This article was downloaded by: [University of Sussex Library]

On: 15 January 2015, At: 13:32

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer
House, 37-41 Mortimer Street, London W1T 3JH, UK

Journal of Adhesion Science and Technology

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/tast20

Improving adhesion of wood fiber with polystyrene

by the chemical treatment of fiber with a coupling
agent and the influence on the mechanical properties
of composites
a b
D. Maldas & B.V. Kokta
a
Centre de recherche en pâtes et papiers, Université du Québec à Trois-Rivières, C.P.
500, Trois-Rivières, Québec, Canada G9A 5H7
b
Centre de recherche en pâtes et papiers, Université du Québec à Trois-Rivières, C.P.
500, Trois-Rivières, Québec, Canada G9A 5H7
Published online: 02 Apr 2012.

To cite this article: D. Maldas & B.V. Kokta (1989) Improving adhesion of wood fiber with polystyrene by the chemical
treatment of fiber with a coupling agent and the influence on the mechanical properties of composites, Journal of
Adhesion Science and Technology, 3:1, 529-539, DOI: 10.1163/156856189X00380

To link to this article: http://dx.doi.org/10.1163/156856189X00380

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall not be
liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities
whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of
the use of the Content.

This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Improving adhesion of wood fiber with polystyrene by the
chemical treatment of fiber with a coupling agent and the
influence on the mechanical properties of composites

D. MALDAS and B. V. KOKTA*

Centre de recherche en pâtes et papiers, Universitédu Québec à Trois-Rivières,C.P.500,
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

Trois-Rivières,Québec, Canada G9A 5H7

Revised version received 13 April 1989

Abstract�The mechanical properties of polystyrene filled with chemithermomechanical pulp and

wood residues of softwood and hardwood species, which were precoated with phthalic anhydride
and various polymers, e.g. polystyrene and PVC, have been investigated. The extent of improvement
in the mechanical properties of the composite materials depends on the coating composition, the
concentration of phthalic anhydride, the nature of the coated polymers, as well as the concentration
of fiber, the nature of the wood species, and the nature of the pulps. Experimental results indicate
that phthalic anhydride acts as a coupling agent, but when its performance was compared to that of
poly[methylene (polyphenyl isocynate)], it seemed inferior to the latter.

Keywords: Thermoplastic composites; polystyrene; wood fiber; phthalic anhydrides; isocyanate;

mechanical properties; coating; adhesion.

1. INTRODUCTION

Due to the wide difference in polarity, cellulose fibers do not disperse easily in
non-polar thermoplastics, e.g. polystyrene. When cellulose fibers are coated with
a hydrophobic polymer prior to being mixed with the plastics, the coating
penetrates into the pores of the filler particles and increases the density of the
filler particles [1, 2]. Moreover, the affinity of the filler particles for the base
polymer can be greatly increased if some coupling agents, e.g. isocyanate, are
used as a coating component [3-7]. As a result, filler particles can combine well
with the composites and cohesion of all the components can thus be enhanced.
The impact of such coating treatments using a compatible polymer, e.g. poly-
styrene and polyvinyl chloride, and a coupling agent, e.g. poly[methylene
(polyphenyl isocyanate)], as coating components on the mechanical properties of
the composite materials has been investigated.

2. MATERIALS

The following thermoplastics were used:

(i) high impact polystyrene (PS 525);

(ii) high heat crystal polystyrene (PS 201), supplied by Polysar Ltd., Sarnia,
Ontario, Canada; and
*Towhom correspondence should be addressed.
 530

(iii) PVC-Goodrich (Geon 110 x 334), supplied by B. F. Goodrich Geon Vinyl

Division, Cleveland, Ohio, U.S.A
In the present study, two different varieties of wood species, namely hardwood
species aspen (Populus tremuloides Michx), and softwood species mixtures (75%
black spruce, 20% balsam, and 5% aspen) were used in the form of wood flour
(sawdust) and chemithermomechanical pulp (CTMP). CTMP was prepared in a
Sund defibrator under the same conditions as described earlier [ 5 ] .
The following coupling agents were used:

(i) phthalic anhydride (PHA), supplied by Anachemia, Montreal, Canada; and

(ii) poly[methylene (polyphenyl isocyanate)] (PMPPIC), supplied by Poly-
sciences Inc., USA.
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

3. EXPERIMENTAL
CTMP aspen pulp and chips for making sawdust were dried in an air circulating
oven at 55°C for 48 h and then ground to a mesh size 60 mixture: 60.5%, mesh
60; 20.2%, mesh 80; 15.5%, mesh 100; and 3.5%, mesh 200, with a Granu
Grinder (C. W. Brabender, Instruments Inc., USA).

3.1. Coating treatment t

Fibers were coated with polymer (10 wt% of fiber) and isocyanate (8 wt% of
fiber) with the help of a Laboratory Roll Mill (C. W. Brabender, Model No. 065)
at 175°C.

3.2. Preparation of the composites

Usually, a 25 g mixture of polymer and pulp/coated pulp (15-35% by weight of

composite) was mixed in the roll mill at 175°C. After mixing 5-10 times, the
resulting mixtures were reground to mesh size 20. The mixtures were then
molded (24 at a time) into shoulder-shaped test specimens (ASTM D638, type
V). Standard molding conditions were: temperature, 175°C; pressure during
heating and cooling, 3.8 MPa; heating time, 20 min; cooling time, 15 min. The
width and thickness of each specimen were measured with the help of a
micrometer.

3.3. Mechanical tests

The mechanical properties (e.g. tensile modulus, tensile strength at yield point,
and the corresponding elongation and energy) of all the samples were measured
with an Instron Tester (Model 4201). A standard general tensile test program
method, called 'PLA 10', was used, and the mechanical properties were auto-
matically calculated by an HP-86B computer. The strain rate was 1.5 mm/min
and tensile modulus was reported at 0.1% strain. The impact strength (Izod, un-
notched) was tested with an Impact Tester (Model TMI, No. 43-01), supplied by
Testing Machines Inc., USA. The samples were tested after conditioning at
23 ± 0.5°C and 50% RH for at least 18 h in a controlled atmosphere. Mechanical
properties were reported after taking the statistical average of six measurements.
 531

The coefficients of variation, 2.5-8.5%, were taken into account for each set of
tests.
'
4. RESULTS AND DISCUSSION

Figures 1-4 show the variation in mechanical properties, e.g. stress, elongation,
energy, and modulus, on the concentration of CTMP in PS 201 based compo-
sites, where the fibers were coated with the same polymer (10 wt% of fiber) and
phthalic anhydride (2-10 wt% of fiber). Figure 1 reveals that the stress of coated
fiber-filled composites is superior to that of non-coated fiber-filled composites,
and it increases with the rise in concentration of the coupling agent (e.g. phthalic
anhydride) at the initial stage, and then decreases with the higher percentages of
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

fiber level. Furthermore, the stress remains unaltered for the change in concen-
tration of the coupling agent when the composites contain either lower or higher
levels of fiber (e.g. 15 or 35 wt%). In fact, for composites containing lower levels
of fiber (e.g. 15 wt%) the stress under all circumstances is superior even to that of
the original polymer. But for composites containing 5% phthalic anhydride-
coated fibers, the stress is superior to the original polymer even up to 25% of
fiber loading.
Figure 2 shows that elongation of the coated fiber-filled composites (except for
composites containing 10% phthalic anhydride) lies between that of the original
polymer and non-coated fiber-filled composites. The spectrum of energy vs.
weight (Fig. 3) of the fiber follows more or less similar trend to that of stress. But
unlike stress, the energy of the composite material with 5% PHA is much higher
than that of the material with 10% PHA. While, the later one is identical with that
with only 2% PHA, especially at 15% fiber loading. Modulus (Fig. 4) of the
coated fiber-filled composites increases with the increase in fiber content of the
composites, and its value exceeds that of the original and non-coated fiber-filled
composites, particularly when higher fiber loading (e.g. 35 wt%) is considered.

WEIGHT
OF FIBER(%)
Figure 1. Variation of the stress with the concentration of filler as well as the composition of coated
materials (PS 201 and phthalic anhydride) for PS 201-CTMP composites.
 532
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

WEIGHT OF FIBER(%)
Figure 2. Variation of the elongation with the concentration of filler as well as the composition of
coated materials (PS 201 and phthalic anhydride) for PS 201-CTMP composites.

WEIGHT
OF FIBERz)
Figure 3. Variation of the energy with the concentration of filler as well as the composition of coated
materials (PS 201 and phthalic anhydride) for PS 201-CTMP composites.

Figures 5-8 represent the mecanical behaviour of PS 525-CTMP composites,

where fibers were coated with PHA (2-10 wt% of fiber) and PVC (10 wt%). It is
found from these figures that the mecanical properties of the fiber-filled
composites improve compared to the original polymer. Most of the mechanical
properties, except modulus, increased compared to non-coated fiber-filled
composites, especially up to the 25% level of fiber loading. Moreover, 10% PHA
seems to be the best as far as the concentration of PHA is concerned. The
modulus of coated fiber-filled composites is inferior to that of non-coated ones.
 533
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

WEIGHT OF FIBER(%)
Figure 4. Variation of the modulus with the concentration of filler as well as the composition of
coated materials (PS 201 and phthalic anhydride) for PS 201-CTMP composites.

WEIGHT
OF FIBER(%)
Figure 5. Variation of the stress with the concentration of filler as well as the composition of coated
materials (PVC and phthalic anhydride) for PS 525-CTMP composites.

The influence of the same coating compositions, e.g. PS 201/PVC (10 wt%)
+ PHA (2-10 wt%), as well as PS 525 + PHA on the mechanical properties of
PS 201 and PS 525-sawdust (both aspen and spruce) was investigated. It appears
from the experimental results that all the mechanical properties follow more or
less similar trends to that discussed earlier. The improvement percentages of the
composite materials compared to those of the original polymers were calculated
and are listed in Tables 1-3 for three types of filler, e.g. CTMP, sawdust aspen,
and sawdust spruce. These tables indicate that the properties of the coated fiber-
 534
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

WEIGHT OF FIBER(%)
Figure 6. Variation of the elongation with the concentration of filler as well as the composition of
coated materials (PVC and phthalic anhydride) for PS 525-CTMP composites.

WEIGHT OF FIBER(%:)
Figure 7. Variation of the energy with the concentration of filler as well as the composition of coated
materials (PVC and phthalic anhydride) for PS 525-CTMP composites.

filled composites are generally superior to the original polymer with some
exception, and except for modulus, the other properties increase even compared
to non-coated fiber-filled composites. The maximum improvements in
mechanical properties, except those of modulus which increase continuously
with the addition of more and more fibers to the composites, occur between 15%
and 25% fiber content, but in a few cases they occur at even 35%. Moreover, the
properties improve more when PVC is used as a coating component compared to
that of PS 525. In these tables, the corresponding results for the composites
 535
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

WEIGHT OF FIBER(%)
Figure 8. Variation of the modulus with the concentration of filler as well as the composition of
coated materials (PVC and phthalic anhydride) for PS 525-CTM composites.

Table 1.
Comparison of the improvement in the mechanical properties of polystyrene-CTMP (aspen)
composites

ablyweight of fiber.
bPoly[methylene(polyphenyl isocyanate)].
 536

Table 2.
Comparison of the improvement in the mechanical properties of polystyrene-sawdust (aspen)
composites
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

°By weight of fiber.

6Poly[methylene(polyphenyl isocyanate)].

where fibers were coated with polystyrene and other coupling agents, e.g.
PMPPIC, are also included. It can be seen that the properties of the composite
materials improve more when fibers are coated with polymers other than base
polymers, e.g. for PS 201-based composites, PS 525 is better than PS 201 as a
coating component; whereas for PS 525-based composites PVC is better than
PS 525. PMPPIC seems better when compared to the performance of PHA.
The impact strength of the composite materials is shown in Table 4. This table
reveals that the impact strength of the PS 201-based composites improved up to
10% of PHA. However, the impact strength of the PS 525-based composites is
inferior to that of the original polymer.
The general improvements in the mechanical properties due to the addition of
PHA to the composites indicate that PHA acts as a reinforcing agent. The
function of PHA as a reinforcing agent can be explained in the following way.
The surface -OH groups of cellulose and of its counterpart lignin can link to the
anhydride groups of PHA, through the formation of either primary types of
linkage, e.g. ester linkage, or secondary types of linkage, e.g. hydrogen bonding.
However, the delocalized ;r-electrons of the benzene rings of both polystyrene
and phthalic anhydride also provide a strong interaction. In this way, PHA
develops an overlapping interface area between fiber and polymer matrices.
Moreover, prior coating of the fiber with polymer and PHA assists in the
formation of a soft film of hydrophobic materials on the surface of the hydro-
philic fiber. As a result, the phase separation between the two different matrices
 537

Table 3.
Comparison of the improvement in the mechanical properties of polystyrene-sawdust (spruce)
composites
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

° Byweight of fiber.
bPoly[methylene(polyphenyl isocyanate)].

Table 4.
Influence of coating compositions on the impact strength of polystyrene-wood fiber composites

a Byweight of fiber.
b Fbers were coated with the corresponding polymer.
 538

might be reduced. In addition, strong fiber-fiber interaction due to inter-

molecular hydrogen bonding has also been diluted, which leads to better
dispersion of the fibers.
The mechanical properties improve independently of the concentration of
PHA because with the increase in concentration of PHA in the composite, the
possibility of the formation of interfacial contact increases. In most cases, a
higher concentration of PHA (e.g. 10%) is detrimental. Excess PHA may act as
an inhibitor. Once again, the extent of improvement varies with the change in the
quality of fiber as well as in the nature of the coating compositions, especially
polymer. In fact, there is a wide difference in morphology, mechanical and
physical properties among the wood species (e.g. hardwood and softwood), as
well as in the quality of the pulps (e.g. CTMP and sawdust); they interfere in the
Downloaded by [University of Sussex Library] at 13:32 15 January 2015

performance of wood fibers in thermoplastic composites [8-11]. Similar to wood

species and the nature of pulps, various polymers, e.g. polystyrene and PVC, and
grades of polymer, e.g. PS 201 and PS 525, possess dissimilar physical and
mechanical behaviors [5], which might be the cause of such a difference in the
performances of these composites.
When comparing the performance of PMPPIC and PHA, one observes that the
former is more efficient as a coupling agent. PMPPIC links the cellulose matrix
through a chain of urethane bonds [5, 6, 12], whereas PHA forms ester linkages
and hydrogen bonds. The former types of chemical linkages are believed to be
more stable than those of the latter types. Moreover, the polymeric nature of
PMPPIC helps to link the cellulose phase and the polymeric phase (polystyrene)
continuously in the interface, while the discrete nature of PHA makes it inferior
in this respect [6].

5. CONCLUSION

The mechanical properties of coated wood fiber-filled composite materials are

generally better than those of the unfilled polymer. Except for the modulus, the
other properties improve even compared to those of non-coated fiber-filled
composites. The concentrations of phthalic anhydride and fiber which produce
maximum improvements in the mechanical properties differ with the change in
coating composition, wood species and pulping technique. Coating of wood fiber
with a polymer and a coupling agent provides a soft film of hydrophobic
materials on the surface of the hydrophilic fiber. As a result, adhesion between
the filler and the thermoplastic increases, which leads to an improvement of the
mechanical properties of the coated fiber-filled composite materials.

Acknowledgements
The authors wish to thank the NSERC of Canada, CQVB of Quebec, and
Polysar Ltd. for their financial support.

REFERENCES
1. Mathisen Macara and Co., UK Patent, 1 498 501 (1978).
2. S. H. Eldin, Canadian Patent, 1 192 102 (1985).
3. L. A. Goettler, UK Patent, 376 144 (1983).
4. T. Imagawa and N. Endo, UK Patent, 4 029 847 (1977).
 539

5. D. Maldas, B. V. Kokta and C. Daneault, J. Appl. Polym. Sci. 37, 751 (1989).
6. D. Maldas, B. V.Kokta, R. G. Raj and C. Daneault, Polymer 29, 1255 (1988).
7. D. Maldas, B. V. Kokta, R. G. Raj and S. T. Sean, Mater. Sci. Eng. A104, 235 (1988).
8. B. V. Kokta, P. D. Kamdem, A. D. Beshay and C. Daneault, in: Polymer Composites,B. Sedlácek
(Ed.), p. 251. Walter de Gruyter, Berlin (1986).
9. J. A. Cleark, Pulp Technology and Treatment for Paper, 2nd edn, Chap 9, p. 184. Miller
Freeman, San Francisco (1985).
10. B. V. Kokta, J. L. Valade and C. Daneault, Pulp. Pap. Can. TR 59 (1979).
11. D. Maldas, B. V.Kokta and C. Daneault, J. Appl. Polym. Sci. 37, (1989).
12. W.E. Johns, J. Adhesion 15, 59 (1982).
Downloaded by [University of Sussex Library] at 13:32 15 January 2015