on the production of radioactive labeled nanoparticles using a … · 2017. 2. 16. · oil is...

On the Production of Radioactive LabeledNanoparticles Using a Cyclotron for Oil

Consumption Measurements

Zürich, 12.09.2016

A. Kleinrahm, F. Oberdorfer, H. Schweickert

S. Jendrzej, B. Gökce, S. Barcikowski

MotivationCombustion engines

up and down movement

Friction Reduction of life time of mashine components

Wear Power losses

Engine oil

Friction and wearreduction by engine oil

e.g. nanoparticles

-1-

MotivationEstablished techniques at Zyklotron AGRTM measurement (Radionuclide Technique in Mechanical Engineering)

A) Thin layer difference method B) Concentration measuring method

-2-

Zyklotron AG, Karlsruhe. Zyklotron AG, Karlsruhe.

MotivationDrawbackEmission norms are tightend

Control and measurement ofoil consumption crucial!

What should be investigated?

Engine test bench

Determination of oil residuals in • Particle filter• Environment

Optimization/evaluation ofsuitability of engine oilsand engines

-3-

How to determine the oil consumption?Previous research Idea

Disadvantages:• Reduced dispersibility of halides

in engine oil

• Precipitation of halidesby reaction with additivesZn2+ + X- ZnX2

Radionuclide 82Br (t1/2 = 36 h)

H. Zellbeck et al., Tribotest 2000, 6(3).

Expected advances:• High nanoparticle dispersibility in

all oil fractions• No precipitation of radioisotopes

Radionuclide [123I] Benzyl Iodide (t1/2 = 13.5 h)

- High affinity of Iodide to gold- Dispersibility of nanoparticles in oil

V. Merk, C. Rehbock, F. Becker, U. Hagemann, H. Nienhaus, S. Barcikowski, Langmuir 2014, 30 (15)

A. Kleinrahm, F. Oberdorfer, H. Schweickert, B. Gökce, S. Jendrzej, S. Barcikowski, Patent, Nanopartikel-basierte radioaktive Tracer in Schmierstoffen, 2016, No. 102016206725.7.

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Radioactive labelingIn situ Ex situCombination of thin layer differencemethod and laser ablation

Laser beam

High specific activityof 50 MBq/mL

Zyklotron AG, Karlsruhe.

Metal/Ceramic

Seperate synthesis of nanoparticlesand radioisotopes

+UDE, Essen. Zyklotron AG, Karlsruhe.


Laser beam

gold

UDE, Essen.

-5-

A. Kleinrahm, F. Oberdorfer, H. Schweickert, B. Gökce, S. Jendrzej, S. Barcikowski, Patent, Nanopartikel-basierte radioaktive Tracer in Schmierstoffen, 2016, No. 102016206725.7. Not established method


Engine testLabelling ofnanoparticles in oil

Production of radioisotopesin a cyclotron

Synthesis of nanoparticles

Process steps


UDE, Essen.

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Production of radioisotopes at a cyclotronProduction of 123I at a cyclotron


Target thickness: 20 MeVCurrent: 200 µAPressure 3 bar cold

10-12 bar @ 120Seals: Metal, FKM, EPDMYield: 6-8 mCi/µAht(irradiadion) 6 h

Proton irradiation of Xe target

KIPROS 120(Karlsruher Iodine-123 Production System)

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Production of radioisotopes at a cyclotronSpecifications for I-123

Radionuclide purity at calibration time 123I: > 99.65 %

Radionuclide impurities at calibration time(Sum of 120I, 121I, 124I, 125I, 121Te): ≤ 0.35 %

Specific activity at calibration time: ≥ 30,000 MBq/mL

Radiochemical purity: ≥ 95 % Iodide

Constitution: Dissolved in 0.02 mol/L (± 10 %) NaOH

Synthesis of [123I] Benzyl Iodide Anion exchange

+ 123I

ICl

+ Cl-

-8-

Synthesis of nanoparticles1) Brust-Schiffrin methodGold nanoparticle synthesis in toluene

subsequent mixing with oil

M. Brust, M. Walker, D. Bethell, D. Schiffrin, R. Whyman, J. Chem. Soc., Chem. Commun. 1994, 7.

2) Dispersion of powder into oil

Drawbacks:• Complex synthesis• Nanoparticle agglomeration

3) Pulsed laser ablation in liquidsDirecte gold nanoparticle synthesis in oil

oil

goldfoil

laserbeam


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Up scaling of pulsed laser ablation method

R. Streubel, S. Barcikowski, G. Gökce, Optics Letters 2016, 41.

5 L Gold colloid in water

1 h of efficient work time

4 g Gold nanoparticles

High-power laser: 500 Watt, 3 ps, 10 MHz

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Economic nanoparticle synthesis for engine testsPerformance of 1 engine test:

5-20 L engine oil

15 pg 123I (4.5 MBq)

Num

berF

requ

ency

PAO2PAO6

PAO10PAO40

PAO650W-40 H2O

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Abl

atio

n ra

te [m

g/m

in]

A

0.2 µL of colloid (50 µg/mL) are requiredfor accumulation of 15 pg 123I

1 min laser ablation in oil could beenough for 200,000 engine tests

Highly economic synthesis

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-12-


Optical properties:

400 500 600 700 800 9000,00,10,20,30,40,50,60,70,80,91,0

Ext

inct

ion

Wavelength [nm]

PAO2 PAO6 PAO10 PAO40 PAO65

broad

narrow

Increase of viscosity

Optical properties of gold in base oils

0 200 400 600 800 1000 1200 1400

1,0

1,5

2,0

2,5

3,0

3,5

Viscosity of base oils at 22 °C [cSt]

Col

loid

al s

tabi

lity

PP

I [45

0 nm

/800

nm

]

Decrease of scattering

High viscosity PAOLow viscosity PAO

Primary particlesAgglomerates

Decrease ofdiffusion/coalescence

Stokes Einstein equation

6

Size distribution of gold in base oils

Au in PAO2 Au in PAO65

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Au nanoparticles in full synthetic engine oil (0W-40)

Au concentration: 100 mg/LOil is compressed to 6 bar in the measurement chamberOil temperature: approx. 150 °CCirculation duration: 2 h8 oil cycles/min

Simulation of first engine tests

400 500 600 700 800 900 1000 11000,0

0,5

1,0

1,5

2,0

2,5

Ext

inct

ion

Wavelength [nm]

0 cycles 120 cycles 240 cycles 360 cycles 480 cycles 600 cycles 720 cycles 840 cycles 960 cycles 1080 cycles 1200 cycles

Extinction increase

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Thank you for your attention !

We gratefully acknowledge the financial contribution by the GDCh

Questions?

on the production of radioactive labeled nanoparticles using a … · 2017. 2. 16. · oil is...

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