Recent Developments in HighPerformance Thermoplastic Composites

Allan Murray, Ecoplexus Inc. Klaus Gleich, Southern Research Institute

ACCE 2003

Overview
Introduction
Materials Process Technology Applications

Why Use Composite Materials ?

Specfic Tensile Properties of Polymer Matrix Composites
4.5 4

3.5

Continuous Unidirectional Carbon Composites

Specific Modulus (x10 in.)

2.5

Glass & Carbon LFT & Continuous Other Fibers Varying Fiber Orientations

1.5

LFT Carbon Composites

1

Metals
LFT Glass Composites Continuous Uni-directional Glass Composites

0.5

Plastics
0 0

Specific Strength (x106 in.)

Thermoplastic Composites
Benefits Unique properties Vibration dampening Light weight Potential for low cost Shelf life Recyclable Durability
Fatigue Corrosion Toughness

Limitations Cost
Materials Manufacturing Tooling

Design know-how Manufacturing knowhow Use temperature

Thermoplastic Composites
Many Polymer Options Polyethylenes Polypropylenes Nylons Polycarbonates Acrylics Polyesters Polyimides Polysulfones Polyketones Polyurethanes the list continues Many Property Options ultimate strain > 100% no microcracking no delamination dampening no water uptake low dielectric properties melt formable weldable elastomeric - plastic - elastic behavior the list continues

Cost Challenge
Typical Aerospace Structure $50 - $100/lb and more
Materials: Carbon Fiber / Epoxy, Carbon Fiber / BMI, Carbon Fiber / PEEK Processes: Hand Lay Up

Costs in $/lb

Apply Materials and Processing Techniques being Developed for Automotive Applications to Aerospace Applications

Innovative Materials and Processes $5 - $20/lb Automotive Structures $1 - $3/lb

Materials: Thermoplastic Woven Sheets, Glass, Carbon and Kevlar Fiber, Engineering Polymers Processes: Co-Compression Molding, CoInjection Molding, Thermoforming

Materials: Glass Fiber / Polypropylene, SMC/BMC Processes: Compression Molding, Injection Molding

High-Performance Thermoplastic Composites

Properties are fiber dominated Oriented long or continuous fiber reinforcement High volume fiber fraction (up to 65% by volume) Key benefits:
Reducing thermal limitations (e.g. creep) caused by the TP matrix system Reducing costs and weight and retaining toughness, formability, weldability, short cycle times, recyclability benefits of the thermoplastic matrix

Thermoplastic Materials

Commercial Materials
GMT (Glass Mat Reinforced Thermoplastics) Pultruded Products
LFT (Long Fiber Reinforced Thermoplastics) CFT (Continuous Fiber Reinforced Thermopastics)

Wire coated products Commingled fibers Powder coated materials Film sticking Slurry processes

Long-Fiber Thermoplastic Composites

New Hot-melt Process Produces Fully Wet-out Composite Products Wide Range of Polymers and Fibers Continuous Tape and Rod Products Discontinuous Products with Any Fiber Length Glass Products <$1.00/lb Carbon Products <$8.00/lb

Pilot Production for Thermoplastic Composites

Short Fiber, Long Fiber and Continuous Fiber Composites

Typical short fiber thermoplastic material, granules with fiber length of approx. 2 to 4 mm, resulting fiber length in a part of approx. 0.4 mm

Long fiber thermoplastic material, pellets of and 1 fiber length, resulting fiber length in a part of approx. 4-6 mm in injection molding and approx. 20 mm in compression molding

Continuous reinforced thermoplastic material, tape used for woven sheets (thermoforming), filament winding or pultrusion

Typical Pultruded Prepregs

Fiber:
E-glass, S-glass, Carbon, Aramid, polymer fibers

Matrix:
PE, PP, PA (6, 6/66, 12, ), PET, PBT, PC, PEI, PPS, SMA, blends,

Fiber content:
20% - 60% standard, some up to 84%

Product forms:
Tape, pellets (0.5, 1), woven tapes more complex textile structures in development

Twintex - The Commingling Concept

Twintex Prepreg Temperature + Pressure

Consolidated Composite

Source: Vetrotex

Twintex The Commingling Concept

E Glass adapted sizing

Plastic filament Additives : - coupling agent - UV stabilizer - natural or black

Source: Vetrotex

Twintex The Manufacturing Process

Extruder Bushing

TP

Glass

Commingling

Roving
Source: Vetrotex

Twintex - Commingled Fiber Products

Specfic Tensile Properties of Polymer Matrix Composites

Fiber/matrix combinations:
E-glass/PP, E-glass/PET

4.5

Continuous Uni-directional Carbon Composites

3.5

2.5

Fiber content:
60 % and 75 % by weight

Twintex
LFT Carbon Composites Metals Twintex LFT Glass Composites

Glass & Carbon LFT & Continuous Other Fibers Varying Fiber Orientations

1.5

Product forms:
Roving, fabric, pellets

Continuous Uni-directional Glass Composites

0.5

Plastics

0 0 1 2 3 4 5 6

Limitations:
Matrix material must be usable for a fiber spinning process limitations in MFI/viscosity, additive type and additive content

Physical Property Data

Vetrotex Twintex
Matrix Reinforcement wt.% reinforcement Orientation Density g/cm3 Tensile Strength MPa Tensile Modulus GPa Flexural Strength MPa Flexural Modulus GPa Flexural Elongation % Compression Strength MPa Shear Strength MPa Impact CHARPY un-notched kJ/m2 J/cm3 Heat deflection temp. (1.82 MPa) oC Specific Tensile Modulus (x10^8in) Specific Tensile Strength (x10^6in) PP glass 60 1/1 1.5 350 15 280 13 2.5 140 22.5 220 8 159 0.4 0.9 PP glass 60 4/1 1.5 500/180 24/8 380/160 18/6.1 2.5/3.6 230/100 24/15 330/90 11/3 159 0.6 1.3 PP glass 75 1/1 1.75 420 21 340 17.5 2.5 160 22.5 300 10 159 0.5 1.0 PP glass 75 UD 1.75 700 38 400 32 2 170 22.5 445 15 159 0.9 1.6 PET glass 65 1/1 1.95 440 25 600 22.5 3.25 410 43 300 10 257 0.5 0.9

Source: Saint-Gobain Vetrotex, Twintex PP and PET Mechanical Properties (non standard)

Powder Impregnated Prepregs The Hexcel TowFlex-Technology

Fiber Creel Racks Fluidized Bed Powder Coating Chamber Puller Take-up System To Weaving To Tapes

IR Oven

To Pellets
Charged Resin Powder
Source: Hexcel

Hexcel TowFlex
Specfic Tensile Properties of Polymer Matrix Composites
4.5

Typical fibers:
Specific Modulus (x108 in.)

TowFlex
Glass Carbon
Glass & Carbon LFT & Continuous Other Fibers ` Varying Fiber Orientations

Carbon, E-glass, Sglass

3.5

Continuous Unidirectional Carbon Composites

2.5

Carbon Towflex

Typical resins:
PP, PA6, PPS, PEI, PEEK

1.5

LFT Carbon Composites Metals

Glass Towflex
LFT Glass Composites

Continuous Uni-directional Glass Composites

0.5

Plastics

Typical product forms:

Flexible Towpreg Woven fabric Braided Sleeving Unidirectional Tape

0 0 1 2 3
Specific Strength (x10 in.)
6

Physical Property Data

Hexcel Towflex
Material Resin Content (weight %) Fiber volume (volume %) Composite density (g/cc) Flexural Strength D790 (MPa) Flexural Modulus D790 (Gpa) Tensile Strength D3039 (MPa) Tensile Modulus D3039 (26 Gpa) Compression Strength D695 (MPa) Compression Modulus D695 (Gpa) Specific Tensile Modulus (x10^8in) Specific Tensile Strength (x10^6in) TF-CN6100 38 51 1.45 1517 107 1655 116 TF-CPP100 38 45 1.31 627 104 TFF-CN6- TFT-CN6100 100 38 51 1.45 827 55 821 66 38 51 1.45 1517 107 1655 116 TFF-CPP- TFT-CPP100 101 38 45 1.31 524 51 655 59 38 45 1.31 627 104 TFFTF-EGN6- TFF-EGN6- TFT-EGN6- TF-CPPS- TFF-CPPS- TFT-CPPS- TF-EGPP- TFFTFT-EGPP- EGPPS100 100 100 103 103 103 101 EGPP-100 100 101 34 46 1.77 1034 34 869 38 34 46 1.77 517 19 352 22 34 46 1.77 1034 34 869 38 43 51 1.59 1724 114 1655 110 43 51 1.59 869 58 869 64 43 51 1.59 1724 114 1655 110 30 46 1.64 600 32 30 46 1.64 386 17 290 18 30 46 1.64 600 32 35 51 1.96 531 27 385 24

945

579

441

945

172

579

634

372

634

1055

448

1055

558

248

558

379

110 3.2 4.6

110

58 1.8 2.3

110 3.2 4.6

49 1.8 2.0

110

34 0.9 2.0

26 0.5 0.8

34 0.9 2.0

112 2.8 4.2

63 1.6 2.2

112 2.8 4.2

37

21 0.4 0.7

37

31 0.5 0.8

Source: Hexcel Composites (March 2003) www.Hexcel.com

Process Technology

Current Composite Materials and Processes

Process Type of Application

Injection Molding

Low-Structural Components

Compression Molding Semi-Structural Components Thermoforming

Hand Lay Up / Vacuum Bag / Autoclave

Structural Components

Composite Performance versus Fiber Length

1.2 1.0

Fillers Short Fiber

Long Fiber Continuous

Relative Property Level

0.8 0.6 0.4 0.2 0.0 0.1 1 Length (mm) 10 100 Modulus Strength Impact Processibility

Source: OCF

The Long Fiber Advantage

Stress is transferred to the fibers - the structural members of the composite Long fibers create a skeletal structure within the molded article that resist distortion and provide unmatched strength, toughness, and overall performance
Source: Ticona

Continuous Fiber Advantage

In continuous oriented fibers the load is ultimately fully transferred to the fiber As a result tensile creep is limited in fiber direction

Manufacturing Processes for HighPerformance TP-Composites

Low volume manufacturing processes
Discontinuous processes
Thermoforming Thermoplastic S-RIM, RTM and VARTM Thermoplastic filament winding Vacuum bag molding Net shape preforming (modified P4)

Manufacturing Processes for HighPerformance TP-Composites

High volume manufacturing processes
Discontinuous processes
Injection molding with
LFT-pellets and concentrates (high performance resin/fiber combinations) Inline compounding (high performance resin/fiber combinations) Back molding / local reinforcement

Compression molding
LFT-pellets and concentrates (high performance resin/fiber combinations) Inline compounding (high performance resin/fiber combinations) Back molding / local reinforcement

Stamp forming
Preheated preforms Matched metal tools Potential to manufacture very thin sections (0.5 to 1 mm) Drapable material required

Continuous processes
Pultrusion LFT-extrusion

Materials Used For Liquid Molding Processes

Materials used for liquid molding processes
Cyclics Reactive nylon Fulcrum

Requirement for these materials

Viscosity less than 3000 mPa.s (cP) (better less than 1000 mPa.s (cP))

Cyclics
Cyclic form of PBT, PET, PC and others Only PBT commercial available Based on a ring shaped cyclical form One or two part systems Solid at room temperature low viscosity resin at elevated temperature (approx. 150 cP) Polymerize into the Polymer using a catalyst Isothermal process Typical process temperature: 180 200 oC

Reactive Nylon

For more information see presentation on Reactive Thermoplastic VARTM/RTM/S-RIM

Fulcrum
ISOPLAST matrix (Dow proprietary engineering thermoplastic polyurethane)
Thermoplastic viscosity issues addressed by ability to reverse polymerization in the melt stage, reducing viscosity to ensure good impregnation Repolymerizes upon cooling, retaining traditional thermoplastic composite advantages
High impact resistance Recyclability High elongation to failure (~2.5%, versus ~1-1.5% for thermosets) Zero-emissions processing

Fulcrum is the combination of ISOPLAST and pultrusion, with specific hardware design Provides 10-fold line speed improvement over typical thermoset pultrusion lines Allows thermoforming, welding, and overmolding of finished pieces

Thermoformed Fulcrum Components

Figures from Fulcrum Thermoplastic Technology; Making High-Performance Composite via Thermoplastic Pultrusion Dow Plastics, J anuary 2000

Physical Property Data

Dow Fulcrum
Matrix Reinforcement v.% reinforcement Density g/cm3 Tensile Strength MPa Tensile Modulus GPa Elongation at Break % Flexural Strength MPa Flexural Modulus GPa Longitudinal Flexural Strength MPa Longitudinal Flexural Modulus GPa Transverse Flexural Strength (MPa) Compressive Strength Compressive Modulus Specific Tensile Modulus (x10^8in) Specific Tensile Strength (x10^6in) Polyurethane Polyurethane Polyurethane Polyurethane glass glass glass glass 76.6 (wt.) 45 55 66 (wt.) 1.91 1.74 1000 980 45 43 2.5 1.5 1150 1050 48 40 1080 1340 35 44 151 122 151 790 430 440 46 35 35 0.9 2.1

45v.% and 55v.% data from Matweb.com 76.6wt.% and 66wt.% data from FULCRUM: Thermoplastic Composite Technology, Making High-performance Composite via Thermoplastic Pultrusion Dow Plastics, January 2000

Reactive Thermoplastic VARTM/RTM/S-RIM

Similar the thermoset process Reaction of at least two components creates a thermoplastic resin that can be melted, preshaped, welded, Low viscosity is required Possible materials: Nylon, TPU, C-PBT (Cyclics)

Problems Connected With Thermoplastic RTM

Reaction can be stopped or made incomplete by
Moisture Chemicals in fiber sizing
Most of the thermoplastic compatible sizings are not developed for such type of processes Availability of compatible sizings in form of fabric is very limited

Oxygen

Only limited support of material manufacturers Material costs (in case of c-PBT)

Thermoforming

Heat in Oven

Thermoforming Operation

Finished Product

Thermoforming
Weight performance:
Good weight/performance ratio for fabric reinforced sheets due to continuous fibers Reduced weight/performance ratio for extruded sheets depending on the resulting fiber length

Design flexibility:
Limited, especially for complex geometries Simulation tools available

Processability:
Stabilization against oxidation necessary Fiber disalignments with continuous fibers possible depending on geometry, material, tooling and process conditions

Recyclability:
High rate of production scrap (fixation) No direct recyclability Use in other processes like plastication of regranulation

TP S-RIM, RTM, VARTM

Weight/performance:
Excellent

Design flexibility:
Limited to preforming capability, flow length and flow behavior of the resin

Processability:
Reaction can be sensitive to moisture and fiber sizing

Recyclability:
Production scrap due to preforming step depending on preforming method No direct recyclability; can be used in other processes

TP Filament Winding
Weight/performance:
Excellent

Design flexibility:
Limited to symmetric parts that can be wound on a mandrel

Processability:
Higher oxidative stabilization required

Recyclability:
Low rate of production scrap No direct recyclability Scrap can be used in other processes

Vaccum Bag/ Hand Lay-Up

Weight/performance
Excellent due to continuous fiber reinforcement

Design flexibility
Limited to drapability and to the posibility of manually lay up

Processability
Higher void content due to low pressure consolidation Using autoclave to reduce void content Often fiber disalignments

Recyclability
High rate of production scrap possible depending on the size of the material sheets and the part geometry No direct recyclability Scrap can be reused in other processes

LFT-Injection Molding
Weight/Performance
Lower end of thermoplastic composites due to reduced fiber length in the final part Improvements possible by using local reinforcements (using pultruded sections, sheets or tapes of continuous composites localized strengthening and stiffening, reduction of warpage)

Design Flexibility
High Flow channels and positions of gates have to be carefully designed

Processability
Highly stable

Recyclability
Low production scrap rate Can be reused in the same process

Compression Molding
Weight/Performance
Medium Retaining fiber length gives excellent properties for a random oriented material, but is lower than using a fabric Local reinforcement or fabric reinforced GMT improve it (using pultruded sections, sheets or tapes of continuous composites localized strengthening and stiffening, reduction of warpage)

Design flexibility
High Special simulation tools available

Processability
Very stable process

Recyclability
Some production scrap due to trim operations Scrap can be added and reused in the same process (GMT only sheets can be reused in the same process, but not recommended)

Curv
Self-reinforced polypropylene Consists of hot compacted polypropylene fiber or tape
Surface of tape or fiber melts during compaction to form the matrix that binds the directional elements together

Oriented morphology provides over six-fold increase in tensile strength and nearly 5-fold increase in tensile modulus over isotropic polypropylene, with ~2% weight penalty Nearly doubles tensile strength of 40% random mat short glass polypropylene, with comparable modulus and 22% weight savings Elimination of glass reinforcement has several advantages:
Increased recyclability Reduced weight Lower temperatures and pressures for thermoforming Reduced irritation in the workplace High strain to failure, with good impact strength

Data from A New Self-Reinforced Polypropylene Composite Jones, Renita S. and Derek E. Riley

Physical Property Data

Curv
Density g/cm3 Tensile Modulus GPa Tensile Strength MPa Heat deflection temperature oC Notched Izod impact J/m Thermal expansion / oC x 10-6 Specific Tensile Modulus (x10^8in) Specific Tensile Strength (x10^6in)
from BP document A New Self-Reinforced Polypropylene Composite Jones, Renita S. and Derek E. Riley, 2002

455 KPa 1820 KPa +20oC -40oC

0.92 5 180 160 102 4750 7500 41 0.2 0.8

Pultrusion
Weight/performance
Good to excellent due to continuous reinforcement

Design flexibility
Low design flexibility Limited to constant cross sections, but can be shaped (pull/press)

Processability
Only limited experience available Depends on stabilization of the material as well as used material form

Recyclability
Low rate of production scrap expected No direct recyclability Can be used in other processes

LFT-Extrusion
Weight/performance
Medium weight performance Depends on retaining fiber length

Design flexibility
Low design flexibility Limited to constant cross sections Can be post shaped or pull formed

Processability
Not a lot of experience A stable process is expected using the right die design

Recyclability
Low rate of production scrap Can be reused in the same process

Economics
Process Thermoforming TP S-RIM, RTM, VARTM Cycle Time Medium Medium to long, up to several minutes Tooling Costs Low VARTM: low, single sited tool RTM: low to medium S-RIM: Medium Low to medium Low, single sided tool Scrap Rate High Depends on preforming technique; often high for complex shaped parts Low Medium to high Overall Economics Good for low volume production with no or limited thickness variation Good for low volume production

TP Filament Winding Vacuum Bag/ Hand Lay-up

Medium to long, depending on number of tapes and heating system Long; manual preparation can be hours for a part

Good for symmetrical parts in low to medium volume production Good for prototyping. Not recommended for production scale.

Injection Molding -LFT -ILC

Compression Molding -GMT -LFT -ILC Pultrusion Extrusion

Short cycle times; typically 50 80 sec.

Short cycle times; typically 35 60 sec.

High; steel tools with ejector pins and slides

High; steel tools with ejector pins and slides

Very low

Excellent for high volume production

Low medium depends on cut outs. Scrap can be reused Low Low

Excellent for high volume production of large components

Continuous process; not enough experience on throughput Continuous process; throughput mainly limited by cooling capacity of calibration die

Medium Medium to high

Limited experience available Expected to be cost effective for profiles

Applications

Applications For High-Performance Thermoplastic Composites

Aerospace and defense:
Radomes, wing and fuselage sextions, anti-ballistics

Infrastructure and Construction

Window profiles, rebar, beams, structures, composite bolts

Consumer / recreational
Orthotics, safety shoes, sporting goods, helmets, personal injury protextion, speaker cones, enclosures, bed suspension slats

Auto and truck

Bumper beams, skid plates, load floor, seat structures

Transportation
Railcar structure, body structure and closures

Energy production and storage

Oil and gas structura tube, wind turbines

BMW M3 Bumper Beam

- Beam and crush columns manufactured using Hexcel TowFlex PA6 - Parts welded by high frequency vibrational welding - 2 versions:
Standard M3 based on glass fiber reinforcement (approx. 40 cars / day) M3 CSL (limited to 1600 total) using Carbon fiber reinforcement

Source: Jacob Kunststofftechnik GmbH & Co. KG www.jacob-kunststofftechnik.de

Helmets
Military helmet for Norwegian Army Made by Cato Composites 50,000/year TEPEX antiballistic 302 Aramid/PA6 continuous reinforcement
Source: Bond-Laminates GmbH www.bond-laminates.com

White water helmet Made by Prijon TEPEX dynalite 701 Glas, Carbon, Aramid/PA6.6 Continuous reinforcement
Source: Bond-Laminates GmbH www.bond-laminates.com

Aircraft Applications
Fixed wing leading edge for Airbus Fokker Special Products/Airbus TEPEX semipreg 107 Non fully consolidated, flexible layers of continuous fiber reinforced thermoplastics Glass/PPS Wing access panel for Airbus Fokker Special Products/Airbus TEPEX semipreg 207 Non fully consolidated, flexible layers of continuous fiber reinforced thermoplastics Carbon/PPS

Mine Sweeper Armouring

Made from TEPEX antiballistic 302 Aramid/PA6 Continuous reinforced Made by Kvaerner
Source: Bond-Laminates GmbH www.bond-laminates.com

Safety Shoes
Composite Toecap
History:
Composite Toecaps were manufactured in the past using GMT with 50% fiber glass content Changing the regulations, this was not sufficient to meet the 200 J requirement

Newer development:
65 g / piece (metal 105 g /piece) 200 J resistance Made from Twintex and LFT, 60% fiber glass, PP Manufactured by Security Composites Ltd. (UK)

Others
GF/PP composite tank Produced by Covess (Belgium) using Twintex and GMT, welded out of 3 pieces and designed to withstand pressure to 100 bar Evaluation of thermoplastic composite rebars made with the Fulcrum process Thermoplastic composite bolts made by Clickbond Inc. using a thermoforming approach Loudspeaker cones, electronic housings and lightweight carbon fiber reinforced structural applications for the automotive industry made by Centrotec AG Prototype of a continuous fiber reinforced PP boat (JEC 2000 Innovation Award) made from Twintex using vaccum bag molding. Developed by Halmatic, Ltd. Golf club shafts made from PPS/carbon prepreg tape with 66 68% fiber content. Multi-step operation including a table rolling, a compression and an oven consolidating step. Manufactured by Phoenixx TPC.

The Future of Thermoplastic Composites

Will go to more structural applications using different technical thermoplastics in combination with glass, carbon and synthetic fibers. Will replace metal applications and reduce weight. Improved processing methods will be developed and applied.

Conclusions
High-performance thermoplastic composites with fiber-dominated properties are a way to
lower cost higher performance short cycle times Recyclability

Pre-impregnation can improve wet out and performance over commingled prepregs Materials and manufacturing methods are available

Acknowledgements

Aaron Brice and Erik Nolte, Stewart Automotive Research, LLC