advanced engineering plastics in high tech applications

Advanced engineering plastics in High Tech Applications

Material selection for thermoplastics

By: Michiel de Schipper (M.Sc.Eng. In plastics)Business Development EngineerCell +31 6 51 50 24 [email protected]

Tielt / B Lenzburg / CH

Reading / USA

Vreden / D Tokyo / J

ReadingAmerican QEPP

Headquarter

Hong KongAsian QEPP

HeadquarterVreden

European QEPP Headquarter

ZurichGlobal

Headquarter

The Americas Europe International

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Our Worldwide Presence

Tuesday 16 june 2015

Lecture by MdS: Advanced Engineering Plastics in High Tech applications

2

TieltGlobal QCMS Headquarter

LenzburgGlobal QPC Headquarter

TokyoMPI/MCHC

Headquarter

Hong Kong / PRC

Quadrant EPP Market Focus



3

Chemical Processing

Construction & Heavy Equip.

Aerospace & Defence

Electronic & Semi Conductor

Food Processing & Packaging

Life Science

Alternative Energy

Radiation Shielding



Slide 4

6 basic steps for material selection in plastics

1. Static or dynamic use2. Temperatures during use3. Chemical exposure4. Other aspects

1. Impact resistance2. Dimensional stability3. UV / high-ionizing radiation resistance4. Flammability5. Electrical properties6. Industry-specific certifications / approvals

5. Base material selection (production process)6. Machine-ability



Slide 5

Dynamic (wear)Static (structural)

Step 1: Static or dynamic use

No elimination of materials yet. Select on structural properties:StrengthStiffness (allowable deformation). Loading timeTemperature

These can be enhanced by fillers:Glass fibersCarbon fibersMica / ceramics

Only choose the semi-crystalline materialsWear rateCoFPV capability

These can be enhanced by internal lubricants:Carbon fibers (!)GraphiteMoS2PTFEWaxOil



Slide 6

Tribological test proceduresimilar to Test Method A: “pin-on-disk”,

as described in ISO 7148-2:1999

Selection guidelines: sliding properties

Tribological test proceduresimilar to Test Method “Thrust Washer” as specified in ASTM D 3702



Slide 7

3 51

28

27

2

95 5

14

36

17

5

105

7

14

6

12

0

20

40

60

80

100

120

CELAZOLE PBI

TORLON 4

203 P

AI

TORLON 43

01 P

AI

KETRON PEEK-1

000

KETRON PEEK-H

PV

KETRON PEEK-G

F30

KETRON PEEK-C

A30

KETRON PEEK-T

X

TECHTRON HPV P

PS

RADEL PPSU 10

00

ULTEM P

EI 100

0PSU 10

00

SYMALIT P

VDF 1000

FLUOROSINT 20

7

PA 66

PET

PTFE

Wea

r ra

te (

µm/k

m)

2500 ⇑

6400 ⇑

1325 ⇑

455 ⇑

WEAR RESISTANCE OF THE QUADRANT AEP(measured on a "plastics pin on rotating steel disk " - tribo system)

1600 ⇑

at 23°C

at 150°C (*)

(*) steel disk heated to 150°C

Test conditions: - pressure: 3 MPa - sliding velocity: 0.33 m/s - surface roughness of the C35 steel mating surface: Ra = 0.70 - 0.90 µm - total distance run: 28 km - normal environment (air, 23°C/50% RH) - unlubricated operation

Wear rates including influence of temperature



Slide 11

Step 2: Temperature influences

Determine continuous use and peak temperaturesAllowable Temperature in Air Defines the maximum temperature based on thermal-oxidative

behaviour Based on 50% reduction in Tensile Strength Usually 2 values: short term (few hours) and long term (10.000

hrs) Not a constant; varies by magnitude & duration of mech load Non reversible !

HDT (Heat Deflection Temperature) Defines the maximum temperature up to which average

mechanically loaded parts can be used as construction material Is reversible



Slide 12

0

50

100

150

200

250

300

350

400

450

0 50 100 150 200 250 300 350

Max. allowable service temperature in air (continuo usly for min. 20,000h) - (°C)

QUADRANT 1000 PSU KETRON 1000 PEEK

KETRON HPV PEEK

ERTALYTE

ERTALON 6 SA

DURATRON T4203/4301/5530 PAI

SYMALIT 1000 PVDF

DURATRON CU60 PBI

KETRON TX PEEK

FLUOROSINT 207TECHTRON HPV PPS

KETRON GF30 PEEK QUADRANT PPSUDURATRON U1000 PEI

FLUOROSINT 500

Tem

pera

ture

of d

efle

ctio

n un

der

load

acc

. to

ISO

75

M

etho

d A

: 1.8

MP

a (

°C)

KETRON CA30 PEEK

FLUOROSINT HPV

DURATRON D7000 PIDURATRON D7015G PI

SYMALIT 1000 PFASYMALIT 1000 ECTFE

TEMPERATURE OF DEFLECTION UNDER LOAD VERSUS MAX. ALLOWABLE SERVICE TEMPERATURE IN AIR

Selection guidelines: thermal properties



Slide 13

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

-50 0 50 100 150 200 250 300

Temperature (°C)

Mod

ulus

of e

last

icity

(M

Pa)

KETRON 1000 PEEK

KETRON HPV PEEK

KETRON GF30 PEEK

KETRON CA30 PEEK

KETRON TX PEEK

TECHTRON HPV PPS

ERTACETAL C

STIFFNESS VERSUS TEMPERATURE (derived from DMA-curves)

Selection guidelines: structural properties AEP


Slide 14

0

1000

2000

3000

4000

5000

6000

7000

8000

-50 0 50 100 150 200 250 300 350

Temperature (°C)

Mod

ulus

of e

last

icity

(M

Pa)

DURATRON CU60 PBI

DURATRON D7000 PI

DURATRON D7015G PI

DURATRON T4203 PAI

DURATRON T4301 PAI

DURATRON T5530 PAI

ERTACETAL C

STIFFNESS VERSUS TEMPERATURE (derived from DMA-curves)

Selection guidelines: structural properties AEP




Slide 15

Effect of temperature (& time) on creep / relaxation of mainly unfilled plastics


Slide 16

Minimum service temperatures - all


TIVAR 1000 is only materialthat can beused down to-200°C



Slide 17

Step 3: Chemicals

Determine chemical resistance needed: During useDuring cleaning of parts after useHydrolisis / steam sterilisation / autoclave abilityUV and radiation resistance

Always check both PH value (indicational only) but also full chemical resistance listGeneral rules: all 4P (PE, PA, POM, PET) are suitable for standard industrial

use, with reasonable chemical resistance Semi-crystalline materials show better chemical resistance

than amorphous materials.


Slide 18 Lecture by MdS: Advanced Engineering Plastics in High Tech applications

Thickness Loss in Oxygen Plasma – Extreme Conditions

Chamber Conditions

• 2.5 KW

• O2 2000 sccm

• 0.4 Torr

• um per hour

MPR-1000 has less than 0.8 um/hr erosion in 2.5 KW O2, 25X better than PI

Semitron® MPR-1000 OEM plasma data

Displays mass loss – All samples started approximately the same size



Slide 19

Semitron® MPR-1000 data

MPR -1000 much lower metal content when adjusted to mass loss in chamber

Ratio of Ionic Purity Data Adjusted for Mass Loss During Erosion

1KW 1200 sccm O3

Element UnitsMPR-1000

Vespel SP1

Ketron PEEK

Aluminum (Al) ppm 0.14 6.11 6.89Barium (Ba) ppm 0.07 0.65 0.36Calcium (Ca) ppm 2.8 0.13 145.12Chromium (Cr) ppm 2.6 0.13 8.89Copper (Cu) ppm 0.14 0.65 3.63Iron (Fe) ppm 2.3 4.68 108.84Lead (Pb) ppm 0 0.65 0.09Lithium (Li) ppm 0 0.65 0.09Magnesium (Mg) ppm 0.3 3.64 14.51Manganese (Mn) ppm 0.11 0.26 3.63Nickel (Ni) ppm 0.36 0.26 7.62Potassium (K) ppm 0.77 1.69 29.02Sodium (Na) ppm 4.4 5.72 8707.20Strontium (Sr) ppm 0.04 0.65 10.88Titanium (Ti) ppm 0.12 0.65 3.27Zinc (Zn) ppm 0 0.26 2.72

2KW 1200 sccm O3

Element UnitsMPR-1000

Vespel SP1

Ketron PEEK

Aluminum (Al) ppm 0.14 2.96 3.72Barium (Ba) ppm 0.07 0.32 0.20Calcium (Ca) ppm 2.8 0.06 78.40Chromium (Cr) ppm 2.6 0.06 4.80Copper (Cu) ppm 0.14 0.32 1.96Iron (Fe) ppm 2.3 2.27 58.80Lead (Pb) ppm 0 0.32 0.05Lithium (Li) ppm 0 0.32 0.05Magnesium (Mg) ppm 0.3 1.76 7.84Manganese (Mn) ppm 0.11 0.13 1.96Nickel (Ni) ppm 0.36 0.13 4.12Potassium (K) ppm 0.77 0.82 15.68Sodium (Na) ppm 4.4 2.77 4704.00Strontium (Sr) ppm 0.04 0.32 5.88Titanium (Ti) ppm 0.12 0.32 1.76Zinc (Zn) ppm 0 0.13 1.47

1KW 1200 sccm O2 2KW 1200 sccm O2



Slide 20

Number of cyclesMaterial 0 50 100 250 500

ACETRON LSG 100 83 80 58 xErtalyte 100 100 32 28 xPSU 1000 LSG 100 x x 62 54PEI 1000 LSG 100 x x 95 94PVDF 1000 100 x x 105 100PPSU 1000 LSG 100 x x 102 102Techtron HPV PPS 100 x x 65 70Ketron PEEK 1000 LSG 100 x x 105 102

The table below shows the effect of repeated steam sterilisation on the Charpy notched impact strength (ISO 179/1eA). The values in this table show the retention of the notched impact resistance in % of the original value after a certain number of cycles

• The test results clearly show that PVDF 1000, PEI 1000 LSG, Ketron PEEK 1000 LSG and PPSU 1000 LSG are very suitable for repeated steam sterilisation

• PSU 1000 LSG and Techtron HPV PPS also offer a good autoclavability up to 500 cycles• Acetron LSG and Ertalyte can be used for parts, which will only be steam sterilised a few

times

Chemical Resistance ∾ Steam Sterilization

Brachy Therapy Prostate Stepper – Quadrant® LSG Naturel PPSU

Application:For treatment of cancer (Brachytherapy), a radioactive probe is positioned into the body to attack the cancer.In the case of prostate cancer, a stepper template is used to position this radioactive probe at the right spot, and its position can be checked by X-rays.After the treatment, the part is cleaned by harsh medical cleaners, plus high temperature autoclave cycle.

Why Quadrant® LSG Naturel PPSU for this application? Biocompatibility

(USP XXIII Class VI and ISO 10993-10 and -11compliant)

Excellent resistance against steam autoclaving

Excellent impact resistance Stepper templates from Nucletron B.V.





Slide 22

Selection guidelines: miscellaneous

Consider additional material characteristics:

Toughness and impact strength / notch sensitivity

Dimensional stability (thermal expansion and moisture absorption)

Regulatory/agency compliance (food contact, biocompatibility, …)

Flammability

Electrical properties (insulating, anti-static)

Others (UV-resistance, resistance against high ionising radiation, resistance against steam sterilisation, outgassing, …)

STEP 4


Slide 23

FLAMMABILITY

(*): there are no "UL File Numbers" for these stock shapes

1.5 mm 3 mm

DURATRON CU60 PBI V-0 V-0 58 DURATRON D7000 PI V-0 V-0 51 DURATRON D7015G PI V-0 V-0 47 DURATRON T4203 & T4503 PAI V-0 V-0 45 DURATRON T4301 & T4501 PAI V-0 V-0 44 DURATRON T5530 PAI V-0 V-0 50 KETRON 1000 PEEK V-0 V-0 35 KETRON HPV PEEK V-0 V-0 43 KETRON GF30 & CA30 PEEK V-0 V-0 40 KETRON TX PEEK V-0 V-0 40 TECHTRON HPV PPS V-0 V-0 44 QUADRANT PPSU V-0 V-0 38 QUADRANT 1000 PSU HB HB 30 DURATRON U1000 PEI V-0 V-0 47 SYMALIT 1000 PVDF V-0 V-0 44 SYMALIT 1000 ECTFE V-0 V-0 52 SYMALIT 1000 PFA V-0 V-0 ≥ 95 FLUOROSINT V-0 V-0 ≥ 95

OXYGEN INDEX (%) according to

ASTM D 2863 & ISO 4589

FLAMMABILITY RATING (*)according to UL 94

thickness

Selection guidelines: miscellaneous AEP




Slide 24

1 gray = 100 rad

106 gray = 100 Mrad

1 Mrad = 10 kJ/kg

The Radiation Index (RI) is defined as the logarithm, base 10, of the absorbed dose in grays at which theflexural stress at break or flexural strain at break of the tested material is reduced to 50% of its originalvalue, under specified conditions of irradiation (the most radiation-sensitive of these two properties ischosen as the reference critical property).

6,5

5,8 6

7,1 7,1 7,1

0

1

2

3

4

5

6

7

8

RADIATION RESISTANCE(Gamma -rays)R

adia

tion

Inde

x -

Log(

gray

)

≈ ≈ ≈ ≈ 3

> > > > 7,5 > > > > 7,5≥ ≥ ≥ ≥ 7≥ ≥ ≥ ≥ 7

≈ ≈ ≈ ≈ 4

≥ ≥ ≥ ≥ 6

≈ ≈ ≈ ≈ 5



Slide 25

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 10 20 30 40 50 60

Test specimen thickness (mm)

Tra

nspa

renc

y (%

)

KETRON PEEK-CLASSIX LSG white

KETRON PEEK-GF30 LSG blue

KETRON PEEK LSG & PEEK-CA 30 LSG

TECHTRON HPV LSG

RADEL PPSU LSG black

PC LSG natural

ACETRON LSG

TRANSPARENCY OF THE QEPP LIFE SCIENCE GRADES TO HIG H ENERGY RADIATION AS A FUNCTION OF THE TEST PLATE THICKNESS (measured at 23°C, applying an energy level of 59 keV*)

* This energy level corresponds with the typical level used in X-ray medical diagnostic equipment (λ = 21 pm).

Life Science ∾∾∾∾ X-Ray transparency / thickness

[Surgical Instruments - Osteosythesis]

[Application: Target Devices in Osteosynthesis]Material [KETRON® PEEK CA 30 LSG and Ketron ® PEEK CC]Processes [Extrusion, Bonding, High Precision Machining]

Target devices are used to help the surgeon to fix the bone in the exact position and need to be very precise and resistant to high press ure.

Properties and benefits of the selected material:

Radiolucency of the material providing visibility during surgery Excellent mechanical strength and stiffness and creep resistance High E-Modulus (PEEK CA30 = 9,2 Gpa at 23 °C, while PEEK CC = 70GPa) &

extremely high dimensional stability Biocompatibility according to ISO 10993 and USP Class VI requirements

(suitability for body contact up to 24 hrs)



Slide 26

Ketron CC PEEK (PEEK + continuous carbon fiber)

Extreme stiffnessLow densityPressed in laminatesup to 2” thickness, suitable for machining



Slide 27

Stiffness indices



Slide 28

key properties on stiffness E/ρ

E/ρ

(indexed;

alu=100%) E^0,5/ρ

E 0,5/ρ

(indexed;

alu=100%) E^0,333/ρ

E^0,3333/ρ

(indexed;

alu=100%)

Materialstiffness [Gpa]

Density [kg/dm3]

CLTE [m/mK]

stiffness (tensile bar)

stiffness (tensile bar)

stiffness (bending beam)

stiffness (bending beam)

stiffness (bending plate)

stiffness (bending plate)

Al 70 2,7 23 25,92593 100% 3,09874 100% 1,52638 100%

Mg 44 1,74 25 25,28736 98% 3,81221 123% 2,02891 133%

Fe 220 7,87 11 27,95426 108% 1,88468 61% 0,76705 50%

PE 500 1,3 0,96 150 1,35417 5% 1,18768 38% 1,13687 74%

TIVAR UHMWPE 0,75 0,93 200 0,80645 3% 0,93121 30% 0,97695 64%

Ertacetal C POM 2,80 1,41 110 1,98582 8% 1,18675 38% 0,99961 65%

Ertalyte PETP 3,50 1,39 60 2,51799 10% 1,34592 43% 1,09229 72%

Ketron 1000 PEEK 4,30 1,31 50 3,28244 13% 1,58293 51% 1,24132 81%

Ketron CA30 PEEK 9,20 1,40 25 6,57143 25% 2,16654 70% 1,49669 98%

Ketron CC PEEK 70,00 1,53 4 45,75163 176% 5,46837 176% 2,69361 176%

bestworst

ESd Materials for Semicon by Thermal Properties

Anti Static Properties

250°°°°C

100°°°°C

tem

pera

ture

Semitron ESd 520HR(PAI)

Semitron ESd 490HR(PEEK)

Semitron ESd 480(PEEK)

Semitron ESd 420 V(PEI)

Semitron ESd 420(PEI)

Ketron CA30 PEEK

Semitron ESd 410C(PEI)

Semitron ESd 225(POM)

102

106

1010

1012 (Ω / sq.)

HighResistancy

Range

Dissipative Range

Conductive Range

Semitron ESd 500(PTFE)

Semitron ESd 300(PET)



Slide 29

SEMITRON ESd 420 (black) - static dissipative PEI

Application:During production of TFT screens (used in mobile phones etc), the tester itself should be fully ESd. The tester should not be too conductive (shortcut) but also not too isolating (sparks).

Why SEMITRON ESd 420 for this application? Permanent static dissipative

(106 - 109 Ohm) Good machinability High stiffness Wear resistant Non-sloughing



Further Outgassing Data on other Quadrant material s…

Outgassing Values of the Quadrant Engineering Plastic Products’ stock shapes .

In 1995, a number of Quadrant Engineering Plastic Products’ stock shapes were tested according to the European Space Agency (ESA) - specification PSS-01 -702 (“A thermal vacuum test for the screening of space materials”). Samples were heated to 125°C for 24 hours, collector plates kept at 25°C and the testing carried out in a vacuum of 0,001 Pa.

MATERIALS TML (%) RML (%) CVCM (%)

Ertalon® 66 SA 1.3 .17 .002

Ertalon® 6 PLA 1.5 .06 .005

Ertacetal® C .34 .13 .016

Ertacetal® H .47 .24 .005

Ertalyte® .33 .20 .005

Ertalyte® TX .25 .03 .003

Ketron® 1000 PEEK .26 .03 .003

Ketron® HPV PEEK .16 .02 .003

Techtron® HPV PPS .06 .02 .003

Duratron® U1000 PEI .82 .32 .002

Quadrant® 1000 PSU .49 .09 .002

Symalit® 1000 PVDF .05 .02 .006

Duratron® T4203 PAl 1.9 .93 .007

Duratron® T4301 PAl 1.4 .42 .018

Duratron® CU60 PBI 2.2 .84 .014

TIVAR® 0.14 NT 0.02

TML = Total Mass Loss RML = Recovered Mass Loss CVCM = Collected Volatile Condensed Material NT = Not Tested

Outgas s ing (ASTM E595)

%TML %CVCM %WVR

Semitron ESD 225 1,000 0,054 0,603

Semitron ESD 410C 0,458 0,000 0,170

Semitron ESD 420 1,810 0,000 0,700

Semitron ESD 500 0,004 0,000 0,000

Semitron ESD 520HR 1,380 0,000 0,470

Techtron PPS 0,038 0,000 n/a

Torlon 5530 0,927 0,000 0,220

Vespel 0,750 0,000 0,490

Ketron peek 1000 0,310 0,000 0,160

Celazole PBI 2,513 0,000 0,388

Ertalyte PET-P 0,127 0,000 n/a

ASTM testing ESA testing



Neutron Radiation Shielding

Alpha, Beta, and Gamma radiation can be blocked with material that has a high electron density (typically high atomic number materials such as lead)

Since neutrons have no charge, they are not effected by materials with high electron densities (such as lead). To slow neutrons down, they need to collide with similar size particles (such as hydrogen).

The process of slowing fast moving neutrons by collisions is called attenuation or thermalization

Once neutrons have been slowed down, they are called thermal neutrons can be absorbed by the surrounding materials atoms



Slide 32

Neutron Particle Through A High Electron Density Material (lead)

Since the nuclei of high electron density materials are significantly larger than the nucleus of the neutron particle, the neutron particle will not transfer a large amount of energy to the material particles when they collide.

Neutron Particle

Neutron Particle

Neutron Particle Through A High Hydrogen Density Material (PolyEthylene)

Since the neutron particle is a similar size to the hydrogen nucleus, every time they collide a significant amount of energy is transferred from the fast moving neutron to the surrounding hydrogen rich material.



Slide 33

Thermal Neutrons

After neutrons are slowed, they are absorbed by the surrounding material. This capture process generally leads the release of high-energy gamma rays (which are dangerous to humans).

If elemental boron is added to the shielding material, it can absorb these slow neutrons and significantly reduces the amount of gamma radiation released.

The most cost effective way to add elemental boron to shielding is to use Borontrioxide (also known as Boric Oxide or B2O3)



Slide 34

• Shielding

material

• Etx.

TIVAR Borotron® - Improved material technologyLife Science &

nuclear medicine

• Neutron Radiation shielding

material

• Low density and weight

• Neutron absorbing

Nuclear industryIn addition to existing sales in Borotron®, Quadrant has long-term experience in manufacturing and supply of PE-HMW and PE-UHMW products to one of the most sensitive radiation shielding applications:

Polyethylene shielding rods and lids in transportation casks for nuclear spent fuel and waste

extremely stringent quality and process control

validated processes

extensive application basedtesting (e.g. CLTE)

one-stop shop: - compression-molding- annealing under N2- machining- inspection and testing

Polyethylene based shielding material in transporta tion cask for nuclear spent fuel and waste (custom formulation) – 2 layers of rods as neutron shielding



Slide 35



Slide 37

Step 6: Production technology of part- machining

Annealing / tempering of base materials. Anticipate on expected internal stress levels.Add rough-machining step if tighter tolerances are requiredTolerances achieved: Total tolerance field = 0,1 – 0,2% of nominal size, with minimum 0,05 mm For Example: diameter 200: 0,2-0,4 mm total field. Best is: dia 200 +0,1 / -0,1 mm

Determine the machine-ability of the selected materialsCoolants:can lead to breakage (amorphous materials)Filled materials (glass, carbon, etc): more abrasive to cutting tools more sensitive for breaking

Special diamond tooling required (Duratron materials)



Slide 38

Very best tolerances possible (Technology Center)Best possible tolerances TC Tielt

0,00

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

0,09

0,10

0,11

0,12

0,13

0,14

0,15

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200

Dimension (mm)

Tot

al to

lera

nce

field

(m

m)

HD PE

standaard / PVDF

PA / POM / F207

PET / PC / PEEK / F500 / PPS / PEI / PPSU / PSU

gevulde PEEK

PAI / PBI

Default tolerance field

These better

tolerances only

possible at extra cost

Duratron® T4203 – Tracking detector clamps in proton collider

Application: Within the Atlas detector at CERN, the path of the particles, which are created during the collision, is measured by many surrounding sensors. These carbon sensors are mounted on a socket, which is made of Duratron T4203. Also the mounting rings on the Printed Circuit Board are made of Duratron T4203.

Material: Duratron® T4203.(plastic part 10 – 20 mm) Dimensional stability

High radiation resistance, and does not disturb measurements

Good mechanical properties (no metal inserts needed around screws)

No interference with protons (transparent)

Low outgassing at vacuumTuesday 16 june 2015




Slide 40

Reducing internal stresses

See on right: Extruded full rod Badly tempered rod cut over

length Quadrant tempered rod cut over

lengthInternal stress level difficult to measure & quantifyWhen ignored, result of machined part can be disasterousQuadrant focusses on lowest-stress materials for machining parts. The extra cost of fully tempered material is quickly regained by saving machining time

Some can do it cheaper... But at what cost?

Slide 41Tuesday 16 june 2015




Slide 42

High Performance in Plastics

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advanced engineering plastics in high tech applications

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