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May 05, 2008 Thermoplastic Polyimide (TPI ... Flipbook PDF
Thermoplastic Polyimide (TPI)-Polyetheretherketone (PEEK) Blends Kapil C. Sheth, Robert R. Gallucci SABIC Innovative Pla
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May 05, 2008
Thermoplastic Polyimide (TPI)Polyetheretherketone (PEEK) Blends Kapil C. Sheth, Robert R. Gallucci SABIC Innovative Plastics, Mt.Vernon, IN, USA
Gurulingamurthy Haralur GE Global Research, Bangalore, INDIA
Outline • Introduction – Amorphous & Crystalline Resins, Blends • New Thermoplastic Polyimide (TPI) – EXTEM* UH Resin • Why TPI-PEEK™ Blends? • Processing • Properties • Markets & Applications • Summary
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* Trademark of SABIC Innovative Plastics IP BV PEEKTM is trademark of Victrex plc
Material Selection
Performance
Imidized Materials
PBI PI PAI
High Performance Polymers
PPSU PEI PSU
Engineering Plastics
PC PPO PS
Commodity Plastics
ABS
Amorphous
Amorphous Benefits
LCP PPS PA POM PP PE
Crystalline
Crystalline Benefits
• Higher glass transition
• Chemical resistance
• Strength & Dimensional
• Processability and
stability (up to Tg) 3
PEEK
Better Flow
Amorphous Vs. Crystalline Polymers (Tg)cryst
Amorphous
(Tg)amor
Tm Onset
Dimension Change
Modulus
Specific Heat
Crystalline
TEMPERATURE
SEMI-CRYSTALLINE
Tg and Tm Transitions Affect • Mold Shrinkage & warpage • Dimensional Stability • Mechanical Properties at temperature 4
(Amorphous + Crystalline) Polymers – Blends Amorphous Benefits
Crystalline Benefits
• Higher glass transition
• Chemical resistance
• Strength & Dimensional
• Processability and
stability (up to Tg)
Better Flow
BLENDS
Commercial – Engineering Resins • Polyphenylene oxide (PPO) – Polyamide (PA) • Polycarbonate (PC) – Polybutylene terephthalate (PBT) Commercial – High Performance Resins • Polyphenylene sulfide (PPS) – Polyetherimide (PEI) • Polybenzimidazole (PBI) – Polyetheretherketone (PEEK) 5
Polyetheretherketone (PEEK) Resin Semi-Crystalline Thermoplastic Tg ~ 143°C Tm ~ 340°C
FEATURES: • High temperature performance
10000 PEEK
• Wear resistance
• Hydrolysis resistance
Modulus
• Chemical resistance
30% GF-PEEK
1000
• Processability / Flow 100
LIMITATION:
0
100
200
Temperature (°C)
• Performance over its Tg
6
300
Aromatic Polyimides FEATURES: • High heat resistance (high glass transition) • Mechanical properties • Electrical properties • Thermal stability • Chemical resistance CHALLENGES: • Melt Processability – mostly solvent based / thermoset like development of Thermoplastic Polyimide (TPI) materials
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Examples of Commercial Polyimides Kapton** film, Apical*** film – Solvent Cast Vespel** – Direct Formed Stockshapes Tg > 360ºC Tm – ND (25-50% crystallinity in Vespel) Thermoset-like behavior
Aurum**** resin Tg ~ 250ºC Tm ~ 380ºC Post-molding Annealing Required to Crystallize
Ultem* Polyetherimide resin Tg ~ 217ºC Amorphous Thermoplastic
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** Trademark of DuPont *** Trademark of Kaneka Corp **** Trademark of Mitsui Chemicals
ULTEM Polyetherimide Resin Amorphous thermoplastic Tg ~ 217°C
10000
• High heat resistance – strength & creep at high temperature
Modulus
FEATURES:
1000
• Dimensional stability • Inherent flame retardancy
ULTEM 1000 ULTEM 2300 100 0
• High limiting oxygen index (LOI)
9
100
200
Temperature (°C)
300
Blend Opportunity? Unfilled
Glass-filled 10000
Modulus
Modulus
10000
1000
1000
ULTEM 1000
ULTEM 2300
PEEK
30% GF-PEEK
100
100 0
100
200
Temperature (°C)
300
0
100
Temperature (°C)
Interesting Crystalline-Amorphous Blend Opportunity!! 10
200
300
ULTEM-PEEK Blends 10000 PEEK
Modulus (MPa)
PEEK-ULTEM (50-50)
1000
100
10 50
100
150
200
250
300
350
Temperature (ºC)
• ULTEM-PEEK blends are completely miscible one-phase single Tg across the entire composition range, blend Tg approximated well by the Fox equation slows down PEEK crystallization immensely Well Behaved Blends – Commercially Uninteresting 11
Ref: J.E.Harris & L.M.Robeson, J Appl Polym Sci, 1877 (1988)
New TPI Resins - EXTEM Portfolio Imidized Materials
PBI
PBI PI
Performance
PAI
High Performance Polymers Engineering Plastics Commodity Plastics
PPSU PEI PSU PC
PPO PS ABS
Amorphous
PI
Expanding High Performance
PEEK LCP PPS
PAI
EXTEM Resins
PA POM
PEI PPSU PES PSU HH PC
PP PE
Crystalline
Amorphous
PEEK PA46 PPA PTFE LCP
PPS
Crystalline
Extem UH Family
Extem XH Family
• Neat TPI resin & blends
• Glass Transition up to 267°C
• Glass Transition up to 311°C
• Enhanced high temp creep and strength
• Excellent chemical resistance
• High flow for thin-wall, complex parts
• High Continuous use temperatures
Additional Extem Resin Features…all families • Exceptional Dimensional Stability • High strength, stiffness and creep resistance at elevated temperatures • Inherent Flame Retardancy & High Limiting Oxygen Index • Outstanding Flame Smoke & Toxicity
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AS-MOLDED Ultra-high Performance with True Thermoplastic Melt Processability
Extem UH Amorphous Blends Portfolio Product Family
Filler Type
Flow
HDT @ 66 psi
Standard Flow
263°C
High Flow
260°C
Standard Flow
~260°C
Filler %
Grade Name UH1006 (M)
(505°F)
Unfilled
Extem UH Series
TPI Resin & Amorphous TPI Blends
Glass Filled
(500°F)
10-30%
Underdevelop ment in ‘08
Mineral Filled Thru LNP Carbon Fiber &/or Lubricated
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UH1016 (M)
(500°F)
Standard Flow
>250°C (480°F)
Rapidly Growing Product Family
0-30%
Underdevelop ment in ‘08
10000
1000
Storage Modulus (MPa)
Storage Modulus (MPa)
EXTEM UH – PEEK Blends
2X @200C PEEK-TPI PEEK
10000
6.5X @200C 1000
TPI-PEEK
PEEK 100
100 0
50
100
150
200
250
Temperature (° °C)
300
350
0
50
100
150
200
250
300
350
Temperature (° °C)
•Extem UH - PEEK blends are immiscible two-phases, two Tg’s fast PEEK crystallization as-molded properties
Improved High Temp Load Bearing & Dimensional Stability in PEEK 14
Extem UH Crystalline Blends Products
Unfilled
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Commercial Name
Description
Max 1000
PEEK-TPI Blend
Max 2000
TPI-PEEK Blend
Spiral Flow 120% 400°C (750°F) 1,378 bar (20,000 psi)
Flow Length
100%
PEEK
80% PEEK-TPI
60% 40%
TPI-PEEK
20% 0% 1
1.5
2
2.5
3
Part Thickness (mm)
16
3.5
4
Melt Processing 10000
10000 380ºC 400ºC
TPI-PEEK
415ºC 1000
100
10 100
1000
10000
Maximum Moisture Content Drying Temperature Drying Time Melt Temperature Nozzle Temperature Front - Zone 3 Temperature Middle - Zone 2 Temperature Rear - Zone 1 Temperature Mold Temperature Back Pressure Screw Speed Shot to Cylinder Size
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% °C hr °C °C °C °C °C °C bar rpm %
430ºC
1000
100 100
1000
10000
Shear Rate (1/s)
Shear Rate (1/s)
PEEK-TPI 0.02 175 6 390-405 385-400 385-400 380-395 370-380 175-200 3-5 30-50 40-70
400ºC 415ºC
Viscosity (Pa-s)
Viscosity (Pa-s)
PEEK-TPI
TPI-PEEK 0.02 175 6 400-415 395-415 395-415 390-405 380-390 175-200 3-5 30-50 40-70
• Typical high performance resin equipment 800°F (427°C) temperature capability high temperature (150-200°C) molds
Melt Processable on Standard Equipment for High Performance Resins
Datasheet Comparison ASTM Testing PROPERTY
Unit
PEEK
PEEK-TPI
TPI-PEEK
Tensile Modulus, 23°C Tensile Strength, 23°C Flexural Modulus, 23°C Flexural Strength, 23°C
MPa MPa MPa MPa
4300 100 4000 170
4200 90 3800 160
4100 95 3800 170
Izod Impact, unnotched, 23°C Izod Impact, notched, 23°C
J/m J/m
NB 59
640 32
1230 48
CTE, 23°C to 125°C, flow HDT, 0.45 MPa, 3.2mm (as-molded) HDT, 1.82 MPa, 3.2mm (as-molded)
ppm/°C °C °C
47 156 146
44 260 160
39 280 230
Density Limiting Oxygen Index (LOI)
g/cc %
1.32 35
1.34 41
1.38 42
AS MOLDED Properties (NO CURING / NO ANNEALING) 18
Dimensional Stability
Dimension Change (%)
3.5 3.0
PEEK PEEK-TPI
2.5
TPI-PEEK
2.0 1.5 1.0 0.5 0.0 0
50
100
150
200
Temperature (°C) 19
250
300
High Temperature Modulus
Modulus (MPa)
10000
Increasing TPI Content
TPI-PEEK
1000
PEEK-TPI PEEK-ULTEM 100 50
100
150
PEEK 200
Temperature (°C) 20
250
300
High Temperature Strength
Flexural Strength (MPa)
160 PEEK
140
PEEK-TPI
120
TPI-PEEK
100 80 60 40 20 0 23°C
21
150°C
200°C
250°C
High Temperature Creep
Strain (%)
10
200°C, 5 MPa
1 PEEK PEEK-TPI TPI-PEEK 0.1 1.0E-02
1.0E-01
1.0E+00 Time (Hours)
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1.0E+01
1.0E+02
High Temperature Compressive Strength 300
300
23°C
PEEK-TPI
TPI-PEEK Stress (MPa)
Stress (MPa)
TPI-PEEK 200
100
0
200
100
0
0
10
20
30
40
50
0
10
Strain (%)
30
40
50
300
PEEK-TPI
PEEK-TPI
200°C
250°C
TPI-PEEK
TPI-PEEK 200
Stress (MPa)
Stress (MPa)
20
Strain (%)
300
100
0
200
100
0
0
10
20
30
Strain (%)
23
150°C
PEEK-TPI
40
50
0
10
20
30
Strain (%)
Compressive Strength (MPa) at 10% Strain 23°C 150°C 200°C 250°C 109 43 27 21 PEEK-TPI 109 55 44 33 TPI-PEEK 0% 28% 65% 62% ∆ (%)
40
50
Chemical Resistance - Example NORSOK oil + sour gas test: Oil immersion @ 200°C for 20 days with H2S gas cap 120% PEEK-TPI TPI-PEEK
110% 100%
109%
105%
97%
90%
84%
80% 70% 60%
58% 46%
50% 40% Tensile Strength
Elongation
Flex. Mod.
• PEEK-TPI outperforms TPI-PEEK • In some media & conditions, PEEK-TPI performance is close to PEEK
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Target Markets & Applications Industrial
Aerospace / Military
• Analytical Equipment
• Composites
• Bearings & Gears
• Connectors
Semicon
Oil & Gas
• Chip Trays
• Down-hole connectors
• Test Sockets
• Seal rings
• Wafer Carriers
High Temperature Mechanical Performance & Dimensional Stability 25
Extem UH – PEEK Blends: Summary • Blends leveraging properties of highest heat amorphous TPI and high performance PEEK resins • Thermoplastic processability on standard equipment • As-molded properties, no curing / annealing required • High temperature strength, creep & dimensional stability • Outstanding chemical resistance • Excellent flame resistance and LOI
ULTRA-HIGH PERFORMANCE MATERIALS FOR DEMANDING APPLICATIONS
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THANK YOU…… Hard Disk Drives
Defense
Automotive Lighting
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Healthcare
Electrical
Telecommunications / Satellites
Wire & Coatings
Consumer
Aerospace & Transportation
Automotive Under the Hood
High Performance Films
Disclaimer:
Disclaimer for product literature and pitches: THE MATERIALS, PRODUCTS AND SERVICES OF SABIC INNOVATIVE PLASTICS HOLDING BV, ITS SUBSIDIARIES AND AFFILIATES (“SELLER”), ARE SOLD SUBJECT TO SELLER’S STANDARD CONDITIONS OF SALE, WHICH CAN BE FOUND AT http://www.sabic-ip.com AND ARE AVAILABLE UPON REQUEST. ALTHOUGH ANY INFORMATION OR RECOMMENDATION CONTAINED HEREIN IS GIVEN IN GOOD FAITH, SELLER MAKES NO WARRANTY OR GUARANTEE, EXPRESS OR IMPLIED, (i) THAT THE RESULTS DESCRIBED HEREIN WILL BE OBTAINED UNDER END-USE CONDITIONS, OR (ii) AS TO THE EFFECTIVENESS OR SAFETY OF ANY DESIGN INCORPORATING SELLER’S PRODUCTS, SERVICES OR RECOMMENDATIONS. EXCEPT AS PROVIDED IN SELLER’S STANDARD CONDITIONS OF SALE, SELLER SHALL NOT BE RESPONSIBLE FOR ANY LOSS RESULTING FROM ANY USE OF ITS PRODUCTS OR SERVICES DESCRIBED HEREIN. Each user is responsible for making its own determination as to the suitability of Seller’s products, services or recommendations for the user’s particular use through appropriate end-use testing and analysis. Nothing in any document or oral statement shall be deemed to alter or waive any provision of Seller’s Standard Conditions of Sale or this Disclaimer, unless it is specifically agreed to in a writing signed by Seller. No statement by Seller concerning a possible use of any product, service or design is intended, or should be construed, to grant any license under any patent or other intellectual property right of Seller or as a recommendation for the use of such product, service or design in a manner that infringes any patent or other intellectual property right. SABIC Innovative Plastics is a trademark of Sabic Holding Europe BV *Trademark of SABIC Innovative Plastics IP BV • Cycolac, Cycoloy, Extem, Geloy, Lexan, Lexan SLX, Lexan EXL, Noryl, Ultem, Valox, Verton, Visualfx, Xenoy, Xylex and LNP are trademarks of SABIC Innovative Plastics IP BV.
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