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New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA Dr. Frank Henning Oliver Geiger

New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

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Page 1: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

New Long Rayon Fiber Reinforced ThermoplasticsUtilizing the LFT-D Process

ACCE, 12.-14. September 2005, Troy, USA

Dr. Frank HenningOliver Geiger

Page 2: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 2

Motivation for a LFT direct process

Semi-finished product

manufacturer

Semi-finished product

manufacturing GMT orLFT-G

Semi-finishedproduct

processing

Glassfibers

Additives

Polymerresin

+

MolderLFT

composite part

LFT direct process

LFT direct process

In-House Recycling

Economical advantageFlexible material composition

Page 3: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 3

Longfiber Reinforced Thermoplastics – New Material Development

Requirements:Mechanical propertiesMaterial homogeneityReproducibilityMaterial data forpart designReduction of localmaterial anisotropy

Definition long fibers:Injection molding:>1 bis 5 mmCompression molding:10 bis 40 mm Toughness

Stre

ngth

/ S

tiffn

ess

Rubber

Short fiber reinforced

plasticsLong fiberreinforced

plasticsParticle filled

plastics

Non reinforcedplastics

Toughness

Stre

ngth

/ S

tiffn

ess

Toughness

Stre

ngth

/ S

tiffn

ess

Rubber

Short fiber reinforced

plasticsLong fiberreinforced

plasticsParticle filled

plastics

Non reinforcedplastics

Page 4: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

2002-09-12 - Page 4

In-line compounder

LFT die

Conveyor belt forLFT strand

HydraulicPress

Provision of rovings

Mixing extruder

Fully automized material handling

AVK-TV Innovationspreis

2001

LFT-D-ILC Base Equipment

Page 5: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 5

Materialproperties

Fiber diameter

Fiber length

Void contentProperties of polymer

Fiber-matrixdispersion

Fiber-matrixadhesion

Fiber orientation

Fiber content Fiber properties

Material development tailored to the application

Page 6: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 6

Adjustment of material properties based on requirements

Possibility of selection of polymer and fiber type

Company specific Know-How – Optimized for customer or applications

Material combination just looks complex – well managable

Individual intensity of backward integration possible (masterbatch)

Superset line control ensures safe and reproducible production

Material Development Flexibility

Page 7: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 7

Compression molding

LFT strand

Mixing extruder (Twinscrew compounder)

IL-Compounder

Presse

Polymers:- Polypropylen- Nylon: PA 6, PA 6.6 etc.- Polyethylenterephtalat (PET)- Styrenic Copolymers: ABS, ASA, SAN etc.- Blends

Reinforcements:- Glass fibers- Natural fibers- Carbon fibers- Synthetic fibers- cellulotic fibers

Flexibility for company specific solutions

Page 8: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 8

Flexibility in selection of matrix resins

60

78

112126

0

20

40

60

80

100

120

140

PP/GF30 ABS/GF30 PA/GF30 PET/GF30

Advanced LFT based on Engineering ThermoplasticsTe

nsile

str

engt

h [M

Pa]

Long fiber reinforced Engineering Plastics offer new applications for LFT´s

Page 9: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 9

Nor

m. P

rope

rties

[ -]

Fiber length l [mm]

1.0

0.8

0.6

0.4

0.2

0.10

100101

95 % level

Source:Schemme, SKZ-Fachtagung „Karosseriekonzepte mit Kunststoffen, Würzburg 2002 Based onThomason & Vlug

Stiffness: Fiber length 0,1 to 1mm Fillers and short fibers

Strength: Fiber length 1 to 10mm Short fibers

Impact: Fiber length > 10mm Long fibers

Strength

Impact

Stiffness

Nor

m. P

rope

rties

[ -]

Fiber length l [mm]

1.0

0.8

0.6

0.4

0.2

0.10

100101

95 % level

Nor

m. P

rope

rties

[ -]

Fiber length l [mm]

1.0

0.8

0.6

0.4

0.2

0.10

100101

95 % level

Source:Schemme, SKZ-Fachtagung „Karosseriekonzepte mit Kunststoffen, Würzburg 2002 Based onThomason & Vlug

Stiffness: Fiber length 0,1 to 1mm Fillers and short fibers

Strength: Fiber length 1 to 10mm Short fibers

Impact: Fiber length > 10mm Long fibers

StrengthStrength

ImpactImpact

StiffnessStiffness

Distribution of Fiber Length – Influence on Material Properties

Page 10: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 10

Mechanical properties DAM @ 23°C

9800

8437

10081

187

142

179

3 2.6 2.10

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

ZYTEL 70G30HSL BK39B, moulded ZYTEL 70G30HSL BK39B, machined N66 LFT 30%, machined0

20

40

60

80

100

120

140

160

180

200

E-modulusStress @ breakStrain @ break

+20%- 20%

Compression Molding(LFT-D)

Injection Molding

CAMPUSDatabase

Tensile Properties of Nylon PA6.6/GF30 @ 23°C

Page 11: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 11

• LFT brings a clear benefit in notched impact• Notched Charpy performance is trippled

KJ/m²

Notched Charpy @23°C

0

10

20

30

40

50

60

70

80

90

30% by weight glass

Injection molding

LFT-D Compression molding

50% by weight glass

Injection Molding

Compression Molding(LFT-D)

Notched Charpy Properties of Nylon PA6.6 and GF50 @ 23°C

Page 12: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 12

• LFT brings a clear benefit in multi-axial impact

2mm specimen thickness

Ene

rgy

(J)

Multiaxial Impact @ 23°C

0

500

1000

1500

2000

2500

3000

3500

70G30reference

Resin 1 Resin 2

Forc

e (N

)

0

2

4

6

8

10

12

14

16

Max. Force (N)Energy (Fmax) (J)Energy (J)

PA6 LFT 30% PA6 LFT 40%

InjectionMolding

CompressionMolding(LFT-D)

Multi-axial Impact of Nylon PA6.6/GF30 and GF40 @ 23°C

Page 13: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 13

Zytel®70G30

PP LFT 30%

Zytel®LFT 30%

Zytel®LFT 50%

Zytel®HTN LFT 50%

Zytel®75LG50HSL BK031

264°C255°C163°C0°C

Zytel®70G50 258°C

259°C

105 - 150°C

180 - 220°C

200 - 250°C

Engineering Polymers

Heat Deflection Temperature @ 1.81 MPA ISO 75-A

Page 14: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 14

PA66 LFT 50%

PA66 LFT 30%

70G35HSLX

PA66 LFT 50%

PA66 LFT 30%

70G35HSLX

• The LFT in-flow tensile modulus is 20% higher compared to 70G35• After 1000 hours, the LFT in-flow tensile modulus is 50% higher • LFT 50% brings another performance increase

Creep Measurements @ 130°C, 4000 MPa

Page 15: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 15

Goal: Modification of LFT-D-ILC process technology developed for the in-linecompounding of glass fibers for the direct incorporation of cellulose regeneratedfibers

Plastifikate

Twin-Screw Mixing Unit

IL-Compounder

Polymer Additives

Compression Molding

FiberRovings

LFT-D Material Development– Cellulose Fiber Reinforced PP

Page 16: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 16

Reduced density compared to glass fibers weight reduction: rCRF= 1,5 kg/dm³ versus rGF=2,5 kg/dm³

High elongation at break results in high impact resistance especially at low temperatures (T = -30°C)

Low sensitivity regarding splintering - qualification of RAYON fiber reinforced composites for automotive interior applications

Combination with biopolymers enable the in-line compounding of 100% renewable LFT

Reproducible material properties and continuous rovings compared to natural grown fibers

Advantages of engineering regenerated cellulotic fibers

Page 17: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 17

Cellulose is the most commonly existing natural product with an annual growth rate of approx. 1010 t

Cellulose = Poly (β-(1,4)-Anhydroglucose) Basic module: AGU = C6H10O5 (chem.),

Cellobiose (phys.)

Physical structure• semi-cristalline (Polymorphy)• fibrillar morphology (streched polymer chain)• physical structure still in discussion

Major problem: structural diversity – distinctive structural imperfection

Problems of industrial processing• Cellulose is not fusible• Cellulose is not soluble in common solvants• Cellulose first has to be isolated (chemical pulp manufacture from wood)

Chemical Structure: clarified by Haworth 1928

Cellulose

Quelle: Fraunhofer IAP

Page 18: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 18

Properties of hemp yarns of different origin

Material Source Yarn count Strenght Elongation Modulus

Provider tex cN/tex % cN/tex

Hanf 2.4/1 Rohemp 357.8 12.2 3.88 593

Hanf 5/1 Rohemp 205.3 12.9 3.80 518

Hanf 10/1 Rohemp 99.5 29.8 3.15 1148

Hanf 10/1 bleached Rohemp 75.8 17.7 1.95 1154

Hanf 10/1 Hattorf 93.6 17.3 2.77 767

Hanf 5/1 Polen 228.4 26.4 3.18 1349

Hanf 7.1/1 Polen 256.9 22.9 2.50 1434

Hanf 10/1 Polen 103.4 23.4 2.66 1253

Engineering Cellulose Stable Fiber Cordenka 244 51,7 12.5

Quelle: Fraunhofer IAP

Page 19: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 19

Cellulose Fibers

Quelle: Fraunhofer IAP

Natural Fibers

Bast Fibers

Seed Fibers

Cellulose Fibers

Leaf Fibers

Cotton woolKapok

FlaxHemp

Agave (Sisal and others)Banana (Manila-Hemp and others)Lilienfaser (New Zealand-Hemp)Coco Fibers (Fruit Fibers)Grass Fibers

JuteRamie

Wood Fibers

HardwoodSoftwood

Viscose Carbamat

Lyocell

Cupro

Enginnering Stable Fibers= cellulosic synthetic fibers= man-made cellulosics= cellulose-stable fibers

Engineering Stable Fibers

Page 20: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 20

CRF in Composites - Processing

Manufacturing of semi-finished products

Injection Molding, Extrusion of PP/CRF-Granulates

Manufacturing of semi-finished products

Injection Molding, Extrusion of PP/CRF-Granulates

Incorporation of continuous fibersIn thermoplastic melt

Incorporation of chopped CRF-Fibers

Incorporation of continuous fibersIn thermoplastic melt

Incorporation of chopped CRF-Fibers

InjectionInjection

CompressionCompression

AutomotiveInterior

AutomotiveInterior

AutomotiveInterior

AutomotiveInterior

InjectionInjection

CompressionCompression AutomotiveInterior

AutomotiveInterior

ElectronicsHousings

ElectronicsHousings

Page 21: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 21

Processing of Granulates by Compression Molding

Granulate PPRayCo25 Basic

BeamStructure

Einschneckenextruder

Compression Molding

Plastifikate

Presse

Melting of granulates insingle-screw extruder

Page 22: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 22

Polypropylene with 25 percent by weight RAYON short fiber reinforcement

Properties Procedure Unit Norm measured value

Matrix resin PPFiber content wt.% 25

Tensile modulus 2mm/min GPa ISO527 2,7

Tensile strength 50mm/min MPa ISO527 72Strain at break (tensile) 50mm/min % ISO527 12

Flexural modulus 2mm/min GPa ISO178 2,1

Flexural strength 2mm/min MPa ISO178 60

Flexural tension at 3,5% 2mm/min MPa ISO178 52

Charpy Impact (un-notched) 23°C, 4J kJ/m2 ISO179 85-18°C, 4J kJ/m2 ISO180 83

Charpy Impact (notched) 23°C, 4J kJ/m2 ISO179 11

-18°C, 4J kJ/m2 ISO180 7

Hardness Shore D 23°C DIN53505 70

Heat deflection HDT-A 1,8 MPa °C ISO75 80

Density calculated g/cm3 0,998

Source: http://w

ww

2.iap.fhg.de/verbundwerkstoffe/de/index.htm

l

Material Properties of Injection Molded Parts (Short Fiber Reinforced)

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LFT – ein Werkstoff mit Zukunft Folie 23

Direct Processing of CRF Composites - Challenges

Chopping of CRF – high elongation

Homogenisation of chopped fibers in matrix polymer by mixing unit

Cutting of CRF-LFT plastificates into strands for compression molding

Compatibility of fibers and polymer – fiber-matrix adhesion

Optimization of flow capability of CRF reinforced polymer

Page 24: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 24

Direct Processing of CRF Composites – Process Modifications

Pressing RollerCRF-Rovings

Compounding-Extruder

Mixing Unit

Polymer-Melt Film

Infeed Zone

Chopped CRF Fibers

Feeding Chute

Cutting Roller

Polymer

Page 25: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 25

Significant improvement of material homogeneity by process optimization

Optimized LFT-D Technology(25 Gew.-% fiber content)

LFT-D Technology – not optimized(25 weight-% fiber content)

Direct Processing of CRF Composites – Material Homogeneity

Page 26: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 26

Polypropylene with 20 percent by weight RAYON long fiber reinforcement (fiber length 12 mm) compared to long glass fiber reinforced PP

Material Properties of Extrusion Compression Molded Parts

Zug-E-Modul

0

1000

2000

3000

4000

5000

Faserorientierung 0° Faserorientierung 90°

[MPa]

LFT-D PP/GF30LFT-D PP/CRF20

Stiffness – E-Modulus

Fiber orientation 0° Fiber orientation 90°

Zugfestigkeit

0102030405060708090

Faserorientierung 0° Faserorientierung 90°

[MPa]

LFT-D PP/GF30LFT-D PP/CRF20

Tensile Strength

Fiber orientation 0° Fiber orientation 90°

Page 27: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 27

Polypropylene with 20 percent by weight RAYON long fiber reinforcement (fiber length 12 mm) compared to long glass fiber reinforced PP

Material Properties of Extrusion Compression Molded Parts

Durchstoßenergie

0

2

4

6

8

10

12

14

16

18

[J]

LFT-D PP/GF30LFT-D PP/CRF20

Falling dart test

Charpy Impact un-notched

01020304050607080

Fiber orientation 0° Fiber orientation 90°

[kJ/m²]

LFT-D PP/GF30LFT-D PP/CRF20

Page 28: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 28

Current Material and Process Developments

Development of a process unit for large scale production equipment in cooperation with Dieffenbacher

Suitable cutting technology for this type of synthetic fibersAutomated handling of LFT-Strands

Optimization of material compositionMixing of Glass and CRF for improvement of HDT ValueStabilization/Additives for flame resistance with respect to railwaytransportation

Use of biopolymersComposites made from 100% renewable RessourcesPolylactid (Polylactic acid PLA) in combination with CRF

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LFT – ein Werkstoff mit Zukunft Folie 29

CRF in Biopolymers – Tensile Strength

124

61

7870

0

20

40

60

80

100

120

140

PP/GF30 PLA/GF30 PP/CRF25 PLA/CRF25

Zugf

estig

keit

[MP

a]

Page 30: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 30

10200

2900

52006500

0

2000

4000

6000

8000

10000

12000

PP/GF30 PLA/GF30 PP/CRF25 PLA/CRF25

Zugm

odul

[MPa

]

CRF in Biopolymers – Tensile Strength

Page 31: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 31

LFT-D Regenerated Cellulotic Fiber Reinforced Polypropylene

Unterbody Cover OPEL Corsa made of

PP/CRF20, 20 weight-% Fibers

VOLVOUnderbody Cover Made of PP/CRF25, 25 weight-% Fibers

Page 32: New Long Rayon Fiber Reinforced Thermoplastics Utilizing ... · New Long Rayon Fiber Reinforced Thermoplastics Utilizing the LFT-D Process ACCE, 12.-14. September 2005, Troy, USA

LFT – ein Werkstoff mit Zukunft Folie 32

Characterisation of combustion behaviour of different composites

25 weight-% CRF reinforcedPolypropylen (IAP granules, short fibers), injection molded

25 weight-% CRF reinforcedPolypropylen (ICT, LFT-D), compression molded

30% glass fiber reinforcedPolypropylen (ICT, LFT-D),compression molded

Length of burning timefor 100mm

229 s

Length of burning timefor 100mm

327 s

Length of burning timefor 100mm

233 s

Flame Retarding Behaviour of CRF Composites

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LFT – ein Werkstoff mit Zukunft Folie 33

Summary

Extended and modified LFT-D-ILC technology employing chopped fiberdosing technology leads to an economic manufacturing of CRF reinforcedparts

Compression molding is an attractive process technology especially whenmanufacturing large parts and a high number of units

High mechanical properties enable the use of the compound for automotiveapplications

Long fibers provide high impact strength and avoid slivering of the part duringdamage

Regarding material homogeneity the process technology was optimized

Successful manufacturing of demonstrator parts

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LFT – ein Werkstoff mit Zukunft Folie 34

http://www.neue-verbundwerkstoffe.de

http://www.ict.fraunhofer.de