innovations in silicone enhanced thermoplastics final · innovations in silicone enhanced...

Innovations in Silicone Enhanced ThermoplasticsKrishna Joshi 乔旭

Multibase, A Dow Corning Company

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Multibase, A Dow Corning Company

ØOur Vision:“We are trusted global partners driven by our passion to create value with innovative and customized thermoplastic solutions”

ØManufacturing Locations : – Saint-Laurent-du-Pont, France – Copley, Ohio, USA– Daman/Mumbai, India

ØServing customers in 50 countries




Multibase World Locations

European Center of ExcellenceMultibase SAZ. I. Chartreuse Guiers38380 Saint Laurent du PontTel: +33 (0)4 76 67 12 12Fax: +33 (0)4 76 67 12 82

Asian Center of ExcellenceSynergy Multibase Ltd.74/5-6 Daman Industrial EstateKadaiya VillageNani DamanDaman 396 210 (U.T.)IndiaTel: +91-260-2220627Fax: +91-260-2221578

Americas Center of ExcellenceMultibase Inc.3835 Copley RoadCopley, OH 44321USATel: +1 330 867 5124Fax: +1 330 666 7419

St Laurent du Pont - France

Copley, OH - USA Daman, Mumbai - India




Products and Markets

ThermoplasticElastomers

55%

RigidCompounds

15%

Masterbatches26%

TollCompounds

4%

Industrial& Consumer

51%

Transportation45%

TollCompounds

4%




Innovations From Multibase

Ø Siloxane Masterbatch– Easy to handle additives of ultra high molecular

weight siloxane in various thermoplastic resin carriers

Ø Multiflex® SiE (Siloxane Enhanced Elastomers)– Unique combinations of SEBS based TPEs and

siloxanes to give excellent appearance, mar and scratch resistance

Ø TPSiV®– Patented TPV technology based on silicone

rubber




Enhancement of Thermoplastics Using Siloxane Masterbatch




PolyDiMethylSiloxane (PDMS)

CH3 CH3 CH3

CH3 - Si - O - (Si - O)n - Si - CH3

CH3 CH3 CH3

Ø Silicones typically have a back bone, which is inorganic like glass

Ø The side groups are organic: in most case methyl

Ø The degree of polymerisation varies from n=1 to several thousand

Ø Silicones show low viscosity, even at very long chain lengths

M w = 250 1 cSt M w = 1,000 10 cSt M w = 5,000 100 cSt M w = 25,000

1,000 cSt M w = 55,000 10,000 cSt M w = 100,000 100,000cSt M w = 300,000 10,000,000cSt

Chain has a spiral shape




• High free volume – fluidity at high molecular weights• Incompatible with majority of thermoplastics• Low surface tension & energy (lubricant, release agent, aesthetic feel)• Heat resistant and weather resistant

Polydimethylsiloxane (PDMS)




Siloxane in ThermoplasticsØSiloxane based mold sprays are commonly used

in injection molding to aide in part releaseØSiloxane fluids or oils (30,000 to 60,000 cSt) are

effective internal and external lubricants Ø Limitations:

– Handling difficulties– Surface adhesion problems (migration)

Ø Innovation from Multibase is use ultra high molecular weight PDMS (15,000,000 cSt) to eliminate these limitations




Siloxane MasterbatchØ 50% UHMW PDMS in various thermoplastic carriers

– Polyolefins, ABS, PC, nylon, HIPS, EVA, TPU, ...Ø Dispersed with an average particle size of 5 micronsØ Si enriches at surface, but UHMW eliminates concerns

of blooming and migration after processing




Benefits of Siloxane Masterbatch

ØProcessing benefits (0.2 – 2% usage)– Added at press, extruder or during compounding– Improved mold release– Improved mold filling (thin walls, ...)– Extruder efficiencies (energy, pressure, ...)– Compounding improvements (disperson, energy, ...)

ØProperty enhancement (1-8% usage)– Reduce COF– Low migration (durability)– Improved mar and scratch




Processing Advantages forInjection Molding

0

20

40

60

80

100

120

0 2

MB50-001 (%)

Part

s rel

ease

d (%

) Natural - Consistent Short Shot

PP+400 ppm UHMW Si- 100% filled

• Effective mold release – less scrap, reduce cycle time• Effective internal lubricant – easier filling of complex parts




0

0.1

0.2

0.3

0.4

0.5

0.05 0.25 0.45 0.65 0.85

Velocity (Ms-1)

Coe

ffici

ent o

f Fric

tion No Siloxane

Siloxane Masterbatch (3% Si)

Effect of Si MB on COF




0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Ambient 50oC 60oC

COF

'Non migratory' SlipFrom DC MB

Erucamide

Temperature (C)

COF – BOPP Film




Mar and Scratch Improvement




Hot Taber Test




Printability Study-3M tape100% Amoco 3243 PP

0.2% Erucamide

1% Erucamide

3% Erucamide

5% Erucamide

0.2% UHMW Si

1% UHMW Si

3% UHMW Si

5% UHMW Si




Effect on Properties/PerformanceØ Negligible effect on mechanical properties in typical

usage range (data for PC)

Ø No negative impact on UV resistance (weatherability) or fogging (data for TPE and TPO)

% PC Based UHMW PDMS Masterbatch

Tensile Strength (psi)

Flexural Modulus (psi)

Izod, Notched (ft-lbs/in)

0 9083 12581 14.281 9293 12256 13.812 8753 12362 14.564 8521 12209 13.28

1 hour 16 hour

Control TPO 84.0 94.7TPO with 4%

UHMW PDMS87.1 93.4

Fog#SampleSample Delta E After 2500 KJ60A TPE 1.16

3% Masterbatch 0.6410% Masterbatch 0.54




Case Histories

HDPE Pipe Kodak Camera

Application Successes Using Siloxane Masterbatch:




Summary – Siloxane Masterbatch

ØUHMW Siloxane Masterbatch from Multibase, A Dow Corning Company is an unique additive that can:

– Solve processing issues (mold release, filling)

– Reduce cycle time and save $

– Enhance surface properties of thermoplastics (reduced COF, improved mar and scratch)




Siloxane Enhanced Elastomers (SiE)




SiE Elastomers

ØMultibase, A Dow Corning Company has commercialized Multiflex® SiE technology by combining our experience in SEBS TPEs and siloxane polymers

ØThis study offers a comparison of properties and performance of SiE and a standard SEBS TPE for general automotive interior applications




SiE General Properties

Test Method 8009 MU5 7009 MU5 6009 MU5 UnitMelt Flow (230oC, 2.16 kg) ISO 1133 1 0.8 0.3 g/10minSpiral Flow Internal 87 89 87 cmSpecific Gravity ISO 1183 0.92 0.91 0.91Tensile Strength ISO 37 11.2 8.7 7.9 MPaTensile Stress at 100% Elongation ISO 37 6.4 4.4 2.9 MPaElongation at Break ISO 37 580 550 600 %Tear Strength ISO 34 58 41 33 kN/mHardness (15 sec) ISO 868 79 70 61 Shore A

Value




Adhesion to Polypropylene

Grade Peak LoadMF SiE A 6009 MU 70 lbs

T-bar peel test at 12 in/min, bond area ~1 square in.




Coefficient of Friction Performance

Ø SiE technology is able achieve a lower Static and Kinetic Coefficient of Friction contributing to a non-tacky surface feel

Static KineticControl TPE 1.940 1.149MF SiE A 6009 MU 1.058 0.811% Reduction 45% 29%

Sample CoF




Scratch Resistance(no scratch whitening)

10N 7N 6N 3N 2N 10N 7N 6N 3N 2N

Control TPE SiE

10N 7N 6N 3N 2N 10N 7N 6N 3N 2N

Control TPE SiE

SiE has better resistance to scratches and no scratch whitening




Abrasion Resistance – Significant Improvement!

Sample Gloss Before Gloss After % Gloss LossControl TPE 2.7 1.1 59%MF SiE A 6009 MU 2.5 1.9 24%

Sample Original Weight, g Cycles Weight After, g % wieght lossControl TPE 18.6444 10,000 16.629 10.8MF SiE A 6009 MU 14.0616 10,000 14.021 0.3




Compression Set Performance

Ø SiE technology is able to maintain a low compression set even at 125C

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

23C 70C 100C 125C

600970098009Log. (6009)Log. (7009)Log. (8009)




Fogging Performance

Ø Testing Conditions: Fogging (LP463DB-12-01, 6h at 95C and 110C heating, 21C cooling, 16 h post

Ø SiE technology is able to maintain fogging requirements even at 110C

MF SiE A 6009 MU 16 hour110 C 91.7 No Droplets or Crystals

MF SiE A 7009 MU 16 hour95 C 90.8 No Droplets or Crystals

110 C 77.9 No Droplets or CrystalsMF SiE A 8009 MU 16 hour

110 C 91.2 No Droplets or Crystals

Sample Fog # Microscopic Examination 40X




Gas Fading PerformanceControl TPE SiE A 6009

Before After Before After

Delta EControl TPE 9.79 1 - 2 Severe color changeMF SiE A 6009 MU 1.69 4 Slight color changeMF SiE A 8009 MU 1.56 4 Slight color change

Sample Gas Fading / Resistance to Burnt GasAATCC rating




Flammability Performance

ØSiE Materials meet FM VSS 302

Grade Time (sec) Burn Rate (in/min) Pass/FailMF SiE A 8009 MU 47.8 1.26 PassMF SiE A 7009 MU 44.1 1.36 PassMF SiE A 6009 MU 66.3 0.90 Pass

FM VSS 302




Soiling and Linting PerformanceGrade Lint Rentention Rating Pass/Fail (2 min.)MF SiE A 6009 MU 1 PassMF SiE A 7009 MU 1 PassMF SiE A 8009 MU 1 PassStandard TPE 1 Pass

Linting (LP-463KB-38-01)

GradeSoil

-IPA no stain no stain no stain-Armor All no stain no stain no stain-Grease no stain no stain no stain-Ketchup stains stains stains-Orange Juice no stain no stain no stain-Coffee no stain no stain no stain-Chocolate no stain no stain no stain-Windex no stain no stain no stain

Cleanability (LP-463KC-04-01)

MF SiE A 8009 MU MF SiE A 6009 MU Standard TPE




UV Resistance

ØTesting completed using SAE J1885 – 1240 kj

Delta L Delta a Delta b Delta EMF SiE A 6009 MU 0.72 0.07 -0.3 0.78MF SiE A 7009 MU 0.67 0.05 -0.04 0.68




Oil Resistance

Before: After:

Ø Paraffin oil rested on part surface at 80 C for 24hrs Ø No adhesion failure (SiE overmolded on PP

substrate) and grain was not washed out




Cocoamide Resistance

Ø Plaques were exposed to the cocoamide for 48 hrs at 23C, 50% RH and then were abraded with a cloth (TSM5100G 4.9.2 - color fastness to wet crocking). Rating 1 indicates that there was no noticeable change in the grain of the plaques.

Grade Rating Pass/FailMF SiE A 7009 MU 1 PassMF SiE A 8009 MU 1 PassStandard TPE 4 Fail

Cocoamide resistance




SiE Applications – Automotive InteriorØ Important Aspects:

– Excellent appearance– Low CoF– Smooth touch– Excellent flow– No blooming– Reduced noise




2008 Corolla Matrix Deck Lid Strips

Skid strips on deck lid




Summary - SiE

ØSiloxane enhanced elastomers (SiE) have superior scratch resistance as compared to standard TPEs and are designed specifically for car interior trim applications (meets stringent UV, fogging, gas fading requirements)

ØSiE is also expected to find use in non-automotive applications that require good scratch resistance and a non-tacky feel




Thermoplastic Silicone Vulcanizates

(TPSiV®)




Outline

ØBasics of Thermoplastic Silicone Vulcanizates

ØTechnology Platforms (Properties and Applications)– Polyamide based– TPU based– Polyolefin based

ØSummary




Basics of Thermoplastic Silicone Vulcanizates

Ø ThermoPlastic Silicone Vulcanizate (TPSiV®)

Ø Alloy TPV consisting of fully cured silicone rubber particles dispersed in a continuous phase of selected thermoplastic

Ø Cured silicone is a clean reaction: no by-products, no odor, no emission

Ø Unique, patented technology of Multibase, A Dow Corning Company (13 patents)

Ø Properties depend on type of plastic, type of silicone, ratios and compatibilization




Challenges with Silicones

Ø Not compatible with majority of thermoplastics

Ø Very dissimilar solubility parameters– PDMS = 14.9 MPa½

– Nylon 6 = 27.8 MPa½

Ø Effective compatibilization is required to create a stable TPV morphology and to achieve acceptable mechanical/physical properties

21 µm21 µm




Compatibilization ExampleØ As disclosed in US patent 6,649,704,

compatibilization of nylon resins and silicone rubber can be accomplished in situ during dynamic vulcanization if an appropriate functionalized PDMS fluid is added (such as epoxy functional)

Ø Forms graft co-polymer of nylon and PDMS, which acts as compatibilizer between nylon and silicone rubber phases

SampleTensile Strength (MPa)

Elongation at Break (%)

No Compatibilizer 7.3 37With Compatibilizer 13.6 178

Nylon 12 Based Silicone Vulcanizate




ThermoplasticSilicone

VulcanizatesTechnology

Polyamide1180-50D

PCT/ 98914571.9

TPU3010, 3011, 3040,

3340, 3111PCT/01920590.5PCT/01959153.6PCT/02786412.3

Polyolefin5300, 5400, 5500

PCT/98914571.9

Product Platforms




PA 6 based Silicone VulcanizateProperty Result Initial:

Specific Gravity (23/23ºC) Hardness (Shore D) Tensile Strength (MPa) Elongation at Break (%) Tear Strength (N/mm) Flex Modulus at 40°C (MPa)

1.09 52 24 207 138 319

1008 hrs in Air at 140°C: Change in Tensile Strength (%) Change in Elongation at Break (%)

-24 -43

Immersion in DOT4 Brake Fluid at 150°C for 168 hrs: Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%)

-26 +0.4 +7.3

Immersion in Automatic Transmission Fluid at 127°C for 1008 hrs: Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%)

-6.8 +38 +23

Immersion in Reference Fuel C at 23°C for 3024 hrs: Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%)

-34 -18 +23




Automotive Hose ApplicationØ Jacket for automotive brakehoseØ Outperforms competitive solutions (CoPE and PP-

EPDM TPV) in terms of– temperature resistance (continue -150°C)– sealing in crimped section




TPU Based Silicone Vulcanizate

ØCombines the advantages of:– Excellent abrasion resistance of TPU– Soft touch of silicone rubber– Significantly lower COF than TPU– As compared to most soft TPU, TPSiV® contains no

plasticizers– Excellent bonding to PC, ABS, …– Excellent retention of properties after heat aging in air– Better compression set than TPU (further improved

after annealing)




Comparison To PP-EPDM TPV

Property Silicone Based TPV

PP-EPDM TPV

Initial: Hardness (Shore A) Tensile Strength (MPa) Elongation at Break (%)

71 16 600

66 6.5 457

70 hrs in Air at 175°C: Change in Hardness (Shore A) Change in Tensile Strength (%) Change in Elongation at Break (%)

+7 +6.3 +12

-5 -32 -20

70 hrs in IRM 903 Oil at 100°C: Change in Hardness (Shore A) Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%)

-9 -23 -2.5 +23

-19 -29 -40 +80




Benefit of annealing on TPU based Silicone Vulcanizates

Mechanical Properties @ 23°C

Standard Units TPSiV® 3010-50A

TPSiV® 3010-60A

Tensile Strength Elongation at break Tear Strength

ASTM D412 ASTM D412 ASTM D624

MPa % N/mm

7.1 473 24

16 500 33

Physical Properties Density Hardness Compression Set 22hrs 23°C 70°C 70°C after annealing* 120°C 120°C after annealing* Abrasion Resistance (Taber)

ASTM 792 ASTM D2240 ASTM D395 ASTM D1044

Shore A % Mg loss

1.12 52

14 49 22 74 53 21

1.2 65

12

70 41 21

*Annealed at 120°C for 22hrs in air




Test for Bonding Strength

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nf Shot 2nf Shot

Hand LoadHand Load

1stShot 1stShot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot1st

Shot1st

Shot HandLoad

HandLoad

2nd

Shot2nd

Shot2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nf Shot 2nf Shot

Hand LoadHand Load

1stShot 1stShot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

OvermoldedT-Bar

1st

Shot1st

Shot HandLoad

HandLoad

2nd

Shot2nd

Shot

PlasticSubstrate

TPSiV™Flow Pathof 1st Shot

Flow Pathof 2nd Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nf Shot 2nf Shot

Hand LoadHand Load

1stShot 1stShot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot1st

Shot1st

Shot HandLoad

HandLoad

2nd

Shot2nd

Shot2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nf Shot 2nf Shot

Hand LoadHand Load

1stShot 1stShot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

2nd Shot 2nd Shot

Hand LoadHand Load

1rst Shot 1rst Shot

OvermoldedT-Bar

1st

Shot1st

Shot HandLoad

HandLoad

2nd

Shot2nd

Shot

PlasticSubstrate

TPSiV™Flow Pathof 1st Shot

Flow Pathof 2nd Shot

Peel Strength tested byASTM D1876




TPEElongates

PeakBond

Strength

Peel starts

Peel ends

Bond Strength

Investigated substrates-PC (cohesive)-ABS (cohesive)-PVC (cohesive)-Nylons (adhesive)




Recommended Products for Overmolding on PC, ABS, …

TESTS ASTM UNITS 3040

-55A

3040

-60A

3040

-65A

3040

-70A

3040

-85A

3340

-55A

3340

-60A

3340

-65A

High UV ResistanceFast Cycle / OvermoldingProduct Feature

Hardness (10 sec) D-2240 Shore A 55 61 65 68 84 55 60 63

Specific Gravity D-792 1.150 1.150 1.150 1.150 1.150 1.150 1.150 1.150

Tensile Strength D-412 Mpa 5.0 7.0 11.0 11.7 11.9 3.0 3.0 4.3

Elongation at Break D-412 % 450 450 600 600 275 400 400 360

Tear Strength D-624 N/mm 23.0 30.0 45.0 47.0 49.0 15.0 15.0 22.0

Abrasion Resistance D-1044 mg loss 90 to 110 50 to 80 60 to 90 60 to 90 30 tot 60 120 to 130 120 to 130 120 to 130

Flammability UL 94 HB HB HB HB HB HB HB HB

High UV ResistanceFast Cycle / Overmolding




Xenon Testing, 5 days, 190 KJ/m2

02468

1012141618

Delta E*ab

3040-70A UVGray

3340-60A UVGray

3340-55A UVOrange

TPSiV® 3040-70A

TPSiV® 3340-60A

UV Color Stability




Application Example

§ Overmolded electronics:ØNokiaØGarminØMotorolaØOthers…




TPSiV® 3340-85A forautomotive interior

§ High flow for injection moulded thin layer§ Matte appearance, low gloss (advantage over TPU)

Reference is related to BMW testing methods

Properties referential Requirements Aliphatic TPU

TPSiV®

Visual aspect ( after heat ageing 80°C/10days)

GS 97034 > 4-5 grey scale Too glossy 5

Visual aspect (after cleaning: dry, wet, cockpit stray, car emulsion, glass cleaner)

GS 97034 > 4-5 grey scale 5 5

Scratch resistance Finger test 5N, 10N, 20N 20N visible

No visible

UV ageing VDA 75202 >7 (1 cycle) >4 (3 cycles)

7 4

8 5

CARB emission GS 97014-2 < 1mg 1.3 1 GP-MS Total VOC GS 97014-3 < 6500 µg/m3 5500 3000 Odor VDA 270 < 3 2 1 Color matching Black,

grey, beige Black, grey, beige




§ Contains no oils or plasticizers!§ Low COF and unique feel § Compatible with TPE-S or O-TPV

NEW ! - Polyolefin based Silicone Vulcanizates

Properties Units Standard TPSIV® 5300-A5501

NAT

TPSIV® 5300-A6502 NAT

Hardness Shore A ISO 868 54 65

Density ISO R1183 0.94 0.92

Spiral flow

cm MDA 179 15 24.8

Tensile Strength at 100%

MPa ISO 37 1.4 2.1

Tensile strength at 200%

MPa ISO 37 1.7 2.5

Tensile strength at break

MPa ISO 37 9.1 11

Elongation at break

% ISO 37 1400 820

Tear strength

kN/m ISO 34 37 35




§ Excellent property retention after heat aging for 1000 hrs at 110 C (typical automotive interior requirement, SAE J 2236)

Heat Aging Performance

-6.6-4.6% Retention

ISO 34Tear Strength

-16+1.6% Retention

ISO 37Elongation at Break

+2.7+14% Retention

ISO 37Tensile Strength

-2+3Change in Shore A

ISO 868

Hardness

TPSIV® 5300 A9003

TPSIV® 5300 A6502 EML1

UnitMethodProperty




§ Low swell is various fluids

Fluid Immersion Performance

5.061.5932.48.95Mineral Oil (200 cPs)

10.24.3211.47.58Acetone

0.240.180.920.19Ethyl Glycol

1.290.761.530.61Ethanol

1.200.261.441.43Brake Fluid

0.250.061.870.29Salt Water (20%)

192 hrs, wt%24 hrs, wt%192 hrs, wt%24 hrs, wt%

TPSiV® 5300 A9003 NATTPSiV® 5300 A6502 NATFluid




Summary – TPSiV®ØThermoplastic silicone vulcanizates are unique

patented materials that offer softness and flexibility without addition of oils or plasticizers– Low emission, low odor

ØVarious property profiles and advantages are gained by the choice of thermoplastic phase– Chemical resistance (nylon)– Low abrasion, scratch resistance, chemical

resistance, bonding to engineering resins (TPU)– Low COF, low fogging, hydrolytic resistance

(polyolefins)




Innovations From Multibase

Siloxane Enhanced Thermoplastics

Siloxane Masterbatch•Easy to handle additive

•Processing benefits•Reduce COF

•Improve scratch resistance

Multiflex® SiE•Siloxane enhanced TPE

•Excellent scratch resistance•Designed to meet auto

Interior requirements

TPSiV®•Patented Si TPV•3 product families

(nylon, TPU, polyolefin)•No plasticizers or oils




GC Contacts大中华区业务联系人

Krishna JoshiAsia Director

Remeng GuoSales

Guangzhou+86 13926024169

[email protected]

Eva BianMarketerShanghai

+86 [email protected]

Carrie ChenSales

Shanghai+86 13701889342

[email protected]

Kim LiMarketerShanghai

+86 [email protected]

Voly WangAETS

Shanghai+86 13816035982

[email protected]

Cocoo LuCustomer Service+86 21 [email protected]

GC Non-Auto Segment GC Auto Segment


mailto:[email protected]








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