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Recent Developments in High-Performance Thermoplastic Composites. Allan Murray, Ecoplexus Inc. Klaus Gleich, Southern Research Institute ACCE 2003. Introduction Materials Process Technology Applications. Overview. Why Use Composite Materials ?. Benefits Unique properties

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recent developments in high performance thermoplastic composites

Recent Developments in High-Performance Thermoplastic Composites

Allan Murray, Ecoplexus Inc.

Klaus Gleich, Southern Research Institute

ACCE 2003

overview
Introduction

Materials

Process Technology

Applications

Overview
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 know-how

Use temperature

Thermoplastic Composites
thermoplastic composites5
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

Thermoplastic Composites
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

High-Performance Thermoplastic Composites
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

Commercial Materials
slide10

Long-FiberThermoplastic 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
short fiber long fiber and continuous fiber 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 ½” 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

Typical Pultruded Prepregs
twintex the commingling concept
Twintex - The Commingling Concept

Consolidated Composite

Twintex® Prepreg

Temperature + Pressure

Source: Vetrotex

twintex the commingling concept15
Twintex – The Commingling Concept

E Glass

adapted sizing

Plastic filament

Additives :

- coupling agent

- UV stabilizer

- natural or black

Source: Vetrotex

twintex the manufacturing process
Twintex – The Manufacturing Process

Extruder

Bushing

Glass

TP

Commingling

Roving

Source: Vetrotex

twintex commingled fiber products
Fiber/matrix combinations:

E-glass/PP, E-glass/PET

Fiber content:

60 % and 75 % by weight

Product forms:

Roving, fabric, pellets

Twintex - Commingled Fiber Products

Twintex

  • Limitations:
    • Matrix material must be usable for a fiber spinning process  limitations in MFI/viscosity, additive type and additive content
physical property data
Vetrotex TwintexPhysical Property Data

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

powder impregnated prepregs the hexcel towflex technology
Powder Impregnated Prepregs – The Hexcel TowFlex-Technology

Fluidized Bed Powder Coating Chamber

Fiber Creel Racks

Take-up System

Puller

IR Oven

To Weaving

To Tapes

To Pellets

Charged Resin Powder

Source: Hexcel

hexcel towflex
Typical fibers:

Carbon, E-glass, S-glass

Typical resins:

PP, PA6, PPS, PEI, PEEK

Typical product forms:

Flexible Towpreg

Woven fabric

Braided Sleeving

Unidirectional Tape

Hexcel TowFlex

TowFlex

Glass Carbon

physical property data21
Hexcel TowflexPhysical Property Data

Source: Hexcel Composites (March 2003)

www.Hexcel.com

composite performance versus fiber length
Composite Performance versus Fiber Length

Fillers

Short Fiber

Continuous

Long Fiber

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

The Long Fiber Advantage

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

Continuous Fiber Advantage
manufacturing processes for high performance 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 High-Performance TP-Composites
manufacturing processes for high performance tp composites28
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

Manufacturing Processes for High-Performance TP-Composites
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))

Materials Used For Liquid Molding Processes
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

Cyclics
reactive nylon
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

Fulcrum

Thermoformed Fulcrum Components

Figures from “Fulcrum Thermoplastic Technology; Making High-Performance Composite via Thermoplastic Pultrusion” Dow Plastics, January 2000

physical property data33
Dow FulcrumPhysical Property Data

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, pre-shaped, welded, …

Low viscosity is required

Possible materials: Nylon, TPU, C-PBT (Cyclics)

Reactive Thermoplastic VARTM/RTM/S-RIM
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)

Problems Connected With Thermoplastic RTM
thermoforming

Finished

Product

Thermoforming

Heat in Oven

Operation

Thermoforming
thermoforming37
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

Thermoforming
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 S-RIM, RTM, VARTM
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

TP Filament Winding
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

Vaccum Bag/ Hand Lay-Up
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

LFT-Injection Molding
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)

Compression Molding
slide43
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

Curv

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

physical property data44
CurvPhysical Property Data

from BP document “A New Self-Reinforced Polypropylene Composite” Jones, Renita S. and Derek E. Riley, 2002

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

Pultrusion
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

LFT-Extrusion
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

Applications For High-Performance Thermoplastic Composites
bmw m3 bumper beam
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
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
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
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)

Safety Shoes
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.

Others
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.

The Future of Thermoplastic Composites
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

Conclusions