Note: Descriptions are shown in the official language in which they were submitted.
2037~ j~
BACKGROUND OF THE INVENTION
The present invention has to do with the preparation of composite materials with
the addition of more than one reinforcement into a thermoplastic resin. More
5 specifically, it deals with the compatibility of at least two normally incompatible fillers,
e.g. inorganic and organic, in an incompatible polymer matrix. This question is
examined by using surface modified fillers.
The present invention also deals with reinforced thermoplastic composites which
exhibit good physical properties, particularly dimensional stability, as well as improved
10 strength or modulus, even after exposure to adverse environments.
Manytypes of composite compositions orthermoplastic orthermoset resins have
been proposed and commercialized. Among the reinforcing fillers used here, only
organic fillers, such as wood flour, wood pulp, non-wQQdy fibers, and inorganic fillers,
such as calcium carbonate, talc, mica, glass are well known. Such materials are
15 described in Woodhams, in U.S. Patent No. 3,764,456, issued October 9, 1973, and
in U.S. Patent No. 4,442,243, which describe mica-reinforced thermoplastic
composites having improved durability, physical and aesthetic properties which are
prepared by mixing the resin and the mica in the presence of propylene polymer wax
The mica can be pretreated to provide functional groups for a subsequent chemical
20 reaction with the propylene polymer wax.
Tatsumi, Japan Patent Kokai No. 252,353/87, issued Nov. 4, 1987, prepared
high-strength building materials from fiber-cement compositions having mica as one
of the constituents.
As described in the 1978 SPI proceedings, mica reinforcement imparts a high
25 degree of stiffness in a polymeric matrix; it also results in improved strength, wrap
resistance and thermal stability, lower shrinkage and cost reduction. Unlike asbestos
and glass, rnica is non-tQxic and does not irritate the skin. AISQ~ being a soft mineral
causes relatively little tool wear.
~3~
Show et al., France Patent No. 7,634,301, issued Nov. 15, 1976, described the
preparation of a new material which can be adapted to different applications. It is
formed by a copolymer or a lignocellulosic element which is bound to a polymer by
grafting in such a manner that the resulting product can play a reinforcement role in
5 the polymer, in the place of highly expensive mineral fibers, such as glass fiber.
Kokta, U.K. Patent No. 2,203,743, found that cellulosic-filled polyethylene
composites compared well to either mica composites. The strength of polyethylene
grafted aspen fiber composites remained virtually unaffected after boiling in water for
3 hours and the cellulosic-filled composites compared well with that of mica.
10 Moreover, cellulosic composites remained dimensionally as stable as mica composites
after 35 days in water at room temperature.
Beshay, U.S. Patent No. 4,717,742, reported that silane grafted cellulose pulp
and polyethylene composites, after being boiled in water for 4 hours, remained
stronger than polyethylene and mica. In addition, grafted aspen pulp-filled composites
15 do not lose their reinforcing properties even at -40C and keep their reinforcing
advantages vis-à-vis mica.
The published literature includes a number of proposals for dispersing and
compatibilising discontinuous cellulose fibers in a thermoplastic matrix.
Hamed, U.S. Patent No. 3,943,079, described the pretreatment of cellulose fibers
20 with a plastic polymer and a lubricant.
Kokta, U.K. Patent No. 2, 192,397, 2,192,398 and 2,203,743, detailed the
precoating of cellulose fibers with a compatible polymer in the presence of silane or
isocyanate coupling agents and prepared the composites of polyvinyl chloride or
polyethylene and coated fibers.
Beshay, U.S. Patent No. 4,717,742, reported on silane grafted cellulose pulp and
polyethylene composites.
Lund, U.S. Patent No. 4,241,133, mixed elongated wood flakes with a binder
(e~g. a polyisocyanate), which were then shaped into a mat and hot-pressed to form
elongated structures such as building beams, posts, etc.
Fujimura, Japan Patent Kokai No. 137,243/78, found that a cellulosic material,
e.g. straw, acetylated with gaseous acetic anhydride, is a good reinforcing filler for
5 polyethylene.
Gaylord, U.S. Patent No.3,485,777, showed the compatibility of grafted cellulose
fibers with polyvinyl chloride or polymethylmethacrylate matrices. In his U.S. Patent
No. 3,645,939, he also reported the good compatibility of plastics, e.g. polyethylene,
polyvinyl chloride or acrylic rubber, with cellulose by precoating the fibers with a
10 thermoplastic, ethylenically unsaturated carboxylic acid or anhydride and a free radical
initiator.
Dainippon Ink and Chemical Inc., Japan Patent Kokai No. 79,064/85, described
the use of a copolymer of maleic anhydride, phthalic anhydride, and the like, and
benzoyl peroxide, as a good prepreg with good blocking resistance on decorative
15 laminated sheets.
Pleska, France Patent No. 2,456,133, showed that a mixture of polyolefin fibril
and polyolefin grafted with a polar monomer (e.g. maleic anhydride) exhibited good
compatibility with cellulose fibers.
Eldin, Canadian Patent No. 1,192,102, described organic and inorganic fiber
20 composites prepreg coated with two different resins, e.g. maleic acid
(derivatives)/hydrantoin vinylether copolymers.
Kansai Kogyo Co. Ltd., Japan Patent Kokai No. 217,552/83, prepared extruded
composites containing pp, wood flour and citric acid ester to produce a composite
sheet with high flexural strength and high heat distortion temperature.
Lachowicz et al., U.S. Patent No. 4,107,110, described that ~c-cellulose fibers,
coated with graft copolymer comprising 1,2-polybutadine to which an acylate, such as
butylmethacrylate, is grafted, could be used in reinforcing PE and other plastic
7 ~
compositions~
SUMMARY OF THE INVENTION
Mica or cellulose fibers, grafted with a compatible polymer or a small amount of
certain bonding agents, such as isocyanate or silane, provide better adhesion when
added to the polystyrene matrix.
Such hybrid composites improved their physical and mechanical properties, as
well as durability, even at sub-zero conditions or at high temperatures.
In the present invention, composites are made of mica surface modified with
silane bonding agents and discontinuous cellulose fibers modified by grafting with
polystyrene, or pre-reacted with silane bonding agen~s such as A-,100, or with
PMPPIC, dispersed in a polystyrene matrix.
Composites containing from 1 to 50% of mica + cellulose fibers by weight, based
15 on the total weight of composites, and 1 to 100 weight ratio of mica and cellulose
fibers are within the scope of the invention.
DETAILLED DESCRIPTION OF THE INVENTION
The mica used in the present invention includes both phlogopite and muscovite
of untreated and surface treated mica in the form of powder, flake, delaminated, highly
delaminated or super-delaminated grades of NP-, FM-, (;~X-, S-, HK-series. Treated
mica, especially silane treated mica, of NP grades offers the best results.
Cellulosic material includes fibers from softwood or/and hardwood pulps, e.g.
25 chemical or mechanical or chemi-mechanical or refiner or stone groundwood or
thermo-mechanical or chemi-thermomechanical or explosion or low-yield or high-yield
or ultra high-yield pulp, nutsheels, corn cobs, rice hulls, vegetable fibers, certain
bamboo type reeds, grasses, bagasse, cotton, rayon (regenerated cellulose), sawdust,
wood flour, wood shavings and the like.
Cellulose fibers from wood sawdust, wood flour, wood pulps, e.g. mechanical
pulps or chemi-thermomechanical aspen pulps, revealed themselves to be the best.
5 Many types of wood pulp are available. They can be classified according to their
treatment (chemical, mechanical, thermal) in the pulp and paper industry. Waste pulp
and /or recycled pulp can also be used. The fibers have an aspect ratio (length
divided by diameter) ranging from 2 to 5 for sawdust, wood flour as well as for
mechanical pulps, from 15 to 50 for chemi-mechanical and chemi-thermomechanical
10 pulps, and from 50 to 150 for low-yield chemical pulps (e.g. kraft, soda or bisulfite).
In some instances, it is preferable to use fiber mixtures with widely different
aspect ratios.
The polymer contained in the matrix is described as being "polystyrene". In fact,
it includes both polystyrene polymer and copolymer (a major proportion of polystyrene
15 with a minor proportion of other vinyl polymer). The polymer "polystyrene" includes
polystyrene of different densities as well as different proportions of crystalline and
amorphous fractions.
It is normal practice to treat the surface of the filler which is used in the
composition to improve its compatibility, dispersibility and adhesion in relation to resin.
20 Thus, the following processes for such treatment were taken into account.
(1 ) Coating process, i.e. a process according to which the surface of the filler is
coated with a coupling agent and, consequently, forms a strong bonding with the filler
and polymer, e.g. polymeric diisocyanate type or the like, and with a substance
compatible with the resin, e.g. rubber-type or vinyl-type of low molecular-weight
25 materials or the like. In preparing the coated cellulose fibers, one of the preferred
techniques is to mix the bonding agent with 5% to 15% by weight of polymer based
on totai polymer weight, and then mix the resulting mixture with cellulosic fibers in a
,J l ~
roll mill. Further details appear in Goettler, U.S. Patent No. 4,376,144, issued Mar.
8, 1983. The latter reported the technique which consists of combining the bonding
agent, e.g. isocyanate, with the cellulose fibers in a pre-treatment stage for cellulose-
PVC composites. Kokta, U.K. Patent No. 2,193,503, issued Feb. 10, 1988, and
5 2,191,398, issued Jan. 13, 1988, reported the post-coating procedure for cellulose
fiber with polystyrene or polyvinyl chloride and isocyanate bonding agent before mixing
the cellulose fibers with polystyrene or polyvinyl chloride composites.
(2) Surface treatment with a coupling agent, e.g. a process according to which
the surface of a filler is treated with a coupling agent, e.g. of a silane type or the like,
10 and a substance compatible with the resin, e.g. rubber-type or vinyl-type of low
molecular weight-materials or the like. This process also consists of adding an
organic peroxide while the filler is heated. Further details appear in Hishida, U.K.
Patent No. 2,090,849. The latter described the surface coating of jute fibers with
various coupling agents, e.g. stearate, silane, titanate, acrylics, etc., and prepared
15 composites of polypropylene and polystyrene. Beshay, U.S. Patent No. 4,717,742,
issued Jan. 5, 1988, reported a technique for grafting a bonding agent, e.g. silane,
onto cellulose fibers in a pre-treatment stage for cellulose-polyethylene composites.
Kokta, U.K. Patent No. 2,192,397, issued Jan. 13, 1988, and 2,203,743, issued Oct.
26, 1988, reported a post-treatment procedure for cellulose fibers with a silane
20 bonding agent before mixing the cellulose fibers with polyvinyl chloride or polysthylene
composites.
(3) Grafting process, e.g. a process according to which a substance compatible
with the resin, e.g. rubber-type or vinyl-type of low molecular-weight materials or the
like, is directly attached to the surface of filler. In preparing the graft copolymer, the
25 xanthate method of grafting is a favorite technique in order to initiate branching on the
cellulose matrix. Further details of this method are given by R.W. Faessinger and J.S.
Conte, U.S. Patent No. 3,359,224, Dec., 1967; E. Ehrnooth, J. Polvm. Sci., Symp. No.
~fti~-! f
42,1569, 1982; V. Hornof, C. Daneault, B.V. Kokta and J. Valade, Modified Cellulosic,
R.M. Rowell and R.A. Young (eds.), Academic Press, New York, 227, 1978; M. H. El-
afie, E.M. Khalil, S.A. Abdez-Hafiz and A. Hebeish, Acta Polvmerica, 36, 668, 1985;
and B.V. Kokta, P.D. Kamdem, A.D. Beshay and C. Daneault, Polvmer Com~osites,
5 B. Sedlacek (ed.), Water de Gruyter and Co., Berlin, 251 (1986). These references
disclose, for example, the grafting of different vinyl monomers onto wood pulps or
cotton fabric.
When selecting the surface-treating agent, it is necessary to take into
consideration the type of resin and the reason for improving the properties of the
10 composition. Since it is only natural to use a surface-treated agent or a compatible
vinyl monomer suitable for this purpose, it is difficult to limit oneself to special
materials.
The use of a combination of fillers with known fillers or additives (taking into
consideration costs and properties of the composites) is of course possible, and such
15 a combination is also within the technical scope of the present invention.
The polymer is added to a mixture of coated mica and uncoated (or coated)
cellulose fibers to form a composite, usually in an internal mixer, in an extruder or in
a roll mill. Other ingredients, such as fillers, plasticizers, stabilizers, colorants, etc.,
an also be added at this point. Apart from mica, inorganic filler materials may be
20 selected: calcium carbonate, talc, glass fibers, etc.
The following specific examples illustrate the use of mixtures of coated mica and
cellulose fibers in polystyrene composites.
EXAMPLE 1
High impact polystyrene (PS 525) was supplied by Polysar Limited, Sarnia,
Ontario, Canada.
Mica-200-NP-Suzorite (200 mesh, silane treated) was supplied by Mariella Co.,
~ U ~ ~ L,~ S
Montréal, Canada.
Hardwood species of aspen (Populus tremuloides Michx) was used in the form
of chemithermomechanical pulp (CTMP), CTMP was prepared in a Sund Defibrator.
Its properties are described in Kokta, U.K. Patent No. 2,193,503.
CTMP aspen pulp was dried in an air circulating oven at 55C for 48 hours, and
then ground to a mesh size 60 mixtures; 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., U.S.A.
The wood fibers were precoated with 10% PS 525 ~ 8% PMPPIC or 4% silane
A-1100 or grafted with polystyrene (89.1 % add-on).
Preparation of the com~osites
A 25 gram mixture of cellulosic fiber + mica (15-35% by weight of composite) and
polymer were mixed in a roll mill at 175C. After mixing 5 to 10 times, the resulting
15 mixtures were reground once again to mesh size 20 and then molded into shoulder-
shaped test specimens (ASTM D-638, Type V). Standard molding conditions were
temperature, 175C; pressure during heating and cooling, 3.8 MPa; heating time, 20
min; cooling time,15 min. Width and thickness of each specimen were measured with
the help of a micrometer.
Mechanical tests
The mechanical properties (e.g. tensile strength at yield point and the
corresponding elongation and energy as well tensile modulus at 0.1 % strain) of all the
samples were measured with an Instron Tester (Model 4201) following ASTM D-638.
25 The mechanical properties were au~omatically calculated by a HP-86B computer. The
strain rate was 1.5 mm/min. The samples were tested after conditioning at 23+0.5C
and 50% R.H. for at least 18 hours in a controlled atmosphere. Mechanical properties
2 ~ ~ ji L,~
were reported after taking the statistical average of six measurements. The
coefficients of variation 2.5-8.5% were taken into amount for each set of tests.
Table I shows the mechanical properties of both treated and untreated
CTMP/treated mica-filled PS 525 composites. The properties of the composites were
5 compared to those of virgin polystyrene. it is obvious that the mechanical properties
of treated CTMP/treated mica-filled composites improved compared to those of both
the original polymer and non-treated CTMP/treated mica-filled composites. In general,
properties are enhanced when compositions of isocyanate-coated CTMP and mica are
taken as 3:1 or 1:3 wt. ratio and up to a 25 wt. % fiber addition. As for 1:1 wt. ratio
10 of silane-coated or grafted CTMP and mica, the tensile strength values ranked best
at a 25 wt. % filler level, whereas modulus improved up to a 35 wt. % filler level. The
best improvements in elongation and energy for the same composites occured at a
3:1 wt. ratio of coated CTMP and mica and at a 25 wt. % filler level. According to
Table 1, properties improved even more when polystyrene-grafted CTMP was used as
15 a hybrid-fiber component.
EXAMPLE ll
The composites were prepared and evaluated as described in Example 1, except
that polystyrene used in this case was high-heat crystal polystyrene (PS 201 ) provided
20 by Polysar Limited of Canada. The mechanical properties are presented in Table ll.
I~ appears from this table that the mechanical properties of treated CTMP and mica-
filled composites increased in many cases compared to those of virgin polystyrene
and those of non-treated CTMP and mica-filled composites. In addition, tensile
strength, elongation and energy for isocyanate-coated CTMP/mica-filled composites
25 ranked best. Silane-coated CTMP/mica, however, provided the best results with
regard to modulus.
EXAMPLE lll
The composites were prepared and evaluated as described in Examples I and
Il, except that the impact strength (Izod, un-notched) of the composites was tested
with an Impact Tester (Model TMI, No. 43-01 of Testing Machines Inc., U.S.A.),
5 following ASTM D-256. The properties appearing in Table lll reveal that impact
strength of PS 201 based composites exceeds that of the original thermoplastic when
silane-coated or grafted CTMP is used as a hybrid filler component. On the contrary,
impact strength of PS 525 based composites is generally inferior to that of the original
polymer.
EXAMPLE IV
The composites of both treated and untreated cellulose fiber/mica were prepared
and evaluated as described in Examples I and ll, except that CTMP aspen was
replaced by sawdust aspen. The tensile properties are presented in Table IV. This
15 table reveals that the properties of the composite materials comprising treated
sawdust and mica improved in many cases, up to 25% of fiber level compared to
those of virgin polymer and those of non-treated sawdust/mica-filled composites.
Moreover, compared with the mechanical properties of treated sawdust/mica-filled
composites, isocyanate-coated wood fibers provided results better than those of
20 silane-coated ones.
EXAMPLE V
The composites of both treated and untreated cellulose fiber/mica fiber and PS
525 were prepared and evaluated as described in Example 1, except that CTMP aspen
25 was replaced by sawdust spruce. The tensile properties are presented in Table V,
wherein the coated sawdust spruce fibers follow nearly similar trends to those of
sawdust aspen fibers (as discussed in Example IV).
EXAMPLE Vl
The composites of both treated and untreated sawdust aspen and sawdust
spruce fibers/mica, and PS 201 and PS 525 were prepared as described in Example
1~ The Izod impact strength of the composites was evaluated as described in Example
5 Ill, while the properties appear in Tables Vl and Vll. In general, the mechanical
properties of treated sawdust/mica-filled composites provided inferior results compared
to those of the virgin polymers. But, in many cases, the impact strength of treated
sawdusVmica-filled composites was better in comparison with that of non-treated wood
fiber/mica-filled composites.
EXAMPLE Vll
The composites of both treated and untreated CTMP aspen as well as sawdust
aspen/mica, and PS 525 were prepared as described in Example 1. However, mica-
200-NP-Suzorite was replaced by mica 60-NP-Suzorite (60 mesh, silane coated). The
15 resulting hybrid composites were exposed to various environmental conditions, e.g.
exposure to boiling water for 24 hours and to heat at +1 05C for 5 days as well as at
a subzero temperature (e.g. -20C). The mechanical properties were tested at room
temperature or at subzero temperature as described in Example 1. A part of the
unexposed samples as well as a part of those which underwent boiling water and heat
20 exposure, were tested at room temperature. The remaining unexposed samples and
boiling water exposed samples were kept at -20C in the Thermostatic Instron
Chamber (Model 311) for 2 hours, and the mechanical properties were evàluated at
that temperature. Tables VIII-XI summarize the percentage change in the mechanical
properties, e.g. tensile strength, elongation, energy and modulus (based on the
25 properties of the original polymer under an identical treatment), of composites
containing a filler content of only 25%, under various extreme conditions. Tables Vlll
and X reveal that the strength of non-treated wood fibers/mica-filled composites
deteriorates, but that the strength of PMPPIC coated wood fiber-filled and/or mica-
filled (e.g. 3:1 weight ratio of wood fibers and mica) composites improved. Under all
extreme conditions, except boiling water exposure, strength improved compared to
that of the original polymer. Again, compared to room temperature, strength improved
5 even more when samples were exposed to high temperatures. At subzero
temperatures, the strength of non-treated wood fibers/mica-filled composites
deteriorated. On the other hand, some properties improved under identical conditions
when treated wood fiber/mica-filled composites were considered. Although only the
strength of wood fiber-filled composites deteriorated due to testing at subzero
10 temperatures after exposure to boiling water, strength improved marginally for wood
fiber/mica-filled composites under identical conditions. Again from Tables Vlll and X,
where modulus of composites under various extreme conditions is compared, it is
observed that modulus follows a similar trend to that of strength. Moreover, in many
cases, modulus of treated wood fiber/mica-filled composites revealed itself to be
15 superior compared to that of non-treated wood fiber/mica-filled composites.
Tables IX and Xl indicate that both elongation and energy of treated wood
fiber/mica-filled composites are superior to those of non-treated wood fiber/mica
composites under all extreme conditions. Due to exposure in boiling water, both
elongation and energy deteriorate for non-treated wood fiber/mica-filled composites.
20 However, these properties improved when treated wood fibers alone, or mixtures of
wood fibers and mica, were used. In most cases, both elongation and energy of non-
teated wood fibers or silane-treated wood fiber/mica-filled composites decreased due
to heat exposure. A contrary result occurred for PMPPIC trea~ed wood fiber/mica-filled
composites. Elongation of treated wood fiber/mica-filled composites improved in many
25 cases, even at subzero temperatures, whereas energy for composites under identical
conditions revealed itself inferior to the original polymer. Once again, elongation and
energy of the composites deteriorated at subzero temperatures after being exposed
to boiling water.
EXAMPLE Vlll
The composites of both treated and untreated CTMP aspen as well as sawdust
5 aspen/mica, and PS 525 were prepared as described in Example 1. The resulting
hybrid composites were exposed to various environmental conditions, e.g. exposure
to boiling water for 24 hours and to heat at +105C for 5 days as described in
Example Vll. Dimensional stability (i.e. change in weight as well as cross section area)
of the composites filled with 25 wt. % of CTMP/mica are presented in Tables Xll and
10 Xlll. It is obvious that both weight and area increased along with a rise in the
proportion of wood fibers in the composites. Non-treated wood fiber/mica-filled
composites showed a greater development in both weight and area, whereas
isocyanate or silane-coated wood fiber/mica-filled composites exhibited a lesser
increase. As a result, treated wood fiber/mica-filled composites provided better
15 dimensional stability, even after being boiled in water for 24 hours. When heated in
an oven at +1 05C for 5 days, the order of stability followed almost exactly the same
trend as that of exposure to boiling water.
Although the present invention has been described in some detail above with the
help of illustrations and examples, it is obvious that certain changes may be practiced
20 within the scope of the appended claims.
~ ~ ~ 7 . .
TABLE I
Composition Tensile Elongation Energy Modulus
of fibersstrength (MPa) (%) (mJ) (GPa)
Weight % of fiber15 25 35 15 25 35 15 25 35 15 25 35
CTMP Mica
16.8~ 1.5~ 17.2~ 1.4
Non-treated CTMP (aspen)
100 0 18.9 22.3 21.5 1.6 1.7 2.2 22.9 25.1 39.7 1.8 2.0 2.3
18.8 17.6 17.0 1.5 1.51.2 21.5 22.2 17.5 1.7 1.9 2.0
18.7 18.2 16.1 1.5 1.5 1.0 22.9 21.4 13.4 1.7 2.1 2.2
17.2 17.0 15.2 1.5 1.5 1.3 22.2 18.8 16.4 1.6 1.7 1.9
0 100 16.3 15.9 15.0 1.3 1.1 1.0 14.7 12.6 11.8 1.8 2.0 2.4
CTMP (aspen) coated wnh PMPPIC (8%~
100 0 17.9 23.3 20.0 2.9 3.7 3.5 46.9 76.8 58.7 1.5 1.7 1.8
19.3 18.6 17.5 1.8 1.7 1.4 26.6 27.7 19.8 1.6 1.7 1.9
18.9 18.2 15.6 1.7 1.4 1.0 25.2 20.4 14.3 1.9 1.9 2.2
18.9 18.9 20.3 1.6 1.6 1.4 23.1 25.8 24.2 1.6 1.9 2.1
CTMP (aspen) coated wnh silane A-1100 (4%~*~
100 0 17.5 20.6 17.9 1.4 1.7 1.5 19.3 29.3 21.2 1.6 1.8 2.0
17.2 18.5 16.0 1.6 1.8 1.2 24.7 28.5 14.3 1.5 1.8 2.0
16.2 19.0 16.6 1.5 1.7 1.2 20.4 28.4 15.0 1.6 2.0 2.2
17.2 17.5 17.4 1.5 1.3 1.3 20.8 18.5 17.7 1.7 2.0 2.2
CTMP (aspen) arafted with polvstyrene (89.1%)~
100 0 18.1 21.1 24.3 4.5 3.6 3.0 79.0 63.4 60.7 1.4 1.5 1.6
17.4 19.9 21.3 1.6 3.0 2.4 23.0 56.4 47.5 1.5 1.7 1.8
17.5 21.8 18.3 1.5 1.9 1.4 20.7 38.3 22.0 1.6 1.8 2.2
16.5 17.2 16.3 1.4 1.6 1.2 19.3 23.6 15.7 1.6 1.9 2.3
PS 525 (virgin)
By weight of CTMP (aspen)
TABLE ll
Composition Tensile Elongation Energy Modulus
of fibersstrength (MPa) (%) (mJ) (GPa)
Weight % of fiber 15 25 35 15 25 35 1525 35 15 25 35
CTMP Mica
41.5* 3.3* 80.5* 1.9*
Non-treated CTMP (aspen)
100 0 36.0 35.8 33.8 2.7 2.6 2.2 63.7 57.9 44.1 1.9 2.0 2.2
3Z.2 28.4 26.1 2.6 1.7 1.6 61.9 37.0 35.0 2.0 2.1 2.3
31.8 27.9 23.2 2.3 1.6 1.3 51.9 30.5 23.2 2.1 2.3 2.4
30.7 26.4 24.7 2.6 1.5 1.3 50.4 26.7 23.2 2.0 2.3 2.6
0 100 29.9 26.8 24.8 1.7 1.5 1.2 35.9 30.0 23.1 2.2 2.6 2.7
CTMP (aspen) coated with PMPPIC (8%)**
100 0 42.7 48.7 46.4 3.5 3.7 3.1 98.0 117.4 90.3 1.9 2.1 2.2
43.0 46.1 33.0 2.7 2.6 1.9 76.2 84.0 38.3 2.2 2.2 2.4
41.2 37.4 33.1 2.8 2.2 1.6 89.0 63.7 33.5 2.1 2.2 2.7
32.6 33.6 30.7 2.1 1.9 1.8 46.1 42.0 35.5 1.9 2.2 2.4
CTMP (aspen) coated with silane A-1100 (4%)**
100 0 35.4 37.2 31.2 2.2 2.3 1.6 51.3 61.6 33.4 2.0 2.2 2.4
39.6 36.6 30.0 2.8 2.5 1.6 88.1 71.1 31.5 2.2 2.4 2.7
41.4 37.9 34.9 2.5 2.4 2.0 70.6 74.3 55.8 2.3 2.3 2.6
30.3 26.7 22.1 2.2 1.6 1.3 55.3 33.1 23.1 2.0 2.4 2.5
CTMP (aspen) grafted with polystyrene (89.1%)**
100 0 43.1 44.8 42.8 3.1 3.1 2.8 77.0 77.4 71.1 2.0 2.0 2.1
39.3 38.5 28.3 2.8 2.3 1.7 76.0 64.3 38.5 2.1 2.2 2.4
34.4 31.9 23.2 2.3 2.2 1.3 59.1 46.1 26.5 2.1 2.2 2.3
* PS 201 (virgin)
** By weight of CTMP (aspen)
203745&
TABLE lll
Izod Impact Strength (J/m)
Composition
(Weight %) Polystyrene 201 Polystyrene 525
Weight % of fiber1 5 2 5 3 5 1 5 2 5 3 5
CTMP Mica
7.8~ 25.2
Non-treated CTMP (aspen)
100 0 6.3 6.1 4.9 12.0 11.3 7.0
6.46.0 4.7 12.312.0 10.2
6.06.2 6.5 12.613.0 10.4
7.57.9 5.2 12.610.5 8.7
0 100 5.75.7 6.4 11.310.2 8.2
CTMP (aspen) coated wnh PMPPIC (8%)~
100 0 5.8 6.3 6.6 11.5 12.2 9.0
6.3 6.6 6.4 10.7 12.4 9.4
6.7 7.6 6.2 11.6 10.6 9.9
6.0 6.2 5.7 11.3 10.9 9.8
CTMP (aspen! coated with siiane A-110Q (8%)~*
100 0 7.4 6.2 5.1 21.5 12.6 8.0
6.3 7.0 4.6 13.0 9.5 9.5
7.7 8.1 7.6 11.8 9.9 8.8
8.1 7.8 7.6 10.6 10.1 7.1
CIMP (aspen) grafted with polystyrene (89.1%)~
- - - 10.9 10.6 7.3
7.06.3 5.7 12.310.8 9.5
8.57.2 5.3 13.811.2 11.1
:
Only polymer
By weight of CTMP (aspen)
203~ 8
TABLE IV
Composition Tensile Elongation Energy Modulus
of fibersstrength (MPa) (%) (mJ) (GPa)
Wei~t % of fiber 15 25 35 15 25 35 1525 35 15 25 35
Sawdust Mica
41.5~ 3.3~ 80.5~ 1.9
Non-treated sawdust (aspen)
100 0 35.6 32.5 30.6 2.5 2.2 2.1 54.7 49.1 40.1 2.2 2.3 2.4
32.1 26.8 25.4 2.1 1.9 1.5 49.5 46.9 25.2 2.0 2.2 2.5
33.7 26.6 25.3 2.1 1.7 1.4 48.6 31.9 25.9 1.8 2.1 2.3
33.4 28.6 23.4 2.5 1.8 1.5 60.9 35.3 28.3 2.0 2.5 2.9
0 100 29.9 26.8 24.8 1.7 1.5 1.2 35.9 30.0 23.1 2.2 2.5 2.6
Sawdust (aspen) coated with PMPPIC (8%)~
100 0 42.6 44.7 38.5 3.4 3.3 2.7 85.5 91.8 68.7 1.9 2.0 2.0
36.7 41.0 31.1 2.2 2.4 1.7 55.4 75.1 40.1 2.1 2.1 2.3
36.1 36.6 31.4 2.1 2.1 1.9 50.6 53.6 39.9 2.1 2.3 2.4
35.2 34.3 31.4 2.1 1.8 1.7 48.0 44.2 36.7 2.2 2.4 2.8
Sawdust (aspen) coated with silane A-1100 (4%)~*
100 0 33.3 36.6 31.6 2.1 2.2 1.8 46.8 57.7 37.2 2.0 2.2 2.2
36.6 37.3 28.7 2.5 2.7 1.8 63.5 86.1 42.8 2.1 2.3 2.3
37.5 35.3 30.6 2.5 2.2 1.5 70.2 60.1 30.7 2.1 2.3 2.7
31.8 31.6 25.1 2.2 1.9 1.4 51.6 45.7 26.0 2.3 2.5 2.6
-
PS 201 (virgin)
By weight of sawdust (aspen)
~7''~3~
TABLE V
Composition Tensile Elongation Energy Modulus
of fibersstrength (MPa) (%) (mJ) (GPa)
Weight % of fiber 15 25 35 15 25 35 15 25 35 15 25 35
Sawdust Mica
16.8* 1.5* 17.2* 1.4*
Non-treated sawdust (aspen)
100 0 17.2 18.2 1,.8 1.8 1.8 1.6 22.7 25.0 21.3 1.7 1.9 2.0
17.5 16.6 16.3 1.5 1.3 1.2 22.6 17.5 16.4 1.7 1.8 2.1
17.2 16.6 15.5 1.5 1.4 1.2 22.2 18.2 14.7 1.7 1.9 2.0
16.1 14.9 14.7 1.3 1.2 1.0 16.5 14.5 12.2 1.8 1.9 2.1
0 100 16.3 15.9 15.0 1.3 1.1 1.0 14.7 12.6 11.8 1.8 2.0 2.4
Sawdust (spruce) coated with PMPPIC (8%)**
100 0 20.0 20.7 18.0 3.1 3.0 2.2 48.7 47.2 32.1 1.4 1.6 1.8
18.4 24.5 19.1 2.0 3.3 1.6 30.8 75.1 25.2 1.5 1.8 1.8
19.2 22.0 18.6 1.8 2.8 1.5 28.3 59.1 23.6 1.7 1.9 1.9
18.0 19.8 - 2.0 2.0 - 33.7 38.8 - 1.6 1.9
Sawdust (spruce) coated with silane A-1100 (4%)**
100 0 18.9 18.5 18.3 4.2 2.1 1.8 77.2 36.1 26.3 1.6 1.7 1.9
17.4 18.7 18.7 1.7 2.4 1.9 23.9 39.4 30.2 1.3 1.6 1.6
16.9 17.2 16.3 1.6 2.0 1.8 23.2 30.9 27.5 1.5 1.7 1.7
17.1 16.5 16.4 1.5 1.4 1.3 21.4 17.9 17.1 1.5 1.8 2.0
* PS 525 (virgin)
** By weight of sawdust (spruce)
r.7 iJ
TABLE Vl
Izod Impact Strength (J/m)
Composition
(Weight) Sawdust (aspen) Sawdust (spruce~
Weight % of fiber 1 5 2 5 3 5 1 5 2 5 3 5
Sawdust Mica
7.8~ 7.8
Non-treated sawdust
100 0 6.9 6.6 6.2 6.5 6.3 5.8
5.9 6.5 5.4 6.36.9 5.2
6.2 6.3 6.3 5.75.8 6.3
9.1 8.3 6.S 7.28.4 5.4
0 100 5.7 5.7 6.4 5.75.7 6.4
Sawdust coated with PMPPIC (8%)**
100 0 6.6 8.5 7.6 6.9 8.3 6.1
6.3 6.9 7.0 6.46.5 6.6
5.4 6.6 7.7 6.47.0 6.7
5.1 6.3 6.5 6.37.1 6.5
Sawdust coated with sLane A-1100 (8%!
100 0 7.7 6.3 5.6 7.3 6.8 6.0
7.5 6.8 ~.4 6.76.5 6.5
6.9 6.5 6.2 6.75.8 5.2
6.8 6.0 5.9 6.55.8 5.4
-
* PS 201 ~virgin)
** By weight of sawdust
^,3 C~
TABLE Vll
Izod Impact Strength (J/m)
Composition
Weight % Sawdust (aspen) Sawdust (spruce~
Weight % of fiber 15 25 35 15 25 35
Sawdust MiGa
- e_
25~2* 252*
Non-treated sawdust
100 0 17.3 11.2 9~8 11 ~8 11 ~4 6~7
14~6 12~6 9~6 11 ~411 ~4 7~7
12~0 12~3 9~8 10~ 4 8~9
11 ~6 10.3 9~2 11 ~210~5 8~2
0 100 113 10~2 8~2 11 310~2 8~2
Sawdust coated with PMPPIC (û%)**
100 0 17~9 12~2 11~4 12~2 14~9 91
14~7 13~4 9~ 1l44 10~9
15~2 123 11~ 8167 103
11~7 11~3 11~0 10~6120 9~6
Sawdust coated with silane A-1100 (8%)**
100 0 169 15~8 11~0 14~7 13~9 12~5
13~2 11 ~6 74 10.0 7~7 7~2
13~3 11~4 7~5 14~7 12~4 10~3
12~1 9~4 9~4 16~0 13~8 13~8
Sawdust grafted with polystyrene (11.8)**
50 10.9 9~2 8~0
.
* PS525 (virgin)
** By weight of sawdust
~7~
TABLE Vlll
-
Composition Improvement~ % of Improvement~ % of modulus
tansile strength
Weight % A B C D E A B C D E
CTMP Mica
Non-treated CTMP (aspen)
100 0 +32.7 28.4 +40.8 +18.6 +14.2 +42.9 15.4 +30.8 +69.2 +30.0
+9.8 27.8 +79.6 +5.0 +14.4 +28.6 7.7 +61.5 +61.5 0
+14.9-19.8 +92.8 +4.2 +24.8 +35.7 +23.1 +92.3 +76.9 +100.0
+5.4 -10.7 - +6.2 +23.1 +35.7 +30.8 - +82.3 +90.0
0 100 +6.0 -4.1 +38.8 +15.6 +15.1 +57.1 +53.8 +99.9 +76.9 +80.0
CTMP (aspen) coated wRh PMPPIC (8%)~
100 0 +38.7 +11.8 +55.1 +18.6 +23.7 +21.4 +15.4 +30.8 +38.5 +50.0
+25.0 +22.0 +65.1 +40.8 +28.9 +28.6 +7.7 +38.5 +70.0 +20.0
+26.2 -12.4 +72.2 +25.0 +23.7 +50.0 +7.7 +71.5 +46.2 +100.0
+32.7 +11.2 +11.0 +16.4 +20.4 +42.9 +38.5 +30.8 +92.3 +101.0
CTMP (aspen) coated with silane A-1100 (4%)*~
100 0 +22.6-6.5 +61.2 +25.9 +17.8 +28.6 0 +69.2 +76.9 +50.0
+11.3-4.1 +39.5 +33.1+26.0 +28.6-15.4 +69.2 +76.9 +70.0
+4.0-10.7 +44.6 +25.8+8.3 +35.7+30.8 +53.9 +106.7 +70.0
+6.2-3.6 +75.8 +14.3+35.9 +28.6+46.2 +69.2+115.4 +123.0
Based on PS 525 (virgin~ after similar treatment
*~ By weight of CTMP (aspen)
A: Testing at room temperature
B: Testing at room temperature after boiling in water for 24 hours
C: Testing at room temperature after heating in an oven at 105C for 5 days
D: Testing at 20C
E: Testing at 20C afler boiling in water for 24 hours
TABLE IX
,.
Composition Improvement~ % of Improvement~ % of energy
elongation
Weight %A B C D E A B C D E
CTMP Mica
Non-treated CTMP (aspen)
100 0+13.3 +47.1 +27.8 +28.6 -41.2 +45.9 +1.0 +84.3 -25.5 -52.7
-6.0 -~6.5 -16.7 -23.8 -51.0+9.3 -11.6+15.3 -67.5 -63.5
+6.7 -4.1 -11.7 +1.0 -53.1+102.3 -16.7+37.9 -45.0 -60.2
-14.7 -15.9 0 -8.1 -58.0-6.4 -24.2 - -56.1 -67.9
0 100 -13.3 -29.4 -49.4 0 -62.8-11.1 -36.4-44.2 -48.1 -71.1
CTMP (aspen) coated with PMPPIC (8%~
100 0 +146.7 +94.1 +177.8 +38.1 -47.7 +346.5 +206.6+343.7 -17.0 -52.6
25 +33.3+142.4 +7.8 +29.1 +43.1 +89.0 +273.7+56.4 +17.0 -51.2
50 +26.7+47.1 +2.2 -22.4 -50.0 +77.9 +54.6 +67.3 -60.4 -56.1
+2.0 -11.8 -22.2 0 -54.5 +34.7-16.2 -25.9 -42.7 -59.1
CTMP (aspen) coated with silane A-1100 (4%~
100 0+13.3+111.8 -22.2 +7.6 -47.1 +70.4 +163.1 -1.0 -40.0 -56.2
25 +20.0+82.4 -32.2 +22.9 -51.0 +37.2 +131.7 -22.5 -21.6 -57.7
50 +20.7-17.7 -34.4 -3.3 -58.0 +48.1 -26.8 +23.4 -45.9 -70.2
-13.3-23.5 -23.3 -14.8 -57.3 -12.2-26.8 +3.5 -54.8 -59.7
Based on PS 525 (virgin) after similar study
~ By weight of CTMP (aspen)
A: Testing at room temperature
B: Testing at room temperature after boiling in water for 24 hours
C: Testing at room temperature after heating in an oven at 105C for 5 days
D: Testing at 20C
E: Testing at 20C after boiling in water for 24 hours
TABLE X
Composition Improvement~ % of Improvement~ % of modulus
tensile strength
Weight % A B C D E A B C D E
Sawdust Mica
Non-treated sawdust (aspen)
100 0 +8.930.2 +37.4 7.6+0.1 +35.7 7.7 +46.2 +46.2 +40.0
25+10.1 24.8 +48.65.4 +6.6 +35.7 o +61.5 +100.0 +10.0
50 +3.7 20.1 +63.3+2.0+8.3 +42.9 +15.4 +84.6 +70.8 +70.0
75 +3.6 -16.0 -12.6+3.1 +6.7 +28.6 +30.8 +7.7+97.7 +102.0
0 100+6.0 -4.1 +38.8+15.6+15.1 +57.1 +53.8 +99.9 +76.9 +80.0
Sawdust (aspen) coated with PMPPIC (8%)**
100 0 +36.9 +13.0 +63.3 +15.1 +18.3 0 0 -15.4 +38.5 +60.0
25+22.6 +0.5 +29.9 +20.0 +28.5 +28.6 +23.1 +15.4 +53.9 +70.0
50+14.5 11.2 +30.5 +0.4 +14.3 +42.9 0 +46.2 +53.9 +90.0
75+17.6 2.9 +25.0 9.6 +26.0 +50.0 +61.5 +76.9 +100.0 +140.0
Sawdust (aspen) coated with silane A-1100 (4%)~*
100 0 +16.117.8 22.7 +4.8+11.0 +14.3 0 30.8 +54.6 +40.0
5.2 11.54.8 +10.2+5.3 +21.4 0 +30.8 +69.2 +40.0
50 +0.6 16.5+26.3+5.114.1 +35.7+23.1+53.9 +84.6 +50.0
3.0 20.1+23.1+6.9 5.8 +35.7+15.4+38.5 +97.7 +90.0
-
* Based on PS 525 (virgin) after similar treatment
*~ By weight of sawdust (aspen)
A: Testing at room temperature
B: Testing at room temperature af~er boiling in water for 24 hours
C: Testing at room temperature afler heating in an oven at 105C for 5 days
D: Testing at 20C
E: Testing at 20C after boiling in water for 24 hours
~7~
TABLE Xl
Composition Improvement~ % of Improvemant~ % of energy
elongation
Weight %A B C D E A E~ C D E
Sawdust Mica
Non-treated sawdust (aspen)
100 0+13.3 +5.9+5.6 0 62.1 +20.4 6.6 +40.6 54.2 75.3
25 17.3 2.4 33.331.9 62.116.924.022.0 71.4 74.6
6.7 11.8 20.415.2 60.10.1 26.86.6 60.5 69.6
75 -20.0 -17.7 -43.9-15.2 -66.7-20.4-28.8-60.4 -59.3 -76.5
0 100-13.3 -29.4 -49.4 0 -62.8-11.1-36.4-44.2 -48.1 -71.1
Sawdust (aspen) coated with PMPPIC (8%)**
100 0 +106.7 +47.1 +61.1 +33.3 -50.7 +153.5 +89.4+160.9 -24.4 60.1
25+66.7 +62.4 +22.2 +20.5 45.7 +136.6 +101.0 +47.7 34.0 53.3
50+13.3 +41.8 22.8 13.8 57.5 +40.8 +40.9 16.8 61.5 66.9
0 25.9 47.2 13.8 68.8 26.8 27.247.0 57.5 70.5
Sawdust (aspen) coated with silane A-1100 (4/O)**
100 0+106.7 +2.4 26.1 +9.6 54.1 +212.2 6.1 52.3 43.4 65.8
25-13.3 +8.8 -38.3 -1.9 -58.1-16.9 +0.5 48.1 51.8 72.4
50-13.3 -5.3 -38.9 -6.7 -65.5-15.1 -13.1 -37.1 -54.9 -79.8
75-13.0 0 -22.2 -11.7 -69.9-25.0 -17.7 +15.6 -56.9 -81.9
* Based on PS 525 (virgin) after similar study
** 8y weight of sawdust (aspen)
A: Testing at room temperature
B: Testing at room temperature after boiling in water for 24 hours
C: Testing at room temperature after heating in an oven at 105C for 5 days
D: Testing at 20C
E: Testing at 20C after boiling in water for 24 hours
20~74 i~
TABLE Xll
Composition Comparison of dimensional stability
(Weight /O)
Weight Cross section area
Weight % B C B C
CTMP Mica
-
+0.7* 0.2* +3.0* +2.3*
Non-treated CTMP (aspen)
100 0 +12.9 0.8 +12.6 0.6
+7.2 0.6 +11.9 0.6
+4.5 -0.5 +7.3 +1.6
+3.5 -0.4 +4.7 +2.8
0 100 +0.4 -0.2 +0.7 +0.7
CTMP (aspen) coated wnh PMPPIC (8%)**
100 0 +5.2 -0.7 +6.5 -1.0
+4.5 -0.5 +5.9 +2.2
+3.8 -0.4 +4.5 +0.8
+2.4 -0.2 +2.9 +0.5
CTMP (aspen) coated with silane A-1100 (8%)~
100 0 +8.4 -0.6 +10.5 +5.0
+6.7 -0.4 +7.0 +3.7
+3.6 -0.3 +4.1 +2.2
+2.7 -0.2 +3.0 +0.7
* PS 525 (virgin)
** By weight of CTMP
B: After boiling in water 24 hours
C: After heating in an oven at 105C for 5 days
2037~a8
TABLE Xlll
Composition
(Weight %) Comparison of dimensional stability
Weight Cross section area
Weight % B C B C
Sawdust Mica
(aspen)
,
+0.7~-0.2~ +3.0* +2.3*
Non-treated sawdust (aspen3
100 0 +7.1 -0.8 +7.9 -1.1
+6.0 -0.4 +6.4 -0.9
+3.9 -0.3 ~4.2 -0.7
+2.9 -0.2 +3.7 +2.8
0 100 +0.4 -0.2 +0.7 +0.7
Sawdust (aspen) coated with PMPPIC l8%3~
100 0 +5.1 -0.8 +5.5 -0.7
+4.0 -0.4 +6.6 +3.5
+3.4 -0.3 +4.5 +2.7
+2.4 -0.2 +3.4 +2.0
Sawdust (aspen) coated with silane A-1100 (8%!~
100 0 +5.7 -0.4 +6.4 +4.9
-~5.0 -0.3 +6.1 +3.1
-~3.3 -0.3 +4.4 +2.5
+2.2 -0.2 +2.9 +2.2
* PS 525 (virgin)
By weight of sawdust (aspen)
B: After boiling in water 24 hours
C: After heating in an oven at 105C for 5 days
