Material Properties of Injection Molded Glass and Carbon Fiber ... · Expenditures for research and development €1,953 million, world leader in chemical industry Around 3,000 research

Material Properties of Injection Molded Glass and

Carbon Fiber Reinforced Thermoplastic Composites –

A Review

SPE Automotive Composites Conference & Exhibition, Sept. 7-9 2016

Mark Cieslinski, BASF - Advanced Materials & Systems Research

© 2016 BASF Corporation

About BASF1

Why Composites?2

What Influences Composite Properties?3

Summary4

5

Outline

2© 2016 BASF Corporation

About BASF1

Why Composites?2


Summary4

5

Outline


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About BASF1

Why Composites?2


Summary4

5

Outline


Metal replacement: comparison with

engineering plastics compounds

Low density even for highly glass fiber filled PA compound is advantageous

Tensile strength of PA compound is high and comparable to “soft“ Al alloys

Stiffness and fracture toughness as well as melting point and thermal conductivity

much lower compared to metals

Material rg/cm³

Tm

°C

E

GPa

s

MPa

KIC

MN/m³/²

l

W/mK

Steel (ferritic, austenitic)

7.8 1150(FeC4)

195 - 210 440 - 750 50 - 200 30 - 60

Steel(High-strength )

7.8 - 195 - 210 1300 - 2100 - -

Al alloys 2.7 577(AlSi12)

60 - 80 300 - 700 23 - 45 121 - 237

PA66 GF50(23 °C, dry conditions)

1.56 260 16.8 240 5 - 10 (~ 0.5)

Steel and Al-alloys: Data taken from Hütte (1996)


Specific tensile strength & stiffness

of PA66 compounds

Specific tensile

strength of highly

GF-filled PA com-

pounds similar to

Al-alloys and higher

than steel

Specific stiffness of

PA/GF compounds

further enhanced by

carbon fibers

Al-alloys

Steel

High-strength steel

Comparison of glass & carbon fibers


About BASF1

Why Composites?2


Summary4

5

Outline


Question:

What injection molding material do we use for

our application?

How do these variables transfer to

mechanical properties?

Modulus

Strength

Impact

Fatigue

Short or Long fiber?

Glass or Carbon fiber?

Resin?

© 2016 BASF Corporation 11

Designations of Fiber Lengths

Short fibers – incorporated into thermoplastic via extrusion compounding,

typical average fiber length < 0.5 mm

Long fibers – composites retain fiber length in molded part > 1.0 mm,

pultrusion or wet-lay processes are used

Extrusion/Injection molding reduces fiber length to a log-normal distribution,

described by:

Number average fiber length, Ln = 𝑁𝑖𝐿𝑖 𝑁𝑖

Weight average fiber length, Lw = 𝑁𝑖𝐿𝑖

2

𝑁𝑖𝐿𝑖

Aspect Ratio = Length

Diameter


Num

ber

of

Fib

ers

, 𝑁𝑖

Fiber Length, 𝐿𝑖

Fiber length

distribution

0

0.2

0.4

0.6

0.8

1

1.2

0.01 0.1 1 10 100

No

rmal

ized

Pro

per

ty

Fiber Length, mm

Modulus

Strength

Notched CharpyImpact

Fiber Length Trends

Modulus – Cox model

Strength – Kelly-Tyson Model

Impact – Thomason-Vlug model

Modulus

Strength

Impact

10-40 wt% glass – Polypropylene

produced via wet-lay process

Normalization trend appears independent of

concentration for Flexural and Tensile data

J. Thomason and M. Vlug, "Influence of fibre length and concentration on the properties of glass fibre-reinforced polypropylene: 4. Impact properties,"

Composites: Part A, pp. 277-288, 1997.

J. Thomason, "The influence of fibre length and concentration on the properties of glass fibre reinforced polypropylene: 5. Injection moulded long and short fiber

PP," Composites: Part A, pp. 1641-1652, 2002.© 2016 BASF Corporation 13

Injection Molded Composites

Long Glass Fiber - Polypropylene

Number Average, Ln

Length Average, Lw

J. Thomason, "The influence of fibre length and concentration on the properties of glass fibre reinforced polypropylene. 6. The properties of injection moulded

long fibre PP at high fibre content," Composites: Part A, pp. 995-1003, 2005.

Fiber length decreases with

increasing concentration


Modulus linearly increasing with

concentration (except >65wt%)

Ultramid® Polyamide Glass Fiber Materials

0

5

10

15

20

25

PA

66

15

% S

ho

rt G

lass

25

% S

ho

rt G

lass

30

% S

ho

rt G

lass

35

% S

ho

rt G

lass

40

% S

ho

rt G

lass

50

% S

ho

rt G

lass

40

% L

on

g G

lass

50

% L

on

g G

lass

60

% L

on

g G

lass

65

% L

on

g G

lass

PA

6

15

% S

ho

rt G

lass

25

% S

ho

rt G

lass

30

% S

ho

rt G

lass

35

% S

ho

rt G

lass

40

% S

ho

rt G

lass

50

% S

ho

rt G

lass

40

% L

on

g G

lass

50

% L

on

g G

lass

60

% L

on

g G

lass

Mo

du

lus,

GPa

Tensile Modulus

Flexural Modulus

PA 66 PA 6

0

100

200

300

400

500

PA

66

15

% S

ho

rt G

lass

25

% S

ho

rt G

lass

30

% S

ho

rt G

lass

35

% S

ho

rt G

lass

40

% S

ho

rt G

lass

50

% S

ho

rt G

lass

40

% L

on

g G

lass

50

% L

on

g G

lass

60

% L

on

g G

lass

65

% L

on

g G

lass

PA

6

15

% S

ho

rt G

lass

25

% S

ho

rt G

lass

30

% S

ho

rt G

lass

35

% S

ho

rt G

lass

40

% S

ho

rt G

lass

50

% S

ho

rt G

lass

40

% L

on

g G

lass

50

% L

on

g G

lass

60

% L

on

g G

lass

Stre

ngt

h, M

Pa

Tensile Strength

Flexural Strength

PA 6PA 66

Modulus Strength


Ultramid® A Ultramid® B Ultramid® A Ultramid® B

Dry as molded

Parallel trends in flexural and tensile moduli and strength

Modulus independent of fiber lengths in test specimens

0

10

20

30

40

50

60

PA

66

15

% S

ho

rt G

lass

25

% S

ho

rt G

lass

30

% S

ho

rt G

lass

35

% S

ho

rt G

lass

40

% S

ho

rt G

lass

50

% S

ho

rt G

lass

40

% L

on

g G

lass

50

% L

on

g G

lass

60

% L

on

g G

lass

65

% L

on

g G

lass

PA

6

15

% S

ho

rt G

lass

25

% S

ho

rt G

lass

30

% S

ho

rt G

lass

35

% S

ho

rt G

lass

40

% S

ho

rt G

lass

50

% S

ho

rt G

lass

40

% L

on

g G

lass

50

% L

on

g G

lass

60

% L

on

g G

lass

Ch

arp

y Im

pac

t St

ren

gth

, kJ

/m² Notched, Dry, 23C

Notched, Dry, -30C

PA 6PA 66Ultramid® A Ultramid® B

Ultramid® Impact properties


Long fiber advantage → Impact performance

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0.1 1 10 100 1000 10000

Stra

in, %

Time, hPA66 Short Fiber - 40 MPa PA66 Long Fiber - 40 MPa

PA66 Short Fiber - 80 MPa PA66 Long Fiber - 80 MPa

Short/Long Creep Performance

Ultramid® A - 50% glass fiber

Short fiber

Long fiber

Creep performance differences more pronounced

at higher time scales and higher loadings


Cra

ck g

row

th r

ate

0

10

20

30 wt% fibers in PP

Fracture Toughness

Parallel to Flow Direction in

Injection Molded Plaque

Fatigue Behavior


10

100

1000

1 10 100 1000 10000 100000 1000000 10000000Te

nsi

le S

tres

s, M

Pa

Number of Cycles

PA66 Short Glass

PA66 Long Glass

Ultramid® A

50% glass fiber

Fatigue performance extend due to long fibers

creating a fiber network

A. Pegoretti and T. Ricco, “Fatigue fracture of neat and short glass fiber

reinforced polypropylene: effect of frequency and material orientation,"

Journal of Composite Materials, vol. 34, no. 12, pp. 1009-1027, 2000.

Short Glass Fibers Short & Long Glass Fibers

Increasing fiber content increases toughness

while inhibiting crack growth

Fiber Diameter Effects (PA66-30wt% glass)

Average Length Average Aspect Ratio

diameter, µm Ln, mm Lw, mm Ln/d Lw/d

10 0.34 0.55 34 55

11 0.4 0.65 36 59

14 0.49 0.73 35 52

17 0.56 0.79 33 46

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

8 10 12 14 16 18

No

rmal

ized

Co

mp

osi

te P

rop

erti

es

Fiber Diameter, µm

Tensile Strength

Tensile Modulus

Tensile Strain

Flexural Strength

Flexural Modulus

Notched Izod Impact Strength

Unnotched Izod Impact Strength

34

36

35

3355

59

52

46

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

8 10 12 14 16 18

Fib

er L

engt

h, m

m

Fiber Diameter, µm

Thomason, "The influence of fibre properties of the performance of glass-fibre-reinforced polyamide 6,6," Composites Science and Technology, vol. 59, pp.

2315-2328, 1999.

Strength – some decrease (14%)

Modulus – no change (2%)

Notched Impact – slight increase (7%)

Unnotched Impact – significant decrease (72%)


0.0

0.5

1.0

1.5

2.0

2.5

3.0

TensileModulus

TensileStrength

Strain atBreak

FlexuralModulus

FlexuralStrength

Charpynotchedimpact

strength

Pro

per

ties

No

rmal

ized

to

40

% S

ho

rt G

lass 40% Short Glass

40% Long Glass

40% Short Carbon

40% Long Carbon

Ultramid® A3W - 40 wt% Short/Long ,

Glass/Carbon Fiber

Typical properties of glass and Carbon fiber Glass Carbon

Density, g/cm3 2.5 – 2.6 1.7 – 1.8 Tensile Modulus, GPa 70 – 80 225 – 275

Tensile Strength, GPa 1.5 – 3.5 2.5 – 5 Elongation at Break, % 0.5 – 2 1.8 – 3.2


Long glass fibers

Impact Properties

Carbon fibers

Stiffness Strength

Relative specific properties to 40% Short Glass

Fiber – Ultramid® A

0

0.5

1

1.5

2

2.5

3

3.5

4

TensileModulus

TensileStrength

Strain atBreak

FlexuralModulus

FlexuralStrength

Charpynotchedimpact

strength

Spec

ific

Pro

per

ties

No

rmal

ized

to

40

% S

ho

rt G

lass

40% Short Glass

40% Long Glass

40% Short Carbon

40% Long Carbon

Specific Property =Property

Composite Density


Advantages of

carbon fiber become

more pronounced for

light-weighting

applications

Long glass fiber

impact properties not

as significant

improvement

Glass and carbon fiber at equal volume% in

polypropylene

0

2

4

6

8

10

12

14

16

0 20 40 60

Ten

sile

Mo

du

lus,

GP

a

Weight %

Short Glass

Short Carbon

0

10

20

30

40

50

60

70

0 20 40 60

Ten

sile

Str

engt

h, M

Pa

Weight %

Short Glass

Short Carbon0

1

2

3

4

5

6

7

0 20 40 60

No

tch

ed C

har

py

Imp

act

Stre

ngt

h,

kJ/m

2

Weight %

Short Glass

Short Carbon

4846

43

39 37

31

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0 20 40 60

Nu

mb

er A

vera

ge F

iber

Len

gth

, mm

Weight %

Short Glass

Short Carbon

Aspect Ratios

Property Carbon Glass

Diameter, µm 7.5 13.8

Tensile Strength, MPa 3950 1956

Tensile Modulus, GPa 238 78.5

S.-Y. Fu, B. Lauke, E. Mäder, C.-Y. Yue and X. Hu, "Tensile properties of short-glass-fiber- and short-carbon-fiber-reinfoced polypropylene composites,"

Composites: Part A, pp. 1117-1125, 2000.

S. Fu, B. Lauke, E. Mäder, X. Hu and C. Yue, "Fracture resistance of short-glass-fiber-reinforced and short-carbon-fiber-reinforced polypropylene under Charpy

impact load and its dependence on processing," Journal of Materials Processing Technology, pp. 501-507, 1999.


Stiffness – translated from fiber properties

Strength & Impact – less driven by fiber properties

more likely aspect ratio & sizing

0

5

10

15

20

25

30

35

40

-40 -20 0 20 40 60 80 100 120 140 160

Ten

sile

Mo

du

lus,

GP

a

Temperature, C

PA66 50% ShortGlassPA66 50% LongGlassPA66 40% ShortCarbonPA66 40% LongCarbonPA66

Dry

Ultramid® Properties with Temperature


PA66

50% Glass

40% Carbon

0

50

100

150

200

250

300

350

-40 -20 0 20 40 60 80 100 120 140 160

Ten

sile

Str

engt

h, M

Pa

Temperature, C

PA66 50% Short Glass

PA66 50% Long Glass

PA66 40% Short Carbon

PA66 40% Long Carbon

PA66

Dry

Fiber network from long fibers improves modulus at elevated temperatures

0

2

4

6

8

10

12

14

16

18

0 10 20 30 40 50 60

Ten

sile

Mo

du

lus,

GP

a

Fiber Content, wt%

Heat Aging Resistant Impact Modified Flame Retardant

Stabilized Stabilized

0

50

100

150

200

250

300

0 10 20 30 40 50 60

Ten

sile

Str

engt

h, M

Pa

Fiber Content, wt%

A3W - High Resistance to Heat AgingA3Z - Impact ModifiedA3X2 - Flame Retardant w/ Red PhosphorusA3E - Resistant to Heat Aging, Weather & Hot WaterA3H - Resistant to Heat Aging, Weather & Hot Water - Engineering Parts

Resin Formulation - Ultramid® A

Short Glass Fiber

Short Glass Fiber

0

5

10

15

20

25

30

35

40

45

0 10 20 30 40 50 60 70N

otc

hed

Ch

arp

y Im

pac

t St

ren

gth

, kJ/

m2

Fiber Content, wt%

Short Glass Fiber

Short Glass Fiber + Impact Modifier

Long Glass Fiber


General trends of property improvement with

concentration appear to be universal

Some additives necessary for the end-use

application can negatively effect properties

General Summary

25

Property Modulus Strength Strain

at

Break

Notched

Impact

Creep Fatigue Performance

at Higher

Temperatures

Increase

Concentration

Increase Fiber

Length-

Carbon Fiber (relative to glass)

-


*Concentration, length and fiber type are not completely independent variables

Properties in the end-use part are largely influenced by processing:

• Fiber Orientation

• Fiber Length (aspect ratio)

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Material Properties of Injection Molded Glass and Carbon Fiber ... · Expenditures for research and development €1,953 million, world leader in chemical industry Around 3,000 research