8th International Conference on Woodfiber-Plastic Composites. May 23-25, 2005.

Wisconsin

Mechanical, thermal and morphological studies of

Poly (lactic acid) PLA/talc/recycled newspaper
fiber hybrid ‘Green’ Composites

Masud S. Huda1, Lawrence T. Drzal1, Amar K. Mohanty2,

Manju Misra1 , Kelly Williams3, & Deborah F. Mielewski3

1Composite Materials and Structures Center, 2The School of

Packaging, Michigan State University, East Lansing, MI-48824,
3 Ford Research and Advanced Engineering Laboratory, Ford

Motor Company, Dearborn, Michigan 48121, USA

 2001 Total Municipal Solid Waste (MSW) Generation –
229 Million Tons: The major share being paper waste:
One of the motivations of this research is to find value-added
applications of wood cellulosic paper waste & thus to improve
the competitive value of US forestry
Yard
Food
trimmings
Scraps
12.2%
11.4%
Other 3.4%
Wood 5.7%
Rubber,
leather &
textiles
7.1%

Plastics
11.1% Paper
35.7%
Metals 7.9%
Glass 5.5%

(Source: http://www.epa.gov/garbage/pubs/msw2001.pdf)
 Advantages of wood cellulose fibers:
1. Inexpensive,
2. Environment friendly,
3. Abundant renewable source,
4. Flexibility during process,
5. Biodegradability, etc.

Save about 25 million trees every year:

„ If everyone in the United States recycled one-tenth of their
newspapers, we could save about 25 million trees every year.
(Source: Browning-Ferris Industries)
„ Each week the average household generates five pounds of
newspaper waste, which can be used to make natural fibers as a
basis for materials for construction, or for manufacturing of
insulation or other building materials.*
*www.storaenso.com
Objectives

•To investigate the processing of the environmentally

friendly hybrid composites from newspaper fibers, talc,
and polylactic acid (PLA).

•To perform the mechanical and morphological

properties evaluation on the newspaper fibers and talc
reinforced hybrid composites and to compare with that
of composites from either of the reinforcement.

•To investigate the effect of the silane treated- and

untreated-talc on the mechanical properties of the
PLA- and Polypropylene (PP)- based hybrid
composites.
 Materials

† Matrix =

„ Poly(lactic acid) (PLA):

Biomer® L9000 – Supplied
by Biomer, Germany. PLA, a corn-based polymer:
Future plastics * (*http://www.mindbranch.com)
„ Polypropylene (PP): Pro-Fax 6523 - Supplied by
Basell Polyolefins, Elkton, MD.

† Reinforcement =
Recycled newspaper fibers (TC 1004)
Obtained from CreaFill Fibers Corp.,Chestertown,MD.
† Filler = Talc

*( Hydrated magnesium
silicate with the chemical
formula Mg3 Si4 O10 (OH)2)

Obtained from
Luzenac America, Inc.

† Coupling agent = Organofunctional silane :

Chemical structure: * Zazenski et al.
Regulatory
Toxicol. Pharm.
21, 218 (1995)
 Poly(lactic acid) (PLA)
O O

n* HO CH C OH H O CH C OH

CH3 CH3
n
Lactic acid PLA
Properties PLA PP PS* PVC*
Tensile Strength (MPa) 62.8 ± 4.9 36.4 ± 3.6 3.4 2.6

Tensile Modulus (GPa) 2.7 ± 0.4 1.2 ± 0.1 - -

Elongation at Break (%) 2.9 ± 0.5 9.8 ± 0.5 2.5 3.0
Flexural Strength (MPa) 98.8 ± 0.9 32.9 ± 1.8 80 90

Flexural Modulus (GPa) 3.3 ± 0.1 1.5 ± 0.2 - -

Notched Izod Impact Strength 25.7 ± 1.3 29.7 ± 3.1 - -
(J/m)
* Mobley, D. P. Plastics from Microbes. 1994
Reinforcement fibers (reclaimed from newspaper/magazine or kraft
paper stock)

( TC 1004 )

The low cost recycled newspaper cellulose fibers (TC 1004: average
price: $0.20 / lb) characteristics:
Fiber type Appearance Cellulose Ash content Moisture
content (maximum) content
(minimum)

TC 1004 Gray fiber 75% 23%* < 5%

*Ash content : carbon and any other organics/non-organics(any clays, inks
lignin’s, tannin’s, extractives, etc.)
Characteristics of the talc used in the present study:
Talc 1 Talc 2 Talc 3

Product name Silverline 002 Nicron 403 Mistron CB

Manufacturing Luzenac Luzenac Luzenac

company America, Inc. America, Inc. America, Inc.
Particle Size 12.5 4.8 2.2
(microns)
Density (lbs/ft3) 50 28 20
Surface area (m2/g) 10.5 12 11
Crystalline Micro- Micro- Micro-
character crystalline talc crystalline talc crystalline talc
Chemically pre-treated No No Silane
with surface modifier

Moisture content (%) 0.15 0.1 0.06

Fabrication of the hybrid composites by micro-
compounding and molding system
 Preparation of the composites by DSM micro-compounding and molding system
O

H O CH C OH
&
(Cellulose)
CH3
n
PLA (a)

(a) Cellulose
(at 183oC for 10 minute fibers
and 100 rpm )

Injection
molding
cylinder

Injection
DSM micro compounding and molding system molder
(inside DSM mini-twin extruder-open: screw
length 150mm, L/D 18, net capacity 15 cm3)
Injection molded composite samples by micro-compounding
and molding system

PLA/Newspaper/Talc
PLA (100%) (60 wt.% / 30wt.% / 10wt.%)
 Testing and Characterizations
z Mechanical testing:
A mechanical testing machine, United Calibration Corp SFM 20,
was used to measure the tensile properties, according to ASTM D
638 standard, and flexural properties according to ASTM D 790.
The Notched Izod impact strength was measured with a Testing
Machines Inc. 43-02-01 Monitor/Impact machine according to
ASTM D256.
z Thermal analysis:
Dynamic mechanical analysis (DMA) : -50 ~ 150oC, 5oC/min, 1 Hz
Thermo gravimetric analysis (TGA) : 25 ~ 600oC, 10oC/min
Differential scanning calorimeter (DSC) : 25 ~ 200oC, 5oC/min
z Morphological study:
Scanning electron microscopy (SEM) : A JEOL 6300 SEM with
field emission filament in accelerating voltage of 10 kV was used
to collect SEM images of the impact fracture surfaces.
The morphological studies of the recycled newspaper
fibers and talc
 Morphology of the Newspaper fibers (TC 1004)
(a)
(c) (b)

Fig. SEM micrographs of the (C)

(c
(d))
Newspaper fibers (TC 1004): (a)
200 µm (—), (b) 50 µm (—), and
(c) 2 µm (—).
The average length of the fibers was 850
microns and the average width was 20
microns (The evidence of fiber breakage
for the newspaper fibers).
 Morphology of the Talc 1 (Silverline 002 )
Fig. SEM micrographs of the (a)
Talc 1: (a) 50 µm (—), (b) 5 µm
(—), and (c) 1 µm (—) .
Silverline 002 (Talc 1) : Particle
Size 12.5 microns.
Small talc plates are clustered
together like a cabbage.
(b)
(c)
Morphology of the Talc 2 (Nicron 403 )
Fig. SEM micrographs of the (a)
Talc 2: (a) 50 µm (—), (b) 5 µm
(—), and (c) 1 µm (—).
Nicron 403 (Talc 2) : Particle
Size 4.8 microns.
Many small talc plates are
clustered together.

(b)
(c)
Morphology of the Talc 3 (Mistron CB )
Fig. SEM micrographs of the (a)
Talc 3: (a) 50 µm (—),(b) 10 µm
(—), and (c) 5 µm (—).
Mistron CB (Talc 3): Particle
Size 2.2 microns.
Platy microcrystalline talc surface
treated with silane coupling agent.
(b)
(c)
The mechanical properties of the PLA- and PP-
hybrid composites
Flexural properties of the talc-filled newspaper fiber reinforced PLA
hybrid composites along with newspaper fiber reinforced PLA composite
160 18
Flexural strength (MPa) 132.6
140 16
Flexural modulus (GPa) 15.3
116 113.3 14
120
98.8 12.5
Strength (MPa)

Modulus (GPa)
12.3 12
100
77.7 10
80
8
60
6
40 4.9
4
3.3
20 2

0 0
PLA (100%) PLA/ PLA / PLA / PLA /
Newspaper Newspaper / Newspaper / Newspaper /
(70/30) Talc 1 Talc 2 Talc 3
(60/30/10) (60/30/10) (60/30/10)
Flexural properties of the talc-filled newspaper fiber reinforced PP
hybrid composites along with newspaper fiber reinforced PP composite
70 59.2 6
Flexural strength (MPa)
57.7 51.6
60 Flexural modulus (GPa) 5.1
5
4.7
50
Strength (MPa)

Modulus (GPa)
39.7 4 4
40 32.9
3
30
2.1 2
20
1.5
1
10

0 0
PP (100%) PP / PP / PP / PP /
Newspaper Newspaper / Newspaper / Newspaper /
(70/30) Talc 1 Talc 2 Talc 3
(60/30/10) (60/30/10) (60/30/10)
Notched Izod impact strength of the talc-filled newspaper fiber
reinforced PLA hybrid composites along with newspaper fiber reinforced
PLA composite
35
25.7 26.1 26.3
30 24.6

25
Impact Strength

20
(J/m)

13.1
15

10

0
PLA (100%) PLA/ PLA / PLA / PLA /
Newspaper Newspaper / Newspaper / Newspaper /
(70/30) Talc 1 Talc 2 Talc 3
(60/30/10) (60/30/10) (60/30/10)
 Notched Izod impact strength of the talc-filled newspaper fiber
reinforced PP hybrid composites along with newspaper fiber
reinforced PP composite
40 35 34.9 33.8
35 29.7 31.2

30
Impact Strength

25
(J/m)

20
15
10
5
0
PP (100%) PP / PP / PP / PP /
Newspaper Newspaper / Newspaper / Newspaper /
(70/30) Talc 1 Talc 2 Talc 3
(60/30/10) (60/30/10) (60/30/10)
The thermo- mechanical properties of the PLA-
and PP- hybrid composites
 18000
PLA/Newspaper /Talc 3 (60/30/10) (a)
16000

Storage Modulus (MPa)

14000
12000 PLA/Newspaper /Talc 1 (60/30/10)
Dynamic
10000 PLA/Newspaper /Talc 2 (60/30/10)
mechanical 8000
properties of the 6000 PLA/Newspaper (70/30)
4000
PLA composites
2000 PLA(100%)
0
-10 10 30 50 70 90
Temperature (deg C)

Polymer/Fiber and/or Filler Storage Reinforcement

(wt%) Modulus imparted by the fibers
(GPa) at 25oC at 25oC(modulus) (%)
PLA(100%) 3.2 -
PLA/Newspaper (70/30) 8.9 178
PLA/Newspaper /Talc 1 (60/30/10) 14.0 337

PLA/Newspaper /Talc 2 (60/30/10) 13.9 334

PLA/Newspaper /Talc 3 (60/30/10) 15.9 396

 Dynamic mechanical properties of the PLA composites (Cont…)

Polymer/Fiber and/or Filler (wt%) Tg * (0C)

PLA(100%) 63
PLA/Newspaper (70/30) 66
PLA/Newspaper /Talc 1 (60/30/10) 69
PLA/Newspaper /Talc 2 (60/30/10) 70
PLA/Newspaper /Talc 3 (60/30/10) 68
3500
PLA/Newspaper /Talc 3
3000 (60/30/10) (b) * obtained from loss modulus curves.
Loss Modulus (MPa)

PLA/Newspaper /Talc 1
2500
(60/30/10)
2000 PLA/Newspaper /Talc 2
(60/30/10)
1500
PLA/Newspaper (70/30)
1000 PLA(100%)
500
0
0 20 40 60 80 100
Temperature (deg C)
 Dynamic mechanical properties of the PLA composites (Cont…)

2.5

2 PLA(100%) (c)
PLA/Newspaper (70/30)
Tan Delta

1.5 PLA/Newspaper /Talc 2

(60/30/10)
1 PLA/Newspaper /Talc 1
(60/30/10)
0.5 PLA/Newspaper /Talc 3
(60/30/10)
0
0 20 40 60 80 100
Temperature (deg C)
 16000 PP/Newspaper/Talc 3 (60/30/10)
14000

Storage Modulus (MPa)

PP/Newspaper/Talc 1
12000
Dynamic 10000
(60/30/10)
PP/Newspaper PP/Newspaper /Talc 2
mechanical 8000 (70/30) (60/30/10)
properties of the 6000
(a)
4000
PP composites 2000 PP (100%)
0
-100 -50 0 50 100 150
Temperature (deg C)

Polymer/Fiber and/or Filler Storage Reinforcement imparted

(wt%) Modulus by the fibers at 25oC
(GPa) at 25oC (modulus) (%)
PP (100%) 3.3 -
PP/Newspaper (70/30) 5.6 69

PP/Newspaper /Talc 1 (60/30/10) 7.5 127

PP/Newspaper /Talc 2 (60/30/10) 7.7 133

PP/Newspaper /Talc 3 (60/30/10) 7.9 139

 Dynamic mechanical properties of the PP composites (Cont…)

Polymer/Fiber and/or Filler (wt%) Tg * (0C)

PP(100%) 13
PP/Newspaper (70/30) 7
PP/Newspaper /Talc 1 (60/30/10) 14
PP/Newspaper /Talc 2 (60/30/10) 15
PP/Newspaper /Talc 3 (60/30/10) 16
900 PP/Newspaper/Talc 3
800 (60/30/10)
PP/Newspaper /Talc 2
* obtained from loss modulus
Loss Modulus (MPa)

700 PP/Newspaper/ (60/30/10)

600 Talc 1 (60/30/10) curves.
500 PP/Newspaper (70/30)
400
300 (b)
200
PP (100%)
100
0
-100 -50 0 50 100 150 200

Temperature (deg C)
 Dynamic mechanical properties of the PP composites (Cont…)

0.2 PP/Newspaper/Talc 3 (60/30/10)

0.18 PP/Newspaper /Talc 2 (60/30/10)
0.16 PP/Newspaper/Talc 1
0.14 (60/30/10)
Tan Delta

0.12 PP/Newspaper
0.1 (70/30)
0.08
PP (100%) (c)
0.06
0.04
0.02
0
-100 -50 0 50 100 150 200
Temperature (deg C)
 Crystallization and melting behavior of the composites:
Degree of crystallinity (χ %) of PLA in the composite, χ = ∆Hm / ∆Hm0 × 100;
where: ∆Hm = experimental melting enthalpy (J/g) and ∆Hm0 = 93.7 J/g*.
Polymer/Fiber and/or Tg Tc ∆Hc ∆Hm χ Tm
Filler (wt%) (0C) (0C) (J/g) (J/g) (%) (0C)
Neat PLA 54 96 27.8 47.9 51.1 172
PLA/Newspaper (70/30) 55 90 23.6 41.2 44.0 172
PLA/Talc 1 (70/30) 56 82 19.7 45.5 48.5 169
PLA/Newspaper/Talc 1 58 82 16.3 32.6 34.8 169
(60/30/10)
PLA/Talc 3 (70/30) 57 84 16.6 38.3 40.8 170
PLA/Newspaper/Talc 3 57 81 14.1 30.3 32.3 170
(60/30/10)
Note: Tg = glass transition temperature, Tc = crystallization temperature, Tm =
melting temperature, ∆Hc = crystallization enthalpy and ∆Hm = melting
enthalpy.
*Fisher E W, Sterzel H J, Wegner G. Kolloid- Z Z Polymere. Vol. 125, p. 980, 1973.
Thermogravimetry Table. TGA characterization of the composites.
Polymer/Fiber and/or Filler(wt%) T5 (0C) T25 (0C) T50 (0C) T75 (0C)
Neat PLA 356 385 401 414
PLA/Newspaper (70/30) 308 336 349 356
PLA/Newspaper/Talc 1 (60/30/10) 325 355 368 380
PLA/Newspaper/Talc 3 (60/30/10) 337 370 387 425
Newspaper fiber (100%) 177 305 330 348
120

100

PLA(100%)
80
Weight (%)

PLA/Newspaper (70/30)
60 PLA/Newspaper /Talc 1 (60/30/10)
PLA/Newspaper /Talc 3 (60/30/10)
40
Newspaper fibers (100%)
20

0
0 100 200 300 400 500

Temperature (deg C)
 A comparison between PLA/Newspaper/Talc 3 (60/30/10)
composite and PP/Newspaper/Talc 3 (60/30/10) composite
160 132.6
140 PP/Newspaper/Talc 3 (60/30/10)
120 PLA/Newspaper/Talc 3 (60/30/10)
100
80 59.2

60 33.8
40 15.3 26.3 15.9
20 5.1 7.9
0
Flexural Flexural Impact Storage
strength modulus strength modulus
(MPa) (GPa) (J/m) (GPa)
The mechanical and thermo-mechanical properties of the PLA hybrid
composites were found to compare favorably with the corresponding
properties of PP hybrid composites.
The morphological studies of the PLA- and PP-
hybrid composites
SEM micrographs of the fracture (a)
surface of Impact specimens of
PLA/Newspaper/Talc 1 composite :
(a) 100 µm (—), (b) 50 µm (—), and
(c) 5 µm (—).
Fibers
¾ Well dispersion of fibers in the PLA
matrix, and indicates that fibers have been
separated during the extrusion process.
¾ The matrix is an indication of good
fiber-matrix adhesion.

(b) (c)

Talc

Fibers
Fibers
SEM micrographs of the fracture
surface of Impact specimens of (a)
PP/Newspaper/Talc 1 composite :
(a) 100 µm (—), (b) 50 µm (—),
and (c) 5 µm (—).
¾ The existence of the aggregation of the Fibers
cellulose fiber like materials in the
composite sample surface.
¾ Some fibers are tightly connected with
the matrix, and some cellulose fibers are
broken and/or torn up.
(c)
(b)
Fibers

Talc
SEM micrographs of the fracture (a)
surface of Impact specimens of
Talc
PLA/Newspaper/Talc 3 composite :
(a) 10 µm (—), (b) 5 µm (—), and Fibers
(c) 1 µm (—).
¾ Good interfacial adhesion between the
matrix and fibers transfers the stress
from the matrix to the fibers improving
the mechanical properties of the
composites.
(b) Talc (c)

Fibers
Talc
Fibers
SEM micrographs of the (a)
fracture surface of Impact
specimens of PP/Newspaper/Talc
3 composite : (a) 50 µm (—), and
(b) 10 µm (—).
¾ There is no indication of
matrix materials on the fiber Fibers
surface. But some fibers are
tightly connected with the matrix.

(b) ¾ Silane-treated talc are tightly

Talc connected with the matrix.
¾ Fibers have tight contact with
matrix to increase the effect
between filler and matrix with the
surface treatment of talc, resulting
Fibers in the regularity of particle
dispersion in the matrix and less
large size aggregate.
 CONCLUSIONS
¾ PLA hybrid composites have mechanical properties of
sufficient magnitude to compare with conventional thermoplastic
composites.
¾ The thermo-mechanical properties of the hybrid composites
were found to be significantly higher than that made from
polymer/newspaper fiber.
¾ The comparison data of mechanical properties between
samples filled with treated and untreated talc fillers showed that
the hybrid composites filled with silane treated talc displayed the
better mechanical prosperities relative to the other hybrid
composites.
¾ The use of recycled newspaper cellulose fibers and Talc, as
reinforcements in PLA, gives interesting alternatives for
production of low cost and ecologically friendly composites.
 Future works

¾ Further improvement of processing and/or use

of the compatibilizer,
¾ Biodegradability evaluation of the
environmentally friendly PLA hybrid composites
(such as degradation tests under different
environmental conditions including full-scale
composting, soil burial, hydrolytic and enzymatic
degradation, etc.).
 Acknowledgements
™ Financial supports from NSF Award DMI-0400296
“PREMISE-II: Design and engineering of ‘green’
composites from biofibers and bioplastics”, USDA-MBI
Award Number 2002-34189-12748-S4057 for the project
“Bioprocessing for Utilization of Agricultural
Resources”, and NSF 2002 Award # DMR-0216865,
under “Instrumentation for Materials Research (IMR)
Program”,
™ Luzenac America, Inc., CO, for Talc,
™ DSM Research, Geleen, The Netherlands for the micro-
compounding and molding system,
™ CreaFill Fibers Corp., MD, for recycled newspaper
fibers,
™ Basell Polyolefins, MD, for PP,
™ Biomer, Germany for PLA,
™ Ford Motor Company for their support and assistance
in this study.