed. The system is operated by Windows Visual Basic 3.0 software,
5
allowing multi task performance. Several electronic interfaces have been developed for operating the electromechanical component of the manifold, thus avoiding the industrial automation equipment such as PLCs. Though not frequently used for automation of industrial processes the operating system and software developed, proved to be 100% reliable.
The automation intends:
o To minimize the personnel's operative interventions involved in the production and consequently to reduce the risk of human error during the process.
o To minimize the time of the operators’ radiation exposure. o To reduce the size of the hot cells.
4.1. PC software to obtain Tl-201
This software possesses a window of graphic interface (Image 1), in which one can control all
electric and electro-pneumatics components integrated in the automatic system.
FIG. 4. Image 1 (Outline of the automatic process).
On the left part of the window there is a panel showing the process diagram, where each
component can be checked by double clicking with the left button of the mouse. On the right part of the window, the storage system of residual liquids is presented. The state of
each of them can be checked as well. During the dissolution of the irradiated P
203PTl electrodeposited on the solid target carrier, one can
obtain a potentiometric dissolution graph (V versus t) curve and a temperature versus time (T versus t) curve. These data sets allow optimization of the dissolution time as a function of temperature.
6
Image 2 (Breakup curve). FIG. 5.
There are two ways to use this software, manual or automatic. In the manual option, the operator controls each component of the system (electronic valves, bombs, ovens heaters, sensors, etc.). The automatic option runs the whole sequence of operations automatically. To implement this option, a micro language of programming of processes has been generated. It is composed of a series of commands allowing control of any of the components of the system. To use the micro language, a program that creates and edits the process performance is introduced. During the automatic operation of a process, a window will be visualized, indicating the data of the program in course. The automatic process could be interrupted at any time without waiting for the whole process program to be completed.
4.2. Editor programs for the process operations
Apart from the possibility of generating the operations in charge to carry out tasks involved in
the process, the software provides a series of commands that allow generating messages to be visualized during the process.
Image 3 (editor of process programs). FIG. 6.
7
4.3. Conclusions
This automatic system has been used successfully in 200 process runs in a prototype hot cell in
the Cyclotron Facility at the Ezeiza Atomic Centre. The mini hot cell has a volume of 0.25 m P
3P and is
fitted with 15cm thick lead walls. The electronic systems are simple parallel interfaces and eight channel analog-digital converters. All built into the PC box. Direct PC interfacing has the advantage that the microprocessor “knows” all the parameters of the radiochemical process and the whole system is very simple and safe.
5. CYCLOTRON P
103PPD PRODUCTION
Four ways to obtain P
103PPd for seed production are proposed, according to the type of cyclotron
and radiochemistry.
5.1. Targets
Main reaction:
P
103PRh (p, n) P
103 PPd E Bp+ B=18-0 MeV Yield= 398 uCi/uA.h
Proposed methods:
• Direct irradiation of Rh wires. • Rh foil irradiation & thermomigration of Pd. (Artyom Arzumanov Method) • Electrodeposited Rh target &thermomigration of Pd. • Electrodeposited Rh target & wet chemistry (Van den Winkel Method).
5.2. Direct irradiation of Rh wires
This system was designed in order to produce directly P
103PPd by irradiation of Rh wires. The
wires have appropriate dimensions to be put into the titanium tubes for brachytherapy seeds. 20 Rh wires (7x 0.5mm) can be assembled in a 7degree target to beam system separated by 4 mm. A graphite mask (1.5 mm) covers the wires, gives mechanical support and acts as energy degradation. Cooling is by direct contact of the backing with water.
Disadvantages:
• Direct irradiation produces Rh 102 (207d), Rh 102m(2.9y), Rh 101m(4.34d), at lower levels than pharmacopoeia accepts for Pd-103 (<2%)
• Necessity to rotate the wires during irradiation (not rigorous) to obtain a more or less homogenous P
103PPd distribution.
• The apparent activity is lower than real activity (due the self shielding). • It is not applicable in high current beams. (< 50µA).
Advantages:
• The stopping power of Rh is sufficient to degrade 18MeV –5 MeV in 0.5mm of Rh in a 7P
oP beam/target geometry. (Sparkly –Program)
• Direct application in seeds.
8
FIG. 7. Direct production of Pd-103 by irradiation over Rh wires.
5.3. Rh foil irradiation & thermomigration of Pd
This method is based on the thermomigration of impurity atoms in a perfect metal lattice. For
Rh it was first developed by N. Gorodisskaya and A. Arzumanov. It consists in direct irradiation of an Rh foil (99.99% purity) 50µm, in direct contact with the backing of the solid target that is water-cooled.
The high Rh melting point allows irradiation up to 100µA without damage in a 7° beam to
target angle. Then the irradiated foil is put into a high temperature oven at 1200°C for 2-3 hours. P
103PPd
is displaced out of the Rh metal matrix. Finally, the foil is washed with HCl 0.1M removing in part the P
103PPd from the surface of the foil.
5.4. Electroplated Rh target and thermodifussion of Pd
In this method, the Rh is electroplated from a chloride Rh bath on a target Cu sheet with a layer
thickness of 50µA. This target tolerates more than 150 µA at 18 MeV. The irradiated target is disassembled and the copper sheet is dissolved in HNO B3 B (c) + HCl (c) (50-60°C). The fragments of Rh obtained are washed with distilled water and then put into a high temperature oven at 1200°C for 2-3 hours. P
103PPd is displaced out of the Rh metal matrix. Finally, the fragments are washed with HCl 0.1M
removing the P
103PPd from the surface of the rhodium.
5.5. Electrodeposited Rh target and wet chemistry method
Van den Winkel has developed this method. The Rh is electroplated (50µm layer) from a
sulphate bath on a target Cu carrier. This target supports much more than 150 µA at 18 MeV. The irradiated target is disassembled and the copper sheet is dissolved with HNO B3B (c) + HCl (c) (50-60°C). The fragments of Rh obtained are dissolved by electrodissolution with bubbling of Cl B2 B gas into the
9
solution of HCl(c) while applying a current of 10 Amp A.C. 60 Hz between two graphite electrodes. The solution obtained is used in the wet radiochemistry procedures.
5.6. Conclusions
All the systems proposed are suitable for Pd-103 production; the choice depends of the beam
current on the target and type of solid target station. The direct method is for low current beams, up to 50 uA, Rh radionuclidic impurities obtained are below the pharmacopoeia limits if the energy of protons is below 18 MeV. The great advantage of this method is the direct application in seeds so that no radiochemistry is needed. The disadvantage is due to the self shielding of the wire; the apparent activity is less than the real one. The Rh foil irradiation method is simple, fast, and the target can be recycled, but the P
103PPd yield is 50–70% of the activity produced. The electroplated Rh method tolerates
more current but needs recovery chemistry for the rhodium; the yield is 50–70%. The electrodeposited Rh method has high yield but needs a complete radiochemical procedure.
The CRP has provided the possibility to investigate and validate methods to produce Pd-103
from Rh targets. The target developed and improvement in Tl-201 production are the main achievements of the CRP The new technology adopted for Tl target electroplating and enriched thallium recovery gives excellent results in a very clean process with yields of 99.9%.
REFERENCES
[1] DEWI M LEWIS, Designing a Radioisotope Facility, Amersham Int. UK, 1996. [2] REDDY A. S.; Solvent Extraction Separation of Tl. J.Radioanalitical Nucl.Chem.Letters 87/6 [3] MALININ S.; Production of Tl-201, JARI Vol 37 No. 7. [4] BRITTO J.L.Q.; A New Production Method for Tl-201. J.Radioanalitical Nucl.Chem.Letters
94/6 1985. [5] BONARDI M., Tl-201 for Medical Use. Radiochem Radioanal. Letters 42/1/1980. [6] ASHOK RAO, Separation of Tl P
3+P from Tl P
+P. J.Radioanalitical Nucl.Chem.Letters 94/6/ 1985.
[7] FERNANDEZ L.; Quality Control of Tl-201 at IPEN. J.Radioanalitical and Nucl.Chem. Vol 172, Nr. 2, 1993.
[8] LAGUNAS SOLAR M. Tl-201 Excitation Functions. JARI Vol 31, pp 117-121. [9] QAIM S.M. et al. Production of Tl-201 and Pb-203 via Proton induced nuclear reaction on
natural thallium. JARI, v. 30 (2), p.85 (1979)
10
A PLATING/ELECTRODISSOLUTION/RECOVERY CYCLE FOR RHODIUM
TARGET MATERIAL USED FOR THE INDUSTRIAL CYCLOTRON
PRODUCTION OF PALLADIUM-103
P. VAN DEN WINKEL, L. DE VIS, R. WAEGENEER, A. DE SCHRIJVER, VUB- Cyclotron, Brussels, Belgium H. AFARIDEH, M. SADEGHI, M. HAJI SAEID NRCAM — Cyclotron Department, Tehran, Islamic Republic of Iran
Abstract
The production of carrier-free Pd-103 solutions by the P
103PRh(p,n) P
103PPd threshold reaction involves three chemical
steps. The first deals with the electroplating of a homogeneous 40-50 µm rhodium layer on a copper target carrier, ensuring to
take full benefit of the excitation function during the irradiation in a 6° beam /target geometry. After irradiation the second
step involves the dissolution of the irradiated rhodium, followed by step number 3, the separation of rhodium and carrier-free
Pd-103. A cylindrical, graphite centrifugal electro-dissolution mini-reactor was developed. It allows time-controlled solution
of rhodium fragments, powder and pieces of foils and wires. Feeding 12 N hydrochloric acid into the system operated at 85°C
and 1000rpm rotation speed and applying a 30 amperes ac-current, up to 3 grams of metal are dissolved in 40 ml of acid at
99% solubilization level in less than 3 hours. Carrier-free Rd 103 was separated and extracted using the solvent-solvent
method. Three different solvents, aqueous Rh B2BO B3B, RhB2B(SO B4B) B3B, RhClB3B, were tried for rhodium electroplating and recovery. The
results indicate that aqueous Rh B2BO B3B works best. To optimize the process, the experiment was repeated for different currents,
temperatures, and pHs. With this method, a completely smooth, reflective, and crack-free electroplated layer with a thickness
of 120 micrometers was obtained.
1. INTRODUCTION
The suitability of a given radionuclide for Brachytherapy is determined by its half-life, the type
of radiation and its energy and the abundance (number per decay) of its emission. Pd-103 with half-life of 17 days is a very low energy photon emitter (21 KeV) available for
permanent interstitial implantation. Pd-103 has better energy and safety characteristics than as I-125. Its initial peripheral dose rate is approximately three times higher than that of I-125. Tis may provide improved control of rapidly proliferating tumours. Pd-103 has been used in treatment of various cancers such as eye, brain, neck, uterus, colon [1], but it is almost exclusively used for prostate cancer as the most common cancer and causing the highest death rate in men.
2. A PLATING/RECOVERY CYCLE FOR RHODIUM TARGET MATERIAL USED FOR THE INDUSTRIAL CYCLOTRON PRODUCTION OF PALLADIUM-103
The aim of the joint research concerned the plating/recovery cycle of rhodium targets. The
ultimate purpose of the experimental work was the production of Cyclone-30 targets that can be used at the NRCAM in Karaj and that can be prepared from chemicals commercially available in Iran or from rhodium recovered from solutions obtained after centrifugal electro dissolution of irradiated targets and extraction of Pd-103. Moreover, attempts were made to obtain deposits showing acceptable qualities to fully exploit the beam current capacity of our accelerator.
2.1. Recovery of rhodium from irradiated target fragments
2.1.1. Introduction
Preliminary experiments showed that high-quality rhodium targets could be obtained from commercially available plating solutions such as Rhodex (Enthone, USA). As the purchase of these baths may be a problem in developing countries and as the price of rhodium compounds suitable for the preparation of solutions for thick-target (40 µm) plating are rather high, the recovery of rhodium from dissolved (irradiated) targets and the preparation of home-made plating baths were studied.
11
The plating from Rhodex is taken as a reference as far as the surface granulometry and the
thermal shock behaviour are concerned.
2.1.2. Reference quality criteria
The simultaneous preparation of four Cyclone-30 rhodium targets (thickness 40 µm, surface plating area 11,69 cm P
2P, rhodium weight 580 mg/target, 6° beam/target irradiation geometry) in the
VUB plating set-up requires the presence of 2,32 g of Rh (116 ml Rhodex of 25g/1250 ml concentrate) in a 450 ml plating volume.
The standard plating procedure is, as follows:
1. Dilute 116 ml Rhodex concentrate to 450 ml with 11% sulfuric acid ( pH = -0.34); 2. Heat up to 60°C and start a 24 hour plating at constant volume and temperature applying a
DC-current of 150 mA per target carrier; 3. Discard the colorless solution (pH = -0.39) and rinse abundantly with water 4. Remove the targets from the plating vessel and rinse with demineralized water 5. Clean the rhodium surface area with CIF detergent, rinse with water and acetone and air-
dry the targets. The SEM (scanning electron microscope) picture at a 250 magnification factor is shown in
Fig. 1.
FIG. 1. Rhodex Reference Rhodium target (SEM X 250).
The reference quality criteria for targets prepared from other plating solutions are: 1. Visual inspection and comparison of the granulometry of the X 250 magnification shot of a
target with that of Fig. 1; 2. The thermal shock test – heating of the target for 1 hour at 500°C in air, followed by prompt
immersion in cold water (15°C) should NOT give rise to crack formation nor to peeling off of the rhodium layer.
2.1.3. Procedures for recovery and plating bath preparation
Upon centrifugal electrodissolution of (irradiated) rhodium fragments and extraction of the Pd-103, a strong (up to 6N) hydrochloric acid solution containing the rhodium is used for the recovery. To prepare a new plating bath, combined recovery solutions holding the required amount of rhodium (2,32 g for the simultaneous preparation of 4 targets of 40 µm) should be involved.
Three procedures were tried :
12
a. Recovery as RhCl B3 B solution after evaporation to near dryness as such. The Cl P
- Pcontent of the
plating solution will be relatively high; b. Recovery as Rh B2B(SOB4B)B3 B solution after addition of H B2 BSOB4B and subsequent evaporation to near
dryness. The chloride content strongly reduced; c. Recovery as solid hydrated Rh B2 BO B3B after evaporation to near dryness as such, followed by
dilution with water and precipitation of Rh B2BO B3B.aq upon addition of concentrated NaOH. The chloride content of the plating solution will be reduced to a mininum.
a. Recovery as RhClB3B solution [2]
- Filter the recovery solution over a 0.45 µm filter (HVLP, Millipore) to remove any solid (Rh) particle present;
- Evaporate under gentle stirring (350°C at the start, 150°C near the end) to near dryness; - Take up in 300 ml of water, heat (150°C) and stir for 30 minutes and then filter through
a 0.45 µm filter; - Add the required quantity of plating additive (sulphamic acid, stress reducing agent); - Adjust pH to the aimed at value by means of 10 N NaOH or 36N H B2BSOB4B; - Make up to 450 ml with water.
In Table I, the data of 11 recovery/plating bath preparations obtained according this procedure
are summarized.
TABLE I. RECOVERY OF RH AS RHCL3
ExperimentNr WEIGHT RH (G)
SULPHAMIC ACID (G)
VOLUME (ML)
pH
C1 2.8 5 450 2.00 C2 3.5 5 450 2.00 C3 4.1 5 450 1.94 C4 4.2 5 450 2.43 C5 3.3 5 450 2.28 C6 3.1 5 450 2.65 C7 3.6 5 450 0.00 C8 3.1 5 450 0.00 C9 1.9 5 450 0.01 C10 2.5 5 450 3.60 C11 1.7 10 450 0.98
b. Recovery as Rh B2 B(SO B4B)B3 B solution[3]
To further reduce the Cl P
-P content of a plating solution, the recovery solution should be taken to
near dryness after the addition of concentrated sulfuric acid: - Filter the recovery solution over a 0.45 µm filter to remove any solid (Rh) particle; - Evaporate under gentle stirring (350°C at the start, 150°C near the end); - Carefully add a suitable volume (2 to 20 ml) of 95% of sulfuric acid; - Evaporate (350°C) until SO B3B fumes evolve and then continue heating and stirring for 30
more minutes; - Carefully add 300 ml water, stir and heat at 150°C for 30 minutes and then filter through a
0.45 µm filter; - Add bath additive (sulphamic acid, stress reducing agent) and adjust pH if desired with 10N
NaOH: - Make up with demineralized water to the volume requested.
13
Details on the preparation of four recoveries are summarized in Table II.
TABLE II. RECOVERY OF RH AS RH B2 B(SOB4B)B3 B SOLUTION
Experiment Nr
Weight Rh (g)
Volume H B2BSOB4 B(ml)
Sulphamic acid (g)
Volume (ml)
Acidity / pH
S1 12.5 20.2 10 900 2 N S2 8.2 8.1 5 450 1.9 N S3 5.7 2 5 450 pH=2 S4 1.5 2 5 150 pH=2
c. Recovery as solid Rh B2 BO B3B.aq
A two-step procedure allows the preparation of a new plating bath.
Step 1: Precipitation of Rh B2 BO B3B.aq
- Filter the recovery solution containing 2 to 6 grams of rhodium through a 0,45 µm filter (to remove any particle);
- Evaporate the filtrate to near dryness (350°C at the start, 150°C near the end); - Take up in 350 ml of demineralized water and heat (150°C) and stir for 15 minutes - Filter through a 0,45 µm filter (2-10 mg of black (Rh) residue is obtained), cool down the
filtrate to room temperature in a water bath; - Neutralize under vigorous stirring with 10N NaOH up to pH = 10 to 10.5. Use a combined
glass electrode as pH sensor; - To improve the filterability of the yellow Rh B2 BOB3 B.aq precipitate, allow to digest for 24 hours
at 50°C and gentle stirring; - Filter the precipitate on a Bleu Band filter paper (Schleich&Scheull 589) and wash at least
ten times with water to remove most of the adsorbed Cl P
-P anions. As some of the yellow
precipitate leaks through the filter, the filtrate is applied to a 0.45 µm filter; - Allow both filters carrying the precipitate to dry at the air for 24 hrs. Then remove the
rhodium oxide, grind the precipitate in an agate mortar and apply a 48 hrs vacuum-drying (350 mbar) at room temperature.
- The results of 14 recovery experiments are shown in Table III.
TABLE III. RECOVERY OF RH AS RH B2 BO B3 B.AQ
Experiment Nr
Weight Rh (g)
Weight RhB2 BO B3 B.aq (Vacuum-dried) (g)
Rh in Rh B2 BOB3 B.aq (%)
O1 3.6 5.77 62.3
O2 3.3 5.88 56.1
O3 1.9 3.02 61.2
O4 3.8 6.40 59.3
O5 2.5 4.24 58.9
O6 2.6 4.06 64.0
O7 3.4 5.67 60.0
O8 5.2 9.93 52.1
O9 2.6 4.70 55.3
O10 3.6 6.88 52.3
O11 3.6 6.71 53.6
O12 3.7 7.23 51.2
O13 2.5 4.77 52.4
O14 3.7 7.23 51.2
Mean 56.4 ± 4.4
14
The mean rhodium content of the precipitate amounts to 56.4 ± 4.4%. For the Rh B2 BOB3 B.5HB2 BO compound referred to in literature, this percentage is 59.9. The difference with the experimental value together with the different colors of the precipitates observed (ranging from lemon-yellow over yellow, yellow-ochre to dark ochre Fig. 2) suggests the composition and/or water content of the precipitate do depend on slightly changing experimental parameters such as rate of neutralization, final pH and digestion conditions. The results imply that the percentage of rhodium in the hydrated oxide must be determined experimentally before the plating of targets. This is done in Section 2.2.3.4.
Hue of vacuum-dried RhB2BOB3B.aq. FIG. 2.
Step 2: Preparation of plating bath from Rh B2 BO B3B.aq To further reduce the Cl P
-P content of the plating solution, the latter is prepared by dissolution of
an appropriate amount of rhodium oxide in boiling concentrated sulfuric acid thus expelling any chloride anion as HCl.
For the simultaneous plating of four 40 µm Cyclone-30 targets and taking the mean rhodium percentage reported in Table III as a reference, the procedure is, as follows:
- Transfer 4,076g of hydrated rhodium-oxide into a 400 ml beaker provided with a
magnetic stirring bar and carefully introduce 10 ml of 95% sulfuric acid. Cover the beaker with a watch-glass supported by glass hooks;
- Heat under gentle stirring (350°C) until SOB3 B fumes evolve and continue for 15 more minutes. A dark yellow-brown concentrate is obtained;
- - Carefully add 250 to 300 ml of water and continue heating (150°C) and vigorous stirring for 15 minutes;
- Filter through a 0,45 µm filter and dilute to about 400 ml with water; - If required, adjust pH to the aimed at value with 10N NaOH after the addition of
plating additives (sulphamic acid or magnesium sulphamate, stress reducing agent); - Make up to 450 ml.
2.2. Plating of rhodium targets from home-made plating solutions
2.2.1. Introduction
The electrodeposition of rhodium targets from homemade plating baths (described in Section I) was carried out with VUB plating equipment that has been used previously for the preparation of Rh targets from the commercially available Rhodex (Enthone). A brief description of the equipment precedes the summary and discussion of the current results.
15
2.2.2. Description of the VUB-plating set-up
The plating vessel (Fig. 3) is hollow perspex cylinder fitted with an axial Pt anode wire mounted in the bottom by means of a tube-end fitting with perforated septum. Four symmetrical windows in the vertical wall allow introduction and positioning of four Cu target carriers. Each slot is provided with an O-ring fitted window, the geometrical shape of which determines the electrodeposition area. Liquid-tightness is realized by stainless steel mechanical pestles mounted in a PVC ring surrounding the plating vessel and by pressing the Cu-carriers against the O-ring.
The external PVC ring is also fitted with four supporting pins to hold a motor-stirrer
combination in position. The stirrer is a hollow perforated POM cylinder mounted on the axis of the motor and surrounding the platinum anode. The stirrer rotation speed is set at 1000 rpm while the direction of rotation is reversed after 8 seconds to improve the homogeneity of the deposit. To maintain the temperature at the required level, a series of six isolated 1Ω/1 W resistors through which an appropriate dc-current is forced (1.1A – 40°C up to 1.8A-60°C) are circularly mounted.
An insulated sensor is introduced through the stirrer support plate to monitor the temperature of
the plating bath. As electrolysis to depletion requires long-time (up to 24 hrs) plating, evaporation of the plating solution occurs. To maintain the liquid at the required value (450 ml), a conductivity glass/graphite sensor monitors the solution level and actuates a peristaltic pump supplying distilled water at a rate to compensate for the evaporation losses.
FIG. 3. Plating set-up Rh-electrodeposition.
As constant current DC power supplies for plating and temperature control, two SM 7020-D (Delta Elektronoca) power supplies are used.
The total cc-dc current through the plating vessel is measured by means of a DVM890 (Velleman) multimeter.
Before the rhodium plating, the copper carriers are etched followed by copper plating on a surface area showing a perimeter that is about 4 mm larger (surface area per window 22,36 cm P
2P) as
compared with that of the rhodium plating area (11,69 cm P
2P).
A second plating vessel with appropriate windows is used therefore. The set-up involving the same cc-dc plating source is shown in Fig. 4.
16
FIG. 4. Copper etching/plating set-up.
2.3. Plating experiments
2.3.1. Pretreatment of copper carriers
The 1 mm copper plates used as target carriers during the experiments, are cleaned with abrasive wool, rinsed with water and acetone and air-dried. Next, four Cu plates are mounted in the plating vessel represented in Fig. 4. The vessel is then filled with 450 ml of Cu etching/plating solution (250 g CuSO B4B.5aq + 25 ml HNO B3,cB + 50 ml H B2BSOB4,c Bmade up to 2.5 L). Under vigorous stirring (1000 rpm / 8:8 seconds) and in the absence of any power supply, the thickness of the copper plate at the window area is reduced with a few µm after 3 hours. Next, a dc power supply is applied resulting in a 200 mA current per target: after 1 hour a 10 µm copper layer in excess is obtained. After removal of the etching/plating solution, the vessel is abundantly rinsed with water. Upon removal of the copper plates, the latter are rinsed with demineralized water and acetone, dried with soft adsorbing tissue and weighed.
2.3.2. Rhodium plating from RhCl B3 B solutions (series C1 to C11)
The plating solutions referred to in Tables I and IV are heated up to 40°C or 60°C and then introduced in the plating set-up shown in Fig. 3. At the end of the experiment, the (pale yellow to colorless) solution is discarded and the plating vessel rinsed abundantly with tap water. Upon removal of the targets, the latter are rinsed with demineralized water and acetone, air-dried and weighed. From this weight, the thickness t BoB of the layers is calculated. As Rh-plating to depletion always gives rise to a black coating of the deposit (Rh-black) near the end of the plating, the rhodium layers were cleaned with a scouring suspension (CIF) and a sponge. After rinsing with water and acetone and air-drying, the weight was determined again. From this weight, a thickness after cleaning t Bc B was calculated.
17
TABLE IV. TPLATING DATA FOR RHODIUM DEPOSITION FROM RHCL3 SOLUTIONS
BathNr
W(Rh) (g)
pH T ° (°C)
I (mA)
T (hrs)
tBo
(µm) tBc B
(µm) L
(%) Comments
C1 2.8 2.00 40 80 24 48.60 48.55 0.10 Reflective, smooth
C2 3.5 2.00 40 80 24 59.48 * - Highly reflective,
smooth C3 4.1 1.94 40 100 28.5 70.10 * - Highly
reflective, smooth
C4 4.2 2.43 40 125 24 71.59 71.25 .47 Reflective, smooth
C5 3.3 2.28 40 150 24 56.30 53.75 4.53 Smooth, grey C6 3.1 2.65 40 200 22 53.60 46.05 14.08 Smooth, dark
grey C7 3.6 0.00 40 200 15.5 61.40 58.95 4.00 Smooth, black C8 3.1 0.00 40 200 21 53.00 50.93 3.90 Smooth, black C9 1.9 0.01 60 150 5.5 33.00 31.10 5.76 Smooth, grey
C10 2.5 3.60 40 150 17 100 Not adherent C11 1.7 0.98 40 125 5 28.6 27.02 5.59 Reflective,
smooth (*) = Not determined
The plating data are summarized in Table IV, where:
- W(Rh) = weight rhodium present in the bath in grams - T P
°P = plating temperature in degrees Celsius
- I = dc current applied per target in milliampere - T = plating time in hours - tBoB and tBcB = mean thickness of rhodium layers in micrometer - L = losses during CIF cleaning in percent
From the results it can be concluded:
- Plating rhodium targets from RhCl B3 B solutions at pH = 1.9 to 2.5 applying a current of 80 to 125 mA per target at 40°C, results in (highly) reflective targets requiring no or limited scouring cleaning. Losses during scouring cleaning are then confined to less then 0.5%;
- Increasing the current per target to more then 125 mA in the same pH range and at the same
temperature, gives rise to increasing losses ( up to about 15% at 200 mA per target) of rhodium during the the cleaning process;
- At lower pH (< 1.0) cleaning losses are about 5% while plating at higher pH (>3.0) results in a non-adherent deposit that is completely removed from the Cu-carrier during the cleaning;
- Though of acceptable quality at visual inspection, the granulometry of all deposits is poor as compared with that of the reference Rhodex plating. The x250 magnification SEM shots of the reference and of the C3 plating are represented in Figs 5 and 6, respectively.
- As far as the thermal shock test is concerned, none of the deposits satisfies the 500°C test: quantitative peeling-off and powdering occurs. All deposits satisfy a 250°C thermal shock test;
- When the copper backing of the Reference Rhodex target is dissolved in concentrated nitric acid in a flow-through stripper, the rhodium may be collected as real rhodium fragments that can be applied easily to the centrifugal electrodissolution unit (see Fig. 7)
- When the stripping procedure is applied to rhodium deposits obtained from RhCl B3 B solutions, the target material disintegrates to a dark-grey black powder that blocks the stripper and that can be recovered difficultly from it.
18
FIG. 5. Rhodex Reference Rhodium target (SEM X 250).
FIG. 6. C3 Rhodium target granulometry (SEM X 250).
FIG. 7. Rhodium reference fragments after Cu stripping.
19
2.3.3. Rhodium plating from Rh B2 B(SOB4 B)B3 B solutions (series S1 to S4)
The solutions S1 to S4 were used for target plating at pH = 2 and in strong sulfuric acid (2N) acid containing 5 g sulphamic acid stress reducing agent.
The date is represented in Table V where:
- W(Rh) = weight rhodium present in the bath in grams - T P
°P = plating temperature in degrees Celsius
- I = dc current applied per target in milliampere - T = plating time in hours - tBo B and t Bc B = mean thickness of rhodium layers in micrometer - -L = losses during cleaning in percent
TABLE V. PLATING DATA FOR RHODIUM DEPOSITION FROM RH B2 B(SOB4B)B3 B SOLUTIONS
Bath Nr
W(Rh) (g)
Acidity or pH
T° (°C)
I (mA)
T (hrs)
tB0
(µm) tBc
(µm) L
(%) Comments
S1 2.24 N=2 60 150 22 38.60 37.62 2.52 Reflecting, smooth
S1 4.63 N=2 60 150 24 79.83 74.70 6.43 Reflecting, smooth
S2 5.92 N=1.9 60 150 15.5 102.02 91.70 10.12 Not adhering S3 5.0 pH=2 40 100 21.5 85.90 - Highly
reflecting, smooth
S4 1.5 pH=2 40 25* 16.5 108.08 106.32 1.63 Smooth,gray (*) Surface area 2.79 cmP
2P
In Figs 8 and 9, the X 250 SEM pictures from deposits obtained at (pH = 2 / I = 100 mA) and
(2N sulfuric acid / 150 mA) respectively, are represented.
FIG. 8. Plating at 2N/150 mA.
20
FIG. 9. Plating at pH=2/100 mA.
From the results, it can be concluded that as compared with the Rhodex reference (Fig. 1), the granulometry of the deposit is poor.
As moreover none of the deposits satisfies the 500°C thermal shock test, no further experiments on this plating technology was done.
2.3.4. Rhodium plating from Rh B2 B(SOB4 B)B3 B baths prepared from RhB2BO B3B.aq (series O1 to O14)
Using the Rh B2 BOB3 B.aq precipitates reported in Table III a series of Rh B2 B(SOB4B)B3 B plating baths containing a minimum amount of chloride ions were prepared. A summary of the plating experiments and - conditions carried out with these solutions are represented in Tables VI, VII and VIII.
TABLE VI. INFLUENCE OF STRESS REDUCING AGENT PLATING CURRENT 150 MA/TARGET; PLATING TEMPERATURE 60°C
W(RhB2 BO B3B) (g)
pH T (hrs)
S.A (g)
W(Rh) (g)
tB0
(µm) tBc B
(µm) L
(%) %Rh
SEM
2.4394(O1)° -0.36 19 0 1.2138 41.87 40.70 2.8 49.7 22 2.4394(O1,O2)° 1.00 17 5.0 1.2271 42.33 41.25 2.6 50.3 24 5.0552(O8) 0.72 6* 30 1.9946 34.40 33.90 1.4 - 34 2.4394(O1)° -0.39 20 54.1* 0.6773 23.36 23.05 1.3 - 23 4.8184(O14) 0.47 18 54.1* 1.8409 31.75 30.20 4.9 - --
TABLE VII. INFLUENCE OF PH, PLATING CURRENT 150 MA/TARGET; PLATING TEMPERATURE 60°C
W(RhB2 BO B3B) (g)
PH T (hrs)
S.A (g)
W(Rh) (g)
tB0
(µm) tBc B
(µm) L (%)
%Rh
SEM
6.0985(O1 to O4) 0.52 19 5.6 2.8951 49.93 49.67 0.51 47.5 27 2.4394(O2) ° 1.00 17 5.0 1.0555 36.41 36.05 0.99 43.3 26 5.6700(O7) 2.09 18 5.0 2.8394 48.97 48.77 0.40 50.1 30 5.7200(O5,O6) 3.03 9 5.0 2.8643 49.40 48.31 2.21 50.1 31
(°) = Two target plating
21
TABLE VIII. INFLUENCE OF CURRENT PER TARGET, PLATING TEMPERATURE 60°C; SULFAMIC ACID 5G
W(RhB2 BO B3B) (g)
PH I (mA)
T (hrs)
W(Rh) (g)
tB0
(µm) tBc B
(µm) L
(%) %Rh
SEM
2.4394(O2) ° 1.00 150 17 1.0555 36.41 36.05 0.99 43.3 26 4.8787(O3toO5) 1.00 200 5 2.2390 38.62 37.90 1.86 45.9 32
3.0337 1.92 100 24 1.5800 27.05 ----- ---- 52.1 15 5.6700(O7) 2.09 150 18 2.8394 48.97 48.77 0.40 50.1 30
(°) = Two target plating
2.3.5. Influence of the presence of stress reducing agent
A first set of experiments deals with the presence/absence of a stress reducing agent on the quality of the deposit. Solutions containing no stress reducing agents or containing sulphamic acid or magnesium sulphamate were prepared. The results are summarized in Table VI,
where :
- W(RhB2 BO B3B) = weight of rhodiumoxide in grams with reference to its origin (O#); - (°) = two-target plating - pH = acidity of solution - T = plating time in hours; T* = not plated to depletion - S.A = weight sulphamic acid or magnesium sulphamate (*) in gram - W(Rh) = weight of rhodium deposited after plating to depletion - tBo B= thickness of the deposit in micrometer - tBc B= thickness of the deposit in micrometer after CIF cleaning - L = loss in percentage due to cleaning - %Rh = percentage rhodium in rhodiumoxide calculated from W(Rh B2 BO B3B) and W(Rh)
From Figs 10 and 11, it follows that the presence of sulphamic acid enhances the quality of the
granulometry. Please note all SEM shots were taken at an X250 magnification factor.
FIG. 10. No stress reducing agent present.
22
Increasing the concentration of sulphamic acid up to 35 grams further improves the quality as can be seen from Figs 11 and 12. Substituting for sulphamic acid by magnesium sulphamate, results in an additional improvement of the quality (Fig. 13). Unfortunately, in the present experimental conditions, the magnesium sulphamate gives also rise to the formation of finely divided rhodium powder that sticks to the electromechanical stirrer and to the walls of the plating vessel such that about 50% of the rhodium present in the plating solution is lost. Experiment 5 for which no SEM shot as taken confirmed this behavior.
FIG. 11. Sulphamic acid (5g) present.
FIG. 12. Sulfamic acid (35g) present.
FIG. 13. Magnesium sulfamate (54g) present.
23
2.3.6. Influence of pH
The influence of the pH of the plating solution on the quality of the rhodium layer was investigated in the range 0.5 up to 3 in the presence of 5 g sulphamic acid. The data are summarized in Table VII. The SEM shots (250 magnification factor) are represented in Figs 14 to 17.
FIG. 14. Plating at pH = 0.52.
FIG. 15. Plating at pH 1.00.
FIG. 16. Plating at pH = 2.09.
24
FIG. 17. Plating at pH = 3.03.
From the pictures it is obvious that plating should be carried out in the range pH = 1 to 2.
Removal of the rhodium black layer by means of a scouring suspension (CIF) then results in a less than 1% loss of target material.
2.3.7. Influence of current density
The effect of the current density was studied out in the 100 to 200 mA per target range. Taking into account the plating surface area (11.69 cm P
2P) this corresponds to a current density (j) 8.55 to 17.11
mA.cm P
-2P. The experiments were performed with solutions containing 5 g sulphamic acid stress
reducing agent, pH was adjusted between 1 and 2 and temperature was set at 60°C. The data are represented in Table VIII. The SEM data are shown in Fig. 18 up to Fig. 21.
FIG. 18. Plating current 150 mA/target.
25
Plating current 200 mA/target FIG. 19.
FIG. 20. Plating current 100 mA/target.
FIG. 21. Plating current 150 mA/target.
26
From the results it follows that 100 mA per target (j = 8.55 mA.cm P
-2P) gives the optimum result.
It should be noted that applying the same current density when plating at pH 1.00 or pH = 2.09 (Figs 18 and 21) gives comparable results, as expected.
From the above it can be concluded: Optimum plating conditions for the simultaneous preparation of four 40 µm Cyclone-30
rhodium targets from Rh B2 B(SOB4B)B3 B solutions prepared from hydrated Rh B2 BO B3 Busing the VUB plating equipment are :
- 1<pH<2 - Current 100 mA/target (j = 8.55 mA.cm P
2P )
- Stress reducing agent: sulphamic acid 5 g/450 ml - Temperature 60°C - The granulometry of the deposit is comparable with that of the Rhodex reference as is
shown in Figs 22 and 23; - Scouring cleaning (using CIF) to remove the shallow rhodium-black deposited near
the end of the plating, results in losses of about 1%: - The deposit satisfies the 500°C thermal shock test as was the case for the Rhodex
reference; - Application of the flow-through copper stripping procedure results in rhodium
fragments as does the Rhodex reference (see Fig. 7); The mean rhodium content of the vacuum-dried (48 hrs, 25°C, 350 mbar) Rh B2 BO B3B.aq precipitates
amounts to 48.2 ± 3.1%. Calibration of the compound can be done by plating-to-depletion.
FIG. 22. Rhodex reference deposit.
FIG. 23. VUB/NRCAM deposit.
27
2.4. Conclusions
1. Recovery of rhodium from (irradiated) hydrochloric acid solutions obtained after centrifugal electrodissolution and extraction of Pd-103, and the preparation of new plating baths from recovered rhodium can be done in two ways:
1.1. Evaporation of the recovery solution (containing about 3 g of rhodium) to near dryness,
uptake of the RhCl B3B concentrate in 300 ml hot water and filtration through a 0.45 µm filter to remove any solid particle, followed by the addition of sulphamic acid stress reducing agent (up to 35 g per bath) and adjustment of the pH to a value 1.9 to 2.5. Upon make up with water to 450 ml, the RhCl B3
Bsolution can be used for the simultaneous plating of four Cyclone-30 targets showing a thickness of 40 µm;
1.2. Evaporation of the recovery solution (containing up to 6 g of rhodium) to near dryness,
uptake of the RhCl B3B concentrate in 300 ml hot water and filtration through a 0.45 µm filter to remove any solid particle, followed by addition of 10 N NaOH up to pH = 10 to 10.5. To enhance the filterability, the hydrated Rh B2 BO B3 B suspension formed is allowed to digest (50°C, gentle stirring) for 24 hrs whereupon filtration through a blue band filter paper is performed. Any colloidal particle in the filtrate is recovered by filtration through a 0.45 µm filter. Upon 24 hrs of air-drying, the precipitate is ground in an agate mortar. The resulting yellow powder is vacuum-dried (room temperature, 350 mbar) during 48 hrs. The mean rhodium contents of the hydrated rhodium oxide powder amounts to 48.2 ± 3.1%.
A new plating solution for the preparation of 4 Cyclone-30 targets (40 µm layers) can be
prepared by dissolution of 6.1 g rhodium oxide in 10 ml boiling sulfuric acid followed by uptake in 300 ml hot water and filtration through a 0.45 µm filter. After addition of 35 g sulphamic acid stress reducing agent, the pH is adjusted to a value between 1 and 2 and the solution made up to 450 ml. The resulting RhB2 B(SOB4B)B3 B solution is ready for plating.
2. The simultaneous plating of 4 Cyclone-30 (40µm) rhodium targets using the VUB plating set
up, can be done from the RhCl B3 Bsolution or from the Rh B2 B(SOB4 B)B3 B solution described above. In either case, the copper target carriers are first etched in an acidic copper sulfate bath followed by plating of a 10µm layer in excess of copper.
2.1. For the preparation from the RhCl B3 Bsolution, the latter is heated up to 40°C and then
transferred to the plating vessel. An optimum current of 100 mA per target (j = 8.55 mA.cm P
-2P) was
determined. Upon plating to depletion (24 hrs), deposits showing a poor granulometry as compared with that of the Rhodex reference plating are obtained. As moreover the 500°C thermal shock test results in quantitative peeling off and powdering, the targets are not suited for high beam current irradiation;
2.2. When the Rh B2 B(SOB4B)B3 B solution is used, a 60°C plating temperature is applied. Again, a 100
mA plating current per target is to be preferred. The granulometry is comparable with that of the Rhodex reference and the 500°C thermal shock test is satisfied. As moreover the removal of the copper backing (using concentrated nitric acid) in a flow-through stripper gives rise to rhodium fragments, as does the reference, it may be concluded that the quality of the deposit is acceptable for high beam current irradiations.
3. CENTRIFUGAL ELECTRODISSOLUTION SYSTEM FOR FRAGMENTED ELECTROPLATED RHODIUM TARGETS USED FOR THE INDUSTRIAL CYCLOTRON PRODUCTION OF PALLADIUM-103
As it is well known from literature, the method to be preferred is the alternative current
electrodissolution [4][5] in hydrochloric acid introduced Box [6]. Though applicable for foils, it
28
suffers from a serious limitation: due to fragmentation the maximum applicable current density (and hence the dissolution rate) is confined to 0.5 A/cm P
2P and the recovery of Pd-103 is less than 90%.
Therefore, a centrifugal high-current density electrodissolution system was developed at VUB.
Preliminary had shown that it allows fast dissolution of fragmented rhodium (up to several grams) within a few hours.
The present experimental work aims at the evaluation and optimization of the performances of
the prototype system.
3.1. Brief description of the system
The homemade experimental set-up is shown in Fig. 24. The PVC frame (PVCF) supporting the
mini-reactor is made up from four circular and parallel supporting-plates held together by cylindrical spacers.
Fig. 24 Schematic set up
The working-electrode (WE) consists of a cylindrical excavated electro-graphite receptacle
(inner diameter 3.6cm, height 1.4cm, surface area vertical walls 15.8 cm P
2P) provided with a screwed-in
perspex top-piece (TP, height 9cm ) to increase the total volume of the system. Liquid-tightness at the graphite/perspex junction is assured by means of a NBR O-ring .To limit upwards lead of small rhodium fragments to the graphite section, the perspex top-piece is fitted with a lower inside flange
29
(IF). A circular insulating Teflon disk (TD) covers the bottom of the working electrode. This entity is fixed onto a stainless steel pin (SSP) connected to the shaft (MS) of a dc motor–tacho-reductor (M/T) combination by means of an insulating Teflon bush (ITB). Home–made electronics allow continuous adjustment and measurement of the rotation speed. The cylindrical graphite rod counter–electrode (CE, diameter 2.6cm, height 16 cm) is mounted in the upper supporting plate such that the distance between the teflon disk and the lower end of the graphite rod equals about 1mm. Vibrations of the system at the current rotation speed are eliminated by high-quality bearings (HQB) clipped onto the motor shaft and fixed into a supporting-plate.
The electrical contact with the ac-power supply is made by inserting a plug (PL) into a notch in
the top of the counter electrode and by two custom made, spring-loaded soft-bronze and parallel-circuited sliding brushes (SLSB) contracting the stainless steel pin supporting the rotating graphite/perspex receptacle.
When filled with a rhodium fragments containing hydrochloric acid solution and by applying a 1000 rpm rotation speed, the design results in the fragments to be collected and current to flow mainly between the side wall of the working-electrode and the lower section of the vertical wall of the counter-electrode, thus ensuring a high current density.
As warming up and evaporation of the solution due to high-current flow and chemical reactions do result in a continuous decrease of volume of the solution present in the reactor, feed-back addition of hydrochloric acid is done by means of home-made conductivity electronics that actuates a peristaltic pump. Therefore a third mini carbon-glass auxiliary electrode (LS) sensing the liquid level (LL) is mounted in the upper supporting-plate. The conductivity measurements that trigger the pump are done between the counter- and the auxiliary electrode.
The hydrochloric acid volume is about 40ml and the maximum rotation speed 1000 rpm. The complete experimental set up is shown in Fig. 25 By means of an auto-transformer (Output
0 to 250V) the voltage applied to the primary coil of a transformer (1250 VA) is varied such that the output current applied to the reactor equals maximum 30 A. This current is monitored by means of a clamp meter.
FIG. 24. Experimental set up.
30
3.2. Performances of the system
From preliminary experiments, it follows that:
- The change of concentration of HCl due evaporation and chemical reactions as a function of time results in a constant concentration after a certain time of operation (for input concentration of 12 N HCl, the equilibrium concentration is about 7 N after about 1 hour at a current of 30 A);
- The rhodium dissolution rate depends on the HCl concentration; - The dissolution rate depends on the applied current; - The dissolution rate depends on the weight of rhodium.
From the experimental data, it follows that the dissolution rate (dW(t)/dt , mg/min) is given by:
dW(t)/dt = K*[1-exp(-b.C(t))][1-exp(-c.∆I)][1-exp(-d.W(t))] with:
- C(t) = C Beq B(1-exp(-a.t))+CB° B.exp(-a.t) (concentration HCl as function of time with a = 0.0727-0.00266 C B0 B)
- C B0B = input concentration (max 12 N) - C Beq B = C B0B (1 – 0.0178*I) (I = current in A) - ∆I = I – 4.75 - K =55.6; b=0.292; c=0.1105 ; d=0.804 - A, b, c and d are experimental constants.
Numerical integration of this equation can be done by any loop algorithm interrupted by an
appropriate condition concerning the aimed at solubilization level, i.e. the fraction (99% level for instance) or weight W of rhodium fragments to be dissolved. The output is then the Time required (T99%) to obtain that solubilization level.
3.3. Experimental results
The goal of the experiments was to determine: 1. The maximum rhodium input weight that results in a T99% in agreement with the calculated
value, i.e. the maximum allowable amount of Rh to be dissolved in a single run. 2. The applicability of the system to dissolve not only rhodium fragments, but Rh powder, wires
and foils. 3. Technical limitations of the reactor prototype and forward suggestions for improvement of
the performances. The rhodium fragments were prepared by dissolution of the copper carriers of electroplated Rh
targets in concentrated nitric acid – giving rise to Rh fragments, which were further grounded in an agate mortar. All experiments were carried out at 80 P
+PB-B 2 P
0PC.
From Fig. 26 it follows that the maximum single run capacity of the system is 3,0 g of rhodium
dissolved in 40 ml of hydrochloric acid.
31
D is s o lu tio n Y ie ld R h v e rs u s w e ig h t R h
60
70
80
90
100
110
0 1 2 3 4 5 6
W e ig h t R h o d iu m (g r)
Dis
so
luti
on
Yie
ld R
ho
diu
m (
%)
FIG. 25. Maximum single run capacity of the system.
From Table IX it can be concluded that the technology is applicable to tune-controlled
electrodissolution of rhodium fragments, cut wires and cut foils as well as to rhodium powder. Suggestions to further improve the performances of the systems are introduction of coolmy and
current sensor allowing feedback stabilizator of bath parameters.
TABLE IX. DISSOLUTION TRIALS WITH RHODIUM POWDER, WIRE, FOIL
Weight Rh (gr)
I (A) Yield%
Normality input
Normality output
T99% (min)
Remarks
2.5067
25
99.8
12
8.3
167
CA80_POWDER
2.5053 25 99.66 12 6.6 167 CA80_POWDER 1.1269 25 99.7 12 6.2 145 CA80_WIRE 1.3340 25 99.8 12 6.7 149 CA80_FOIL
3.4. Conclusions
1. From Fig. 26 it follows that the single run capacity of the system operating at 25 A, hydrochloric acid input concentration P
12PN and a reactor volume of 40 ml is limited to 3.0 gr irradiated
rhodium. 2. The system can be used for rhodium powder, cut rhodium wires and foils, and for rhodium
fragments (Table IX) obtained upon nitric acid dissolution of the Cu-target carrier of electroplated rhodium targets.
3. To avoid local boiling and current drops, a temperature sensor must be introduced into the
system. A mini-diode integrated in a bridge circuitry proved to be an excellent temperature sensor. Coupled to a differential amplifier /comparator/current-booster/valve set-up, compressed air-cooling of the graphite limits the temperature to 80±2 C°. In this way the system proves to be very stable at 25 A a.c electrodissolution current.
32
REFERENCES
[1] M.S.PORRAZZO ET AL. “Permanent Interstitial Implantation using Pd-103: the New York
Medical College Preliminary Experience “, Int. J. Radiation Oncology Biol. Phys. 1992, Vol 23 (5), pp. 1033-1036.
[2] PLETCHER D., URBINA R.I. Electrodeposition of rhodium. Part 1. Chloride solutions. J. Electroanalytical Chemistry, v. 421 (1-2), (1997), pp.137-144.
[3] PLETCHER D., URBINA R.I. Electrodeposition of rhodium. Part 2. Sulphate solutions. J. Electroanalytical Chemistry, v. 421(1-2), (1997), pp.144-151.
[4] LAGUNAS-SOLAR M.C., ET AL. Targetry and radiochemical methods for the simultaneous cyclotron production of no-carrier-added radiopharmaceutical quality Pd-100, Ru-97 and Rh-sup.(101m). J. Appl. Radiat. Isot. 38 (2) (1987), pp. 151-157.
[5] LAGUNAS-SOLAR M.C., ET AL. Cyclotron production of no-carrier-added 97Ru by proton bombardment of 103Rh target. J. Appl. Radiat. Isot. 34 (6) (1983), pp. 915-922.
[6] GAITA R., AL-BAZI S.J. An ion-exchange method for selective separation of palladium, platinum and rhodium from solutions obtained by leaching automative catalytic converters. Talanta, v. 42 (2) (1995), pp. 249-255.
[7] LAGUNAS-SOLAR M.C. ET AL. Cyclotron production of Rh-sup(101m) via proton induced reactions on Rh-103 targets. J. Appl. Radiat. Isot., v. 35 (8) (1984), pp. 743-748.
[8] RAMLI M., SHARMA H.L. Radiochemical separation of Rh-101m via Pd-101 from a rhodium target. J. Appl. Radiat. Isot. v. 48 (3) (1997), pp. 327-331.
[9] CHUNFU Z., ET AL. Cyclotron production of no-carrier-added palladium-103 by bombardment of rhodium-103 target. J. Appl. Radiation and Isot. v. 55 (4), (2001), pp.441-445.
[10] TARAPCIK, P., MIKULA, J.V., Separation of Pd-103 from cyclotron irradiated rhodium targets. J. Radiochem. Radioanal. Letters., 48 (1) (1981), pp. 15-20.
33
NEW TECHNOLOGY FOR THE INDUSTRIAL PREPARATION OF HIGH
QUALITY TL-203 CYCLOTRON TARGETS BY CONSTANT CURRENT
ELECTROPLATING
P. VAN DEN WINKEL, L. DE VIS, M. DE VREESE, R. WAGENEER, A. DE SCHRIJVER, A. ARZUMANOV, Vrije Universiteit Brussel, Cyclotron Department, Brussels, Belgium N. GORODISKAYA, P. ZHELTOV Institute of Nuclear Physics, Almaty, Kazakhstan
Abstract
A new technology for the industrial preparation of high quality Tl-203 cyclotron targets was developed. It consists of
ac-constant current electrodeposition of Tl-203 from an alkaline (pH> 12) EDTA plating solution containing appropriate
amounts of an anodic depolarizer (hydrazine) and of non-incorporated neutral wetting agent (BRIJ-35). As plating waveform
a bipolar chopped sawtooth (f BST B=100 Hz, f BCHB = 100 Hz) is applied while the optimum current density equals 2-3 mA.cm P
-2P.
When plating up to 50% depletion is performed, the current efficiency is 100% allowing time-controlled plating of up to
eight targets simultaneously. A single plating solution can be reused up to 10 times upon simple addition of the appropriate
amount of TlB2BO B3B after each batch.
1. INTRODUCTION
To be up to standard, plated cyclotron targets must meet a set of requirements. First, the target
layer should adhere strongly to the target carrier up to irradiation temperature. Secondly, it should be smooth (not spongy and dendrite-free), dense (no occlusions nor vacuoles), stress-free and homogeneous (+/- 5%) and show a well-defined thickness that may vary from a few tens up to several hundreds of µm, depending on the beam/target angle. Finally, the metal deposit and the carrier/layer interface should be free of traces of organic plating bath additives such as complexing agents, surfactants or stress reductants.
With reference to the upper requisites, “poor quality” of Tl-203 target layers means that one or
more of these conditions are not satisfied. The main causes that give rise to poor quality are: - gas (hydrogen) evolution at the cathode during plating resulting in spongy and irregular
deposits; - concentration polarization of the electro-active species (i.e. the hydrated or complexed
target metal ion) giving rise to treelike structures called dendrites, requiring post-plating mechanical fashioning as rolling with enhanced risk of plating solution occlusions;
- ill-considered choice of additives such as organic complexing agents and tensides bringing about peeling off of the target layer and/or target damage on irradiation;
- unidirectional stirring and maladjusted plating temperature causing inhomogeneous layers and dendrites;
- non-homogeneous electrical field and maladjusted plating voltage wave form causing inhomogeneous layers and dendrites.
In the frame of industrial routine production the plating solution, the electromechanical and
electronic set-ups and the target carrier should currently meet a number of imperative additional requirements such as:
34
- the plating solution must be free of toxic anions (especially CN P
-P) and well suited for repetitive
plating (up to 10 batches per cycle) upon simple adjustment of the Tl-203 contents of the bath. At the end of a plating cycle any enriched material remaining in a partially depleted bath must be recovered quantitatively in a physico-chemical form so that it can be reused as such for the preparation of a new plating solution;
- plating bath and set-ups must allow multi-target preparation (minimum 4 per batch) at room temperature with a duty cycle allowing finishing at least one batch per shift (= 7 hours);
- the thickness of the layer must be time-controlled; - post-plating mechanical fashioning (rolling) of the target layer must be excluded. In spite of excellent physico-chemical qualities of the Tl-203 deposit, the ultimate goal, the
availability of a target showing a high maximum allowable target beam current load (> 300 µA, future 500-2000 µA) can not be reached in the absence of appropriate deposit and coolant channel geometry, linear coolant flow rate, beam diagnostics and beam wobbling. The optimization of beam parameters and cooling are not included in this work.
2. OPTIMIZATION OF THE PLATING TECHNOLOGY
2.1. Choice of the plating method
Fundamentally, one of the four available plating methods can be used.
In Constant Voltage Electrolysis (CVE), a fixed voltage is applied between the anode and the
target carrier cathode immersed in the plating bath. As the electrolysis progresses the current decreases as a result of depletion of the electro-active species (hydrated or complexed metal ions) and the cathode potential shifts towards more negative values entailing an enhanced risk for hydrogen evolution. This can be prevented by the addition of a suitable cathodic depolarizer (NO B3PB
-P) that fixes the
cathode potential at a constant value and that is reduced to a non-volatile species (NH B4PB
+P) in acid
medium. Though this technique is frequently used in industrial coating and in analytical electro-gravimetry, the current efficiency (and hence the plating current density) varies during the plating process and is generally much less than 100%, making the method non attractive for time-controlled layer thickness plating.
In Constant Current Electrolysis (CCE) a fixed current is forced through the electrochemical
cell and the applied plating voltage automatically adjusted (i.e. increased) such that the set current is kept up. Using concentrated solutions of appropriate composition that show a limited depletion ratio for the electro-active species (maximum 50%) at the end of the plating and applying an optimized plating current density, a 100% current efficiency can be easily obtained. For time-controlled layer thickness plating this technique must be preferred.
Controlled Cathode Potential Electrolysis (CCPE) involves the introduction of a reference
electrode into the system. The potential of the cathode is set at a fixed value versus the potential of the reference electrode. This value corresponds to 99.99% depletion of the electro-active species, i.e. to the lower limit of its discharge interval. The current decreases exponentially as the process progresses and its reading may be used to monitor the depletion of the bath. CCCPE is well suited for quantitative separation of metals and is a very attractive tool in the frame of the recovery of enriched target material.
Internal Electrolysis (IE) does not involve the application of an external voltage or current
source to the electrochemical cell build up from two non-indifferent electrodes. External short-circuiting of both electrodes results in a spontaneous current that decreases exponentially as a function of time. The anode dissolves and the electro-active species wanted is quantitatively plated out onto the
35
cathode. This method has limited number of applications and was frequently used in destructive neutron activation analysis in the sixties. It is not suited for thick target preparations.
From the above it is obvious that CCE should be preferred for the preparation of high current beam cyclotron targets and that CCPE should be used for purification and recovery of enriched material.
2.2. Composition of the plating bath solution
In general, thallium plating solutions contain a readily soluble inorganic Tl salt (sulphate, perchlorate…) and free acid (mostly sulphuric or perchloric acid) or base (sodium hydroxide). In most cases additives to improve the quality of the metal deposit are present: these compounds (complexing agents, surfactants, anodic depolarizers and stress reductants) mainly affect the tendency towards gas evolution, the maximum allowable plating current density and the oxidation of the Tl deposit.
Gas (hydrogen) evolution at the cathode can be prevented by adjusting the pH of the solution to a value higher than 12. This is feasible as TlOH is a strong base.
Concentration polarization linked up to plating current density and plating bath additives
strongly affects the quality of the deposit. The higher the current density the smaller the crystal size and the better the physical properties of the metal layer: smooth, strong and adherent deposits are made up of very fine crystals obtained at higher current densities. Moreover, higher current densities result in a higher over voltage for hydrogen thus reducing the risk for gas evolution at the cathode. However, very high current densities do result in extremely high concentration polarization that leads to dendrite formation. From the foregoing, it follows that an optimum current density is to be expected. Its value may be increased and the plating time hence reduced by:
Plating from concentrated Tl-203 solutions such that the metal concentration at the end of
plating procedure remains high, meaning that the depletion ratio (DR) of the plating bath is relatively low. From experiments, it follows that a DR up to 50% is acceptable for many plating vessel geometries and target windows. This implies that the Tl-203 contents of the plating solution equals at least twice the amount deposited on the target carriers;
Addition of complexing agents showing a low stability constant for monovalent thallium and for
which the electron transfer rate at the solution/metal layer interface is high as compared with that of the hydrated Tl P
+P cation. Experimentally it was found that out of eight complexing agents tried, only
EDTA 0,5M at pH>12 (pK BsB=6.55) is well suited for this purpose on the condition that no trivalent thallium is present. Indeed, Tl P
+3P forms strong complexes with EDTA (pK BsB= 24.0) resulting in a large
shift of the discharge interval of the metal towards more negative values with possible hydrogen generation as a consequence. The addition of an anodic depolarizer such as hydrazine prevents the oxidation of monovalent Thallium in solution and of the metallic deposit as well.
Addition of a tensio-active agent that causes a decrease of the surface tension of the solution
resulting in a decrease of the thickness of the hydrodynamic layer at the metal/solution interface. Hence, the transfer rate of the electro-active species (i.e. complexed Tl ions) to the cathode surface is enhanced and the concentration polarization reduced. Though many organic surfactants of acceptable purity are commercially available, the practical choice is very limited because most of them tend to stick at copper/thallium interface or are incorporated in the thallium lattice.
Upon irradiation and heating up, the organic material is carbonized thus producing volatile
decomposition compounds that lead to eruptions and crater formation resulting in the loss of enriched material and in a decrease of the irradiation yield. Out of 12 (anionic, cationic and neutral) compounds tried, a single one, BRIJ-35 (0,05% w/v) non-ionic polyoxyethylene ether, frequently used as wetting agent in automated continuous flow analyzers, met the requirements.
36
Simultaneous multi-target plating that results in homogeneous Tl-203 layers requires an appropriate plating vessel design to ensure a homogeneous electric field all over the plating area and a well designed stirring system that avoids local concentration gradients -and hence local concentration polarization - of the electro-active species.
Plating vessel geometry: practically, the above requirements can be met by using a hollow
perspex cylinder (maximum volume 500 ml), fitted with a single axial and grounded Pt anode wire mounted in the bottom and with four vertical slots in the outside wall allowing the introduction of four target carriers, as electrodeposition vessel. Appropriate choice of the diameter of the cylinder and shielding of the anode wire allows a quasi homogeneous electrical field to be realized at the surface of the four cathodes.
Stirring system: efficient homogenization of the plating solution can be achieved by introducing
as a stirrer a hollow perforated perspex cylinder surrounding the Pt anode and mounted on the axis of a DC motor-tachogenerator combination with variable (up to 1200 rpm) rotation speed. The direction of rotation can be reversed after a predetermined time. Vigorous bi-directional stirring then reduces the thickness of the hydrodynamic layer and hence the concentration polarization. The geometry of the stirrer needs optimization for each target configuration.
Plating temperature: increase of the plating temperature may be an important quality parameter.
At higher temperature the viscosity of the solution decreases and the mobility of the ions increase while in well-stirred conditions, the thickness of the Nernst layer is substantially reduced. Higher temperature hence reduces concentration polarization. On the other hand, over voltages are lowered at higher temperatures, even for heavy metals as Tl, with as a result an increased risk for gas evolution. Furthermore, the required electromechanical plating set-up should be much more sophisticated (heating elements and associated electronics for temperature control, solution level monitoring and feed back electronics to add water to compensate for evaporation) while the optimum temperature for a given electrolysis can be determined by experiments only. Weighing the pros and contras against each other, it was decided to develop a technology applicable at room temperature, a decision that was highly appreciated by industrial users.
2.4. Plating voltage waveform
In spite of the optimized conditions discussed above, a slight tendency towards dendrite
formation is found when DC constant current electroplating is performed. This phenomenon can be suppressed completely by application of AC voltages and currents. During the cathodic part of the applied signal, deposition with micro dendrite formation takes place, during the anodic part the metal is redissolved. This redissolution rate is higher for fine treelike structures (showing a high surface area per unit of mass) than for real massive crystals. Appropriate choice of the wave form of the AC signal and of the amplitudes of the cathodic (i Bc B) and anodic ( i Ba B) currents ( iBc B > i Ba B ) results in a net cathodic deposition with suppressed dendrite formation.
Out of four different wave forms tried, a bipolar chopped sawtooth gave optimum results in the
case of Tl. The signal frequency equals 100Hz, the chopper frequency is 1000Hz and the chopper duty cycle amounts to 60%. The wave form is schematically represented in Fig. 1.
37
2.3. Electromechanical set-up, stirring system and plating temperature
Ia
Ic
FIG. 1. Bipolar chopped sawtooth plating voltage.
2.5. Experimental
2.5.1. Preparation of the plating solution
The following alkaline Tl-203 containing EDTA solution holding appropriate amounts of BRIJ-35 surfactant and hydrazine depolarizer is used for the repetitive preparation of four IBA external beam Tl targets used in the Cyclone 30 accelerator. The metal layer is deposited on IBA’s finned copper carrier.
2.5.2. Reagents and products
The chemicals used for the preparation of the plating bath are summarized in Table I.
2.5.3. Cleaning of target carriers (Cu backings)
The Cu carriers are cleaned by rubbing the Tl deposition area with abrasive wool, followed by rinsing abundantly with demineralized water and acetone and paper drying.
1. rub the deposition area of the Cu backing successively with abrasive wool type 1
and type 2 for 1 min respectively;
2. rinse with water;
3. rinse with acetone;
4. dry the carrier with adsorbing paper and weigh the carriers;
5. introduce the backings in the four slots of the deposition vessel and turn the knobs of the mechanical pestles in pairs clockwise to ensure liquid tightness.
38
TABLE I. REAGENTS USED TO PREPARE A TL-203 PLATING SOLUTION
TlB2BOB3B Enriched P
203PTl oxide, compound obtained by the purchase
of the enriched material
P
203PTlEDTAP
3-P
Final product obtained in the VUB-recovery cycle of the enriched material
EDTA (ethylene-dinitrilo-tetra-acetic acid, di-sodium salt) – Titriplex III p.a. (Merck - 1.08418)
NaOH Sodium hydroxide pellets p.a. (Merck - 6495)
Hydrazine hydrate (55%) (Aldrich - 22.581-9)
BRIJ-35 (30%) (Technicon Diagnostics - T 21-0110-17)
HB2BSOB4B (95 - 97%) p.a. (Merck - 731)
Perhydrol (30%) p.a. (Merck – 1.07209)
HB2BO Demineralized water - conductivity < 0.1 µS/cm
Acetone (purum) (Belgolabo 94-90013)
Parafilm "M" American National Can
pH indicator strips (Merck 9535)
Abrasive wool Type 1: F12/002 very fine (Abrasive center) Type 2: F12/012 ultra fine (Abrasive center)
2.5.4. Preparation of the first electroplating bath
Though the volume of the plating bath is not very critical, it should be kept between 420 and 450 ml. The solution is 0,5 M EDTA showing a pH > 12.5 and contains 9 g of enriched P
203PTl together
with 1% hydrazine hydrate and 0.2% of BRIJ-35.
• put 360 ml demineralized water in a 600 ml beaker (B1) fitted with a Teflon coated magnetic stirring bar;
• add 84 grams solid EDTA and 20 grams of NaOH pellets and stir until a colorless solution is obtained;
• add 10 ml hydrazine hydrate and 1 ml BRIJ-35 and homogenize (Solution-1);
• transfer quantitatively 9760 mg enriched 203Tl2O3 to a second 600 ml beaker (B2) also fitted with a magnetic stirrer bar;
• transfer Solution-1 by means of a peristaltic pump into beaker B2 at a flow-rate of 10 ml/min. Cover beaker B1 with Parafilm;
• reduce the stirring rate of the stirring bar in B2 and rinse the wall of this beaker with 1 ml hydrazine hydrate (If any yellow-brown color persists in the foam layer, gently swirl the beaker until the color disappears). Check pH by means of an indicator strip. The pH should be > 12,5;
• continue slow stirring of B2 for five more minutes.
Solution-2 (in B2) is now ready for electrodeposition.
39
2.6. Electromechanical set-up
The electromechanical set-up is represented in Fig. 2. The electrodeposition vessel is a hollow perspex cylinder fitted with an axial Pt anode wire
mounted in the bottom by means of a tube-end fitting with perforated septum. Four vertical slots in the outside wall allow introduction and positioning of four Cu target carriers.
Each slot is provided with an O-ring fitted window, which geometrical shape determines the
electrodeposition area. Liquid tightness is realized by stainless steel mechanical pestles mounted in a PVC ring surrounding the electrodeposition vessel and by pressing the Cu carrier against the O-ring.
The external PVC ring is also fitted with four supporting pins to hold the motor-stirrer
combination in position. The stirrer is a hollow perforated cylinder mounted on the axis of a DC motor-tachogenerator combination and surrounding the Pt anode. The rotation speed is adjustable up to 1200 rpm while the direction of rotation can be reversed after a predetermined time (8sec/8sec).
Electromechanical set-up. FIG. 2.
2.6.1. Electronics
The schematic diagram of the home developed plating electronics is represented in Fig. 3. A
stable multivibrator (AMV-1) generates a saw-tooth (ST) signal of appropriate frequency and duty cycle. The ST signal is amplified by a non inverting amplifier (NIA) and summed with a positive DC offset voltage (P-DC-O) by an inverting sum amplifier (ISA-1) which output forms the base for the positive alternation of the compound signal. The ST signal is amplified by an inverting amplifier (IA)
40
and summed with a negative DC offset voltage (N-DC-O) by an inverting sum amplifier (ISA-2) which output forms the base for the negative alternation of the compound signal.
A stable multivibrator (AM-2) generates a square wave (SW), with appropriate frequency and
duty cycle, which chops the output of ISA-1 and ISA-2 in such a way that only one alternation is active at the same time. The outputs of the negative alternation chopper (NAC) and the positive alternation chopper (PAC) are summed in an inverting (ISA-3) which output delivers the compound signal. This signal is fed into four independent voltage-to-current (V/I) convertors with associated push-pull current boosters (IB) and grounded load. This circuitry allows the simultaneous deposition of four Tl targets at identical or at four different current densities using a single and grounded Pt-anode.
The electrodeposition electronics consists of a rack with eight Eurocards: two power supplies;
one stirrer controller; one signal generator; four voltage-to-current (V/I) convertors with associated push-pull current boosters (IB).
FIG. 3. Schematic diagram of the electronics.
2.7. Electroplating of P
203PTl targets
Electrodeposition of four targets is carried out after the transfer of Solution-2 to the plating
vessel fitted with four cleaned target carriers.
1. Pour Solution-2 into the plating vessel. Do not rinse the beaker but cover it with Parafilm;
2. connect the four outputs of the current boosters to the cathodes by introducing the four
black male plugs into the wholes of the pestles;
3. introduce with care the electromagnetic stirrer such that the central Pt-anode wire fits into the hollow perforated stirring cylinder. Rotate the stirrer until an appropriate mortise and tenon joint between the stirrer assembly and the vessel is obtained;
41
4. connect the motor cable plug to the female connector at the top of the stirring motor housing. Start stirring motor (rotational speed: 1200 rpm; Period: 16 sec)
5. start the electrolysis by introducing the common (red) output plug of the I-boosters
into the female connector at the bottom of the deposition vessel;
6. note the time; the four current indicators should give a 25.0 ± 0.2 mA reading after a few minutes of deposition. With a 100% current efficiency a Tl-203 deposition rate of 7,57 mg/mAh is obtained, for a 1092 mg P
203PTl deposit per target the plating time
equals 5,77 hrs, i.e.: 5hrs 46min;
7. after 5hrs 46min of electrolysis, stop the stirring motor, disconnect the plug at the top of the motor housing and carefully remove the stirring assembly. Do not rinse the perforated hollow cylinder, but quickly introduce it into a 250 ml perspex holder;
8. pour the 50% depleted plating solution into beaker B2. Rinse the deposition vessel
with 3 times 15 ml of demi-water and collect the rinsing liquid in a third 250 ml beaker (B3). Cover the beaker B3 with Parafilm;
9. unscrew the pestles, remove the pestle holder and collect the four targets. Rinse each
of the targets extensively with hard water (waste), followed by rinsing with demi-water (waste);
10. dry the targets by means of adsorbing paper and weigh. Determine the current
efficiency by calculating:
100*1092
W i=
iη with :
ηBiB =current efficiency for target i WBiB =weight (mg) of target i
The current efficiency should be 100 ± 0,2%
11. wipe off the surface oxide layer by means of adsorbing paper and store the targets in a
vacuum desiccator or under nitrogen. Wiping off may result in a loss of a few mg of P
203PTl.
If not acceptable, the adsorbing paper frotti's should be collected and later on destructed in an HClO B4B/HB2 BO B2B mixture. After catalytic elimination of H B2BO B2B by introducing a Pt electrode, a bulk recovery of Tl can be carried out.
2.7.1. Preparation of the second .up to the tenth) plating bath using Tl B2 BO B3B
As stated earlier, the partially depleted plating bath must be reusable as such upon simple adjustment of the Tl-203 contents. This can be done, as follows:
1. transfer quantitatively 4880 mg enriched P
203PTlB2BOB3B to beaker B1 fitted with a magnetic
stirring bar;
2. transfer the 50% depleted plating solution from beaker B2 to B1 by means of a peristaltic pump at a flow-rate of 10 ml/min. Cover beaker B2 with Parafilm;
3. reduce the stirring rate in B1 and rinse the walls of this beaker with 1 ml hydrazine
hydrate (If any yellow-brown color persists in the foam layer, gently swirl the beaker until the color disappears);
42
4. continue slow stirring of B1 for five more minutes. Check pH by means of an indicator
strip. The pH should be > 12, if not add a few drops of 10% NaOH;
5. proceed as described in 3.4.
The procedures 4 and 5 can be repeated up to maximum 10 times (due to degradation of the surfactant) where after a bulk recovery of the 50% depleted bath is necessary. This should be done by controlled cathode potential electrolysis.
3. RESULTS AND CONCLUSIONS
Constant current electrolysis (CCE) of Tl-203 from alkaline (pH>12), concentrated (i.e. holding
an amount of Tl that is equal to twice the amount plated out) solutions of monovalent Tl, 0.5 M in EDTA and containing a non-incorporated surfactant (BRIJ-35) and a strong reducing anodic depolarizer (hydrazine hydrate) result in a plating technology that meets all metal layer quality requirements and all industrial demands. Indeed, by applying a bipolar chopped sawtooth (f BST B= 100Hz; fBCH B= 1000 Hz; CDC=60%) to the cylindrical plating vessel, fitted with a single, grounded and axially mounted Pt anode and four slots that hold the Cu target carriers and by vigorous bi-directional stirring (1200 rpm) by means of a cylindrical perforated electromechanical stirrer surrounding the Pt anode and mounted on the axis of a DC motor-tachogenerator combination, the following results are obtained:
- relatively high maximum allowable current density (2 to 3 mA.cm P
-2)P) allowing simultaneous
time-controlled (plating current efficiency = 100%) production of 4 targets carrying more than 100 mg Tl-203 per square centimeter within less than 6 hours and requiring no post-plating mechanical fashioning;
- plating performed from cyanide free solutions that are well-suited for repetitive plating cycles
(up to 10 batches) by simple adjustment of the metal contents of the plating bath and from which the remaining enriched material can be readily recovered by controlled cathode potential electrolysis;
- target layers are homogeneous (< 5%), smooth (dendrite free), dense neither occlusions nor
vacuoles) and free of traces of organic bath additives (EDTA, BRIJ-35). The layer remains intact and strongly sticks to the copper target carrier up to 270°C, i.e. up to an irradiation temperature about 30°C below the melting point of the metal.
At present, the plating technology presented was successfully used for the preparation of twelve
targets geometries used for routine production of Tl-201. Up to now Tl-203 layers (surface area 11,6 cm P
2P, total amount of Tl 1.1gram) P
Pplated on IBA
copper carriers withstand a non-loss 9 hours irradiation with a circularly wobbled 270 µA proton beam. Recent heat production and heat removal calculations resulting in a new target carrier and coolant channel geometry and in an optimum linear coolant flow rate show that a beam current burden up to 400 µA must be feasible. The new design that should fully make use of the Cyclone–30 external beam current output on a single target will be tested next year.
REFERENCES
[1] Electroplating, F. A. Lowenheim Editor, 3rd Edition, John Wiley & Sons, 1973 [2] Les Réactions Chimiques en Solution Aqueuse, G. Charlot, 7th Edition, Masson, 1983 [3] Chemical Analysis, H. A. Laitinen, Mac Graw-Hill, 1960
43
[4] The Canning Handbook on Electroplating, W. Canning Ltd, E.& F.N. Spon Ltd, 1977 [5] Electroplating Engineering Handbook, L. J. Durney, 4th Edition, Chapman & Hall, 1996
44
CYCLOTRON PRODUCTION OF IODINE-123 AND PD-103
ZHOU WEI, WANG YONGXIAN, ZHANG CHUNFU Shanghai Institute of Nuclear Research, Chinese Academy of Science, China
Abstract
The tellurium-124 target was prepared by electroplating of tellurium-124 on the Ni/Cu target carrier and was
irradiated with a proton beam of 25 MeV energy. The loss of the target material was also determined. The overall
radiochemical yield was typically greater than 92% and the recovery of P
124PTe was greater than 99%. The layer of rhodium on
the target was prepared by periodic reverse plating. After irradiation of the rhodium target, the electrodissolution and
oxidation dissolution method were evaluated and the Molecular plating of Pd-103 onto silver rod was validated in this work.
1. INTRODUCTION
The P
123PI(TB1/2B=13.2h, Eγ=159keV) radioisotope has found wide application in diagnostic nuclear
medicine. Of the many methods reported for the production of the medically important radioisotope P
123PI, the two most important processes, according to the present state of knowledge, involve the
P
123PXe→ P
123PI generator method and the P
124PTe→P
123PI reaction. The latter method is more suitable for
production at low-energy cyclotrons. Precise excitation function measurements for the P
124PTe(p, n)P
124PI
and P
124PTe(p, 2n)P
123PI reactions showed that highly enriched P
124PTe is necessary to produce P
123PI containing
relatively P
124PI impurity. Considerable advances in targetry and chemical separation of radioiodine have
been reported. Irradiation of 2π or 4π water –cooled P
124PTe target at medium currents, followed by wet
chemical separation of radioiodine and recovery of the enriched P
124PTe-target material has also been
reported. Interstitial implantation of radiation-emitting materials has been long recognized as effective
method for tumour therapy. The advantage of interstitial implants is an opportunity to concentrate the radiation at the tumour site while minimizing radiation exposure to normal tissue. Commonly used implantable materials include radioactive gold-198 and radon-222. Use of these radioactive sources is not without shortcomings, however, since the highly penetrating radiation that is emitted not only subjects normal tissues to more destructive radiation, but can also make it difficult to adequately shield personnel. Another important radioisotope commonly used for permanent implantation is iodine-125.
Palladium-103 has more favorable physical properties, including its low energy, rapid dose fall-
off, short half-life, and total cumulative dose delivery at a higher dose rate than iodine-125 and is a promising radioisotope for localized tumour treatment. Production of palladium-103 can be accomplished by either cyclotron production or reactor production.
For nuclear reactor production, palladium-103 is produced by bombarding a target containing
enriched palladium-102 with neutrons. In contrast to cyclotron production of palladium-103 where carrier-free palladium-103 can be produced, nuclear reactor production is not carrier free, and the product always contains palladium-102. In addition, palladium-109, palladium-111, and other palladium contaminants can also be present.
One drawback of reactor-produced palladium-103 is that the specific activity cannot be adjusted
to provide for the production of a seed of predetermined therapeutic or apparent activity. A further possible disadvantage resides in the fact that large amounts of stable palladium-102 remain which may shield the low energy X-ray released when the palladium-103 nuclei disintegrate. Reactor-produced palladium-103 from enriched palladium-102 is also expensive because of the difficulty in enriching palladium-102 (only 1.02% natural abundance) from palladium metal. This paper discusses a method that can be used for commercial production of no-carrier-added palladium-103 with cyclotron.
45
2. METHOD
2.1. Iodine-123
2.1.1. Targetry
The Ni plating solution was prepared by dissolving 250g NiSO B4B·6H B2BO and 30g NiCl B2 B·6HB2BO in 500ml H B2BO. To which 35g H B3 BBOB3 B was added and the final volume adjusted to 1.0L. The pH of the solution should be 3 - 4. Ni surface of 200-300 ug/cm P
2P was electroplated onto the Cu plate using a
current of 200mA for 10 min. The current efficiency was 90%. A platinum electrode was used as the anode and the Cu plate as cathode. The dry weight of the Ni/Cu plate was determined after washing the plate with distilled water, organic solvent and drying at 110 P
0PC.
The stock solution for electrodeposition of the enriched P
124PTeO B2B was typically prepared by
dissolving 1g tellurium-to-tellurium oxide in 50 ml concentrated HNO B3 B. After evaporation to dryness, the tellurium oxide was dissolved by 30g KOH and 150 ml distilled water. The pH of the solution should be adjusted to 10―11.
The enriched P
124PTe was electrodeposited on a 10 cm P
2P area of electroplated Ni on a Cu plate. The
Te cover was formed onto the Ni surface by electroplating with a current of 100mA for 60 minutes and the thickness was 10―12mg/cmP
2P. The plate was determined after rinsing the plate with distilled
water and drying with acetone.
2.1.2. Irradiation
The target was irradiated with a proton beam of 25 MeV energy. The loss of the target material was determined after bombarded with different beam current from 10uA up to 100uA. The loss of P
124PTe was greater than 3% as the beam was above 80 uA. The loss of the target material on different Ni
layers was also determined.
2.1.3. Separation of iodine-123 from tellenium
After irradiation, the P
124PTe coated on the Cu/Ni target plate was dissolved in a mixture of 1 ml 5
M NaOH, 2ml of 30% H B2BO B2 Band the deionized water was needed to cover P
124PTe deposit. After
dissolution, the solution was transferred to a flask containing 250mg of aluminum power. The target plate and holder were rinsed three times with 5ml of water. Solution was heated gently until the reaction was complete and all H B2 BOB2 Bwas decomposed. Filtered carbon dioxide gas was bubbled through the solution for 5 min. The volume of the solution was reduced by heating gently on a hot plate. The solution was filtered through a glass frit and the iodine-123 solution was obtained.
2.1.4. Recovery of the enriched tellurium
The powder was dissolved in 10 ml of 7M H B2BSOB4 B and then 1.5ml of 30% H B2BO B2 B was added in small portions at which point a clear solution was obtained. 25ml of distilled water was added to cooled mixture and 25 ml was distilled off. This fraction contained the iodine-124. Then 10 ml of 50% hypophosphorus acid was added to cooled solution to precipitate the tellurium. The solution was filtered and the filtrate washed and dried.
2.2. Palladium-103
2.2.1. Targetry and irradiation
The layer of rhodium on the target was prepared by periodic reverse plating. The target carrier was a ten centimeter long, one centimeter wide and 0.1 millimeter in depth copper support. Rhodium (ΙΙΙ) chloride hydrate (99.99% Merk product) is main component of the electroplating solution.
46
Electroplating temperature was 45 P
0PC. The negative electrode current density was 0.2A/cm P
2P and
the positive one was 0.15A/cm P
2P. Time ratio of the two electrodes (tBk B/tBA B) was 15(s):5(s).
The irradiation of the rhodium-coated target was performed with a Cyclone 30 cyclotron
manufactured by IBA. The irradiation lasted for 10 hours at the 21 MeV energy of proton and a beam current intensity is 200 µA, measured by integrating the charge collected on the target.
2.2.2. The dissolution of irradiated target
We evaluated the electrodissolution and oxidation dissolution method in this work. All the targets were dissolved four days after the end of bombardment (EOB).
Electrodissolution. The dissolution of the target was performed using the improved electrolysis apparatus. The rhodium metal target with thin layer of copper on the back, which was peel off from the bulgy part of copper support by cutting machine, was placed onto the graphite plate (the positive electrode) and sealed by a rubber P
“PO P
”P ring and a 0.5A/cm P
2P current density then applied. The
fragmentation rate, referring to proportion of the weight of rhodium powder produced by electrodissolution to the weight of target, was determined by measuring the content of rhodium in the electrolyte using UV-240 Visible Recording Spectrophotometer, which was more accurate than weighting method. 2-(2-thiazolylazo)- 5-diethylaminobenzoic acid was used as the selective developer for rhodium and absorbency was determined at 674 nm. The improved eletrodissolution cell is more suitable for routine, large-scale production as well as more useful and considerably safer when handling a highly radioactive target in a remotely controlled processing system intend for this work.
Oxidization dissolution. The rhodium target, dissolving the thin layer of copper with HNO B3 B on the back, was crushed down and put into 10 ml concentrate HCl with a stoichiometric level of KAuCl B4,
heated,B and stirred for five hours.
2.2.3. Radiochemical separation of palladium-103 from rhodium solution
Separation of palladium-103 was performed using anion-exchange chromatography. A 1.5 cm inner diameter glass column filled with Dowex 1×8(ClP
−P) 100-200 mesh resin to a height of 10cm was
used. After preconditioning the resin with 6M HCl, the rhodium solution was loaded on to the column. The eluants consisted of 0.03M HCl, 6M HCl and NH B3 B+NHB4 BCl (1:1). The separation efficiency for palladium and rhodium was monitored by measuring the activity of palladium-103 and rhodium-102 in the eluant fractions using γ spectroscopy.
2.2.4. Molecular plating of Pd-103 onto silver rod
The electroless-plating bath consists of palladium chloride, formic acid, formaldehyde and nitric acid. The silver rod (99.99%) is 3mm in length and 0.5mm in diameter. Reactor is a glass tube with 4mm inner diameter and 3 cm in length. The concentration of Pd-103 was about 120mCi/ml and the nuclide purity was greater than 99.95%. Silver rods were added and a NaI scintillation detector was used to measure the activity change of plating solution before and after electroless plating. The rods were washed by water and acetone three times, respectively.
3. RESULTS AND DISCUSSION
3.1. Iodine-123
The Ni surface provided greatly increased adhesion for electrodeposited P
124PTe. Ni did not
interfere in the radiochemical separation. The relationship between the loss of Te and the beam current intensity was shown in Fig. 1, when the beam current intensity was less than 80 uA, the loss of the Te target material was less than 3%.
47
The relationship between loss of Te and the thickness of Ni layer was also shown in Fig. 2, as the Thickness of Ni layer was between 9-13 mg/cm P
2P, the loss of Te was less than 3%.
The method for the separation of iodine-123 from tellurium was adapted from the reported
methods. After dissolution of tellurium, aluminum power was added. Aluminum can reduce Te(+IV) to Te(0). During the reaction, a dark coloration was observed due to the formation of tellurides and tellurides were oxidized to Te(0) by stream filtered air. Aluminum was precipitated as the hydroxide. The overall radiochemical yield was typically greater than 92% and the recovery of P
124PTe was greater
than 99%.
3.2. Palladium-103
Metallic rhodium was selected as the target because of its favorable physical properties, such as high resistance to corrosion and high melting point. The advantage of periodic reverse plating is that we can obtain even rhodium plating layer with uniform in depth and little eyelet. The yield of palladium-103 was about 1250 mCi at the EOB.
The electrodissolution results of different mass rhodium target with rectangle shape are
summarized in Table I. With the increase of current density, the fragmentation increased dramatically, but the time for dissolution decreased greatly. The optimal selection of the current density was between 0.4 and 0.6 A/cm P
2P as the result of faster dissolution with less fragmentation. The
measurement of content of rhodium in the electrolyte using visible spectrophotometer was more accurate than weighting method. Under the radiation conditions, the electrodissolution was judged as the most suitable method with regard to personnel safety and environmental protection.
KAuCl B4 B was selected as the oxidant to dissolve rhodium target because it is simple and an easily
manageable method. The chemical potential of the reaction is:
E=0.572+0.0394lg[Cl P
-P]+0.0197lg[AuCl B4 PB
-P]/[RhClB6 PB
-P]
At a given [Cl P
-P], the last item- lg[AuClB4PB
-P]/[RhCl B6 PB
-P]-gives little contribution to the potential,
which can also be seen from the experimental results (Table II). Temperature is the key factor affecting the reaction. Between room temperature and 60 P
0PC, there was almost no dissolution of the
target but at 100 P
0PC about 40% of the target dissolved. Using this approach with the residue under the
same conditions did not dissolve the solid. Our inability to dissolve the residue in this way could result from formation of a layer of a compact insulation gold film on the surface of the target, which inhibits further reaction. In addition, rhodium was passivated at high temperature.
Based on the differences in the affinity of doubly charged PdCl B4PB
2-P and triply charged RhCl B6 PB
3-P, an
ion-exchange method was developed for the separation of palladium from rhodium. After eluting with 100ml 0.03M HCl, which is intended to remove Cu P
2+P and micro-base metal ion such as Zn P
2+P, Fe P
3+P, the
resin was eluted with 120 ml with 6M HCl at a 4ml/min flow rate. As shown in Fig. 2, 99.82% of rhodium was released by 120 ml of 6M HCl solution. The amine complex of palladium behaves as a cation, so Pd is easily released from the anion resin with ammonia, but the efficiency of elution was about 73% (Fig. 4). When ammonium chloride was added to the ammonia solution palladium was eluted more rapidly with high efficiency. About 70% of palladium was washing out in the first 10ml and 95% of palladium was released from the resin with only 50ml mixture (Fig. 5).
Electroless-plating is a better method than electroplating for coating Pd-103 onto silver, because
of more uniform-plated layer, stronger affinity of the plated layer to the substrate and simple technique used on micro scale. The optimum composition of the plating bath and ideal operating conditions are palladium chloride 0.1mol/l, formic acid 0.4mol/l, formalhyde 2mol/l, and nitric acid 1mol/l, temperature of electroless-plating bath at 30 P
0P C and the reaction time of 25 min.
48
20 40 60 80 100
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
loss o
f T
e (
%)
beam current intensity (uA)
Fig.1 relationship between loss og Te and beam current intensity
Current integration:100 uAhr
2 4 6 8 10 12 14 16 18 20
0
2
4
6
8
10
12
14
16
loss o
f T
e (
%)
thickness of Ni layer (mg/cm2
)
Fig.2 relationship between loss of Te and thickness of Ni layer
beam current intensity:50uA
current integration:200uAhr
49
TABLE I. EXPERIMENTAL CONDITION AND DISSOLUTION RATES FOR ELECTRODISSOLUTION OF METAL RHODIUM TARGETS IN 6M HCL
Area (cm P
2P)
Current (A)
Current density (A/ cm P
2P)
Fragmentation (%)
Time (h)
1×10 10 1 78 0.20
1×3.5 2.8 0.8 50.3 0.50
1×3 1.8 0.6 24.2 0.62
1×10 5 0.5 8 1.50
1×1.8 0.72 0.4 5.1 0.64
TABLE II. PERCENT OF DISSOLVED RHODIUM AT DIFFERENT TEMPERATURE
Temperature Molar ratio of KAuCl B4 B to rhodium Percent 60 1:1 Very little 70 2:1 4.25% 80 1:1 15.26% 90 5:1 28.20%
100 5:1 40.00%
0 20 40 60 80 100 120
0
20
40
60
80
100
Pecen
t o
f R
ho
diu
m(%
)
V(ml) of 6M HCl
Fig.3 Elution profile of rhodium with 6M HCl as eluant
50
0 20 40 60 80 100
30
40
50
60
70
80
perc
ent
of
Pd-1
03 (
%)
V(ml) of conc. ammonia
Fig.4 Elution profile of Pd-103 with ammonia as eluant
10 20 30 40 50
65
70
75
80
85
90
95
100
perc
ent
of
Pd-1
03 (
%)
V(ml) of NH3+NH
4Cl(1:1) mixed eluant
Fig.5 Elution profile of Pd-103 with NH3+NH
4Cl(1:1) as eluant
51
REFERENCES
[1] S.M.QAIM, G.STOCKLIN. Production of some medically important short-lived neutron-deficient radioisotopes of halogens. Radiochimica Acta. v. 34, pp. 25-40, 1983
[2] R. M. LAMBRECHT, M. SAJJAD, R. S. SYED, W. MEYER. Target preparation and recovery of enriched isotopes for medical radionuclide production. Nuclear Instruments and Methods in Physics Research, A282, pp. 296-300, 1989
[3] R. M. LAMBRECHT, M. SAJJAD, M. A. QURESHI, S. J. AL-YANBAWI. Production of iodine-124. J. Radioanal. Nucl. Chem., Letters, 127, pp. 143-150, 1988
[4] P. TARAPCIK, V. MIKULAJ. Separation of P
103PPd from cyclotron irradiated rhodium targets. J.
Radiochem. Radoanal. Letters, 48, pp. 15-20, 1981 [5]
52
PRODUCTION OF DIAGNOSTIC AND THERAPEUTIC RADIONUCLIDES
S. TAKÁCS Institute of Nuclear Research of the Hungarian Academy of Sciences, Debrecen, Hungary
Abstract
This work was done in the frame of the research program of “Standardized High Current Solid Targets for Cyclotron
Production of Diagnostic and Therapeutic Radionuclides” co-ordinated by the International Atomic Energy Agency. The aim
of the work was to collect, evaluate and calculate cross-section data for proton and deuteron induced reactions on stable
isotopes of tellurium, rhodium and palladium in order to produce iodine, palladium and thallium radionuclide respectively for
diagnostic and therapeutic purposes. A simple calculation tool was developed to estimate the amount of different
radionuclide produced during proton or deuteron bombardment of targets with different enrichments. Using tabulated yield
information absolute and relative activity can be calculated for any valid input parameters.
1. INTRODUCTION
Production of radioisotopes at a small cyclotron always requires optimization because of the
limited bombarding energy and the interfering contaminating side-reactions. The needed radionuclide impurity level frequently requires highly enriched therefore expensive target materials. Knowing the excitation function of the contributing reactions, an optimization calculation can be performed. The optimization calculation is based on a database containing the relevant information about the nuclear reactions involved in the production process. The required experimental data are the cross-sections of the reactions and the stopping parameters of the target material used or integral yield as a function of energy. In order to be able to perform the necessary calculation experimental cross-section data were collected and measured to complete the required database. Where no experimental were available result of model calculation was used instead.
2. PRODUCTION OF P
123PI RADIOISOTOPE
2.1. Nuclear data measurements
Basic nuclear data regarding the production of P
123PI was studied at our institute. Cross-section of
P
123PTe(p,n)P
123PI was measured [1] up to 18 MeV. Using the results, we could resolve and clarify the
discrepancies between the reported experimental data. By measuring the excitation function of the P
122PTe(d,n)P
123PI reaction we showed that the experimental data reported by Zaidi in 1983 is shifted by
more than 2 MeV to higher energies [2]. With the correct cross-section data, it was concluded that production of P
123PI radionuclide is possible via the P
122PTe(d,n)P
123PI reaction with important yield. Although
the yield of the (d,n) reaction is lower on P
122PTe than the yield of (p,n) reaction on P
123PTe it can be
economical and more safe to use the (d,n) production route at small cyclotrons since the P
122PTe enriched
target material is much cheaper than the enriched P
123PTe one [3]. The production technology uses TeO B2B
targets on platinum backing. Therefore, we have also investigated the reactions of the platinum induced by proton and deuteron bombardment in order to be able to estimate the total activity level associated with an irradiated production target. The results will be published in Radiochimica Acta [4].
2.2. Production experiences
At the Debrecen cyclotron, we produced P
123PI isotope using highly enriched P
123PTeO B2B target
material melted onto platinum target backing. The production details are given in [5]. Using a target 10 mm in diameter and vertical beam perpendicular to the target surface it was found that 8-10 µA beam current causes no problem to the target yet. A new target system was also developed to irradiate at a horizontal beam line at 30 degrees to the target surface. Using this arrangement the target surface increased the thickness of the TeO B2B layer can be decreased which resulted in better cooling parameters of the target and increased production yield.
53
2.3. Optimization of production using nuclear data
Production of radioisotope with the needed radionuclide impurity level frequently requires highly enriched therefore expensive target materials. It is always recommended to make an apriori optimization calculation to determine the best target and irradiation parameters. Doing this calculation a database is needed containing the relevant information about the nuclear reactions (main and side reactions) involved in the production process. The required basic information is: the excitation function of the reactions, stopping parameters of the target material for the available bombarding particles and in the irradiation energy range.
2.3.1. Calculation of the total absolute activity
A simple calculation tool was developed in EXCEL format to calculate the absolute activity and activity ratios of different radioactive products at any target enrichments and irradiation parameter combinations.
The required input parameters are:
- Target composition (absolute ratio of each of the stable isotopes in the target normalized to 1.)
- Irradiation parameters o . type of the bombarding particle (proton, deuteron) o . irradiation time (in hours) o . bombarding beam current (in µA units) o . primary on-target bombarding particle energy (MeV) o . outgoing bombarding particle energy (MeV) o . cooling time (in hours)
2.4. Production of Iodine radioisotopes
The production of iodine radioisotopes with the needed radionuclide impurity level requires
highly enriched and expensive Te-targets. The amount of produced activity and radionuclide impurity levels can be calculated from the relevant data of excitation functions, the thickness of the target or the energy range used at irradiation and finally the isotopic composition of the target. To fulfill this requirement experimental data were collected for proton and deuteron induced nuclear reactions on different stable isotopes of tellurium. In addition, theoretical calculation was made using the Alice-IPPE computer code.
For the proposed calculation in the case of P
123PI and P
124PI products, experimental data were
evaluated and recommended cross-sections were given for the investigated reaction [6]. In those cases where only limited experimental data were available, only a spline fit was applied and a smooth curve was calculated over the experimental data. Reactions for which no experimental data were published the results of the Alice-IPPE theoretical model calculation were used. Based on the available cross-section data tabulated yield was calculated for all the contributing reactions and was applied to estimate the activity produced during production process.
By using a calculation tool it is easy to estimate the amount of main iodine isotope to be
produced under realistic production circumstances as well as the amount of other iodine radionicludes produced in any side reactions. The amounts of produced radionuclide are given in MBq and in µCi activity units with correction for decay during irradiation and after irradiation during any cooling or waiting time. We have to note that in those cases when no experimental data were available the result of Alice-IPPE calculation was used. The theoretical calculation results in as a general tendency an excitation function having higher maximal value than the experimental one. The difference can be as high as a factor of two.
54
Tables I and II give information about the reactions take place on different Te isotopes for proton and deuteron bombardment respectively. The most probable contributing reactions are considered only. These are (p,n), (p,2n) and (p,3n) for proton irradiation, and (d,n), (d,2n), (d,3n) and (d,4n) for deuteron irradiation. In the last column of the tables the type of the data used in the calculation is given.
Three different types of data were used, experimental, evaluated and theoretical. Explanation of the data types:
- Experimental evaluation: Evaluated experimental data. Several series of experimental
data points exist, critical selection is made, and overall fit is calculated. Recommended cross-section data are given.
- Experimental: Only limited amount of experimental data points exist but a statistical spline fit over the experimental points is possible to calculate.
- Theoretical: The result of the Alice IPPE theoretical model calculation is used. - Experiment & theory: The result of theoretical calculation is normalized to
experimental data. The fit of the experimental data points is completed with the normalized theoretical calculation.
Figs 1–24 show the excitation functions of the different possible contributing reactions used in
our calculation for proton bombardment of tellurium target. Figs 25–53 show the excitation functions of the different possible contributing reactions used in the calculation for deuteron bombardment of tellurium target.
2.5. Production of Pd-103 radio isotope
Production of P
103PPd radioisotope by accelerators can be made by proton and by deuteron
bombardment of Rh target. Rhodium has one stable isotope on which the main reaction and some side reactions can take place during bombardment. Similarly to the iodine production a calculation tool was developed to calculate the activity of P
103PPd and the activity of the simultaneously produced other Pd
and Rh radioisotopes. To estimate the level of the contaminating radioisotopes the cross-sections of the relevant reactions were used. The cross-sections were determined experimentally using stacked target activation technique. Results for proton and deuteron bombardment were published separately in Nuclear Instruments and Methods B [7] and [8] respectively. Statistical spline fit was applied over the experimental data and the result was used for calculating tabulated yield for each of the reactions. Tables III and IV summarize the investigated radioactive products, the contributing reactions, the Q-value of the reactions and the type of the data used in the calculation to estimate the total activity of the products.
Figs 54–60 show the excitation functions of the different possible contributing reactions used in
the calculation for proton and deuteron bombardment of rhodium target.
2.6. Production of Tl-201 radioisotope
High specific activity, carrier free Tl-201 radioisotope is produced in proton bombardment of thallium target followed by chemical separation of lead radioactive isotopes. The separated lead isotopes decay into thallium by electron capture or positron emission. In order to increase the radionuclide purity of the produced P
201PTl it is necessary to optimize the irradiation parameters. The
(p,xn) reactions result in different radioisotopes of lead. The yields of the produced lead isotopes depend on the primary bombarding proton energy and the target thickness. For estimating the level of the contaminating radioisotopes the cross-section of the relevant reaction is used. The measured experimental cross-sections were collected and when there were enough data points available critical evaluation and selection of the data series were made and recommended cross-sections were determined using the selected experimental data [6]. Table V. gives information on the investigated radioactive products, the contributing reactions, the Q-value of the reactions and the type of the data used in the calculation to estimate the total activity of the products.
55
Figs 61–69 show the excitation functions of the different possible contributing reactions used in the calculation for proton bombardment of thallium target.
REFERENCES
[1] MAHUNKA I., ANDO L., MIKECZ P., TCHELTSOV A.N. SUVOROV I.A. Excitation function of P
123PTe(p,n)P
123PI reaction for direct production of P
123PI by small cyclotron, Annales
Universitatis Turkuensis, Ser. D. Medica – Ondotologica 88. Medical Application of Cyclotrons VI: Proceedings of the Sixth Symposium on the Medical Application of Cyclotrons, June 1-4, 1992. Turku, Finnland. Ed.: L.-M. Voipio-Pulkki, U. Wegelius, (1992) 11.
[2] TAKÁCS S., AZZAM A., SONCK M., SZELECSÉNYI F., KOVÁCS Z., HERMANNE A., TÁRKÁNYI F., Excitation function of P
122PTe(d,n)P
123PI nuclear reaction: production of P
123PI at a low
energy cyclotron. Applied Radiation and Isotopes 50 (1999) 53. [3] SCHOLTEN B., TAKÁCS S., KOVÁCS Z., TÁRKÁNYI F., QAIM S.M.: Excitation function
of deuteron induced reactions on 123Te: Relevance to the production of 123I and 124I at low and medium sized cyclotron. Applied radiation and isotopes 48 (1997) 267.
[4] TÁRKÁNYI F., HERMANNE A., TAKÁCS S., SHUBIN YU, DITYUKA.I. Cross-sections for production of therapeutic radioisotopes P
198PAu and P
199PAu in proton and deuteron induced
reactions on P
198PPt, will be published in Radiochimica Acta.
[5] TÁRKÁNYI F., ANDÓ L., SZŰCS Z., MAHUNKA I., KOVÁCS Z. Solid targets and Irradiation facilities for production of diagnostic and therapeutic radioniclides at the Debrecen cyclotron. Report on the 1 P
stP RCM of the CRP on “Standardized High Current Solid Targets for
Cyclotron Production of Diagnostic and Therapeutic Radionuclides”, 27-30 November 2000. Brussels, Belgium.
[6] TÁRKÁNYI F., TAKÁCS S., GUL K., HERMANNE A., MUSTAFA M. G., NORTIER M., OBLOZINSKY P., QAIM S. M., SCHOLTEN B., SHUBIN YU. N., YOUXIANG Z. Beam Monitor reactions. IAEA TECDOC-1211. Charged particle cross-section database for medical radioisotope production: diagnostic radioisotopes and monitor reaction, chapter 4, IAEA, Vienna, May 2001, p. 50. Web version at URL: Thttp://www-nds.iaea.org/medicalT.
[7] HERMANNE A., SONCK M., FENYVESI A., DARABAN L. Study on production of P
103PPd
and characterization of possible contaminants in the proton irradiation of P
103PRh up to 28 MeV.
Nuclear Instruments and Methods in Physics Research B 170 (2000) 281-292. [8] HERMANNE A., SONCK M., TAKÁCS S., TÁRKÁNYI F., SHUBIN Y.: Study on alternative
production of P
103PPd and characterization of contaminants in the deuteron irradiation of P
103PRh up
to 21 MeV. Nuclear Instruments and Methods in Physics Research B 187 (2002) 3-14.
56
TABLE I. THE IODINE RADIOACTIVE ISOTOPES PRODUCED IN PROTON BOMBARDMENT ON TE TARGETS, CONTRIBUTING REACTIONS, Q-VALUES AND TYPE OF DATA USED IN THE CALCULATION TO ESTIMATE THE TOTAL PRODUCED ACTIVITY
Product Half-life Contributing Reaction
Q-value (MeV)
Used data
P
118m,gPI 13.7 m P
120PTe(p,3n)P
118gPI -25.634 theory
P
119PI 19.1 m P
120PTe(p,2n)P
119PI -14.583 experimental
P
120gPI 81.0 m P
120PTe(p,n)P
120gPI
P
122PTe(p,3n)P
120gPI
-6.402 -23.447
experimental
P
120mPI 53 m P
120PTe(p,n)P
120mPI
P
122PTe(p,3n)P
120mPI
-6.402 -23.447
experimental experimental
P
121PI 2.12 h P
122PTe(p,2n)P
121PI
P
123PTe(p,3n)P
121PI
-12.876 -22.315
experimental theory
P
122PI 3.63 m P
122PTe(p,n)P
122PI
P
123PTe(p,2n)P
122PI
P
124PTe(p,3n)P
122PI
-5.016 -11.955 -
21.379
experimental theory theory
P
123PI 13.27 h P
123PTe(p,n)P
123PI
P
124PTe(p,2n)P
123PI
P
125PTe(p,3n)P
123PI
-2.024 -11.448 -
18.023
eval. exp. eval. exp. theory
P
124PI 4.176 d P
124PTe(p,n)P
124PI
P
125PTe(p,2n)P
124PI
P
126PTe(p,3n)P
124PI
-3.942 -10.517 -
19.631
eval. exp. theory theory
P
125PI 59.408 d P
125PTe(p,n)P
125PI
P
126PTe(p,2n)P
125PI
-0.968 -10.082
theory theory
P
126PI 13.11 d P
126PTe(p,n)P
126PI
P
128PTe(p,3n)P
126PI
-2.937 -18.01
theory theory
P
128PI 24.99 m P
128PTe(p,n)P
128PI
P
130PTe(p,3n)P
128PI
-1.245 -16.53
experimental theory
P
129PI 1.57 10 P
7P y P
130PTe(p,2n)P
129PI -7.70 theory
P
130m,gPI 12.36 h P
130PTe(p,n)P
130gPI -1.21 experimental
57
TABLE II. THE PRODUCED IODINE RADIOACTIVE ISOTOPES IN DEUTERON BOMBARDMENT ON TE TARGETS, CONTRIBUTING REACTIONS, Q-VALUES AND TYPE OF DATA USED IN THE CALCULATION TO ESTIMATE THE TOTAL PRODUCED ACTIVITY
Product Half-life Contributing reaction
Q-value (MeV)
Used data
P
103PI 19.1 m P
120PTe(d,3n)P
119PI -16.82 theory
P
120gPI 81.0 m P
120PTe(d,2n)P
120gPI
P
122PTe(d,4n)P
120gPI
-8.62 -25.67
exp. + theory theory
P
120mPI 53 m P
120PTe(d,2n)P
120mPI
P
122PTe(d,4n)P
120mPI
-8.62 -25.67
exp. + theory theory
P
121PI 2.12 h P
120PTe(d,n)P
121PI
P
122PTe(d,3n)P
121PI
P
123PTe(d,4n)P
121PI
+1.95 -15.10 -
22.03
theory experimental
theory
P
122PI 3.63 m P
122PTe(d,2n)P
122PI
P
123PTe(d,3n)P
122PI
P
124PTe(d,4n)P
122PI
-7.24 -14.17 -23.59
experimental theory theory
P
123PI 13.27 h P
122PTe(d,n)P
123PI
P
123PTe(d,2n)P
123PI
P
124PTe(d,3n)P
123PI
P
125PTe(d,4n)P
123PI
+2.69 -4.24 -13.67 -
20.24
experimental exp. + theory exp. + theory
theory
P
124PI 4.176 d P
123PTe(d,n)P
124PI
P
124PTe(d,2n)P
124PI
P
125PTe(d,3n)P
124PI
P
126PTe(d,4n)P
124PI
+3.26 -6.16 -12.74 -
21.86
experimental experimental
theory theory
P
125PI 59.408 d P
124PTe(d,n)P
125PI
P
125PTe(d,2n)P
125PI
P
126PTe(d,3n)P
125PI
+3.38 -3.19 -
12.31
theory theory theory
P
126PI 13.11 d P
125PTe(d,n)P
126PI
P
126PTe(d,2n)P
126PI
P
128PTe(d,4n)P
126PI
+3.95 -5.16 -
2023
theory exp. + theory theory
P
128PI 24.99 m P
128PTe(d,2n)P
128PI
P
130PTe(d,4n)P
128PI
-4.26 -18.76
exp. + theory theory
P
129PI 1.57 10 P
7P y P
128PTe(d,n)P
129PI
P
130PTe(d,3n)P
129PI
+4.57 -9.93
theory theory
P
130m,gPI 12.36 h P
130PTe(d,2n)P
130PI -3.43 exp. + theory
P
131PI 8.02 d P
130PTe(d,n)P
131PI +5.17 exp. + theory
58
TABLE III. P
103PPD AND CONTAMINATING RADIOISOTOPES PRODUCED BY PROTON
BOMBARDMENT ON P
103PRH TARGETS, Q-VALUES AND TYPE OF DATA USED TO
ESTIMATE THE TOTAL PRODUCED ACTIVITY
Product Half-life Contributing Reaction Q-value(MEV) Used data
P
103PPd 16.97 d P
103PRh(p,n)P
103PPd -1.33 experimental
P
101PPd 8.47 h P
103PRh(p,3n)P
101PPd -19.52 experimental
P
103mPRh 56.1 m P
103PRh(p,n)P
103mPRh 0.0 experimental
P
102mPRh 2.9 y P
103PRh(p,pn)P
102mPRh
P
103PRh(p,d)P
102mPRh
-9.32 -7.09
experimental
P
102gPRh 207 d P
103PRh(p,pn)P
102gPRh
P
103PRh(p,d)P
102gPRh
-9.32 -7.09
experimental
P
101mPRh 4.34 d P
103PRh(p,p2n)P
101mPRh
P
103PRh(p,nd)P
101mPRh
P
103PRh(p,t)P
101mPRh
-16.76 -14.53 -
8.27
experimental
P
101gPRh 3.3 y P
103PRh(p,p2n)P
101gPRh
P
103PRh(p,nd)P
101gPRh
P
103PRh(p,t)P
101gPRh
-16.76 -14.53 -
8.27
experimental
TABLE IV. P
103PPD AND CONTAMINATING RADIOISOTOPES PRODUCED IN DEUTERON
BOMBARDMENT ON P
103PRH TARGETS, CONTRIBUTING REACTIONS, Q-VALUES AND
TYPE OF DATA USED TO ESTIMATE THE TOTAL PRODUCED ACTIVITY
Product Half-life Contributing Reaction Q-VALUE(MEV)
Used data
P
103PPd 16.97 d P
103PRh(d,2n)P
103PPd -3.55 experimental
P
101PPd 8.47 h P
103PRh(d,4n)P
101PPd -21.74 experimental
P
103mPRh 56.1 m P
103PRh(d,d)P
103mPRh
P
103PRh(d,np)P
103mPRh
0.0 -2.22
experimental
P
102mPRh 2.9 y P
103PRh(d,p2n)P
102mPRh
P
103PRh(d,dn)P
102mPRh
P
103PRh(d,t)P
102mPRh
-11.54 -9.32 -
3.06
experimental
P
102gPRh 207 d P
103PRh(d,p2n)P
102gPRh
P
103PRh(d,dn)P
102gPRh
P
103PRh(d,t)P
102gPRh
-11.54 -9.32 -
3.06
experimental
P
101mPRh 4.34 d P
103PRh(d,p2n)P
101mPRh
P
103PRh(d,dn)P
101mPRh
-11.54 -14.53
experimental
P
101gPRh 3.3 y P
103PRh(d,p3n)P
101gPRh
P
103PRh(d,d2n)P
101gPRh
P
103PRh(d,tn)P
101gPRh
-18.98 -16.74 -
10.50
experimental
59
TABLE V. THE P
201PPB AND THE CONTAMINATING RADIOACTIVE ISOTOPES PRODUCED
IN PROTON BOMBARDMENT ON P
203PTL AND P
205PTL TARGETS, CONTRIBUTING
REACTIONS, Q-VALUES AND TYPE OF DATA USED IN THE CALCULATION TO ESTIMATE THE TOTAL PRODUCED ACTIVITY
Product Half-life Contributing Reaction Q-value (MeV)
Used data
P
203PPb 51.9 h P
203PTl(p,n)P
203PPb
P
205PTl(p,3n)P
203PPb
-1.77 -15.96
experimental
P
202mPPb 3.62 h P
203PTl(p,2n)P
202mPPb
P
205PTl(p,4n)P
202mPPb
-8.68 -22.88
experimental
P
201PPb 9.4 h P
203PTl(p,3n)P
201PPb -17.41 experimental
P
200PPb 21.5 h P
203PTl(p,4n)P
200PPb -24.52 experimental
P
204mPPb P
205PTl(p,2n)P
204mPPb -7.56 experimental
P
202PTl 12.23 d P
natPTl(p,x)P
202PTl P
203PTl(p,d)P
202PTl P
203PTl(p,pn)P
202PTl
P
205PTl(p,2nd)P
202PTl
P
205PTl(p,3np)P
202PTl
-5.62 -7.85 -19.83 -
22.05
experimental separated curves
P
201PTl 73.1 h P
natPTl(p,x)P
201PTl
P
203PTl(p,t)P
201PTl P
203PTl(p,dn)P
201PTl P
203PTl(p,2np)P
201PTl
P
205PTl(p,2nt)P
201PTl
P
205PTl(p,3nd)P
201PTl
P
205PTl(p,4np)P
201PTl
-6.24 -12.5 -14.72 -20.44 -20.7 -
28.92
experimental separated curves
60
120Te(p,3n)
118I
0
100
200
300
400
500
600
20 30 40 50 60Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
Alice IPPE
FIG. 1. Excitation function of the
P
120PTe(p,3n)P
118PI reaction calculated by using
Alice IPPE model code.
120Te(p,2n)
119I
0
200
400
600
800
1000
1200
0 10 20 30 40 50 60 7
Proton energy (MeV)
Cro
ss
se
cti
on
(m
b)
0
Alice IPPE
Hohn 98
spline fit
FIG. 2. Excitation function of the
P
120PTe(p,2n)P
119PI reaction calculated by using
Alice IPPE model code. Experimental data
fitted by using spline method.
120Te(p,n)
120I
0
100
200
300
400
500
600
700
800
900
1000
0 5 10 15 20 25 30 35 40
Proton energy (MeV)
Cro
ss
se
cti
on
(m
b)
Alice IPPE
Hohn 98 I-120m
Hohn 98 I-120g
spline fit I-120g
spline fit I-120m
FIG. 3. Excitation function of the
P
120PTe(p,n)P
120m+gPI reaction calculated by using
Alice IPPE model code.
Experimental data of P
120mPI and P
120gPI were fitted
by using spline method.
122Te(p,3n)
120I
0
100
200
300
400
500
600
700
800
20 30 40 50 60
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Zweit 96 I-120
Hohn 97 I-120m
Hohn97 I-120g
Alice IPPE
spline fit I-120m
spline fit I-120g
FIG. 4. Excitation function of the
P
122PTe(p,3n)P
120m+gPI reaction calculated by using
Alice IPPE model code.
Experimental data of P
120mPI and P
120gPI were fitted
by using spline method.
122Te(p,2n)
121I
0
200
400
600
800
1000
1200
1400
0 10 20 30 40 50 60 70
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Hohn 97
Scholten 89
Zweit 96 I-121
Alice IPPE
spline fit
FIG. 5. Excitation function of the
P
122PTe(p,2n)P
121PI reaction calculated by using
Alice IPPE model code. Experimental data
were fitted by using spline method.
123Te(p,3n)
121I
0
200
400
600
800
1000
1200
0 10 20 30 40 50 60 7
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 6. Excitation function of the
P
123PTe(p,3n)P
121PI reaction calculated by using
Alice IPPE model code.
61
122Te(p,n)
122I
0
200
400
600
800
1000
0 5 10 15 20 25 30
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)Hohn 97
Alice IPPE
Spline fit
FIG. 7. Excitation function of the P
122PTe(p,n)P
122PI
reaction calculated by using Alice IPPE model
code.
Experimental data were fitted by using spline
method.
123Te(p,2n)
122I
0
200
400
600
800
1000
1200
0 10 20 30 40 5
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Sholten 89
Alice IPPE
FIG. 8. Excitation function of P
123PTe(p,2n)P
122PI
calculated by using Alice IPPE model code.
124Te(p,3n)
122I
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60 70
Proton energy (MeV)
Cro
ss S
ectio
n (
mb
)
Alice IPPE
FIG. 9. Excitation function of the
P
124PTe(p,3n)P
122PI reaction calculated by using
Alice IPPE model code.
123Te(p,n)
123I
0
100
200
300
400
500
600
700
800
900
1000
0 5 10 15 20 25 30 35
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
Mahunka96
Scholten89 I-123
Van den Bosch77 I-123
Hupf 68 I-123
Barrall 81 I-123
Zweit 92 nat
Scholten 89 nat
Acerbi 75 nat
Alice IPPE
Spline fit of norm. Alice
FIG. 10. Excitation function of the
P
123PTe(p,n)P
123PI reaction calculated by using
Alice IPPE model code.
Experimental data were fitted by using spline
method.
124Te(p,2n)
123I
0
200
400
600
800
1000
1200
1400
1600
1800
2000
5 10 15 20 25 30 35 40
Proton energy [MeV]
Cro
ss s
ecti
on
[m
b]
Van den Bosch77
Kondo77a I-123
Kondo77b I-123
Scholten 95 I-123
Acerbi 75 I-123
Alice IPPE norm.
spline fit
FIG. 11. Excitation function of the
P
124PTe(p,2n)P
123PI reaction calculated by using
Alice IPPE model code.
Experimental data were fitted by using spline
method.
125Te(p,3n)
123I
0
200
400
600
800
1000
1200
0 10 20 30 40 50 60 7
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 12. Excitation function of the
P
125PTe(p,3n)P
123PI reaction calculated by using
Alice IPPE model code.
62
124Te(p,n)
124I
0
100
200
300
400
500
600
700
800
0 5 10 15 20 25 30 35
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
Van den Bosch77
Kondo77a I-124
Kondo77b I-124
Scholten95 I-124
Acerbi 75 I-124
Acerbi 75 nat
Zweit 92 nat
Scholten 89 nat
Alice IPPE
Spline fit
FIG. 13. Excitation function of the
P
124PTe(p,n)P
124PI reaction calculated by using
Alice IPPE model code.
Experimental data were fitted by using spline
method.
125Te(p,2n)
124I
0
200
400
600
800
1000
1200
0 10 20 30 4
Proton energy (MeV)
Cro
ss s
ecti
on
(M
eV
)
0
Alice IPPE
FIG. 14. Excitation function of the
P
125PTe(p,2n)P
124PI reaction calculated by using
Alice IPPE model code.
126Te(p,3n)
124I
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 5
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 15. Excitation function of the
P
123PTe(p,n)P
123PI reaction calculated by using
Alice IPPE model code.
125Te(p,n)
125I
0
100
200
300
400
500
600
700
800
0 5 10 15 20 25 30
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Johnson58
Zweit 92nat
Alice IPPE
FIG. 16. Excitation function of the
P
125PTe(p,n)P
125PI reaction calculated by using
Alice IPPE model code.
126Te(p,2n)
125I
0
200
400
600
800
1000
1200
0 10 20 30 40 5
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 17. Excitation function of the
P
126PTe(p,2n)P
125PI reaction calculated by using
Alice IPPE model code.
128Te(p,3n)
126Te
0
200
400
600
800
1000
1200
0 10 20 30 40 50 60 7
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 18. Excitation function of the
P
128PTe(p,3n)P
126PI reaction calculated by using
Alice IPPE model code.
63
126Te(p,n)
126I
0
100
200
300
400
500
600
0 5 10 15 20 25 30
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)Scholten 89nat
Zweit 92nat
Acerbi 75nat
Alice IPPE
FIG. 19. Excitation function of the
P
126PTe(p,n)P
126PI reaction calculated by using
Alice IPPE model code.
128Te(p,3n)
126Te
0
200
400
600
800
1000
1200
0 10 20 30 40 50 60 7
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 20. Excitation function of the
P
128PTe(p,3n)P
126PI reaction calculated by using
Alice IPPE model code.
128Te(p,n)
128I
0
50
100
150
200
250
300
350
400
450
500
0 5 10 15 20 25 30
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Blaser51
Johnson58
Acerbi 75nat
Zweit 92nat
Scholten 89nat
Alice IPPE
Alice norm. to exp.
FIG. 21. Excitation function of the
P
128PTe(p,n)P
128PI reaction calculated by using
Alice IPPE model code.
Experimental data were fitted by using spline
method to Alice IPPE calculation normalized
to experimental data.
130Te(p,3n)
128I
0
200
400
600
800
1000
1200
0 10 20 30 40 50 60 7
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 22. Excitation function of the
P
130PTe(p,3n)P
128PI reaction calculated by using
Alice IPPE model code.
130Te(p,2n)
129I
0
500
1000
1500
0 5 10 15 20 25 30 35 40
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Alice IPPE
FIG. 23. Excitation function of the
P
130PTe(p,2n)P
129PI reaction calculated by using
Alice IPPE model code.
130Te(p,n)
130I
0
50
100
150
200
250
300
350
0 5 10 15 20 25 30 35
Proton energy [MeV
Cro
ss s
ectio
ns [
mb
]
Blaser51Daly64Johnson58Zweit 92natScholten 89natAcerbi 75natAlice IPPEFit Alice norm to exp.
...
FIG. 24. Excitation function of the
P
128PTe(p,n)P
128PI reaction calculated by using
Alice IPPE model code.
Experimental data were fitted by using spline
method to Alice IPPE calculation normalized
to experimental data.
64
120Te(d,3n)
119I
0
200
400
600
800
1000
1200
0 10 20 30
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
40
Alice IPPE
FIG. 25. Excitation function of the
P
120PTe(d,3n)P
119PI reaction calculated by using
Alice IPPE model code.
120Te(d,2n)
120mgI
0
200
400
600
800
1000
1200
1400
0 10 20 30 4
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Qaim I-120m
Qaim I-120g
I-120 Alice IPPE
I-120 Alice IPPE norm.
FIG. 26. Excitation function of the
P
120PTe(d,2n)P
120m+gPI reaction calculated by using
Alice IPPE model code.
The theoretical curve was normalized to
experimental data.
122Te(d,4n)
120I
0
100
200
300
400
500
600
700
0 10 20 30 40 50
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
60
Alice IPPE
FIG. 27. Excitation function of the
P
122PTe(d,4n)P
120PI reaction calculated by using
Alice IPPE model code.
120Te(d,n)
121I
0
100
200
300
400
500
600
700
0 5 10 15 20 25
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
Qaim I-121
Alice IPPE
FIG. 28. Excitation function of the
P
120PTe(d,n)P
121PI reaction calculated by using
Alice IPPE model code.
122Te(d,3n)
121I
0
200
400
600
800
1000
1200
1400
0 10 20 30 40
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Zaidi83
Shifted Zaidi83
Alice IPPE
Spline fit
FIG. 29. Excitation function of the
P
122PTe(d,3n)P
121PI reaction calculated by using
Alice IPPE model code.
Spline fit was applied to the experimental data.
123Te(d,4n)
121I
0
100
200
300
400
500
600
700
800
900
0 10 20 30 40 50 6
Deuteron energy(MeV)
Cro
ss s
ecti
on
(M
eV
)
0
Alice IPPE
FIG. 30. Excitation function of the
P
123PTe(d,4n)P
121PI reaction calculated by using
Alice IPPE model code.
65
122Te(d,2n)
122I
0
200
400
600
800
1000
1200
1400
0 10 20 30 4
Deuteron energy [MeV]
Cro
ss s
ecti
on
s (
mb
)
0
Zaidi83
shifted Zaidi83
Alice IPPE
Spline fit
FIG. 31. Excitation function of the
P
122PTe(d,2n)P
122PI reaction calculated by using
Alice IPPE model code.
Spline fit was applied to the experimental data
shifted in energy by 2 MeV down.
123Te(d,3n)
122I
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25 30 35
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
Alice IPPE
FIG. 32. Excitation function of the
P
123PTe(d,3n)P
122PI reaction calculated by using
Alice IPPE model code.
124Te(d,4n)
122I
0
100
200
300
400
500
600
700
800
900
0 10 20 30 40 50 6
Deuteron energy(MEV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 33. Excitation function of the
P
124PTe(d,4n)P
122PI reaction calculated by using
Alice IPPE model code.
122Te(d,n)
123I
0
50
100
150
200
250
300
350
400
450
0 5 10 15 20 25 30 35
Proton energy (MeV)
Cro
ss s
ecti
on
s (
mb
) Zaidi83
Takacs97
Shifted Zaidi83
AliceIPPE
Spline fit
FIG. 34. Excitation function of the
P
122PTe(d,n)P
123PI reaction calculated by using
Alice IPPE model code.
Spline fit was applied to the experimental data.
123Te(d,2n)
123I
0
200
400
600
800
1000
1200
1400
0 10 20 30 4
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
0
Scholten 97
Alice IPPE
extrapolated fit
FIG. 35. Excitation function of the
P
123PTe(d,2n)P
123PI reaction calculated by using
Alice IPPE model code.
Spline fit was applied to the experimental data
extrapolated up to 40 MeV using the
normalized Alice calculation.
124Te(d,3n)
123I
0
200
400
600
800
1000
1200
1400
0 10 20 30 4Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
0
Firouzbakht 93
Alice IPPE
Alice IPPE norm.
FIG. 36. Excitation function of the
P
124PTe(d,3n)P
123PI reaction calculated by using
Alice IPPE model code.
The theoretical curve was normalized to
experimental data.
66
125Te(d,4n)
123I
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 6
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 37. Excitation function of the
P
125PTe(d,4n)P
123PI reaction calculated by using
Alice IPPE model code.
123Te(d,n)
124I
0
20
40
60
80
100
120
140
0 5 10 15 20 25
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Scholten 97
Alice IPPE
fit of Scholten + Alice IPPE
FIG. 38. Excitation function of the
P
123PTe(d,n)P
124PI reaction calculated by using
Alice IPPE model code.
Spline fit was applied to the experimental data
extrapolated up to 22 MeV using the
normalized Alice calculation.
124Te(d,2n)
124I
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25 30
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Firouzbakht 93
Bastian 01
Alice IPPE
spline fit
FIG. 39. Excitation function of the
P
12PTe(d,2n)P
124PI reaction calculated by using
Alice IPPE model code.
Spline fit was applied to the experimental data.
125Te(d,3n)
124I
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25 30 35
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
Alice IPPE
FIG. 40. Excitation function of the
P
125PTe(d,3n)P
124PI reaction calculated by using
Alice IPPE model code.
126Te(d,4n)
124I
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 6
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 41. Excitation function of the
P
126PTe(d,4n)P
124PI reaction calculated by using
Alice IPPE model code.
124Te(d,n)
125I
0
50
100
150
200
250
300
0 10 20 30 4
Deuteron energy(MEV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 42. Excitation function of the
P
124PTe(d,n)P
125PI reaction calculated by using
Alice IPPE model code.
67
125Te(d,2n)
125I
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25 30
Deuteron enegy (MeV)
Cro
ss s
ecti
on
(m
b)
Alice IPPE
FIG. 43. Excitation function of the
P
125PTe(d,2n)P
125PI reaction calculated by using
Alice IPPE model code.
126Te(d,3n)
125I
0
200
400
600
800
1000
1200
1400
1600
0 10 20 30 40 50 6
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 44. Excitation function of the
P
126PTe(d,3n)P
125PI reaction calculated by using
Alice IPPE model code.
125Te(d,n)
126I
0
10
20
30
40
50
60
70
80
90
0 5 10 15 20 25 30 35
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
Alice IPPE
FIG. 45. Excitation function of the
P
125PTe(d,n)P
126PI reaction calculated by using
Alice IPPE model code. P
126Te(d,2n)
126I
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25 30Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Pement66
Alice IPPE
Alice IPPE norm.
FIG. 46. Excitation function of the
P
126PTe(d,2n)P
126PI reaction calculated by using
Alice IPPE model code.
Theoretical curve was normalized to the
experimental data.
128Te(d,4n)
126I
0
200
400
600
800
1000
1200
0 10 20 30 40 50 6Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 47. Excitation function of the
P
128PTe(d,4n)P
126PI reaction calculated by using
Alice IPPE model code.
128Te(d,2n)
128I
0
200
400
600
800
1000
1200
0 10 20 30 4
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
0
Pement 66
Pimentel 88
Alice IPPE
Alice IPPE norm.
FIG. 48. Excitation function of the
P
128PTe(d,2n)P
128PI reaction calculated by using
Alice IPPE model code.
Theoretical curve was normalized to the
experimental data.
68
130Te(d,4n)
128I
0
200
400
600
800
1000
1200
0 10 20 30 40 50 6
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 49. Excitation function of the
P
130PTe(d,4n)P
128PI reaction calculated by using
Alice IPPE model code. P
128Te(d,n)
129I
0
10
20
30
40
50
60
70
80
90
100
0 10 20 30 4Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 50. Excitation function of the
P
128PTe(d,n)P
129PI reaction calculated by using
Alice IPPE model code. P
130Te(d,3n)
129I
0
200
400
600
800
1000
1200
1400
1600
0 10 20 30 40 50 6
Deuteron energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Alice IPPE
FIG. 51. Excitation function of the
P
130PTe(d,3n)P
129PI reaction calculated by using
Alice IPPE model code. P
130Te(d,2n)
130I
0
200
400
600
800
1000
1200
0 5 10 15 20 25 30
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Pement 66
Otozai 68
Nishi 69
Pimentel 88
Zaidi 83 nat
Alice IPPE
Alice IPPE norm.
FIG. 52. Excitation function of the
P
130PTe(d,2n)P
130PI reaction calculated by using
Alice IPPE model code.
Theoretical curve was normalized to the
experimental data.
130Te(d,n)
131I
0
50
100
150
200
250
300
350
0 5 10 15 20 25 30
Deuteron energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Otozai 68
Nishi 69
Zaidi 83 nat
Alice IPPE
Alice IPPE norm.
FIG. 53. Excitation function of the
P
130PTe(d,n)P
131PI reaction calculated by using
Alice IPPE model code.
Theoretical curve was normalized to the
experimental data.
103Rh(p,n)
103Pd
0
100
200
300
400
500
600
700
800
900
0 10 20 30Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
40
Harper
Albert
Johnson
Hansen
Blaser
Hermanne-X
Mukhamedov
Sudár
spline fit
FIG. 54. Excitation function of the
P
103PRh(p,n)P
103PPd reaction. Spline fit was made
over the selected data as recommended cross-
section.
69
103Rh(p,3n)
101Pd
0
50
100
150
200
250
300
350
400
450
500
0 10 20 30 4Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
101Pd
spline fit
FIG. 55. Excitation function of the
P
103PRh(p,3n)P
101PPd reaction. Spline fit was made
over the experimental data.
103Rh(p,x)
101m,gRh
0
100
200
300
400
500
600
0 10 20 30
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
40
101mRh101gRhspline fitspline fit
FIG. 56. Excitation function of the
P
103PRh(p,x)P
101m,gPRh reactions. Spline fit was
made over the experimental data.
103Rh(p,x)
102m,gRh
0
20
40
60
80
100
120
140
160
0 10 20 30 4Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
102mRh102gRhspline fitspline fit
FIG. 57. Excitation function of the
P
103PRh(p,x)P
102m,gPRh reactions. Spline fit was
made over the experimental data.
103Rh(d,2n)
103Pd
0
200
400
600
800
1000
1200
0 5 10 15 20 25
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b) Pd-103-x
spline fit
FIG. 58. Excitation function of the
P
103PRh(d,2n)P
103PPd reactions. Spline fit was made
over the experimental data. Experimental data
were measured by using X-ray radiation.
103Rh(d,x)
101m,gRh
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0 5 10 15 20 25
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
Rh-101m
Rh-101g
spline fit Rh-101m
spline fit Rh-101g
FIG. 59. Excitation function of the
P
103PRh(d,x)P
101m,gPRh reactions. Spline fit was
made over the experimental data.
103Rh(d,x)
102m,gRh
0
5
10
15
20
25
30
35
40
45
0 5 10 15 20 25
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
Rh-102mRh-102gspline fit Rh-102mspline fit Rh-102g
FIG. 60. Excitation function of the
P
103PRh(d,x)P
102m,gPRh reactions. Spline fit was
made over the experimental data.
70
203Tl(p,3n)
201Pb
0
200
400
600
800
1000
1200
1400
1600
15 20 25 30 35
Particle energy (MeV)
Cro
ss s
ecti
on
(m
b)
Bonardi (83)b
Hermanne (92)
Lagunas-S. (78)
Qaim (79)
fit Spline
FIG. 61. Selected experimental cross-sections
for P
203PTl(p,3n)P
201PPb reaction and recommended
cross-section calculated by using spline
method.
203Tl(p,2n)
202mPb
0
20
40
60
80
100
120
140
5 10 15 20 25Particle energy (MeV)
Cro
ss s
ecti
on
(m
b)
Bonardi (83)b
Hermanne (92)
Lagunas Solar (78)
Qaim (79)
fit Pade
FIG. 62. Selected experimental cross-sections
for P
203PTl(p,2n)P
202mPPb reaction and
recommended cross-section calculated by
using Pade method.
203Tl(p,4n)
200Pb
0
200
400
600
800
1000
1200
26 27 28 29 30 31 32 33 34 35 36
Particle energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Bonardi (83)bHermanne (92) Lagunas-S. (78)Qaim (79)fit Spline
FIG. 63. Selected experimental cross-sections
for P
203PTl(p,4n)P
200PPb reaction and recommended
cross-section calculated by using spline
method.
203Tl(p,n)
203Pb
0
20
40
60
80
100
120
140
0 5 10 15 20 25 30
Particle energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
Qaim79 norm.
Spline fit
FIG. 64. Experimental cross-sections for
P
203PTl(p,n)P
203PPb reaction and statistical fit
extended to higher energy by using spline
method.
205Tl(p,2n)
204mPb
0
20
40
60
80
100
120
140
160
180
0 10 20 30 40 50 6
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
0
Lagunas-Solar78
Hermanne 91Qaim79
Lagunas-Solar80spline fit
FIG. 65. Selected experimental cross-sections
for P
205PTl(p,2n)P
204mPPb reaction and statistical fit
calculated by using spline method.
205Tl(p,3n)
203Pb
0
200
400
600
800
1000
1200
1400
10 20 30 40 50 60
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b) Lagunas-Solar80
Hermanne 91
Lagunas-Solar78
spline fit
FIG. 66. Selected experimental cross-sections
for P
205PTl(p,3n)P
203PPb reaction and statistical fit
calculated by using spline method.
71
205Tl(p,4n)
202mPb
0
50
100
150
200
250
300
350
400
20 25 30 35 40 45 50 55 60
Proton energy (MeV)
Cro
ss s
ecti
on
(m
b)
Hermanne 91
Lagunas-Solar78
Lagunas-Solar80
spline fit
FIG. 67. Selected experimental cross-sections
for P
205PTl(p,4n)P
202mPPb reaction and statistical fit
calculated by using spline method.
natTl(p,x)
202Tl
0
10
20
30
40
50
60
70
80
0 10 20 30 40
Particle energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
50
Qaim79
natTl(p,x)202Tl
203Tl(p,x)202Tl
205Tl(p,x)202Tl
natTl(p,x)
201Tl
0
20
40
60
80
100
120
0 10 20 30 40 5
Particle energy (MeV)
Cro
ss s
ecti
on
s (
mb
)
0
Qaim79
spline fit natural
203Tl(p,x)201Tl
205Tl(p,x)201Tl
FIG. 68. Experimental cross-sections for P
natPTl(p,x)P
202PTl process and arbitrary separation
into the two contributing processes using
spline fitting method.
FIG. 69. Experimental cross-sections for
P
natPTl(p,x)P
202PTl process and arbitrary separation
into the two contributing processes using
spline fitting method.
72
HIGH CURRENT TL-203, RH-103 TARGETS PREPARATION FOR
CYCLOTRON PRODUCTION OF TL-201 AND PD-103 RADIONUCLIDES
A. ARZUMANOV, V. BERGER, A. BORISSENKO, N. GORODISSKAYA, I. ILMATOV,
A. KNYAZEV, V. KOPTEV, S. LYSSUKHIN, A. PLATOV, G. SYCHIKOV, D. ZHELTOV.
Institute of Nuclear Physics, National Nuclear Center, Kazakhstan
Abstract
The objectives of the present work are to increase thermal stability of cyclotron targets for production of Tl-201
isotope, increase Tl-203 regeneration rate at radiochemical reprocessing of the targets and develop production technology for
radiochemical sources based on Rd-103 isotope. Electrochemical coating of copper substrate with Tl increased the beam
current at target irradiation from 100 µA to 125 µA. Further increase of the beam current results in sharp decrease of target
stability time at irradiation to 15 min at beam current 150 µA. Thermal calculations and tests at the electron-beam stand
predict satisfactory stability at such currents. The discrepancy with the irradiation results has not been explained. More
accurate specification of regimes for Tl-203 electrochemical recovery from irradiated targets and better matching of the
electrolyte composition made it possible to increase the recovery rate up to 99.5%. Before the present Project, the INP had no
experience in production of radioactive sources based on Pd-103. Thermo-diffusion extraction of Pd-103 from irradiated
rhodium foil has been chosen as a technology-defining method. The process assures good extraction rate and high purity of
extracted isotope. Production of Pd-103 sources based on this technology is much simpler compared to the same based on
electrochemical processes
1. INTRODUCTION
The Project works were performed at the INP during 2000-2003 by a research group consisting
of 12 people. The investigations were performed on the basis of isochronous cyclotron U-150M and
the Laboratory of Radioactive Isotopes. Chronologically, the following tasks were solved:
Year 2001:
Investigations of new electroplating techniques and testing of the targets at high beam current
for production of Tl-201.
Calculations of heat distribution and target recovery.
Year 2002:
Continued works on optimization of the post irradiation chemistry and target recovery
procedures for production of Tl-201 at beam current up to 150 µA.
Initiation of designing and development of a solid target for production of Pd-103 from Rh,
including the post irradiation chemistry.
Year 2003:
Tl-203 target optimization for high current irradiation at cyclotron.
Development of the thermal diffusion method for Pd-103 separation from Rh target.
Therefore, the investigations were mainly focused on technology development for production of
two medical radioisotopes Tl-201 and Pd-103.
2. RADIOISOTOPE PRODUCTION IN THE CYCLOTRON AT THE INP [1].
2.1. Status of the Cyclotron
Kazakhstan’s variable energy isochronous cyclotron K=50 MeV is a 150 cm compact-pole 3
sector positive ion machine. It generates various beams of light ions: protons 6 – 30 MeV, deuterons
12.5 – 25 MeV, He-3-ions 18.5 – 62 MeV, and alpha-particles 25 – 50 MeV.
73
In the last years, the cyclotron is rather intensively used for radioisotope production to meet the
needs of the Republic of Kazakhstan. Main users of radioisotope products are the institutes of the
Ministry of Public Health and oil-chemistry, metallurgy, mining enterprises and scientific institutes.
The radioisotope production program shares the cyclotron facilities with the basic nuclear
physics research program. For radioisotopes production both external and internal targets are used.
Irradiation of external target is typically used during several years. The beam intensity on the external
target is equal to 40 µA for protons. Extracted beam intensity is limited by power dissipation in the
electrostatic deflector at the level of 1 – 2 kW.
For homogeneous target irradiation, the circular beam scanning system is used. Transversal
rotating magnetic field is generated by the stator of an electro-motor and it shifts the beam from the
transport channel axis for up to 12 mm. Swept beam spot can be adjusted to get uniformity of beam
power distribution better than 80% inside the scanning circle of 30 mm diameter. High intensities,
typically several hundred µA, are available at the internal target. In order to enlarge the beam spot on
the target and, therefore, to reduce beam power density on the target, the target is declined with respect
to the beam axis at the angle of 18º. Fig. 1 illustrate the technology of irradiation with the internal
beam.
2.2. Target device.
Target design provides:
- Remote target insertion into the cyclotron tank through vacuum sluice;
- Target assembling between dees on final accelerating orbit R=646 mm under 18° to the beam
axis, which ensures complete beam overlapping by target (beam width on final orbit is 15mm).
- Target’s head is a composite and it consists of a body and a changeable backing; the body is
made of slightly activated aluminum alloy, which ensures its reuse. Backing is made of copper, a
material with good thermal conductivity, and intended for single use. Irradiated material is plated on
backing by electroplating. Backing is attached to the body by two screws that ensure head’s quick
disassembling and reliable seal. Copper backing thickness is equal to 1 mm for water pressure 5 bar
and 2 mm for 20 bars. Maximal water supplying and removal holes have the section of 28 mm P
2P.
Irradiated surface has dimensions 20 х 40 mm. View of the head of the target and its constituents are
shown in the Fig. 2.
2.3. Electron beam stand
Trend to the commercial production of radioactive isotopes requires reliability of all kinds of
work involved, their efficiency and safety, and this, for the first turn, refers to the process of target
irradiation. Therefore, the problems related to the technology development for production of targets
and their thermal testing are very topical. For this purpose, the electron beam stand has been created
[2].
The stand’s vacuum tank is made of stainless steel and has the following dimensions: diameter
340 mm and length 600 mm. Electron gun and target device are installed in ends of the tank. Electron
gun was chosen as heater because it is easy in operation with heat power taken up by the target and
there is a possibility to displace the heating region across surface of the target.
Electron units for beam focusing and deflection in vertical and horizontal directions assure
beam diameter of ∅ 1.5 mm and its scanning across target surface. Scanning frequencies are
horizontal one – 50 Hz and vertical one – 1200 Hz what provides homogenous target heating. There is
an opportunity of fixed beam spot moving at any point of the target surface.
74
There is a system of vacuum pumping (up to 5 P
.P10P
-4P Pa): vacuum monitoring is proceeded with
ion and thermocouple converters. Electron beam has the following parameters: energy of electrons up
to 25 keV, beam intensity up to 200 mA. The water pressure in cooling system is equal to 20 bar what
provides water velocity in the cooling cannel equal to 30 m/s.
Target tests on the stand enable to determine maximal allowed heat flows that are fixed at
melting point of the target material. Energy loss caused by reflected and second electrons are
accounted on basis of known reference data. Electron beam density distribution influences the results
of thermal endurance. Measurements, which were made using wire and pinhole methods, showed that
the most acceptable beam has dimension of ∅ 5 mm and Gaussian distribution. It should be noted that
irradiation at the stand is not exactly equal to irradiation at the cyclotron. At the last one, the energy
absorption takes place in a deeper layer. Thus, the temperature distribution in the target because of
irradiation with protons is different from the case with electron irradiation. This fact was taken into
account by testing of the targets at the stand.
The electron-beam stand is used in the present work for development of electroplating technique
and for final testing of the targets before their irradiation at the cyclotron.
2.4. Calculation of thermal properties for Tl target.
Beam current density distribution for different irradiating modes is obtained by means of
radiography technique and was used in the temperature calculations.
Cooling of the backing is carried out with forced convection. The cooling efficiency depends on
cooling surface geometry, cooling channel geometry, physical properties and velocity of cooler. The
heat transfer coefficient is determined on the basis of similarities theory by means of the Reynolds’s,
the Prandtl’s and the Nusselt’s numbers. Usual water at 14°C is used as cooler. Parameters of backing
and cooling system are, as follows: smooth cooling surface, water channel gap is equal to 0.5 mm; the
water pressure in the cooling system is equal to 20 bar. All this provides the heat-transfer coefficient
equal to 12.7 W/cm P
2.PK.
Numerical determination of the target thermal properties is based on solution of the thermal
conductivity differential equation. The adiabatic equation was solved for a region with heat sources,
and for a region without ones – the Laplace equation. The region with the sources consists of two
layers – a target layer and that segment of the backing where complete stop of charged particles
happens. Full temperature inflection in the target is calculated as:
h
qcqbqbqaqT +⋅+⋅+⋅+⋅=∆
22
2
2
1
1
1
22 λλλλ , (1)
where:
qB1 B and q B2B – heat flow density, emitted in the 1st and 2nd layers, correspondingly (W/cm P
2P); q –
full heat flow density (W/cm P
2P); a, b, c, - widths of 1-st, 2-nd and 3-d layers (cm); λB1 B; λB2B – target and
backing material thermal conductivity (W/cm K); h – heat transfer coefficient (from backing to water)
(W/cm P
2PK).
Temperature of cooling surface depends on amount of heat flow density and increases with its
growth up to T Bb B, when bubble boiling forms (at water pressure in the cooling system equal to 20 bar
T Bb B=215°C). All calculations for maximal allowed heat flows are carried out taking into account
achievement this temperature or the melting point of target material (for easily melted materials).
Verification of the temperature calculations was carried out at the cyclotron and at the electron beam
stand by achieving the melting of different metals.
75
For that there were used Sn, Bi and Pb metals (melting points are equal to 232°C, 271°C and
327°C and flow temperature is equal 190°C, 206°C, 260°C, correspondingly.) Results of the
experiments confirmed the calculations.
3. PREPARATION OF HIGH CURRENT TL-203 TARGETS FOR CYCLOTRON PRODUCTION
OF TL-201 RADIONUCLIDES [3,4].
3.1. Electroplating technique for target preparation.
Thickness of Tl layer is equal to 160 µm. It is determined for 6 MeV energy loss of incident 28
MeV proton beam. Target is inclined at 18° to the beam axis.
Two methods of electroplating were used:
1. Thallium electroplating from sulphurous electrolyte of the following content:
Thallium sulfate (refereed to metal) – 35 g/l, H B2 BSOB4 B – 25 g/l, Phenol – 10 g/l, Gelatin – 1 g/l.
Tl electroplating was carried out on copper plate S=8cm P
2P, stable electrolyze mode with the use
of direct current Pt anode was used. During the process of Tl plating cathode current density was
varied and average rate of Tl plating was calculated. For current densities in the range from 5 up to 15
mA/cm P
2P, velocity of plating was changed from 20 up to 50 µm/h, it must be noted that in the range 10
– 15 mA/cm P
2 Pplating rate changes very slightly. For noted above conditions, fine precipitation of Tl of
grey color was obtained. But the detail examination of its structure by optical microscope
(magnification x250) had shown that Tl precipitated in the form of fine plane crystallites slightly
tightened with each other, i.e. precipitates have low density and therefore they are unlikely to be used
for cyclotron irradiation. This forced us to look for new electrolytes for Tl electroplating.
2. Tl electroplating from ethylenedemintetracetic (EDTA) electrolyte of the following content:
Tl – 20g/l, EDTA – 200 g/l, KOH – ≈80g/l, Phenol – 10 g/l, Hydrazine hydrate (55%) – 25g/l.
The use of noted above electrolyte provides very fine-grain density precipitates with thickness
up to 50 µm and thick precipitates of average grain size are produced. Platinum anodes were used for
the plating. Following thallium precipitation mode was experimentally chosen: cathode current density
9-10 mA/cm P
2P, t P
oP=20-25P
oPC, current reverse: ratio of the straight period to reverse one (7÷8 s). Under
the noted conditions Tl plating rate was equal to 15÷25 µm/h. No special preparation of copper
backing was needed prior the electroplating. Precipitates testing with the use of net with fracture had
shown good Tl adhesion with backing; testing of precipitates’ behavior at high temperatures has been
carried on.
The used device for electroplating of Tl was supplied in frame of IAEA TC Project by Prof. Dr.
P. Van den Winkel (Vrije Universiteit Brussel). An installment for electrodepositing of thallium is
presented in the Fig. 3. Recovery of Tl-203 from the targets has been performed at the same
installment with corresponding changes in electrolyte and regimes at the electrodes.
3.2. Irradiation of Thallium target at the cyclotron.
Production of the radiopharmaceutical “thallium-201 chloride” was achieved and it was
delivered to medical institutions in Almaty. Several test irradiations have also been performed. At the
initial stage of the project the available technology enabled to irradiate targets at the cyclotron with the
beam current up to 100 µA. Developed technologies (mainly electroplating) made it possible to
increase the irradiation current value up to 125 µA. Further increase in the beam current results in
sharp worsening of target stability and at 150 µA current the target destructs after 15-min irradiation.
76
Thermal calculations and tests at the electron-beam stand predict satisfactory stability at such
currents. The discrepancy between the irradiation results and the predictions has not been definitely
explained yet.
Irradiation at the cyclotron was performed during 9 hours. Typical radioisotope yields are 3 –
3.2 Ci of P
201PPb and about 300 mCi of P
201PTl. Targets irradiation modes are presented in the Table II.
3.3. Radiochemical reprocessing of the irradiated targets.
The technology that implies thallium-201 production in two stages was chosen for the
radiochemical separation and extraction of Tl-201 from a thallium target irradiated with protons of 28
MeV energy. The stages are:
1. Extraction of radioactive plumbum-201 by the co-precipitation and its optimal ageing (~26
hours) for thallium-201 accumulation.
2. Separation of the accumulated thallium-201 from the parent plumbum-201 radionuclide by
means of the extraction method.
3. The produced thallium-201 chloride solution is corrected, analyzed according to the
normative values (pH, content of NaCl, volume activity, radiochemical purity, content of
radionuclides and non-active impurities).
4. The thallium-201 radionuclide production technology provides the radionuclide
technological yield ~ 75%. Enriched P
203PTl in metal form is recuperated to the Tl target
production cycle from the spent solutions and the electrolyte. The procedure implies
electrolysis with controlled cathode potential (CCPE). The recovery rate is ≥99.5%.
4. DESIGN AND DEVELOPMENT OF CARRIER-FREE P
103PPD CYCLOTRON PRODUCTION
Interstitial implantation of radiation-emitting materials has been long recognized as an effective
method for tumour therapy. Currently P
125PI and P
103PPd are used for this technique. P
103PPd has more
favorable physical properties than P
125PI, including low energy, rapid dose fall-off, short half-life and
total cumulative dose delivery and it is predestine a promising beginning of P
103PPd for localized tumour
treatment. P
103PPd was proposed by Harper in 1958. It was not used until 1987 when encapsulated
sources became commercially available in the USA. There are some modifications of Pd-103 sources
differing in fact in the matrix material that carries P
103PPd. High-molecular substance or carbon packing
is to be in routine as carrying agents of P
103PPd. The gold compound as a rule is used for «marker»
material.
4.1. Cross-section and evaluation data.
Production with proton bombarding of P
103PRh is based on the data of Harper and Dmitriev on
cross-section, thick target yields and possible contaminants (Fig. 4). In accordance with excitation
function the optimum of energy for irradiation was determined in energy range of 7-20 MeV.
Increase of incident energy above 18 MeV for production of medical P
103PPd is not acceptable due
to two major reasons:
- the contamination with P
102mP, P
102gP,P
101gPRh results in radiological hazard;
- additional yield is negligible (less than 4% increase between 18 and 20 MeV).
77
The energy range 18-8 MeV is considered by convention to be optimal for irradiation of Rh at
the cyclotron. There is no unitized method for P
103PRh-target preparation available due to baffling
complexity of Rh plating and intractable problem of Rh dissolution. It is of general knowledge that
separation of P
103PPd from rhodium with anion-exchange chromatography does not require special
conditions; it is easy to separate these elements with high precision and yield. The main problem of
P
103PPd radiochemical separation stage is dissolution of target material due to extremely low chemical
reactivity of rhodium metal towards acid, alkaline and to other corrosive reagents. The most
convenient technology used in developed countries such as the USA, Belgium, France, and China is
electrodissolution of target and electroplating recovery of rhodium.
4.2. Study on alternative production of P
103PPd.
This work has been performed within the IAEA Research-project with primary accent on design
and development of innovative technology. It is of common knowledge that production of any
radionuclide consists of five general steps: target preparation; target irradiation; radiochemistry
separation; preparation of isotope marketed form; recovery of target material. In all directions of
investigation we try to find simple and effective scientific and engineering approaches.
4.3. Targetry and irradiation.
First successful engineering approach was used in a new target construction. Rhodium foil was
put on cooling side of the backing. The thickness and area of backing can be varied according to initial
energy of irradiation and this technique of irradiation allows adjusting energy range and dose absorbed
with rhodium foil. Direct cooling of target with water flow allows increasing proton energy in time of
irradiation.
4.4. Radiochemistry separation (extraction of Pd-103).
For radiochemistry separation and extraction of P
103PPd from irradiated Rh foils alternative
method of thermal diffusion was used. The rhodium foils were put in tubular construction of vacuum
furnace, heated at different temperatures within half an hour, hardened and treated with weak
hydrochloric acid. As a result the P
103PPd was kept in the form of Pd chloride solution. Measurements for
P
103PPd were done using the X-line as well as the E Bγ B=357.7 keV line (Fig. 5).
Increasing yield of P
103PPd activity is formal validation of the method of thermal diffusion
acceptability for separation. Having experimental data on Pd-103 yield it is rather easy to calculate Pd-
103 diffusion coefficient. Like that the stage of radiochemistry separation by «dry» method of thermal
diffusion allows simplifying essentially the technology since there is no need for: target preparation
stage; target dissolution stage; target recovery stage. Purity of final product is 99.99.
4.5. Sealed sources.
For the brachytherapy goals P
103PPd becomes really interesting in the form of sealed source.
Equipment for P
103PPd labeling and packing of special compound is very expensive. The proposal of the
technology consists in utilizing of silver wire as a basis for P
103PPd absorption and as a material for
determination of localization into tissue simultaneously. As a «marker» silver can be detected with X-
ray method (Fig. 6).
The high catalytic reactivity of Pd and the electrochemical properties of Ag have allowed using
a method of metallic cementation for preparation of «active» part.
Due to coloring power of Pd salts the method of isotopic dilution was used for visual indication
of deposition process and the method of UV-spectrophotometry – for quantitative estimation.
Series of experiments on a deposition of Pd on Ag from weak solution of Pd chloride have
showed the following stable behavior:
78
- the process of cementation occurs evenly and rather at the dynamic conditions of deposition
(shaking apparatus) than at the static ones;
- the rate of Pd deposition linearly depends on concentration of Pd what allows calculating a
cementation coefficient of process;
- the coefficient of cementation (Kc, mg/cm2*min) linearly depends on concentration of Pd in
range of concentrations 0.125-0.5 g/l according to the equation: Kc=14.06*CPd+0.95 (Fig.7);
- the linear character of functional dependence of cementation coefficient on concentration of
Pd allows calculating and varying most important conditions of the process such as:
o concentration of electrolyte;
o volume of solution;
o time of deposition.
The obtained results make it possible to propose a quite simple technology for production of
radioactive sources based on Pd-103 for medical applications. A flow chart of the source production is
presented at Fig. 8. Details of the technology obviously need further investigations stipulated by its
simplicity.
5. CONCLUSION
The works performed on the project made it possible to develop the production technology of
radiopharmaceutical preparation “Tl-201 chloride” at the INP:
- target irradiation current has been increased from 100 µА at the beginning of the
project up to 125 µА
- there has been achieved the thallium target recovery rate of 99.5%.
There has been proposed a new technique of P
103PPd extraction from irradiated Rh foil by the
method of thermal diffusion without destruction of target matrix; the technique allows to:
- exclude the stage of target preparation;
- exclude the stage of target recovery;
- use Rh foils for multiple irradiation;
- reduce quantity of radioactive waste to minimum;
- reduce quantity of chemical reagents and materials used to minimum;
- produce final product with 99.99% purity.
6. EQUIPMENT AND MATERIAL
Power controller; 115 VAC, 60 Hz, temperature controller, flexible wire probes, infrared
heating lamp, equipment for electrodeposition and recovery of Thallium target and Rhodium foil (0.25
mm thick, 99.8% (metal basis) 25 x25 mm) are provided by IAEA.
REFERENCES
[1] A.ARZUMANOV, V.BATISCHEV ET AL., “Status and development of the Kazakhstan
isochronous cyclotron”, presented at the XV Int. Conf. Appl., East Lansing, Michigan, USA,
12-17 May, 2001.
[2] A.ARZUMANOV, A.BORISENKO ET AL. – “Electron-Beam Stand for the Solid Isotope
Targets Tests” paper in Russian at the International Conference “Nuclear and Radiation
Physics”, Almaty, 2001.
[3] A.ARZUMANOV, V.BATISCHEV ET AL. “Radioactive Isotopes Got on the Cyclotron” //
Abstract in Russian at the International Conference “Nuclear and Radiation Physics”, Almaty,
1997.
[4] A.ARZUMANOV, V.BATISCHEV ET AL. “Radioisotope production at the cyclotron in
Almaty ”Proc. Int. Conf. Cycl. Appl. Caen, France, 14-19 June 1998, 58-61.
79
TABLE I. IRRADIATION MODES FOR DIFFERENT MATERIALS
Irradiated material Tl Tl Bi Sn
Target thickness, µm 160 160 50 50
Proton energy (MeV) 28 28 22 22
Target current (µA) 100 150 420 390
Duration of irradiation, h 9 2
TABLE II. SUMMARY OF THE P
103PPD PRODUCTION
N Activity of Pd-103, kBq, before
annealing
Temperature of
annealing, ºC
Activity Pd-103,
kBq, after
annealing
Yield of
Pd-103,%
1 410 1050 330 19.5
2 297 1200 120 59.6
3 1250 1400 375 70
80
FIG. 1. Position of a target in the cyclotron tank. FIG. 2. Head of the internal target.
0
100
200
300
400
500
600
0 4 8 10 14 18 22
Partical energy, MeV
Cro
ss s
ecti
on
, m
b
0
2
4
6
8
10
12
Yie
ld,
MB
q/u
Ah
FIG. 3. An instalment for electrodepositing and
recovery of thallium targets.
FIG. 4. Excitation function and thick target yield
for the P
103PRH(p,n)P
103PPd reaction.
FIG. 5. Gamma-spectrum of final product.
81
y = 14,06x + 0,95
0.00
2.00
4.00
6.00
8.00
10.00
0.125 0.25 0.375 0.5
CPd,g/l
Kc,
mg
/cm
2m
in
FIG. 6. Proposed design of P
103PPD sources. FIG. 7. Dependence of cementation coefficient on
concentration of PD.
Rh irradiation
103Pd extraction
with
thermodiffusion
103Pd deposition with isotopic
dilution and cementation
Sources
encapsulation
PdCl2(stab)
HCl (weak)
Rh
foils
FIG. 8. Flow chart of P
103PPD sources production technology.
82
RESEARCH AND TECHNOLOGICAL DEVELOPMENT
FOR THE PRODUCTION OF PD-103 AT THE U-120 CYCLOTRON
FROM BUCHAREST
P.M. RACOLTA, D. DUDU
Horia Hulubei National Institute for Research and Development
on Physics and Nuclear Engineering; Bucharest, Romania.
Abstract
Research and development for the production of Pd-103 at U-120 Cyclotron in Bucharest was undertaken based on
demand of two hospitals in Bucharest interested in brachytherapie of prostate cancer using Pd-103 seeds. The work done
during three year project activity has been focused on design and adaptation of dedicated beam line at NIPNE-HH U-120
Cyclotron for experiments of Pd-103 production. Experiments were conducted to obtain nuclear data to find optimal
parameters of target irradiation. Post irradiation characterization of the radionuclides activated in target was performed as
well. The results obtained are promising and will be developed further in the next two years in the frame of a national
research program for implementation of brachytherapie of prostate cancer with Pd-103 seeds.
1. INTRODUCTION
Historically [3-9], P
103PPd, a short-lived isotope for permanent implant treatment of early stage
prostate cancer, was generated via the P
102PPd(n,γ)P
103PPd reaction which relied on the availability of 1%
naturally abundant P
102PPd in an enriched form and its moderately high neutron capture cross-section [1].
For the last 12 years, the accelerator production method for P
103PPd has been based on the irradiation of
the rhodium metal with rather low energy protons via the reaction P
103PRh(p,n) P
103PPd [1]. Big
corporations from USA operate more than 10 dedicated accelerators to produce this nuclide. The
prostate cancer market with 180,000 new cases reported annually justifies the effort for this
radionuclide production. Recently, a manufacture in Europe also brought the USA patented type of
P
103PPd seed implants on the world market.
Now, there are the initiatives to explore other uses of Pd-103 in non-oncologic disease states
such as restenosis following coronary interventions, age-related macular degeneration as well as
potential diagnostic applications.
Romania used irradiations with neutron fluxes at nuclear reactors (VVRS/NIPNE-HH Bucharest
and Triga/SNC-Pitesti) to produce some radioisotopes (P
32P P, P
60PCo, P
131PI, P
192PIr, P
197PAu,etc.).
In NIPNE-HH from Bucharest, the U-120 Cyclotron is a classical, constant gradient, accelerator
with variable energy, delivering internal beams up to 200µA and external beams up to 50µA of
protons (up to 14MeV), deuterons (up to 13.5MeV) and alpha particles (up to 27MeV).
We produced P
109PCd, P
55PFe for XRF applications, P
123PI (only few hundred of mCi for experimental
hospital applications) and as laboratory test procedures P
67PGa, P
22PNa, P
48PV, P
68PGe and P
103PPd.
After the appropriate irradiation of dedicated solid targets, these one were processed in the
Center for Radioisotopes Production. This lab is licensed for some radionuclides separation and
radiopharmaceutical production as tritium labeled compounds, P
131PI for endotherapy and diagnosis, P
125PI
labeled RIA kits, Technetium generators etc.
In spite of all these, there have not yet been finalized production lines for radiopharmaceutical
products with short lived radioisotopes.
83
2. DESIGN AND ADAPTATION OF DEDICATED BEAM LINE AT NIPNE-HH U-120
CYCLOTRON FOR EXPERIMENTS OF PD-103 PRODUCTION.
At the beginning of March 2000, we finished the rehabilitation of U-120 Cyclotron as a
multipurpose facility dedicated for applications of accelerated ion beams. Our efforts were dedicated
not only to repair, but also to upgrade or improve some associated systems or equipment as is:
- accelerating structure;
- power RF generator;
- vacuum system;
- beam transport and diagnosis.
Consequently, we obtained an improved reliability of the accelerator as well as much stable and
reproducible beam parameters. On the dedicated beam line for small scale radioisotope production, the
main parameters of available beams are shown in Table I.
TABLE I. BEAM PARAMETERS OF U-120 CYCLOTRON FOR RADIOISOTOPES
PRODUCTION
Beam current (µA)
No. PARTICLE
Energy
(MeV)
FBe B/2k+1
(kHz) Extracted On Target
Transversal area
of the beam (cm P
2P)
1 H P
+P 14 15.400/1 50 1÷30 0,1÷2
2 P
2PHP
+P 13,5 11.300/1 60 1÷30 0,1÷2
3 P
4PHeP
+2P 27 11.300 40 1÷20 0,1÷2
The target system was designed to permit irradiation of metallic Rh in stacked foils of 25µm
thickness at normal incidence of the beam or 100µm Rh deposited on 2mm Cu backing at 30 P
oP
incidence of beam (Figs 1 and 2). Both target systems are provided with appropriate collimator,
secondary electron suppressor and water cooling circuits as shown in Fig. 3.
FIG. 1. Control room of U-120 Cyclotron
84
FIG. 2.
Secondary
electron
suppressorFaraday-cup-
like target Water
cooled
Water
cooling
In/Out
To current
Beam Rh Rh foil
To negative DC
supply
To current meas. and digital
integrator
FIG. 3.
FIG. 4. Schematic view of target systems.
Beam line used in experiments for radioisotopeproduction.
85
2.1. Experiments to obtain home made nuclear data to find optimal parameters of target
irradiation and post irradiation characterization of the radionuclides obtained in target.
Experiments have been done using a stack containing 8 high purity 25µm Rh foils (Goodfelow)
which has been irradiated in the external beam of U-120 Cyclotron with protons of 14MeV. All foils
were irradiated in a Faraday-cup-like target holder equipped with a collimator (effective beam
diameter on target is 6mm) and a secondary electron suppressor. The total charge on target was
derived from the measured current on the target holder using a digital integrator. Beam current
stability during the irradiation was 10%. The incident energy (14MeV) with an uncertainty of 0.5MeV
was derived from earlier calibrations based on time-of-flight and activation techniques.
The irradiation was done with a total charge on the target of 20mC, which correspond to a mean
beam current of 1.56µA and an irradiation time of 13000s.
Measurements for the activity of produced P
103PPd were done in the X-line region as well as for
gamma-lines as is published by Hermanne et al. [1] using high resolution X- and gamma-spectrometry
(FHWM resolution of 200eV at 21keV respectively 1.9keV at 847keV).
Each sample was measured (without any chemical treatment) several times at X-ray
spectrometer from shortly after EOB up to 2 weeks, and for gamma spectrometry, the measurement
was done after 11.67days after EOB.
The activities derived in these two ways are in good agreement with the results and yields
measured by Hermanne et al. [1] and by Dimitriev [2].
Fig. 4 shows the corresponding activity obtained on each foil measured with gamma
spectrometer (Foil no. 8 is the first one seen by the beam).
8 6 4 2 0
1000
2000
3000
4000
5000
6000
7000
Activity [
kB
q]
Foil no.
FIG. 5. Measured activity of Rh foils.
According to published experimental data [1], in our experiments was not observed the presence
of P
101PPd, P
101m, 101gPRh and P
102m, 102gPRh, due to the rather low energy of proton beam (14MeV). In addition,
P
56PCo contamination is observed, most probable in agreement with the Fe impurities in Rh foils. This
contamination level with respect to the P
103PPd activity is negligible (less than 0.01%). In Table II are
given the results of gamma spectrometry for Rh foils and in Fig. 5 a spectrum of gamma ray for one
Rh foil.
86
0 200 400 600 800 1000 1200 1400 1600 1800 2000
0
200
400
600
800
1000
103
Pd
357.34
103
Pd
497.02
56
Co
846.51
56
Co
1037.58
56
Co
10238.14
Counts
Energy (keV)
Rh foil no. 6
T=12.778 days after EOB
56
Co
1771.67
FIG. 6. Gamma ray spectrum for the sixth Rh foil.
The production of large amounts of P
103PPd is not a real task for this moment since the technology
for the production of P
103PPd seeds is not yet available in Romania. However, the necessary parameters
for irradiation of Rh targets were derived from the results presented above in correlation with other
assumption as is following.
According to published data concerning the use of P
103PPd seeds, the mean activity per patient is
less than 37MBq (1mCi) distributed on 20÷30 seeds. Even for 50% efficiency of transferring the P
103PPd
activity in seeds, 3.7GBq (100mCi) of produced P
103PPd in Rh target will cover at least 50 patients.
Therefore, at 8.64MBq/µAh yield of P
103PPd production with 14MeV protons [1], it is necessary an
integral charge of the beam on Rh target of 428 µAh (1.54C) to produce the required activity of
3,7GBq, respectively 4280 µAh for 37GBq (1Ci).
For the available external beams at U-120 Cyclotron, the possible irradiation parameters at
normal incidence of the beam are summarized in Table III.
TABLE II. GAMMA-RAY SPECTROMETRY FOR RH FOILS
Elem E[keV] Tc[d] Tm[s A Bnet B
Pγ TB1/2 B[d] Eff. Λ[Bq] Λ[µCi] Λ[µCi]
CoP
57P 121.78 11.667 8000 280.31 0.856 271.8 0.013157 3.205085807 0.000086626 0.00009
Pd P
103P 357.33 11.667 8000 10399.62 0.00022 16.96 0.0057459 1649004.058 44.57155545
Pd P
103P 496.99 11.667 8000 1234.96 0.00004 16.96 0.0042581 1460364.366 39.46096488
42.0
CoP
56P 846.48 11.667 8000 2252.87 0.999 78.8 0.0026552 117.6395703 0.003179448
CoP
56P
1237.77 11.667 8000 1216.53 0.67 78.8 0.0019128 131.4796328 0.003553504
1
CoP
56P 1771.125 11.667 8000 176.54 0.155 78.8 0.0014139 111.5765053 0.003015581
0.003
CoP
57P 121.78 11.788 8000 267.43 0.856 271.8 0.013157 3.058758622 0.000082669 0.00008
Pd P
103P 357.33 11.788 8000 17461.71 0.00022 16.96 0.0057459 2782522.621 75.20985817
Pd P
103P 497.01 11.788 8000 2023.94 0.00004 16.96 0.0042581 2405213.586 64.99203286
70.1
CoP
56P 846.5 11.788 8000 3985.32 0.999 78.8 0.0026552 208.3256462 0.005630423
CoP
56P 1037.58 11.788 8000 567.24 0.141 78.8 0.0022830 244.3341046 0.006603624
CoP
56P
1237.93 11.788 8000 1801.91 0.67 78.8 0.0019128 194.953482 0.005269013
2
CoP
56P 1771.49 11.788 8000 347.51 0.155 78.8 0.0014139 219.8665594 0.005942339
0.006
Pd P
103P 357.33 11.993 8000 27654.06 0.00022 16.96 0.0057459 4463465.146 120.1117593
Pd P
103P 497 11.993 8000 3184.5 0.00004 16.96 0.0042581 3988257.415 103.1198731
111.6
CoP
56P 846.49 11.993 8000 5555.28 0.999 78.8 0.0026552 290.9140657 0.007862542
CoP
56P
1037.59 11.993 8000 745.85 0.141 78.8 0.0022830 321.8487843 0.008698616
CoP
56P 1237.97 11.993 8000 2720.76 0.67 78.8 0.0019128 294.8976226 0.007970206
3
CoP
56P 1771.63 11.993 8000 427.71 0.155 78.8 0.0014139 271.0968147 0.007326941
0.008
87
Pd P
103P 357.32 12.118 8000 36721.24 0.00022 16.96 0.0057459 6013534.445 160.3107484
Pd P
103P 497 12.118 8000 4197 0.00004 16.96 0.0042581 5055362.345 136.6025361
148.5
CoP
56P
846.5 12.118 8000 6844.29 0.999 78.8 0.0026552 358.8133561 0.009697658
CoP
56P 1037.57 12.118 8000 655.58 0.141 78.8 0.0022830 283.206748 0.007654236
CoP
56P 1237.97 12.118 8000 3370.32 0.67 78.8 0.0019128 365.7039886 0.009883892
CoP
56P 1771.51 12.118 8000 516.59 0.155 78.8 0.0014139 322.0745644 0.008704717
0.009
Pd P
103P 357 13.09 8000 15251.56 0.00022 16.96 0.0020224 7231582.687 196.8353083
Pd P
103P 497.02 13.09 8000 1482.52 0.00004 16.96 0.0014986 5372424.078 142.6602264
169.7
CoP
56P 846.5 13.09 8000 2783.25 0.999 78.8 0.0009474 412.4482707 0.011147251
CoP
56P 1037.61 13.09 8000 298.31 0.141 78.8 0.0008016 370.1750373 0.010004731
5
CoP
56P 1237.98 13.09 8000 1446.91 0.67 78.8 0.0006957 435.372356 0.01176682
CoP
56P 1771.49 13.09 8000 116.68 0.155 78.8 0.0005273 200.2272068 0.005411546
0.01
Pd P
103P
357.34 12.778 8000 15796.15 0.00022 16.96 0.0020224 7402846.895 201.2807168
Pd P
103P
497.02 12.778 8000 1660.45 0.00004 16.96 0.0014986 5678525.502 157.7576159
179.5
CoP
56P 846.51 12.778 8000 3280.83 0.999 78.8 0.0009474 484.8518995 0.013104105
CoP
56P 1037.58 12.778 8000 334.83 0.141 78.8 0.0008016 414.3542371 0.011198763
CoP
56P 1238.14 12.778 8000 15522.7 0.67 78.8 0.0006957 4657.948694 0.012589055
6
CoP
56P 1771.71 12.778 8000 235.94 0.155 78.8 0.0005273 403.7721386 0.010912761
0.012
Pd P
103P
357.33 12.986 8962 16478.31 0.00022 16.96 0.0020224 6969585.57 189.034257
Pd P
103P
497.02 12.986 8962 1562.38 0.00004 16.96 0.0014986 4784130.833 133.6374338
161.3
CoP
56P 846.53 12.986 8962 3729.49 0.999 78.8 0.0009474 492.8950597 0.013321488
CoP
56P 1037.59 12.986 8962 430.04 0.141 78.8 0.0008016 475.9221511 0.012862761
7
CoP
56P 1238 12.986 8962 1875.79 0.67 78.8 0.0006957 503.3745995 0.013604719
0.013
Pd P
103P
357.33 12.887 8000 12185.10 0.00022 16.96 0.0020224 5792418.732 155.9605308
Pd P
103P
497.01 12.887 8000 1017 0.00004 16.96 0.0014986 3581202.096 97.0555043
126.5
CoP
56P 846.49 12.887 8000 3379.26 0.999 78.8 0.0009474 499.8772603 0.013510196
CoP
56P 1037.83 12.887 8000 358.06 0.141 78.8 0.0008016 443.5265558 0.011987204
CoP
56P 1237.83 12.887 8000 1655 0.67 78.8 0.0006957 497.0977918 0.013435075
8
CoP
56P 1771.67 12.887 8000 262.76 0.155 78.8 0.0005273 450.101464 0.012164904
0.013
Pd P
103P
357.33 13.803 500 4532.14 0.00022 16.96 0.0020224 36349461.59 963.5347146
Pd P
103P
497.02 13.803 500 405.87 0.00004 16.96 0.0014986 29733982.27 643.3756372
803.5
CoP
56P 846.46 13.803 500 1066.96 0.999 78.8 0.0009474 2545.711455 0.068803012
CoP
56P 1037.49 13.803 500 138.21 0.141 78.8 0.0008016 2761.35697 0.074631269
CoP
56P 1237.92 13.803 500 549.33 0.67 78.8 0.0006957 2661.315838 0.071927455
Sta
ck
CoP
56P 1771.73 13.803 500 61.34 0.155 78.8 0.0005273 1694.783431 0.045804958
0.065
TABLE III. IRRADIATION PARAMETERS FOR EXTERNAL BEAM AT U-120
CYCLOTRON
Required activity of P
103PPd in the Rh target 3,7GBq (100mCi) 37GBq (1Ci)
Integrated charge (µAh) 428 4280
Beam current (µA) 5 10 20 5 10 20
Irradiation time (h) 86 43 21 860 430 210
Cross-section of the collimated beam (cm P
2P) 0,25 0,25 1 0,25 0,25 1
Beam power (W) 70 140 280 70 140 280
Density of dissipated power on the target for
normal incidence of the beam (W/cm P
2P)
280
560
280
280
560
280
As is shown in Table III, the corresponding irradiation time will be 86h, 43h, or 21h depending
on the used beam current to produce 3,7 GBq of P
103PPd. For not long irradiation time, the preferred
intensities are 10 or 20µA. Even for ten times more activity (37GBq) produced at 20µA beam current,
the irradiation time is still convenient (below the saturation time of the yield).
From Fig. 5, result that an effective thickness of approximate 200µm for Rh target is necessary
to obtain the mentioned yield.
88
Since the dissipated power on the target is rather high and the same is the superficial density of
this power, it is more convenient to irradiate the target at a grazing angle of 30°or even 15° because
the cooling of the target is considerably improved. Another advantage is that the effective thickness is
increased two or four times and the Rh film deposited could be thinner.
We checked our target systems by irradiating metallic Zn targets at 10µA and normal incidence
and 20µA at 30° grazing angle with an aperture of collimators of 6mm respectively 10mm. The Zn
targets had 2mm thickness and a rectangular shape of 9mmx16mm respectively 15mmx30mm total
area. Cooling was done by 2l/min. flow of distilled water. After 10h of irradiation, no visible damages
of targets were observed.
2.2. Investigations and experiments for post-irradiation procedures; development of QC
procedures.
Two important steps in the technology of P
103PPd seeds are related to post-irradiation procedures
and to QC procedures required by internal and international rules.
A team from our Center for Radioisotopes Production investigated the available data (published
or collected from participants at this CRP) concerning post-irradiation procedures, which comprise
separation of P
103PPd from Rh target, recovery of Rh after the separation of Pd and preparation of sealed
sources for treatment of prostate cancer.
Some experiments for dissolution of Rh target and separation of P
103PPd were performed but no
relevant results were obtained because of the absence of some technological facilities, as is ion
exchange chromatography or special equipment for electro-dissolution and electroplating.
The same team was involved in developing QC procedures according to GMP requirements for
some radiopharmaceutical products and it is possible to extend these procedures in future for P
103PPd
sources.
3. CONCLUSIONS
A dedicated beam line and appropriate irradiation systems were developed at U-120 Cyclotron
for the production of P
103PPd by bombarding Rh targets with 14MeV protons beam.
Experiments for optimal irradiation parameters and post-irradiation characterization were
performed.
The obtained results are in agreement with published data and are useful for routine production
of P
103PPd in Rh targets in future.
The results obtained in this project are promising and will be developed in the next two years in
the frame of a national research program for implementation of brachytherapie of prostate cancer with
Pd-103 seeds.
REFERENCES
[1] A. HERMANNE, M.SONCK, A.FENYVESI, L.DARABAN, “Study on Production of Pd-103
and Characterisation of Possible Contaminants in the Proton Irradiation of Rh-103 up to 28
MeV”, NIM B 170 (2000) 281-292.
[2] P.P. DMITRIEV, “Radionuclide Yield in Reactions with Protons, Deuterons, Alpha Particles
and Helium – 3, INDC (CCP) –263/G +CN + SZ, Vienna, 1986.
89
[3] Z.FUKS, S.A.LERBEL, K.E.WALLNER ET AL. 1991, “The Effect of Local Control on
Metastatic Carcinoma of the Prostate: Long Term Results in Patient Treated with I-125”, Int. J.
Radiat. Oncol. Biol. Phys., 21, 537-547.
[4] M.S.PORRAZZO ET AL. “Permanent Interstitial Implantation using Pd-103: the New York
Medical College Preliminary Experience “, Int. J. Radiation Oncology Biol. Phys. 1992, Vol 23.
pp.1033-1036.
[5] D.M.LEWIS, “Production of Medical Isotopes for Therapy”, Synthesis and Applications of
Isotopically Labelled Compounds 1997. Edited by J.R.Heys and D.G.Melilo, 1998 John Wiley
&sons Ltd., 231-237.
[6] IAEA TECDOC-1211. Charge-particle cross-section database for medical radioisotope
production: diagnostic radioisotopes and monitor reactions, IAEA, Vienna, May 2001.
[7] D.DUDU, V.POPA, P.M.RACOLTA, N.TETCU, DANA VOICULESCU, “Status and
perspectives for the Pd-103 radioactive seeds production at the Cyclotron IFIN-HH from
Bucharest”, poster presentation at the “International Symposium on Utilization of Accelerators”,
held in Sao Paulo, Brazil, from 26 to 30 November 2001.
[8] SHARKEY I ET AL. Outpatient ultrasound-guided Pd-103 brachytherapy for localized
adenocarcinoma of the prostate. A preliminary report of 434 patients. UROLOGY 51: (5), 796-
803 May 1998
[9] WARETMAN FM, YUL N., CORN B.W., DICKER A.P. Edema associated with I-125 or Pd-
103 prostate brachytherapy and its impact on post-implant dosimetry: An analysis based on
serial CT acquisition. International Journal of Radiation Oncology, Biology Physics 41:(5)
1069-1077 July 1998.
90
AN OPERATED SOLID TARGET DEVICE DESIGN
FOR IODINE-123(124) PRODUCTION
L.M. SOLIN, V.A. JAKOVLEV, A.I. BARANOV, A.A. TIMOFEEV, D.A. ZUBOV
V.G. Khlopin Radium Institute, Saint-Petersburg, Russian Federation
Abstract
The aim of the present work was to design and build a solid target device with remote control system to be used on
the proton beam with the energy of about 15 MeV to produce iodine-123 (124) via p,n reaction with an enriched tellurium-
123 (124). It has a motor drive for target compressing. The control system is based on microcontroller and interface converter
RS485. It is being used to control water and helium cooling, target compressing and dropping it into the container. The test of
the system operation was successful.
1. INTRODUCTION
Radium Institute cyclotron MGC-20 is used since 1990. The main objective of the cyclotron is
to provide radioisotopes for medicine. P
123PI radionuclide is one of the most promising isotopes in
nuclear medicine [1]. The iodine-labeled compounds are more natural for human organism, than many
other radiopharmaceuticals. Huge advantages of iodine-123 are low radiation exposure to the patient
and a high quality image.
The production of P
123PI via P
123PTe(p,n)P
123PI reaction is attractive because a small-size cyclotron with
14-16 MeV protons can be used. Iodine-123 is produced by proton bombardment of enriched
tellurium-123 (in dioxide form) deposited on the platinum backing. After irradiation the target is
heated and escaped iodine is absorbed and solved in NaOH solution. There are no principal limitations
for achieving radionuclidic purity close to 100%.
The first radiopharmaceutical produced by Radium Institute was “sodium iodide solution,
iodine-123”. We have started hospital deliveries in 1990. By now we have developed fast technology
for four radiopharmaceuticals labelled by iodine-123. Besides “sodium iodide solution, iodine-123”
there are sodium OIH, MIBG and BIMPP. It takes no more than 4 hours after EOB to prepare
injection ready radiopharmaceuticals for application. Every week we provide about 20 Saint-
Petersburg hospitals with radiopharmaceuticals labeled by iodine-123.
For ten years we have developed technology of iodine-123. Grave attention was paid to improve
all stages of technology: target preparation, target irradiation, iodine extraction, tellurium regeneration,
radionuclidic purity and radiation safety also. It is obvious that those stages are strongly connected
with the target.
When target is being irradiated there is a problem to prevent melting of tellurium oxide under
proton beam bombardment. Tellurium dioxide has melting point about 733P
oPC, but it is possible to have
temperature above melting point at separate target spots because of low heat conductivity of tellurium
dioxide and because of beam nonuniformity. In this case we may have a loss of iodine escaped from
the target and a loss of target material, which is very expensive. To decrease this danger we have
developed a special target device and a device to spread the beam on the target surface. Target device
provides water cooling of platinum backing (back side of target) and helium cooling of tellurium
dioxide (front side of the target).
91
2. STATEMENT OF PROBLEM
The first target device had a rather simple construction but it was sophisticated in operation. It
took rather a long time to remove device from the beam line and to extract target from device.
Therefore, employees received considerable doses. Moreover we used helium without flow in a small
volume before target.
Next modifications of the device avoided disadvantages of the first target device. Nevertheless
to take off the target it is necessary to make some operations with cooling systems (to close some
valves and to open the others).
The main objectives of a new device design were:
- to reduce occupation dose by means of:
- reduction induced activity of device elements,
- introducing automatic operation of cooling system valves,
- extraction of the target by remote-control mechanism
- to guarantee appropriate cooling by means of the monitoring of water and helium
flow, temperature and pressure.
- to provide measurement of proton beam current simultaneously from the target and
from the diaphragm before target
To perform these tasks the following steps were carried out:
- appropriate modification of the existing target device
- improvement of the helium flux on the target.
- installation of aluminum inner part of device
- increasing of volume of platinum water cooling
- providing the possibility of automatic operation
- developing the automatic/manual device for target compression and throw down
- developing target cooling system equipped with valves and sensors for automatic/
manual operation
- developing software for monitoring and control of target device
3. MAIN PART OF THE ASSEMBLY
A target device operated by hand was designed and manufactured. In the design process for a
new automated target device, particular importance has been attached to the simplicity, reliability and
convenience of the system. As a basis, the previously designed manually operated target device was
used.
The following alterations and additions were introduced to the manually operated target device:
- Electromechanical drive with a system of contact stopping devices, marginal current
sensor for the electric motor and a switch to the manual mode of operation.
- The system of water and helium cooling is equipped with electromagnetic-driven
faucets, duplicated by the corresponding stop-cocks to ensure the opportunity for
transition to the manual operation of the system and also equipped with sensors of
water flow and pressure.
In the design process for a target device, particular importance has been attached to the
reduction of the induced activity level. Major part of the induced activity from the target device, if no
special measures are undertaken, is contributed by the γ emission of Cobalt-56, formed through a
reaction between the scattered protons of the beam and the inner walls of the target device.
92
To exclude this effect, all the inner walls of the target device are faced with a lining of
chemically pure aluminum. Protective lining was mechanically attached to avoid the loss of
mechanical durability due to inadequate firmness of aluminum.
A flowchart of the target device’s cooling system is shown in Fig. 1. The cooling of the target is
performed using running water that washes the back side of the target backing, and a helium flow
cooling the front side. The system of water cooling of the target includes a supplementary contour for
blowing the channels and the volume behind the target with a compressed air using a compressor (pos.
3). The shutdown of the water cooling and the connection of the blowing contour are performed using
four operated faucets (pos. 10 and 12) or manually using four stop-cocks (pos. 11 and 13). Water
cooling system is equipped with the measuring instruments for pressure, flow and temperature on the
inlet and on the outlet of the target.
The system of helium cooling consists of a cooling contour and a subsystem for filling. The
cooling contour incorporates a ballast volume (pos. 7) filled with helium at the pressure of 1.0 – 1.5
atmospheres, an inner compressor (pos. 8) and tubes with faucets (pos. 15) and stop-cocks (pos. 15).
The subsystem for filling consists of a highly pressurized container with helium (pos. 6), a reducer
(pos. 5), and faucets (pos. 19 and 20). The cooling contour and the subsystem for filling are connected,
through a system of pipes and faucets, to a common pre-vacuum pump (pos. 9). The cooling contour is
equipped with helium flow and temperature measuring instruments on the inlet and the outlet of the
target volume. To increase reliability of the target system at accidents a possibility of a fast switch to
manual operation is provided for. To make it feasible, all the electromagnetic-driven faucets of water
and helium cooling are duplicated by the corresponding stop-cocks.
A draft of the target assembly design is represented in Fig. 2. The target unloads by falling out
into the container following the guides. The target volume is separated from the beam line of the
cyclotron with an inlet window made of 0.1 mm thick aluminum foil (pos. 4).
Before the target unloading, water and helium cooling are switched off, water from pipes and
the volume behind the target is removed with an air flow from the compressor. Further, the clamping
part of the target device is withdrawn to its utmost backward position, using a motor (pos. 15) or in a
manual mode (pos. 15). At that the guides (pos. 10) are detaching the target from a rubber sealing ring
of water cooling (pos. 5), and the target is dropped into a lead protective container (pos. 8). In the
automatic mode, clamping drive is positioned using a small roll (pos. 20) fixed on the drive gear (pos.
17), and three contact switches (pos. 19). The first contact switch fixes the position of the clamping
drive at loading the target device with a target. The second contact switch serves to stop the drive at an
utmost position at the tightening, in case when a marginal current sensor of the electric motor is out of
order. The third contact switch restricts the drive’s motion at the target unloading.
The operation mode switch, from automatic to manual, is done by disengaging the gears (pos.
16 and 17), using an arm (pos. 18). While falling into the container, the target closes the electric
contacts (pos. 12) of a system that controls fall-out of the target (at that a LED lightens up on the
control panel). For loading the target and for eliminating the risk of its cocking at unloading in the
target device, two locking bars (pos. 11), that ensure a stable centering of the target in the intermediate
position of the clamping part of the target device.
4. TARGET DEVICE CONTROL SYSTEM FOR IODINE-123 PRODUCTION
The main task of the next step was a remote control of the target device. Target transfer by
compressed air, make-and-break of water and helium cooling, removing the remaining water and
dropping the target into the lead container are the tasks of the control system. The proposal and
practical solution were realized at the Radium Institute Nuclear Medicine Laboratory.
93
4.1. Goals
The target device control system is intended for control, visualization and storage of
information on the operation of different elements.
It has the following functions:
- local and remote controls of the target compressor motor, water and helium supply valves;
- beam current measurements from the target and from the diaphragm (before the target);
- cooling water temperature, pressure and flow measurements;
- information transmission to the controlling computer.
The connection of the control system to the computer is through RS-485 interface.
4.2. Performance specifications
Ac power supply - 220 ± 25 V, 50 ± 1 Hz
Measurements channel capacity for:
- temperature 2
- pressure 1
- water flow 1
- beam current 2
Measuring range:
- temperature 0 – 50 °С
- pressure 0 – 4 bar
- water flow 0 – 4 l/min
- beam current 0 – 50 µA
Estimated error for all the channels is 0.2%.
Working conditions
- ambient temperature +10 - +40 °С
- dust and moisture protection class - IP65
- relative air humidity at the temperature of +20°С is no more than 80%/
4.3. Control system structure chart.
The control system structure chart is shown in Fig. 3. It consists of:
- microcontroller
- keyboard controller
- keyboard
- display device
- converters of input signals
- commutator;
- AD converter
- buffer amplifier
- 5 drive mechanism control units
- interface converter RS485
94
The microcontroller is a principal controlling device of the system. It operates according to a
developed algorithm. The keyboard controller provides the status poll of keyboard and the
transmission on the keystroke to the microcontroller. The display device is responsible for the LED
target device status. Six converters of input signals are used for sensor signal normalization and
multiplication. Normalized signals go through the commutator to the AD converter input.
Microcontroller control signals through the buffer amplifier go to the solid-state relays, which are used
to control water and helium cooling systems, the compressor and the target compressor driver.
Interface converter RS485 supplies conditioning between RS-485 and TTL levels.
4.4. Control system’s electrical scheme.
The system is realized on the base of microcontroller AT89C52 from Atmel. It has resident data
memory of 256K × 8, resident program memory of 8K × 8 and 32 in-out lines divided into 4 bi-
directional ports. Ten unit ADC (Analog Devices Company) - AD7813YN is being used to register
sensing devices signals. Commutation of input signals is realized with the help of analog signal
commutator ADG608BN. Software for monitoring and control of target device was developed and
tested at the Laboratory.
5. CONCLUSION
The solid target device with remote control system was designed and built. The target device
was tested with the remote and local controls. It was used in iodine-123 production. The average beam
current was 6.5 µA, proton energy of 15 MeV and irradiation run for 14 hours. All elements of the
system were operating satisfactorily. Now the system is under routine operation for iodine-123
production.
FIG. 1. Flowchart of the cooling system of the target device.
1 – target device, 2 – the inlet and the outlet of water cooling, 3 – compressor for blowing the water volume, 4 –
water drainage, 5 – reducer, 6 – highly pressurized container with helium (20 ATM), 7 – ballast volume with
helium (1.5 ATM), 8 – compressors of helium cooling, 9 – the outlet of helium cooling system at the vacuum pump,
10 – electromagnetic faucets of the system for water supply, 11 – water stop-cocks for the water supply system, 12 -
electromagnetic faucets of the system for water blowing, 13 - water stop-cocks for the water blowing system, 14 -
electromagnetic faucets of the system for helium supply, 15 – gas stop-cocks for the helium supply system, 16 –
helium compressor switch, 17 - water blowing compressor switch, 18 – exhaustion faucet of the target volume, 19
- exhaustion faucet of the system for filling the ballast volume, 20 – faucet of the system for filling the ballast
volume, 21 – stop-cock for the high-pressurized container.
95
FIG. 2. Target device with a manual operation and with an operation from the panel.
1 – Tellurium target, 2 – tubes/pipes of water cooling, 3 – clamping/tightening ring and a disk/washer for the
attachment of the outlet window, 4 – aluminum inlet window, 5 – rubber/elast(omer)ic tightening vacuum rings, 6 –
protective aluminum insert, 7 - tubes/pipes for flooding and escape of helium, 8 - lead(en) container, 9 – sliding
container cover/lid, 10 – guides for the target fall-out, 11 - locking device/stopper/ plug for the target fall-out, 12 –
electric contacts of the alarm system for the target fall-out, 13-- cover of the inlet window for inserting the target 14
- arms for manual tightening and unloading the target, 15 – electromechanical motor, 16 – gear of the motor drive,
17 – gear of the clamping device drive, 18 – arm to switch from an automatic mode to a manual operation and
inversely, 19 – contact switch, 20 – wheel for switching the contact switches (and, consecutively, for positioning the
clamping device drive)
96
FIG. 3. The con
Keyboard
Keyboard controllerADC
Water
Helium sup
Water supply
Commutator
Microcontroller
Buffer amplifier
T
Interface
converter
RS485
Display
device
To PC
I
REFER
[1] BOURGUIGNON M.H., PAUWELS E.K.
radiopharmaceuticals and single-photon em
Journal Nuclear Medicine, 24 (3), (1997), p
arget compression driver
nput signals converters
trol system structure chart.
Helium pump
compression
ply
ENCE
J., LOC'H C., MAZIIBRE B., Iodine-123 labelled
ission tomography: a natural liaison. European
p. 331-344.
97
STANDARDIZED HIGH SOLID TARGETS FOR CYCLOTRON
PRODUCTION OF DIAGNOSTIC AND THERAPEUTIC RADIONUCLIDES
TS. AL JAMMAZ, S. AL-YANBAWI, S. MELIBARI, RAHMA T
King Faisal Specialist Hospital & Research Centre, Riyadh, Saudi Arabia
Abstract:
Using the new technology described for electrodeposition of elemental thallium-203, zinc-68 and tellurium-124, it
was possible to produce simultaneously four targets in each shift. These dense, smooth and homogeneous targets were being
able to tolerate high beam currents without loosing or burning enriched material. As a result, radiochemical yields for Tl-201,
Ga-67 and I-123 were increased by 22%, 17% and 31% respectively.
1. INTRODUCTION
Cyclotron produced radiopharmaceuticals are being increasingly utilized in nuclear medicine
for both research and routine clinical diagnosis of an extensive variety of diseases. Indium-111,
Gallium-67 and Thallium-201 cyclotron produced metallic radionuclides are extensively used in a
wide range of diagnostic nuclear medicine application. In addition to Iodine-123, Gallium-67 and
Thallium-201 are enjoying spectacular use as Single Photon Emission Computerized Tomography
(SPECT) radionuclides. Iodine-124, which can be used for Positron Emission Tomography (PET)
studies as well as radiotherapy, is another radioisotope that shows great promise.
The most widely used radioactive tracer for myocardial perfusion imaging is Tl-201. Although,
various methods have been proposed for the production of P
201PTl for injection, the method first reported
by Lebowitz et al. [1] and worked out in detail by Lagunas-Solar et al. [2] and Qaim et al. [3] is still
the most commonly used one.
In the early fifties, Gallium-67 was produced from enriched Zinc-68 using the nuclear reaction
P
68PZn (p,2n) P
67PGa [4-6]. Later, several nuclear reactions were reported for the production of Gallium-67
by either 8 MeV deuteron or 23 MeV alpha bombardment of natural zinc [7]. The finished product
Gallium-67 citrate has been widely employed in the detection of inflammation, infections and tumours
[8].
In the early sixties Meyers and Anger described the potential of iodine-123 (I-123) for use in
diagnostic nuclear medicine due to favorable and almost ideal physical properties [9]. Since then, I-
123 is enjoying spectacular use as SPECT radionuclides. There are numerous different nuclear
reactions leading to the production of I-123, many of which have been studied and reported. Among
these reported methods is the nuclear reaction P
123PTe (p,n) P
123PI suggested by Meyers and Anger. Later
this was worked out by Hupf and et. al and Barrall et. al to produce hundred-millicurie amounts of I-
123 suitable for diagnostic procedures using isotopically enriched Te-123 [10,11]. This was followed
by producing very pure I-123 through bombardment of different isotopically enriched tellurium
isotopes with alpha and helium-3 particles from a low energy cyclotron [12,13].
In addition, one more nuclear reaction used for the production of pure I-123 in large quantities
have been developed in the last two decade using high energy cyclotron (> 60 MeV) is P
127PI (p,5n) P
123PI
[14]. Nevertheless, the most widely used nuclear reaction to produce large quantities of I-123 with
high energy protons (25 MeV) is P
124PTe (p,2n) P
123PI [15-18]. Moreover and lately, it has been a routine
practice in many centers to produce the ultra-pure iodine-123 in large amounts via highly enriched
Xenon-124 gas utilizing the following nuclear reaction P
124PXe(p,2n) P
123PI [14].
The finished product P
123PI-sodium iodide is used most commonly for the measurement of thyroid
uptake and thyroid imaging. In addition, radioiodinated compounds have been widely employed in the
detection of cardiological, neurological and oncological diseases [14].
98
Recently, inadequate supply of Tl-201, Ga-67 and I-123 due to the limited capability of the
solid targets of handling high beam current becomes a major obstacle in meeting the needs of nuclear
medicine demands. Here, we report the development of Tl-201, Ga-67 and I-123 production utilizing
new electroplating technology as member of the International Atomic Energy Agency’s co-ordinated
meeting entitled: Standardized High Solid Targets for Cyclotron Production of Diagnostic and
Therapeutic Radionuclides.
2. MATERIALS AND METHODS
The chemicals used in this study were all purchased from Aldrich (USA), and were used
without further purification unless stated. Enriched Tl-203, Zn-68 and Te-124 were purchased from
Isotopes (Russia). Copper target plates, aluminum target holders, plastic target carrier and
electroplating vessels were all fabricated at the precision machine shop attached to our cyclotron
(Fig. 1). Each newly fabricated plates/holders/carriers and vessels were inspected and conditioned
taking in consideration many critical steps [11].
Copper target plate, aluminum target holder and electroplating vessel. FIG. 1.
99
2.1. Thallium-203
2.1.1. New Thallium-203 Target Plating Solution Preparation
In a 600mL beaker (B1) fitted with a Teflon coated magnetic stirring bar, 360 mL of deionized
water was placed. To that EDTA (84 g), NaOH pellets (20g) were added and stirred until obtaining a
colorless solution. In another beaker (B2) fitted with a Teflon coated magnetic stirring bar, hydrazine
hydrate (10mL) and BRIJ-35 (1mL) were homogenized followed by the addition of P
203PTl B2 BOB3 B (7.65 g)
with continues stirring until yellow-brown color disappears. Solution in B1 finally added to B2 with
continuous stirring to give the final electroplating solution with pH>12.5.
2.1.2. New Thallium-203 Target Electroplating
The freshly prepared solution of a pH>12.5 was poured in the plating vessel. The four outputs
of the current booster were connected to the cathodes by introducing the four block male plugs (copper
targets, 1.5 cm thickness). This was followed by the introduction of the electromagnetic stirrer in a
way that the central Pt-anode wire fits into hollow stirring cylinder. The rotational speed of the stirrer
is 1200 rpm for a 16 second period. The electrolysis starts by introducing the common output plug of
the boosters into the bottom of deposition vessel with 16 mA current. After 3.30 hours of electrolysis,
which is needed for producing four thallium-203 targets (400 mg ± 10% each), the stirring motor
stopped and the four electroplated targets were removed and rinsed extensively with deionized water
then dried, weighed and finally stored in a vacuum desiccator.
2.1.3. New Thallium-203 Recovery from Depleted Plating Solution
Pt-wire (Anode)/Pt-gauze (Cathode) electrodes connected to the current output of constant
current source were introduced to the depleted plating solution which embodies almost 1 g of the
enriched Tl-203 material in the plating vessel. The current was adjusted to 200 mA and the electrolysis
continued for 15 hours. The amount of enriched Tl-203 in the depleted solution was checked and
found to be less than 1 mg.
2.1.4. Irradiation and Extraction of Pb-201 from Enriched Tl-203
Lead-201 was produced by the bombardment of enriched Tl-203 targets (400 mg ± 10% each)
with 26 MeV protons from the CS-30 Cyclotron internal beam P
Pusing theP
203PTl(p,3n) P
201PPb(E.C.) P
201PTl
nuclear process. The proton current was ranging between 70-105 µA and the irradiation time was 9.5
hours. The irradiated targets were dissolved in H B2BSOB4B (2.5 mL, 4.0 mol dm P
-3P) under a heating lamp.
Aqua-regia solution (20 mL conc. HCl + 3 mL conc. HNO B3 B) was added to maintain the Tl P
+3P oxidation
state. This was followed by addition of n-Butylacetate (50 mL) previously equilibrated with HCl (6
mol l P
-1P) with continuous shaking. After several separations of the two phases the aqueous layer was
collected in a flask containing concentrated HNO B3 B (3 mL), then, left for 32 hrs, which is needed for Tl-
201 to grow. The enriched Tl-203 in organic layer was saved to be recovered using the previous
method.
2.1.5. Extraction of radiochemical Tl-201 from Pb-201
After 32 hours, which is sufficient for the growth of Tl-201, the aqueous layer was extracted
with Diisopropyl Ether (DIPE, 40 mL) equilibrated with HCl (6.0 mol dm P
-3P). This was followed by
washing DIPE layer (organic) twice with HCl (6.0 mol l P
-1P, 20 mL). Then, back extract Tl-201 from the
DIPE with two portion of sterile water (10 mL) previously treated with SO B2 B to reduce thallic (Tl P
+3P) to
thallous chloride (Tl P
+P). Furthermore, the aqueous layer, which contains Tl-201, was evaporated to
complete dryness and a calculated amount of sterile water was added. Then the activity transferred
into pre-weighed sterile serum bottle. Finally, 0.8 mL of the Tl-201 bulk solution was given to quality
control for radionuclidic purity, copper, iron and inactive thallium tests.
100
2.2. Zinc-68
2.2.1. New Zinc-68 Target Plating Solution Preparation
In a 200 mL beaker, P
68PZnO (4.5 g) was added, followed by the addition of NaCN (3.2 g), NaOH
(6.8 g) and deionized water (20 mL). Solution was filtered (if necessary) and the filtrate was diluted to
50 mL with another portion of deionized water to be ready for electroplating.
2.2.2. New Zinc-68 Target Electroplating
The freshly prepared solution of Zn-68 was poured in the plating vessel. The four outputs of the
current booster were connected to the cathodes by introducing the four block male plugs (copper
targets, 1.5 cm thickness). This was followed by the introduction of the electromagnetic stirrer in a
way that the central Pt-anode wire fits into hollow stirring cylinder. The rotational speed of the stirrer
is 1200 rpm for a 16 second period. The electrolysis starts by introducing the common output plug of
the boosters into the bottom of deposition vessel with 100 mA current. After four hours of electrolysis,
which is needed, for producing four Zinc-68 targets (425 mg ± 10% each), the stirring motor stopped
and the four electroplated targets were removed and rinsed extensively with de-ionized water then
dried, weighed and finally stored in a vacuum desiccator. The same procedure was repeated with
addition of hydrazine (10 mL) to the plating solution.
2.2.3. Irradiation and extraction of gallium-67 from enriched zinc-68
Gallium-67 was produced by the bombardment of enriched zinc-68 targets (325 mg old system
and 425 mg new system ± 10%) with 26 MeV protons from the CS-30 Cyclotron internal beam P
Pusing
theP
68PZn(p,2n) P
67PGa nuclear process. The proton current was ranging between 40-65 µA and the
irradiation time was ranging between 6-7.5 hours. The irradiated targets were dissolved in HCl (20
mL, 7.5 mol dm P
-3P). This aqueous layer was extracted with Diisopropyl Ether (DIPE, 50 mL)
equilibrated with HCl (7.0 mol dm P
-3P). This was followed by washing DIPE layer (organic) three times
with HCl (7.0 mol dm P
-3P, 20 mL) (first wash contain 1 ml of 20% titanium chloride solution). Then,
back extract Ga-67 from the DIPE with three portion of sterile water (10 mL). Furthermore, to the
aqueous layer, which contains Ga-67, sodium citrate (0.1 mL of 2.5%) was added and evaporated to
complete dryness. The dried Ga-67 was transferred to a pre-weighed collection bottle using sodium
citrate (2.9 mL of 2.5%) and sodium chloride (27 mL of 0.9%). Finally, 0.6 mL of the Ga-67 bulk
solution was given to quality control for radionuclidic purity, titanium, copper, iron and gallium tests.
2.3. Tellurium-124
2.3.1. Nickel Target Electroplating
Copper plate was cleaned using sandpaper (320-500) grade followed by rinsing copper plate
with de-ionized water. The copper plate was placed in 1000 mL beaker containing nickel sulfate
plating solution. Copper plated was connected to the power supply, as cathode while the platinum
electrode is the anode. Power supply was turned on and the current was adjusted to 400–800 mA and
allowed for 3 minutes, giving the nickel-electroplated target. After turning off the power supply
electrodes were disconnected and rinsed with deionized water and acetone to accelerate drying.
2.3.2. New Tellurium-124 Target Plating Solution Preparation
In a 500 mL flask, P
124PTeO2 (3.0 g) was added, followed by the addition of KOH (7.5 g) and de-
ionized water (250 mL). The homogenized solution filtered through fine glass filter (0.45 µm) to
remove any residual particles if necessary to be ready for electroplating.
2.3.3. New Tellurium-124 Target Electroplating
The freshly prepared solution of tellurium-124 was poured in the plating vessel. The four
outputs of the current boosters were connected to the cathodes by introducing the four block male
101
plugs (copper-plated-nickel targets, 1.5 cm thickness). This was followed by the introduction of the
electromagnetic stirrer in a way that the central Pt-anode wire fits into hollow stirring cylinder. The
rotational speed of the stirrer is 1200 rpm. The electrolysis starts by introducing the common output
plug of the boosters into the bottom of deposition vessel with 300 mA current. After one hour of
electrolysis that is needed for producing four tellurium-124 targets (90 mg ± 10% each), the stirring
motor stopped and the four electroplated targets were removed and rinsed extensively with de-ionized
water then dried, weighed and finally stored in a vacuum desiccator. This refined procedure is a result
of several repeated experiments with different concentrations of KOH and electroplating currents.
2.3.4. Irradiation and extraction of iodine-123 from enriched tellurium-124
Iodine-123 was produced by the bombardment of enriched tellurium-124 targets (90 mg ± 10%)
with 26 MeV protons from the CS-30 Cyclotron internal beam using the 124Te(p,2n) 123I nuclear
process. The proton current was ranging between 18-45 µA and the irradiation time was between 2.0-
2.75 hours. The irradiated targets were dissolved in a mixture of NaOH (1.0 mL, 5.0 mol l-1), H2O2
(3.0 mL, 30%) and Milli-Q water (6 mL). The dissolved Te-124 was transferred in 250 mL quarts
reaction flask containing aluminum powder (160 mg) that was boiled until reaction is completed.
Solution was bubbled with air for five minutes followed by bubbling with CO2 for additional five
minutes. The bubbled solution was then carefully filtered through fine fritted glass and on-line
AG50W-X8 column into pre-weighed serum vial. If necessary pH is adjusted in the range between 5-7
value with NaOH (0.01 mol l-1). Finally, 0.6 mL of the NaI-123 bulk solution was given to quality
control for radionuclidic purity, specific concentration, pH, tellurium and aluminum tests.
3. TRESULTS AND DISCUSSION T
The new electroplating technology has produced high quality Tl-203, Zn-68 and Te-124 targets.
These targets and through microscopic inspection appear to be dense, smooth and homogeneous
(Figs 2 and 3). Prior to that, the solid state targets in general were mainly prepared by constant voltage
electrolysis from rather intricated plating solutions, which mostly results in dendrite formation and
non-uniformed plates due to gases evolution making mechanical rolling (smoothing) post
electroplating a general requirement. Such rolling produces non-homogeneous layers. As a result,
crater formation and peeling-off of such layers when bombarded with high beam current. This will
decrease the radionuclide yield and more importantly loss of very expensive enriched materials inside
the cyclotron, which raise the multi-pacting effect that consequently decreases the vacuum.
The new electroplating simultaneously allows preparation of four dense, smooth and
homogeneous targets within acceptable shift taking in consideration three important parameters. These
parameters are 1- composition of plating solution, 2- stirring and 3-the current density range. The new
plating solution for thallium contains EDTA as complexing agent for Tl P
+P at pH more than 12 to lead to
smoothly electroplating of Tl-203 on the cathode. In addition, hydrazine as an anodic depolarizer that
is oxidized faster than water, this prevents oxygen evolution at the anode and the cathode, which may
oxidize Tl P
+1P to Tl P
+3P or Tl P
oP to Tl B2 BO B3B respectively. In addition, a non co-deposited tenside BRIJ-35
should be introduced to the electroplating solution to reduce or to prevent to some extent dendrite
formation.
When hydrazine is introduced to the zinc plating solution, oxygen evolution at the anode and
the cathode was prevented. As a result, the electroplating efficiency was increased to nearly 100%
without affecting electroplating quality.
Unlike the old electroplating solution, the electroplating efficiency of the new basic
electroplating solution of tellurium which contains potassium hydroxide as complexing agent for
tellurium has increased the to nearly quantitative. While not more than 85% was obtained in the old
system. In addition, the new system produced 20 high quality plated targets from each electroplating
solution bath taking in consideration the depletion of the solution does not go more than 40%.
102
When the same amount of NaOH solution was used to dissolve the proper amount of tellurium
instead of KOH, electroplating progresses smoothly. However, after sometime, the electroplated
targets started to dissolve and the whole solution turned to dark color. This dark color is originated
from undissolved tellurium oxides. This could be attributed to the high dissolution and complexing
capacity of KOH as compared with NaOH [19]. In addition, when hydrazine was used, metallic
tellurium begins to precipitate.
Ultimately, the higher the current, the faster the electrodeposition, however, each metal should
have optimum current since the increase in current density may result in increasing gases evolution
which consequently reduces the electroplating uniformity. The optimum currents for Tl-203, Zn-68
and Te-124 were found to be around 16, 100 and 75 mA respectively.
Moreover, these high quality (dense, smooth and homogeneous) electroplated Tl-203, Zn-68
and Te-124 targets did not require any post electroplating mechanical smoothing. Accordingly, beam
currents up to 125 uA for Tl-203, 65 uA for Zn-68 and 45 uA for Te-124 were tolerated without
loosing or burning natural material.
Several targets prepared by the new techniques were irradiated with 26 MeV protons using
internal beam withP
Pcurrent ranging between 70-105, 40-65 and 20-45 µA for Tl-203, Zn-68 and Te-
124 respectively.
The yield, target weight, current and irradiation time for the new target irradiated plates for Tl-
203, Zn-68 and Te-124 are illustrated in Tables I, II and III, respectively.
The results in Tables I, II and III elucidate an increase in the yield while increasing the current,
however, when exceeding 95, 45 and 24 uA beam currents for Tl-203, Zn-68 and Te-124 respectively;
yield tends to declines, which make 95, 45 and 24 uA currents to be the optimum for such internal
target design. This decrease might be attributed to the high heat generated from the high beam currents
that necessitate new development on the cooling parameters. This development included electroplating
of natural Tl-203 on a thin copper plates (0.5 mm), modifying the target holder by introducing a
narrow coolant channel and optimizing the geometry of inlet and outlet coolant channel (Fig. 4).
Results in Table IV proved that such development was ineffective in improving final yield. Thus,
more elaborate development on the beam position, density, distribution and cooling parameters is
required. Such development will include harmonic coil settings and their influence on beam position
on internal targets.
Nevertheless, by using the new electroplating, we were able to increase Tl-201, Ga-67 and
iodine-123 final yields to nearly 22%, 17% and 31% respectively.
On the other hand, the new electroplating technique has shown superiority by recovering more
than 99.9% of the enriched Tl-203 from the depleted solution in a simple manner when compared with
the laborious old method. Yet, quality control tests regarding radionuclidic purity, copper, iron and in
active thallium were found to be the same.
As part of the development on beam position and distribution, several radiograms of thallium,
gallium and iodine targets were taken. These radiograms were found to be different from plate to plate.
Accordingly, radiograms were scanned to obtain a digitized image and treated using an in-house
developed computer program called TargetIMX to normalize all images to a graphical presentation of
target’s beam position.
After normalization, images scanned in vertical direction from top and bottom to pre-defined
homogenous beam density. The same process was repeated changing from vertical to horizontal
direction and the centerline of beam position was calculated as will as sensible picture was generated
(Fig. 5).
103
Using the information generated from the TargetIMX program, beam’s intensity distributions
were determined when beam hit either the upstream or the downstream sides of the target. In the
former, the angle of incandescence is larger resulting in very short and intense beam spot (Fig. 6).
Whereas some of the beam does not hit the target material in the latter (Fig. 7). By using the above
settings and interpolating to the center of these settings, intensity distribution in Fig. 8 was obtained.
This study will allow us to have a better control on the beam position and intensity helping to
eliminate the target’s hot spots that contribute to the evaporation of the radioactive products and
consequently reduces the yield.
T4. TTCONCLUSIONS
Differences between the old and the new electroplating methods in terms of yield when a
similar beam current is used were not observed. However, the new electroplating technologies that
have been transferred under this CRP produced high quality electroplates. That has allowed the
increase of beam current without damaging or burning the targets, resulting in a dramatic increase in
the final yields as well as ensuring reliability of radiopharmaceuticals’ production. In addition, the new
electroplating technique has shown superiority by recovering enriched material in a simple manner as
compared with the laborious old methods.
TABLE I. DATA GENERATED FROM USING THE NEW THALLIUM-203
ELECTROPLATING TECHNOLOGY
Current (uA) Time (hour) Weight (mg) Activity (mCi)
1 77 9.5 388.4 ± 19.8 283.7 ± 8.2
2 85 9.5 392.5 ± 14.1 308.4 ± 15.5
3 90 9.5 408.6 ± 23.3 340.8 ± 35.5
4 95 9.5 403.1 ± 18.7 368.5 ± 10.6
5 100 9.5 404.3 ± 21.1 321.8 ± 28.4
6 105 9.5 425.0 ± 2.0 318.2 ± 3.5
TABLE II. DATA GENERATED FROM USING THE NEW ZINC-68 ELECTROPLATING
TECHNIQUE
Current (uA) Time (hour) Weight (mg) ± 10% Yield (mCi/uA.h)
1 40 6.5 405 3.97
2 42 7.5 328 4.33
3 45 7.5 321 4.68
4 50 7.0 522 3.62
5 60 6.0 391 3.37
104
TABLE III. DATA GENERATED FROM USINF THE NEW TELLURIUM-124
ELECTROPLATING TECHNIQUE
Current
(uA)
Time (hour) Weight (mg) ±
10%
Yield (mCi/uA.h) Yield (mCi)
1 20 2.75 86.3 12.75 ± 1.93 136.02 ± 43.1
2 22 2.75 86.8 13.72 ± 2.61 175.63 ± 26.9
3 24 2.75 91.5 16.61 ± 0.78 234.50 ± 22.4
4 25 2.75 89.3 13.19 ± 0.34 178.42 ± 15.6
5 30 2.25 100.4 8.50 ± 1.31 126.39 ± 31.4
6 35 2.0 105.8 7.33 ± 1.05 119.86 ± 26.8
TABLE IV. DATA GENERATED FROM USING THE NEW NATURAL THALLIUM
ELECTROPLATING TECHNIQUE WITH OPTIMIZED TARGET DESIGN
Current (uA) Time (hour) Weight (mg) ± 10% Yield (mCi/uA)
1 100 0.5 408 6.47
2 105 0.5 171 5.20
3 110 0.5 186 4.80
4 115 0.5 157 4.68
5 120 0.5 156 2.97
A B C
FIG. 2. Microscopic inspection of zinc targets, A old, B new and C new with hydrazine.
105
FIG. 3. Microscopic inspection of tellurium targets, old and new.
FIG. 4. Developmental work on target plate and target holder.
106
FIG. 5. Centerline picture of the calculated beam position.
FIG. 6. Intensity distribution of beam hitting down streamside of the target.
FIG. 7. Intensity distribution of beam hitting up streamside of the target.
107
FIG. 8. Intensity distribution of interpolated position.
REFERENCES
[1] LEBOWITZ, E., GREENE, M. W., FAIRCHILD, R., BRADLEY, R., MOORE, P. R.,
ATKINS, H. L., ANSARI, A. N., RICHARDS, P., BELGRAVE, E. Thallium-201 for medical
use. J. Nucl. Med., v. 16 (2), p. 151 (1975).
[2] LAGUNAS-SOLAR, M. C., JUNGERMAN, J. A., PEEK, N. F., THEUS, R. M. Thallium-201
yields and exication functions for the lead radioactivity produced by irradiation of natural
thallium with 15-60 MeV protons. Int. J. Appl. Radiat. Isot. 29 (3), p. 159 (1978).
[3] QAIM, S. M., WEINREICH, R., OLLIG, H. Production of Tl-201 and Pb-203 via proton
induced nuclear reactions on natural thallium. Int. J. Appl. Radiat. Isot. v. 30 (2), p. 85 (1979).
[4] GRUVERMAN J. AND KRUGER P. Cyclotron produced carrier free radioisotopes. Int. J.
Appl. Radiat. Isotopes, v. 5, p. 21, 1959.
[5] SUBRAMANIAN G, RHODES B., COOPER J. AND SODD V. Production and use of I-123.
International Symposium on radiopharmaceuticals, Atlanta, Georgia, USA, Feb.1974.
Radiopharmaceuticals, New York. Society of Nuclear Medicine. Inc. 1975, p.125.
[6] DAYANIKLI B.F., WEISSMAN A. AND WAHL R. Successful Gallium-67 Imaging of North
American Pulmonary Blastomycosis. J. Nuc. Med., v. 34 (6), p. 958, 1993.
[7] MEYERS W. AND ANGER H. Radioiodine – 123. J. Nucl.Med. v. 3, p.183, 1962.
[8] HUPF H., ELDRIGE J. AND BEAVER J. Production of Iodine-123 for Medical Applications.
Int. J. Appl. Radiat. Isotopes, v. 19, p. 345, 1968.
[9] BARRAL R., BEAVER J., HUPF H. AND RUBIO F. Production of Curie Quantities of High
Purity I-123 with 15 Mev Protons. Eur. J. Nucl. Med. v. 6 (9), p.411, 1981.
[10] LAMBRECH R. AND WOLF A., P
122PTe( P
4PHe, 3n) P
123PXe betaP
+P, EC/2.1 hr, P
123PI generator. Radiat.
Res. 52 (1), p.32, 1972.
[11] HOMMA Y. AND MURAKAMI Y. The Production of Xe-125 for Medical Use by the He-3
Bombardment of Natural Tellurium. Int. J. Appl. Rad. Isot. 1977, v. 28 (8), p.738.
[12] SAHA G., Fundamentals of Nuclear Pharmacy, 4 P
thP Edition, New York, 1977.
[13] LEBOWITZ E., GREENE M. AND RICHARDS P. On the production of I-123 for medical use.
Int. J. Appl. Radiat. Isot. v. 22 (8), p. 489, 1971.
[14] ZIELINSKI F., MacDONALD N. AND ROBINSON G. Radiopharmaceutical Development. J.
Nucl. Med., 18, 1, 67, 1977.
[15] VAN DEN BOSCH R., GOEIJ J., VAN DER HEIDE J., TERTOOLEN J., THEELER H. AND
ZEGERS C. A new approach to target chemistry for the iodine-123 production via the
P
124PTe(p,2n) reaction. Int. J. Appl. Radiat. Isotopes, v.28 (3), p. 255, 1977.
[16] KONDO K., LAMBRECH R. AND WOLF A. Iodine-123 production for radiopharmaceuticals.
Int. J. Appl. Radiat. Isotopes, v. 28 (4), p.395, 1977.
[17] LEDDICOTTE G., The Radiochemistry of Tellurium, Nat. Acad. of Scie. NAS-NS 3038, USA
1971.
108
USEFUL CONCEPTS IN SOLID STATE TARGET TECHNOLOGIES
D.J. SCHLYER, R.A. FERRIERI
Brookhaven National Laboratory, New York, United States of America
Abstract
This paper presents some common characteristics of all solid targets. The effect of power density in solid targets is
explored. The transfer of heat from the target to the water cooled target carrier is examined in terms of the laws of heat
transfer which will allow transfer out of the target and into the cooling water. Some common types of solid targets are
explored including both internal and external targets. Some possibilities for the extraction of the radioisotopes from the target
matrix are presented including physical extraction, chemical extraction or extraction using supercritical fluids. Methods of
recovery for the enriched target materials are also presented.
1. INTRODUCTION
In general, radioisotopes fall into two basic groups, those which are neutron rich and those
which are neutron deficient. Those that are neutron rich are usually made in a nuclear reactor while
those that are neutron deficient are produced by bombarding a suitable target with protons, deuterons
or helium particles. Particle accelerators and in particular cyclotrons, were very important in the
preparation of radioisotopes during the years of 1935 to the end of World War II. The amount of
radioactive material which could be produced in an accelarator was many times greater than the
amount which could be produced using the alpha particles from naturally occurring radioactive
elements.
After World War II, reactors were used to produce radioactive elements and the use of
accelerators for this purpose became less common. However, as the techniques for using radiotracers
became more sophisticated, it became clear that reactor produced radionuclides could not satisfy the
growing demands and therefore accelerators were needed to produce new radioisotopes which could
be used in new ways.
There are three major reasons the accelerator produced radioisotopes are used more widely that
reactor produced radionuclides. These are:
1. The radioisotopes produced in a reactor may have unfavorable decay characteristics (particle
emission, half-life, gamma rays, etc.) for a particular application.
2. The radioisotope cannot be produced in a reactor with high specific activity
3. Access to a reactor is limited. The number of reactors available has become many fewer than
the number of cyclotrons available to the scientific community, or the radioisotope has too
short a half-life to be transported to the site where it is needed.
There are wide varieties of nuclear reactions which are used in an accelerator to produce the
artificial radioactivity. The bombarding particles are usually protons, deuterons, or helium particles.
The energies which are used range from a few MeV to hundreds of MeV. There is a minimum energy
required to overcome the Coulomb barrier. Particles with energies below this barrier have a very low
probability of reacting.
1.1. Number of isotopes with solid targets
Table I in the appendix is a list of the isotopes which have value in medical applications or
which seem promising for development. The radioisotopes which can be made using solid targets are
marked with an “X”.
109
2. GENERAL CONSTRAINTS
2.1. Power deposition
One of the main concerns in solid targets is the deposition of power in the matrix during
irradiation. If the power deposited exceeds the ability of the target to remove the heat, the targe will
eventually be destroyed or the target material will be melted or volatilized. The power deposited in the
material is very simple to calculate. It is the beam current in microamps multiplied by the energy in
MeV and the result is the number of watts deposited. The exact position of the heat deposition will of
course depend on the dE/dx (stopping power) of the beam in the target material with most of the heat
being deposited near the end of the particle range in the Bragg peak. A simple approximation for the
stopping power is given by the relation [1]:
− =ℑdE
dx
z e
mV
Z
A
mV
I
4 22 4
0
2
0
2πln
where:
- dE/dx = energy loss per unit length
- z = the atomic number of the projectile
- e = elementary charge 4.803 x 10 P
-10P (erg-cm)P
1/2P
- m B0 B = the electron rest mass
- V = relativistic projectile velocity
- A P
0P = Avogadro’s number
- Z = atomic number of the target material
- I = adjusted ionization potential of the target material
Some additional helpful approximations are that the relativistic velocity is given by the relation:
VE
mcm= − −
1384 109 1
. sec
where:
- E = particle energy in MeV
- m = particle atomic mass number
The other useful approximations for the adjusted ionization potential are [2]:
I = 13 Z eV if Z < 13
I = 9.76 Z + 58.8 Z P
-0.19P if Z > 13
The stopping powers of particles other than protons are given by the relationships:
- deuterons S Bd B(E) = SBp B(E/2)
- tritons S BtB(E) = SBp B(E/3)
- P
3PHe S BB(E) = 4SBpB(E/3)
- P
4PHe S BB(E) = 4SBp B(E/4)
2.2. Heat transfer in Solids
Heat transfer in solids is somewhat simpler than in other media since the heat usually flows
through the target matrix mainly by conduction. The heat will be conducted form the hotter region of a
material to the cooler region according to Fourier's Law which is in one dimension:
110
Q BcondB = -kA dT/dx
where:
o Qcond = heat transferred by conduction (watts)
o A = cross-sectional area (cm2)
o k = thermal conductivity (watts/cm-°C)
o dT = temperature differential (°C)
o dx = distance differential (cm)
If this equation is integrated holding k, A and q constant, then the result is the heat transfer
equation in one dimension given by:
Q BcondB = -kA(T1-T2)/x (7)
where:
o k = coefficient of thermal conductivity (watt/cm-°C)
o A = cross-sectional area (cm2)
o x = distance (cm)
o T1 = temperature of the hotter part (°C)
o T2 = temperature of the cooler part (°C)
Once the heat has been transferred to the cooled surface of the target, the heat will usually be
removed by a fluid such as water flowing against the back of the target. This convective heat transfer
is another topic which will not be discussed.
A picture of the target material points up several design considerations for solids. This is shown
in Fig. 1.
Water Cooling
Backing Material
Target Material
FIG. 1. Schematic diagram of solid target configuration.
The transfer of the heat through the target material and through the backing material is
straightforward. The real surprises in designing solid targets come in the interfaces where the target
material meets the backing material. This is where many problems arise and the more secure one can
make this interface, the better the heat transfer will be and the less likely one is to have problems with
loss of target material or damage to the target during the irradiation.
3. TARGET PREPARATION
3.1. Solids
By far the easiest target preparation is that for a solid metal. The metal target is merely mounted
on a water cooled backing plate and placed in the particle beam. There are several examples of targets
such as this. One such target is the one fro making Cd-109 which consists of a silver plate mounted on
an aluminum backing plate which is water cooled. An example of such a target is shown in Fig. 1.
111
3.1.1. TCompressed solidsT
A typical method for making targets composed of oxides or other compounds that are not
amenable to electroplating is to place the material in a depression and then press the material under
high pressure in order to obtain a uniform layer. An example of this is the tellurium oxide target,
which is used for the production of Iodine-124. The tellurium oxide is pressed into a depression under
15,000 psi. It is also possible to add some metal to help with the heat conduction out of the target
oxide.
3.1.2. TChemical Vapor Deposition T
Chemical vapor deposition (CVD) is the process in which a film is deposited by a chemical
reaction or decomposition of a gas mixture at elevated temperature at the wafer surface or in its
vicinity, see Fig. 2 for a schematic view of the CVD process.
FIG. 2. Schematic diagram of the typical chemical deposition process. The solid film is
produced concurrently with the formation of a gaseous product.
4. TYPICAL TARGETS
4.1. Perpendicular Incidence
For some targets where the material is a good conductor, the matrix is not sensitive to heat, the
quantities required are small or the isotope being used as the target is very rare, a perpendicular target
may be used. A schematic diagram of such a target is shown in Fig. 3.
Target for Irradiation of Solid Powders
Thin Window Target Material
FIG. 3. Schematic diagram of a solid powder target used for radioisotope production.
112
4.2. Inclined Incidence
Internal - A schematic diagram of the inclined plane internal target is shown in Fig. 4.
RAM
LeadingMonitor
TrailingMonitor
Alpha beam
Target Material
Base Plate
FIG. 4.
FIG. 5.
Schematic diagram of an inclined plane target used internally in the cyclotron. The
target uses glancing incidence of the beam to spread out power density of the beam.
External – A schematic diagram of an external inclined plate target is shown in Fig. 5.
Schematic diagram of an inclined plane target, which is used external to the
cyclotron.
5. RADIOISOTOPE RECOVERY
5.1. Dissolution
A common method for the recovery of the radioisotope is to dissolve the target and then extract
the desired radioisotope from the solution. This is often done by solvent extraction or by ion
chromatography. An example of this method is given in the following example for Tl-201. In a typical
procedure, the thallium target is dissolved in 4 UM U H B2BSOB4 B and then transferred to a cation exchange
column. The thallium can then be eluted off the column with 1 UM U H B2 BSOB4B and saved for recovery. The
column is then rinsed with sterile water. The Pb-201 is eluted off the column with 2 UM U HCl. The
thallium-201 is then allowed to grow in. After the grow-in period, the Tl-201 can be separated from
the Pb-201 by extraction with di-isopropylether in a separatory funnel.
The aqueous phase that contains the Pb-201 is separated and saved for later processing. The
organic phase is washed and then the thallium-201 is back extracted from the organic phase into water
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that has been treated with sulfur dioxide. The solution is evaporated to dryness and then dissolved in
enough normal saline to give the desired final concentration.
5.2. Distillation
5.2.1. During irradiation
To Radiochemist ryLab orato ry
Qu artz Ho lder
Grap hite Second aryHo lder
Proton Beam
.0 03 " Mo lyb denumFoil
C-13 Pow der
Sprin g Lo adin g
Helium Inlet
FIG. 6. Solid carbon-13 powder target.
In certain situations, it is possible to distill the radioisotopes out of the solid matrix by using the
heat of the beam to aid in separating the radioisotope from the solid matrix where it is contained. This
technique is successful only if the radioisotope being produced can be volatilized and carried out of
the target. An example of this type of target is given by the carbon-13 powder target for the production
of nitrogen-13. A diagram of this type of target is given in Fig. 6. Temperatures inside the matrix can
easily exceed 600 P
oPC.
5.2.2. Post-irradiation
The most common method for the removal of radioisotopes from a solid target matrix is a post-
irradiation distillation. In this technique, the target plate is removed from the target holder and placed
in a furnace. The temperature is increased until the radioisotope is released. In some targets this occurs
when the target melts while in other targets, the volatilization of the material occurs at a temperature
below the melting point of the matrix. An example of this type of distillation is shown in Fig. 7. This
is the distillation of I-124 from the tellurium dioxide matrix, which is irradiated. The I-124 is
volatilized and transported into a base solution [3].
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O + He Gas Inlet
I-124 Out
Furnace
Thermocouple Probe
TeO Target Holder
2
2
FIG. 7. Furnace for the distillation of I-124 from the solid [P
124PTe]TeOB2B matrix of the target.
5.2.3. Supercritical extraction
Supercritical fluids are attractive as media for both chemical reactions, as well as process
extraction since their physical properties can be manipulated by small changes in pressure and
temperature near the critical point of the fluid. Such changes can result in drastic effects on density-
dependent properties such as solubility, refractive index, dielectric constant, viscosity and diffusivity
of the fluid. This suggests that pressure tuning of a pure supercritical fluid may be a useful means to
manipulate chemical reactions based on a thermodynamic solvent effect. It also means that the
solvation properties of the fluid can be precisely controlled to enable selective component extraction
from a matrix. In recent years, there has been a growing interest in applying supercritical fluid
extraction to the selective removal of trace metals from solid samples. Much of the work has been
done on simple systems comprised of inert matrices such as silica or cellulose. Recently, this process
as been expanded to environmental samples as well. However, very little is understood about the exact
mechanism of the extraction process. Of course, the widespread application of this technology is
highly dependent on the ability of scientists to model and predict accurate phase equilibrium in
complex systems [4].
6. TARGET MATERIAL RECOVERY
6.1. Precipitation
One of the ways of the radionuclide production increasing on present cyclotrons is the use of the
targets from enriched stable isotopes for irradiation. This allows to raise the productivity in two or
more times in some cases and to increase a radionuclidic purity. Enriched stable isotopes are very
expensive; therefore, it is advisable to recycle such raw materials as many times as possible. As an
example of this process, the recovery of zinc-67 or zinc-68 is given below.
Depending on gallium-67 production method, (deuteron or proton bombardment) the targets
from zinc-67 or zinc-68 are used. The target represents a copper block with a thin nickel layer covered
with stable zinc by electrodeposition. Its treatment includes the dissolution of irradiated zinc in
hydrochloric acid and following organic solvent extraction of gallium-67.
The remaining solution contains some quantities of copper, nickel and cobalt-57 besides the
zinc. The technique is based on the well-known anion-exchange behavior of the relevant elements in
hydrochloric acid. During zinc target irradiation, the zinc-65 (T B½ B / = 244 d) is obtained. These
procedures do not provide for the zinc isotope separation.
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FIG. 8. Scheme of zinc-67, 68 recovery.
This type of scheme results in a recovery of the enriched isotope of greater than 95%.
7. CONCLUSIONS
As can be seen from these examples and the table, most of the radioisotopes can or are being
produced by irradiation of solid targets. The targets have a wide variety of designs, but can be grouped
into three basic groups that are perpendicular external targets, inclined external targets and inclined
internal targets. The target type being used is dependent on a number of factors, which include the
amount of isotope being produced, the sensitivity of the target material to heat, the cost of the target
material and the type of cyclotron available for the irradiation.
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TABLE I. LIST OF RADIONUCLIDES PRODUCED WITH A CYCLOTRON
Product Solid Half Nuclear Nominal Demand Other Reactions Impurity
Nuclide Target Life Reaction Energy mCi/yr for Impurities Half-life
Be-7 X 53.3 d P
7PLi(p,n) 20 15
Na-22 2.6 y P
22PNe(p,n) 15 1500
X P
25PMg(p,a) 20
Mg-28 X 21 h P
27PAl(a,3p) 45 P
27PAl(g,n) P
26PAl 73,000 y
V-48 X 16 d P
48PTi(p,n) 11 50 P
49PTi(p,a) P
46PSc 83.8 d
P
49PTi(p,n) P
49PV 337 d
P
47PTi(p,a) P
44mPSc 2.44 d
P
50PTi(p,a) P
47PSc 3.3 d
X P
47PTi(d,n)* 10 P
48PTi(d,n) P
49PV 337 d
Fe-55 X 2.73 y P
55PMn(p,n) 20 100 P
55PMn(p,pn) P
54PMn 312 d
Co-55 X 17.5 h P
56PFe(p,2n) 25 1000 P
56PFe(p,n) P
56PCo 77.3 d
Co-57 X 271 d P
60PNi(p,a) 25 15000
X P
55PMn(3He,n) 40
Cu-61 X 3.35 h P
61PNi(p,n)* 12 50 P
61PNi(p,a) P
58mPCo 9.1 h
X P
64PZn(p,a)* 22
Cu-64 X 12.7 h P
67PZn(p,a)* 20 50 P
67PZn(p,n) P
67PGa 3.3 d
P
66PZn(p,n) P
66PGa 9.5 h
X P
66PZn(d,a)* 20 50 P
66PZn(d,n) P
67PGa 3.3 d
P
66PZn(d,2n) P
66PGa 9.5 h
Zn-62 X 9.2 h P
63PCu(p,2n) 22 2000 P
65PCu(p,n) P
65PZn 244 d
P
65PCu(p,pn) P
64PCu 12.7 h
Ge-68 272 d P
69PGa(p,2n)* 30 2000 P
71PGa(p,n) P
71PGe 11.4 d
As-73 X 80.3 d P
74PGe(p,2n)* 11 100 P
74PGe(p,n) P
74PAs 17.8 d
As-74 X 17.8 d P
74PGe(p,n)* 15 100 P
74PGe(p,2n) P
73PAs 80.3 d
Br-77 X 2.37 d P
78PSe(p,2n) 20 100 P
80PSe(p,a) P
77PAs 38.6 h
P
77PSe(p,a) P
74PAs 17.8 d
Y-88 X 106.6 d P
88PSr(p,n) 11 100 P
88PSr(p,2n) P
87PSr 3.3 d
Zr-89 X 3.27 d P
89PY(p,n) 15 100 P
89PY(p,2n) P
88PZr 83.4 d
Tc-95m X 61 d P
96PMo(p,2n)* 25 10 P
96PMo(p,n) P
96PTc 4.3 d
Tc-96 X 4.3 d P
96PMo(p,n)* 15 100 P
96PMo(p,2n) P
95mP Tc 61 d
Ru-97 X 2.89 d P
95PMo( P
3PHe,n) 45
Cd-109 X 462 d P
109PAg(p,n) 20 5000
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I-124 X 4.2 d P
124PTe(p,n)* 26 500 P
124PTe(p,2n) P
123PI 13.1 h
X P
121PSb(a,n)* 30 P
123PSb(a,n) P
126PI 13.0 d
Xe-122 X 20.1 h P
122PTe(3He,3n)* 50 P
122PTe(3He,2n) P
123PXe 2.0 h
Xe-127 36.4 d P
127PI(p,n) 20 300 P
127PI(p,pn) P
126PI 13.0 d
Ba-128 2.43 d P
126PXe(3He,n)* 30
Ce-139 X 137.6 d P
139PLa(p,n) 11 10
Ta-179 X 1.8 y P
180PHf(p,2n)* 22 1000 P
180PHf(p,4n) P
177PTa 2.4 d
W-178 X 21.6 d P
181PTa(p,4n) 38 100
Pt-195m X 4.02 d P
192POs(a,n) 40
Hg-195m X 1.67 d P
197PAu(p,3n) 30 100 P
197PAu(p,n) P
197PHg 2.7 d
X P
194PPt(3He,2n)* 40 P
194PPt(3He,a) P
193mPPt 4.3 d
Pb-203 X 2.2 d P
203PTl(p,n) 20 200
Bi-205 X 15.3 d P
207PPb(p,3n)* 30
X P
206PPb(p,2n)* 22
Bi-206 X 6.2 d P
207PPb(p,2n)* 22
X P
206PPb(p,n)* 15
At-211 X 7.2 h P
209PBi(a,2n) 46 200 40 hr
Pu-237 X P
237PNp(p,n)* 25 10 10 hr
* Uses isotopically enriched target material.
REFERENCES
[1] JANNI, J. “Stopping Power and Ranges”. Air Force Weapons Laboratory Report AFWL-TR-
65-150, 1965.
[2] DECONNINCK, G. Introduction to Radioanalytical Physics, Nuclear Methods Monographs
No.1, Elsevier Scientific Publishing Co., Amsterdam, 1978.
[3] FIROUZBAHKT, M.L; SCHLYER, D.J; FINN, R.D; LAGUZZI, G; WOLF, AP. Iodine-124
production: excitation function for the 124Te(d,2n)124I and 124Te(d,3n)123I reactions from 7
to 24 MeV. Nucl. Inst. Meth. In Physics Research B, v.79 (1-4), (1993), pp. 909-910.
[4] ERKEY, C, Supercritical carbon dioxide extraction of metals from aqueous solutions: a review.
Journal of Supercritical Fluids, (2000), 17, pp. 259–287.
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