Note: Descriptions are shown in the official language in which they were submitted.
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Composite Article and Method of Manufacturing Same
FIELD OF INVENTION
[0001] The present invention relates generally to a composite article and a
method of
manufacturing such a composite article.
SACKGROUND OF THE INVENTION
[0002] Polyurethane resins are a family of resins that contain a significant
number of
urethane linkages within its molecular chains. Polyurethane resins are
produced by
reacting a diisocyanate with an organic compound containing two or more active
hydrogen atoms, such as polyols, in predetermined proportions, which react
under the
influence of heat or certain catalysts to form a polymer resulting in a
thermosetting
material. A composite article may be produced by impregnating reinforcement,
such as
glass or carbon fiber, with a polyurethane resin and allowing the resin to
react to form a
thermosetting composite material using applications known in the art, such as
pultrusion,
resin injection molding, filament winding, resin transfer molding, and hand
lay-up
forming applications and the like.
[0003] Filament winding is a well known process for the production of
composites. In a
typical filament winding operation, as disclosed in US 2005/0038222 (which is
incorporated herein by reference), a continuous filament of reinforcing
material, such as
glass fiber, is passed through a liquid resin bath and then wound around a
mandrel in
order to form a hollow cylindrical object, such as a utility pole. The resin
is typically
cured by application of heat and/or radiation in order to form the final
composite shaped
article.
[0004] Aromatic polyisocyanate is most widely used in polyurethane resins to
manufacture composite articles, due to its strength properties and economic
value. The
resulting aromatic isocyanate composite material however, is prone to tum
yellow on
exposure to UV radiation. The color integrity of an aromatic isocyanate
composite
material quickly diminishes and eventually the resin property of the composite
will be
weakened after prolonged UV exposure and weathering. Therefore, polyurethane
composite articles, especially those utilized in the outdoor environment that
are exposed
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to prolonged periods of UV radiation and other weathering (such as, but not
limited to
utility poles) need extra protection require extra protection.
[0005] Various attempts have been made to maintain the color and integrity of
aromatic
isocyanate based polyurethane composite articles, for example, by brush
painting, spray
painting and roller painting the articles with various paint types that are
typically resistant
to UV radiation. However, these attempts have found little acceptance in view
of the
expense, technical difficulties and questionable durability of these paints,
especially when
the polyurethane composite articles are large infrastructure products such as
utility poles.
[0006] US Patent 6,420,493 (which is incorporated herein by reference)
describes the use
of volatile organic compound (VOC) fiee polyurethane composite resins for
composite
materials. Although a VOC free aliphatic polyisocyanate has superior
resistance to
chemicals and ultra violet (UV) rays, it is typically much more expensive than
a VOC
free aromatic polyisocyanate. It is therefore taught in US Patent 6,420,493,
that in order
to obtain a balance between physical properties and cost a polyisocyanate
component
comprising a homogeneous blend ofat least 15% by weight of an aliphatic
polyisocyanate
with the remainder being an aromatic polyisocyanate is used in the resin.
There remains a
need for a composite article with improved UV and scratch resistance and for a
method of
manufacturing such an ai-ticle.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a composite article and a method of
manufacturing such a composite article.
[0008] It is an object to provide a polyurethane composite articles and a
method of
manufacturing such composite articles.
[0009] According to the present invention, there is provided a composite
article
comprising:
an inner core comprising a first composite material; and
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one or more than one outer layers comprising a second composite material
overlaying the inner core, the second composite material comprising an
aliphatic isocyanate polyurethane;
wherein the concentration of aliphatic isocyanate in the second composite
material is
greater than the concentration of aliphatic isocyanate in the first composite
material.
[0010] The present invention pertains to a composite article as just defined
wherein the
first composite material may comprise a resin with no aliphatic isocyanate
therein. The
first composite material may comprise from about 20 to about 85% by weight, or
any
amount therebetween, of a reinforcement and from about 15 to about 80% by
weight, or
any amount therebetween of a polyurethane resin. The polyurethane resin of the
first
composite material may comprise from about 20 to about 80% by weight, or any
amount
therebetween, of an aromatic polyisocyanate and from about 20 to about 80% by
weight,
or any amount therebetween, of a polyol. Other polyisocyanates may be present
in the
polyurethane resin of the first composite material, for example, the
polyurethane resin
may comprise from about 0% to about 40% by weight, or any amount therebetween,
of an
aliphatic polyisocyanate, provided that the amount of aliphatic isocyanate in
the second
composite material is greater than the amount of aliphatic isocyanate in the
first
composite material. The polyurethane resin of the first composite material may
have a
OH/NCO weight ratio from about 0.1:1 to about 5:1 (preferably from about 0.4:1
to about
1.5:1), or any amount therebetween. The second composite material may comprise
from
about 20 to about 85% by weight, or any amount therebetween, of a second
reinforcement
and from about 15 to about 80% by weight, or any amount therebetween of an
aliphatic
isocyanate polyurethane resin. The alipJ.iaticiso.c_yanate-pal-y -ur-ethane-
res-in o-f-the-seeond-
composite material may comprise from about 20 to about 80% by weight, or any
amount
therebetween, of an aliphatic polyisocyanate and from about 20 to about 80% by
weight,
or any amount therebetween, of a polyol. Other polyisocyanates may be present
in the
aliphatic isocyanate polyurethane resin of the second composite material, for
example, the
aliphatic isocyanate polyurethane resin may comprise from about 0% to about
40% by
weight, or any amount therebetween, of an aromatic polyisocyanate, provided
that the
amount of aliphatic isocyanate in the aliphatic isocyanate polyurethane resin
of the
second composite material is greater than the amount of aliphatic isocyanate
in the
polyurethane resin of the first composite material. The aliphatic isocyanate
polyurethane
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resin of the second composite material may have a OHJNCO weight ratio from
about
0.1:1 to about 5:1 (preferably from about 0.4:1 to about 1.5:1), or any amount
therebetween.
[0011] The present invention pertains to a composite article as just defined
wherein the
composite article is a multi-layered filament wound composite article produced
by a
filament winding process. The multi-layered filament wound composite article
may be a
utility pole.
[0012] The present invention pertains to a multi-layered filament wound
composite
article as just defined wherein the composite article is a composite module
configured for
use in a modular pole assembly, the composite module comprising a hollow
tapered
tubular pole section having an open base end and an opposed tip end, the
diameter of the
tip end being less than the diameter of the base end, such that the tip end of
one module
can fit into the base end of another module to a predetermined length to
provide a
modular pole assembly.
[0013] The present invention pertains to a composite module configured for use
in a
modular pole assembly, the composite module comprising:
an inner core comprising a first composite material; and
one or more than one outer layers comprising a second composite material
overlaying the inner core, the second composite material comprising an
aliphatic isocyanate polyurethane;
wherein the concentrati-on o~aliphatic-isocyanate-in the-second composi am
ter~aI'is
greater than the concentration of aliphatic isocyanate in the first composite
material;
and the composite module comprises a hollow tapered tubular pole section
having an
open base end and an opposed tip end, the diameter of the tip end being less
than the
diameter of the base end, such that the tip end of one module can fit into the
base end
of another module to a predetermined length to provide a modular pole
assembly.
[0014] The present invention pertains to a composite article as just defined
wherein the
first composite material may comprise a resin with no aliphatic isocyanate
therein. The
first composite material may comprise from about 20 to about 85% by weight, or
any
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amount therebetween, of a reinforcement and from about 15 to about 80% by
weight, or
any amount therebetween of a polyurethane resin. The polyurethane resin of the
first
composite material may comprise from about 20 to about 80% by weight, or any
amount
therebetween, of an aromatic polyisocyanate and from about 20 to about 80% by
weight,
or any amount therebetween, of a polyol. Other polyisocyanates may be present
in the
polyurethane resin of the first composite material, for example, the
polyurethane resin
may comprise from about 0% to about 40% by weight, or any amount therebetween,
of an
aliphatic polyisocyanate, provided that the amount of aliphatic isocyanate in
the second
composite material is greater than the amount of aliphatic isocyanate in the
first
composite material. The polyurethane resin of the first composite material may
have a
OH/NCO weight ratio from about 0.1:1 to about 5:1 (preferably from about 0.4:1
to about
1.5:1), or any amount therebetween. The second composite material may compi7se
from
about 20 to about 85% by weight, or any amount therebetween, of a second
reinforcement
and from about 15 to about 80% by weight, or any amount therebetween of an
aliphatic
isocyanate polyurethane resin. The aliphatic isocyanate polyurethane resin of
the second
composite material may comprise from about 20 to about 80% by weight, or any
amount
therebetween, of an aliphatic polyisocyanate and from about 20 to about 80% by
weight,
or any amount therebetween, of a polyol. Other polyisocyanates may be present
in the
aliphatic isocyanate polyurethane resin of the second composite material, for
example, the
aliphatic isocyanate polyurethane resin may comprise from about 0% to about
40% by
weight, or any amount therebetween, of an aromatic polyisocyanate, provided
that the
amount of aliphatic isocyanate in the aliphatic isocyanate polyurethane resin
of the
second composite material is greater than the amount of aliphatic isocyanate
in the
polyurethane resin of the first composite materi.al. The_aliphatic-isooyanate-
pol-yur-ethane-
resin of the second composite material may have a OH/NCO weight ratio from
about
0.1:1 to about 5:1 (preferably from about 0.4:1 to about 1.5:1), or any amount
therebetween.
[0015] The present invention further pertains to a modular pole assembly
comprising a
plurality of composite modules of the present invention staked to form a
vertical structure
of selected height, wherein the base end of an overlying module is mated with
the tip end
of an underlying module.
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[0016] The present invention further provides a method of manufacturing a
composite
article (Method A) comprising:
providing a core comprising a reinforcement impregnated with a first resin;
mixing an aliphatic isocyanate component and a polyol component to produce
a reaction mixture;
impregnating a second reinforcement with the reaction mixture to produce an
impregnated reinforcement;
applying the impregnated reinforcement over an outside surface of the core;
and
allowing the reaction mixture to set to produce a composite article with one
or
more than one outer layers of aliphatic isocyanate composite materzal;
wherein the concentration of aliphatic isocyanate in the reaction mixture is
greater
than the concentration of aliphatic isocyanate in the first resin.
[0017] The present invention pertains to a method of manufacturing a composite
article
as just defmed (Method A) wherein the first resin may contain no aliphatic
isocyanate.
The first resin may be a polyurethane resin and the core may comprise from
about 20 to
about 85% by weight, or any amount therebetween, of the reinforcement and from
about
15 to about 80% by weight, or any amount therebetween of the polyurethane
resin. The
polyurethane resin of the core may comprise from about 20 to about 80% by
weight, or
any amount therebetween, of an aromatic polyisocyanate and from about 20
t2a.b4ut_.80%-
by weight, or any amount therebetween, of a polyol. Other polyisocyanates may
be
present in the polyurethane resin of the core, for example, the polyurethane
resin may
comprise from about 0% to about 40% by weight, or any amount therebetween, of
an
aliphatic polyisocyanate, provided that the concentration of aliphatic
isocyanate in the
reaction mixture is greater than the concentration of aliphatic isocyanate in
the first resin.
The polyurethane resin of the core may have a OH/NCO weight ratio from about
0.1:1 to
about 5: 1 (preferably from about 0.4:1 to about 1.5:1), or any amount
therebetween. The
one or more than one outer layers of aliphatic isocyanate composite material
may
comprise from about 20 to about 85% by weight, or any amount therebetween, of
the
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second reinforcement and from about 15 to about 80% by weight, or any amount
therebetween of the reaction mixture (aliphatic isocyanate polyurethane
resin). The
reaction mixture may comprise from about 20 to about 80% by weight, or any
amount
therebetween, of the aliphatic isocyanate component and fiom about 20 to about
80% by
weight, or any amount therebetween, of the polyol component. The aliphatic
isocyanate
component of the reaction mixture may comprise at least 15 weight percent of
an
aliphatic polyisocyanate to give the required characteristics of UV stability
and abrasion
resistance. Other polyisocyanates may be present in the reaction mixture, for
example, the
reaction mixture may comprise from about 0% to about 40% by weight, or any
amount
therebetween, of an aromatic polyisocyanate, provided that the concentration
of aliphatic
isocyanate in the reaction mixture is greater than the concentration of
aliphatic isocyanate
in the first resin. The reaction mixture may have a OH/NCO weight ratio from
about
0.1:1 to about 5:1 (preferably from about 0.4:1 to about 1.5:1), or any amount
therebetween.
[0018] The present invention pertains to a method of manufacturing a composite
article
as just defined (Method A) wherein the aliphatic isocyanate component
comprises
hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or a mixture
thereof.
Preferably the aliphatic isocyanate component comprises a mixture of aliphatic
hexane
1,6-diisocyanato- homopolymer and hexamethylene diisocyanate (HDI).
[0019] The present invention pertains to a method of manufacturing a composite
article
as just defined (Method A) wherein the polyol component comprises from about
60 to
about 100 weight percent polyether polyol and from about 0 to about 40 weight
percent
polyester polyol.
[0020] The present invention pertains to a method of manufactLuing a composite
article
as just defined (Method A) wherein the polyether polyol has an equivalent
weight in the
range from about 70 to about 2500 and an hydroxyl functionality equal to or
greater than
about 2. Preferably the polyether polyol has an equivalent weight in the range
from about
70 to about 400 and an hydroxyl functionality in the range from about 2 to
about 6.
[0021] The present invention pertains to a method of manufacturing a composite
article
as just defined (Method A) wherein the polyester polyol has an equivalent
weight in the
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range from about 70 to about 1000 and an hydroxyl functionality equal to or
greater than
about 2. Preferably the polyester polyol has an equivalent weight in the range
from about
100 to about 300 and an hydroxyl functionality in the range from about 2 to
about 6.
[0022] The present invention pertains to a method of manufacturing a composite
article
as just defined (Method A) wherein the reaction mixture further comprises a
catalyst
selected from the group consisting of tin, bismuth, zinc, titanium and
mixtures thereof.
[0023] The present invention pertains to a method of manufacturing a composite
article
as just defined (Method A) wherein the composite article is produced using
filament
winding. The composite article may also be produced using pultrusion.
[0024] The present invention also pertains to a method of manufacturing a
multi-layered
filament wound composite article (Method B) comprising:
providing a core comprising reinforcement impregnated with a first resin;
mixing an aliphatic isocyanate component and a polyol component to produce
a reaction mixture;
impregnating a fibrous reinforcement with the reaction mixture to produce an
impregnated fibrous reinforcement;
winding the impregnated fibrous reinforcement around an outside surface of
the core to form a shaped article; and
allowing the reaction mixture to set to produce a multi-layered filament wound
-20- connposite ar iE o1e with one or more than one outer layers of aliphatic
isocyanate composite material;
wherein the concentration of aliphatic isocyanate in the reaction mixture is
greater
than the concentration of aliphatic isocyanate in the first resin.
[0025] The present invention further pertains to a method of manufacturing a
multi-
layered filament wound composite article (Method C) comprising:
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impregnating a fibrous reinforcement with a first resin to produce an
impregnated fibrous reinforcement;
winding the impregnated fibrous reinforcement around an outside surface of a
mandrel to form a shaped core;
mixing an aliphatic isocyanate component and a polyol component to produce
a reaction mixture;
impregnating a second fibrous reinforcement with the reaction mixture to
produce a second impregnated fibrous reinforcement;
winding the second impregnated fibrous reinforcement around an outside
surface of the core to form a shaped article; and
allowing the reaction mixture to set to produce a multi-layered filament wound
composite article with one or more outer layer of aliphatic isocyanate
conlposite material;
wherein the concentration of aliphatic isocyanate in the reaction mixture is
greater
than the concentration of aliphatic isocyanate in the first resin.
[0026] The present invention pertains to a method of manufacturing a multi-
layered
filament wound composite article as just defined (Method C) wherein the first
resin
contains no aliphatic isocyanate. The first resin may be a polyurethane resin
and the core
may comprise from about 20 to about 85% by weight, or any amount therebetween,
of the
fibrous reinforcement and from about 15 to about 80% by eight, or any_amount-
therebetween of the polyurethane resin. The polyurethane resin of the core may
comprise
from about 20 to about 80% by weight, or any amount therebetween, of an
aromatic
polyisocyanate and from about 20 to about 80% by weight, or any amount
therebetween,
of a polyol. Other polyisocyanates may be present in the polyurethane resin of
the core,
for example, the polyurethane resin may comprise from about 0% to about 40% by
weight, or any amount therebetween, of an aliphatic polyisocyanate, provided
that the
concentration of aliphatic isocyanate in the reaction mixture is greater than
the
concentration of aliphatic isocyanate in the first resin. The polyurethane
resin of the core
may have a OH/NCO weight ratio from about 0.1:1 to about 5:1(preferably from
about
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0.4:1 to about 1.5:1), or any amount therebetween. The one or more than one
outer layers
of aliphatic isocyanate composite material may comprise from about 20 to about
85% by
weight, or any amount therebetween, of the second reinforcement and from about
15 to
about 80% by weight, or any amount therebetween of the reaction mixture
(aliphatic
isocyanate polyurethane resin). The reaction mixture may comprise from about
20 to
about 80% by weight, or any amount therebetween, of the aliphatic isocyanate
component
and from about 20 to about 80% by weight, or any amount therebetween, of the
polyol
component. The aliphatic isocyanate component of the reaction mixture may
comprise at
least 15 weight percent of an aliphatic polyisocyanate to give the required
characteristics
of UV stability and abrasion resistance. Other polyisocyanates may be present
in the
reaction mixture, for example, the reaction mixture may comprise from about 0%
to
about 40% by weight, or any amount therebetween, of an aromatic
polyisocyanate,
provided that the concentration of aliphatic isocyanate in the reaction
mixture is greater
than the concentration of aliphatic isocyanate in the first resin. The
reaction mixture may
have a OH/NCO weight ratio from about 0.1:1 to about 5:1 (preferably from
about 0.4:1
to about 1.5:1), or any amount therebetween.
[0027] The present invention pertains to a method of manufacturing a multi-
layered
filament wound composite article as just defmed (Method C) wherein the
aliphatic
isocyanate component comprises hexamethylene diisocyanate (HDI), isophorone
diisocyanate (IPDI) or a mixture thereof. Preferably the aliphatic isocyanate
component
comprises a mixture of aliphatic hexane 1,6-diisocyanato- homopolymer and
hexamethylene diisocyanate (HDI).
_[0Q28]-The-pr-esent-inuentian per-tain- s to-a-method of-manufaeturing-a-
mult'r--Iayered-
filament wound composite article as just defmed (Method C) wherein the polyol
component comprises from about 60 to about 100 weight percent polyether polyol
and
from about 0 to about 40 weight percent polyester polyol.
[0029] The present invention pertains to method of manufacturing a multi-
layered
filament wound composite article as just defined (Method C) wherein the
polyether
polyol has an equivalent weight in the range from about 70 to about 2500 and
an hydroxyl
functionality equal to or greater than about 2. Preferably the polyether
polyol has an
CA 02595201 2007-07-18
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equivalent weight in the range from about 70 to about 400 and an hydroxyl
functionality
in the range from about 2 to about 6.
[0030] The present invention pertains to a method of manufacturing a multi-
layered
filament wound composite article as just defined (Method C) wherein the
polyester polyol
has an equivalent weight in the range from about 70 to about 1000 and an
hydroxyl
functionality equal to or greater than about 2. Preferably the polyester
polyol has an
equivalent weight in the range from about 100 to about 300 and an hydroxyl
fixnctionality
in the range from about 2 to about 6.
[0031] The present invention pertains to a method of manufacturing a multi-
layered
lo filament wound composite article as just defmed (Method C) wherein the
reaction
mixture farther comprises a catalyst selected from the group consisting of
tin, bismuth,
zinc, titanium and mixtures thereof.
[0032] The present invention pertains to a method of manufacturing a multi-
layered
filament wound composite article as just defined (Method C) wherein the
composite
article is an utility pole.
[0033] The present invention pertains to a method of manufacturing a multi-
layered
filament wound composite article as just defined (Method C) wherein the
composite
article is a composite module configured for use in a modular pole assembly.
[0034] By manufacturing a composite article with an outer layer that comprises
reinforcement embedded in a thermosetting polyurethane resin, the polyurethane
resin
characterized as having a concentration of an aliphatic isocyanate from about
20 to about
80% by weight, or any amount therebetween, and trom about 20 to about 80% by
weight,
or any amount therebetween, of a polyol, the composite article is well suited
for uses that
involve UV exposure. Furthermore, by manufacturing the composite article with
an inner
core comprising reinforcement embedded in an aromatic isocyanate polyurethane,
or
other resin, for example, but not limited to, polyester, epoxy, or vinylester
resin or
mixtures thereof, with little or no aliphatic isocyanate polyurethane, the
composite article
maintains the strength and durability associated with composite articles, yet
the cost of
the composite article is significantly less than that of a composite article
manufactured
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with a homogenous distribution of aliphatic isocyanate polyurethane throughout
the
article. Polyurethane resins have the additional advantage of typically being
VOC free.
[0035] This summary of the invention does not necessarily describe all
features of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] These and other features of the invention will become more apparent
from the
following description in which reference is made to the appended drawings, the
drawings
are for the purpose of illustration only and are not intended to in any way
limit the scope
of the invention to the particular embodiment or embodiments shown, wherein:
[0037] FIGURE 1 shows a schematic side elevation view of an example of an
embodiment of the composite module pole assembly of the present invention,
where a
series of composite modules are used to construct a range of 30 ft poles of
varying
strength and stiffness.
[0038] FIGURE 2 shows a schematic side elevation view of an example of an
embodiment of the composite module pole assembly of the present invention,
where a
series of composite modules are used to construct a range of 45 ft poles of
varying
strength and stiffness.
[0039] FIGURE 3 shows a schematic side elevation view of an example of an
embodiment of the composite module pole assembly of the present invention,
where a
series of composite modules are used to construct a range of 60 ft poles of
varying
strength and stiffLiess_
[0040] FIGURE 4 shows a schematic side elevation view of an example of an
embodiment of the composite module pole assembly of the present invention,
where a
series of composite modules are used to construct a range of 75 ft poles of
varying
strength and stiffness.
[0041] FIGURE 5 shows a schematic side elevation view of an example of an
embodiment of the composite module pole assembly of the present invention,
where a
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series of composite modules are used to construct a range of 90 ft poles of
varying
strength and stiffiiess.
[0042] FIGURE 6 shows a schematic view of an example of an embodiment of the
composite module of the present invention, showing seven differing sizes of
modules.
[0043] FIGURE 7 shows a schematic view of an example of an embodiment of the
composite module of the present invention, with modules being nested together
in
preparation for transport.
[0044] FIGURE 8 shows an exploded perspective view, in section, of an example
of an
embodiment of the composite module pole assembly of the present invention,
where
several composite modules are staclced one on top of the other, together with
mating top
cap and mating bottom plug.
DETAILED DESCRIPTION
[0045] The present invention relates to a composite article and a method of
manufacturing such a composite article.
[0046] The following description is of a preferred embodiment.
[0047] The present invention provides a multi-layered composite article that
has an inner
core comprising a first composite material with one or more than one outer
layers of a
second composite material, the second composite material comprising an
aliphatic
isocyanate polyurethane overlaying the inner core. The concentration of
aliphatic
isocyanate in the aliphatic isocyanate polyurethane composiIe-
nateriaL(the_second_
composite material) is higher than the concentration of aliphatic isocyanate
in the fiirst
composite material.
[0048] Preferably, the one or more than one outer layers of aliphatic
isocyanate
composite material bind to the inner core to provide an integral composite
article.
[0049] Aliphatic isocyanate polyurethane resin has superior resistance to
weathering and
UV rays, however aliphatic polyisocyanate polyurethane resin is generally much
more
expensive than other resins, such as, but not limited to, aromatic
polyisocyanate
polyurethane resin, polyester, epoxy, or vinylester resin or mixtures thereof.
A composite
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article having one or more outer layers of an aliphatic isocyanate
polyurethane composite
material and an inner core made from a different composite material with a
lower
concentration of aliphatic isocyanate therein (and preferably no aliphatic
isocyanate
therein) advantageously possesses UV stability and superior abrasion
resistance, while
being less expensive to produce than a composite article manufactured with a
homogenous distribution of aliphatic isocyanate polyurethane throughout the
article. This
is particularly beneficial for large composite articles that are to be
utilized outside for
long periods of time, such as, but not limited to, utility poles, pipes,
posts, fencing
materials, guard rails, scaffolding, building materials, and other materials
that may be
used outdoors.
[0050] The first composite material preferably comprises an aromatic
isocyanate
polyurethane composite material. Aromatic polyisocyanates are typically less
expensive
than aliphatic polyisocyanates and produce polyarethane composite material
with good
strength characteristics. A composite article with an aromatic isocyanate
polyurethane
composite core and an outer layer(s) of aliphatic isocyanate polyurethane
composite
material has the combined advantages of strength, UV stability and abrasion
resistance,
while being economic to produce even when large composite articles are
required, such
as, but not limited to, utility poles or posts, building, and other structural
materials.
[00511 In an embodiment of the present invention, there is provided a method
of
manufacturing a composite article comprising:
providing a core comprising reinforcement impregnated with a first resin;
mixing an aliphatic iso~yanate-component-and-a-pol-yol eomponentto produce
a reaction mixture;
impregnating a second reinforcement with the reaction mixture to produce an
impregnated reinforcement;
applying the impregnated reinforcement over an outside surface of the core;
and
allowing the reaction mixture to set to produce a composite article with one
or
more than one outer layer of aliphatic isocyanate composite material;
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CA 02595201 2007-07-18
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wherein the concentration of aliphatic isocyanate in the reaction mixture is
higher than
the concentration of aliphatic isocyanate in the first resin.
[0052] The first resin may be a polyurethane resin and the core may comprise
from about
20 to about 85% by weight, or any amount therebetween, of the reinforcement,
for
example 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54,
56, 58, 60, 62,
64, 66, 68, 70, 72, 74, 76, 78, 80 and 82 weight percent, or any amount
therebetween, and
from about 15 to about 80% by weight, or any amount therebetween of the
polyurethane
resin, for example 18, 20, 22, 24, 26 28, 30, 32, 34, 36, 38, 40, 42, 44, 46,
48, 50, 52, 54,
56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76 and 78 weight percent, or any
amount
therebetween.
[0053] The first resin may comprise predominantly an aromatic isocyanate
polyu.rethane
resin, from about 20 to about 80% by weight, or any amount therebetween, of an
aromatic
polyisocyanate, for example 22, 24, 26 28, 30, 32, 34, 36, 38, 40, 42, 44, 46,
48, 50, 52,
54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, and 78 weight percent, or any
amount
therebetween, and from about 20 to about 80% by weight, or any amount
therebetween,
of a polyol, for example 22, 24, 26 28, 30, 32, 34, 36, 38, 40, 42, 44, 46,
48, 50, 52, 54,
56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, and 78 weight percent, or any
amount
therebetween,. Other polyisocyanates may be present in the polyurethane resin,
for
example, the polyurethane resin may comprise from about 0% to about 40% by
weight, or
any amount therebetween, of an aliphatic polyisocyanate, for exainple 2, 4, 6,
8, 10, 12,
14, 16, 18, 20, 22, 24, 26 28, 30, 32, 34, 36 and 38 weight percent, or any
amount
therebetween, provided that the concentration of aliphatic isocyanate in the
reaction
-rnixtureis_greater-than the-cancentration of-al-iphatic-isoeyanate-in the-
first-resin.-
[0054] The polyurethane resin of the core may have a OH/NCO weight ratio from
about
0. 1:1 to about 5:1, or any amount therebetween, for example a ratio of 0.2:1,
0.3:1, 0.4:1,
0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1,
1.6:1, 1.7:1, 1.8:1,
1.9:1, 2.0:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3.0:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1,
4.0:1, 4.2:1,
4.4:1, 4.6:1, and 4.8:1, or any amount therebetween and preferably has a ratio
from
about 0.4:1 to about 1.5:1, or any amount therebetween, for example a ratio of
0.5:1,
0.6: l, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1 and 1.4:1, or any amount
therebetween.
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[0055] The first resin of the core may be allowed to set before or after the
reaction
mixture impregnated reinforcement is applied to an outside surface of the
core, or it may
be used after a predetermined amount of set time. The core maybe pre-
manufactured at a
different time, location, or both. The first resin may contain no aliphatic
isocyanate and
may comprise an aromatic isocyanate polyurethane resin.
[0056] The one or more than one outer layers of aliphatic isocyanate composite
material
may comprise from about 20 to about 85% by weight, or any amount therebetween,
of the
second reinforcement, for example 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42,
44, 46, 48,
50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80 and 82 weight
percent, or any
amount therebetween, and from about 15 to about 80% by weight, or any amount
therebetween of the reaction mixture (aliphatic isocyanate polyurethane
resin), for
example 18, 20, 22, 24, 26 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52,
54, 56, 58,
60, 62, 64, 66, 68, 70, 72, 74, 76 and 78 weight percent, or any amount
therebetween.
[0057] The reaction mixture may comprise from about 20 to about 80% by weight,
or
any amount therebetween, of the aliphatic isocyanate component, for example
22, 24, 26
28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64,
66, 68, 70, 72, 74,
76, and 78 weight percent, or any amount therebetween, and from about 20 to
about 80%
by weight, or any amount therebetween, of the polyol component, for example
22, 24, 26
28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64,
66, 68, 70, 72, 74,
76, and 78 weight percent, or any amount therebetween.
[0058] The aliphatic isocyanate component of the reaction mixture may comprise
at least
15 weight percent of an aliphatic polyisocyanate to give the required
characteristics of
-IIVstability and abrasion resistance. The amount of aliphatic isocyanate in
the aliphatic
polyisocyanate component may be from about 15 to about 100 weight percent or
any
amount therebetween, for example 18, 20, 22, 24, 26 28, 30, 32, 34, 36, 38,
40, 42, 44,
46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78 80, 82, 84,
86, 88, 90, 92,
94, 96, 98 and 100 weight percent, or any amount therebetween. Preferably the
aliphatic
isocyanate content of the aliphatic polyisocyanate component is from about 30
to about
100 weight percent, or any amount therebetween, or from about 50 to about 100
weight
percent or any amount therebetween. The present invention also contemplates
that the
16
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only isocyanates present in the aliphatic polyisocyanate component may be
aliphatic
isocyanates.
[0059] Other polyisocyanates may be present in the reaction mixture, for
example, the
reaction mixture may comprise from about 0% to about 40% by weight, or any
amount
therebetween, of an aromatic polyisocyanate, for example 2, 4, 6, 8, 10, 12,
14, 16, 18,
20, 22, 24, 26 28, 30, 32, 34, 36 and 38 weight percent, or any amount
therebetween,
provided that the concentration of aliphatic isocyanate in the reaction
mixture is greater
than the concentration of aliphatic isocyanate in the first resin.
[0060] The reaction mixture may have a OH/NCO weight ratio from about 0.1:1 to
about
5:1 , or any amount therebetween, for example a ratio of 0.2:1, 0.3:1, 0.4:1,
0.5:1, 0.6:1,
0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1,
1.8:1, 1.9:1, 2.0:1,
2.2:1,2.4:1, 2.6:1, 2.8:1, 3.0:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4.0:1, 4.2:1,
4.4:1, 4.6:1,
and 4.8:1, or any amount therebetween and preferably has a ratio from about
0.4:1 to
about 1.5:1, or any amount therebetween, for example a ratio of 0.5:1, 0.6:1,
0.7:1, 0.8:1,
0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1 and 1.4:1, or any amount therebetween.
[00611 A polyurethane resin or reaction mixture is made by mixing a polyol
component
and a polyisocyanate component. Other additives may also be included, such as
fillers,
pigments, plasticizers, curing catalysts, UV stabilizers, antioxidants,
microbiocides,
algicides, dehydrators, thixotropic agents, wetting agents, flow modifiers,
matting agents,
deaerators, extenders, molecular sieves for moisture control and desired
colour, UV
absorber, light stabilizer and fire retardants.
-[0062-]-By-the-termaliphati c-i-s ocyanate" it is meant-an iso' cy-an-ate ui
wlu-'ch-NCO groups
are either attached to an aliphatic center or not attached duectly to an
aromatic ring. It is
also within the scope of the present invention that the term "aliphatic
isocyanate" means
an isocyanate in which the NCO groups are attached to an aliphatic center.
Aliphatic
isocyanates described in US Patent 6,420,493 (which is incorporated herein by
reference)
may be used in the resin compositions described herein. Aliphatic isocyanates
may
include, but are not limited to, hexamethylene diisocyanate (HDI), isophorone
diisocyanate (IPDl), dicyclohexane-4,4' diisocyanate (Desmodur W),
hexamethylene
diisocyanate trimer (HDI Trimer), isophorone diisocyanate trimer (IPDI
Trimer),
17
CA 02595201 2007-07-18
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hexamethylene diisocyanate biuret (HDI Biuret), cyclohexane diisocyanate, meta-
tetramethylxylene diisocyanate (TMEXDI), and mixtures thereof. The aliphatic
isocyanate
may include a polymeric aliphatic diisocyanate, for example, but not limited
to a
uretidione, biuret, or allophanate polymeric aliphatic diisocyanate, or a
polymeric
aliphatic diisocyanate in the symmetrical or asymmetrical trimer form, or a
mixture
thereof, which typically does not present a toxic hazard on account of
extremely low
volatility due to very low monomer content. The aliphatic isocyanates,
employed to
produce the composite article of the present invention or that are used in the
method of
the present invention maybe hexamethylene diisocyanate (HDI), isophorone
diisocyanate
(IPDI) or a mixture thereof, and is preferably a mixture of aliphatic hexane
1,6-
diisocyanato- homopolymer and hexamethylene diisocyanate (HDI). Hexamethylene
diisocyanate polyisocyanates described in EP-A 668 330 to Bayer AG; EP-A 1002
818 to
Bayer AG; and WO 98148947 to Valspar Corp (which are incorporated herein by
reference) may be used in the aliphatic isocyanate resin composition described
herein.
[0063] By the tenn "polyol" it is meant a composition that contains a
plurality of active
hydrogen groups that are reactive towards the polyisocyanate component under
the
conditions of processing. Polyols described in US Patent 6,420,493 may be used
in the
resin compositions described herein. The polyol component may include, but is
not
limited to, a polyether polyol, a polyester polyol, or a mixture thereof. The
polyester
polyol may be, but is not limited to a diethylene glycol-phthalic anhydride
based polyester
polyol. The polyether polyols may be, but is not limited to, polyoxyalkylene
polyol,
propoxylated glycerol, branched polyol with ester and ether groups, amine
initiated-
hydroxyl terminated polyoxyalkylene polyol and mixtures thereof.
[0064] By the term "aromatic isocyanate" it is meant an isocyanate in which
NCO
groups are attached to an aromatic ring. Aromatic isocyanates described in US
Patent
6,420,493 maybe used in the resin composition described herein. Aromatic
isocyanates
may include, but are not limited to, methylene di-p-phenylene isocyanate,
polymethylene
polyphenyl isocyanate, methylene isocyanatobenzene or a mixture thereof. The
aromatic
polyisocyanate may include from about 30% to about 60% by weight, or any
amount
therebetween, of methylene di-p-phenylene isocyanate, from about 30% to about
50% by
weight, or any amount therebetween of polymethylene polyphenyl isocyanate,
with a
balance of methylene isocyanatobenzene.
1s
CA 02595201 2007-07-18
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[0065] By the term "composite material" it is meant a material composed of
reinforcement embedded in a polymer matrix or resin, for example, but not
limited to,
polyester, epoxy, polyurethane, or vinylester resin or mixtures thereof. The
matrix or
resin holds the reinforcement to form the desired shape while the
reinforcement generally
improves the overall mechanical properties of the matrix.
[0066] By the term "reinforcement" it is meant a material that acts to
fiirther strengthen a
polymer matrix of a composite material for example, but not limited to,
fibers, particles,
flakes, fillers, or mixtures thereof. Reinforcement typically comprises glass,
carbon, or
aramid, however there are a variety of other reinforcement materials, which
can be used
as would be known to one of skill in the art. These include, but are not
limited to,
synthetic and natural fibers or fibrous materials, for example, but not
limited to polyester,
polyethylene, quartz, boron, basalt, ceramics and natural reinforcement such
as fibrous
plant materials, for example, jute and sisal.
[0067] By the term "aliphatic isocyanate composite material" it is meant a
composite
material comprising reinforcement embedded in an aliphatic isocyanate
thermosetting
polyurethane resin predominantly comprising an aliphatic polyisocyanate
component and
a polyol component. The thermosetting resin is set or cured to provide a
substantially
solid matrix for the reinforcement. Other components may also be present in
the aliphatic
isocyanate thermosetting polyurethane resin, for example, but not limited to
aromatic
polyisocyanate provided that the concentration of aliphatic isocyanate in the
reaction
mixture is greater than the concentration of aliphatic isocyanate in the first
resin. The
"second composite material" may be comprised predominantly of reinforcement
and an
aliphatic isocyanatethermo.setting po-lyur-ethane-r-esin,-an-d-may-be-referred-
to as an
aliphatic isocyanate composite material.
[0068] By the term "aromatic isocyanate composite material" it is meant a
composite
material comprising reinforcement embedded in a aromatic isocyanate
thermosetting
polyurethane resin comprising predominantly an aromatic polyisocyanate
component and
a polyol component. The thermosetting resin is set or cured to provide a
substantially
solid matrix for the reinforcement. Other components may also be present in
the
aromatic isocyanate thermosetting polyurethane resin, for example, but not
limited to an
aliphatic isocyanate, provided that the concentration of aliphatic isocyanate
in the
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CA 02595201 2007-07-18
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reaction mixture is greater than the concentration of aliphatic isocyanate in
the first resin.
The "first composite material" may be comprised predominantly ofreinforcement
and an
aromatic isocyanate thermosetting polyurethane resin, and may be referred to
as an
aromatic isocyanate composite material.
[0069] The aliphatic polyisocyanate component of the aliphatic isocyanate
thermosetting
polyurethane resin may comprise at least 15 weight percent of an aliphatic
isocyanate to
give the required characteristics of UV stability and abrasion resistance. The
amount of
aliphatic isocyanate in the aliphatic polyisocyanate component may be from
about 15 to
about 100 weight percent or any amount therebetween, for example 18, 20, 22,
24, 26 28,
30, 32, 34, 36, 38, 40,42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68,
70, 72, 74, 76,
78 80, 82, 84, 86, 88, 90, 92, 94, 96, 98 and 100 weight percent, or any
amount
therebetween. Preferably the aliphatic isocyanate content of the aliphatic
polyisocyanate
component is from about 30 to about 100 weight percent, or any amount
therebetween, or
from about 50 to about 100 weight percent or any amount therebetween. The
present
invention also contemplates that the only isocyanates present in the aliphatic
polyisocyanate component may be aliphatic isocyanates.
[0070] The aromatic polyisocyanate component of the aromatic isocyanate
thermosetting
polyurethane resin may comprises at least 20 weight percent of an aromatic
isocyanate to
give the desired strength characteristics. The amount of aromatic isocyanate
in the
aromatic polyisocyanate component may be from about 20 to about 100 weight
percent or
any amount therebetween for example 20, 22, 24, 26 28, 30, 32, 34, 36, 38, 40,
42, 44,
46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78 80, 82, 84,
86, 88, 90, 92,
94, 96, 98 and 100 weightpercent or an~an~omnt_therebetw-een. P-referably-the-
aromatic-
isocyanate content of the aromatic polyisocyanate component is from about 30-
100
weight percent or any amount therebetween, or from about 40 to about 100
weight
percent, or any amount therebetween. It is also contemplated that only
isocyanates present
in the aromatic polyisocyanate component may be aromatic isocyanates.
[0071] The polyol component may comprise from about 60 to about 100 weight
percent
polyether polyol, or any amount therebetween, for example 62, 64, 66, 68, 70,
72, 74, 76,
78, 80, 82, 84, 86, 88, 90, 92, 94, 96 and 98 weight percent, or any amount
therebetween.
The polyether polyol may have an equivalent weight between about 70 and about
2500,
CA 02595201 2007-07-18
WO 2006/081685 PCT/CA2006/000162
or any amount therebetween, for example, 100, 130, 160, 190, 220, 250, 280,
310, 340,
370, 400, 430, 460, 490, 520, 550, 580, 610, 640, 670, 700, 730, 760, 790,
820, 850, 880,
910, 940, 970,1000,1100,1200,1300,1400,1500,1600,1700,1800,1900, 2000, 2100,
2200, 2300, and 2400 or any amount therebetween, and preferably has an
equivalent
weight between about 70 and about 400, or any amount therebetween, and an
hydroxyl
functionality of between about 2 and about 6 or any amount therebetween, for
example,
2.2, 2.4, 2.6, 2.8, 3Ø 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0,
5.2, 5.4, 5.6, and 5.8 or
any amount therebetween.
[0072] The polyol component may comprise from about 0 to about 40 weight
percent
polyester polyol or any amount therebetween, for example 2, 4, 6, 8, 10, 12,
14, 16, 18,
20, 22, 24, 26, 28, 30, 32, 34, 36 and 38 weight percent, or any amount
therebetween.
The polyester polyol may have an equivalent weight between about 70 and about
1000, or
any amount therebetween, for example,100,130,160,190, 220, 250, 280, 310, 340,
370,
400, 430, 460, 490, 520, 550, 580, 610, 640, 670, 700, 730, 760, 790, 820,
850, 880, 910,
940, 970, and 1000 or any amount therebetween, preferably has an equivalent
weight
between about 100 and about 300, or any amount therebetween, and an hydroxyl
functionality of between about 2 and about 6 or any amount therebetween, for
example,
2.2, 2.4, 2.6, 2.8, 3Ø 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0,
5.2, 5.4, 5.6, and 5. 8 or
any amount therebetween.
[0073] The aromatic or aliphatic thennosetting polyurethane resin utilized by
the present
invention may fiuther comprise from about 2 to about 20 weight percent of a
suitable
chain extender, or any amount therebetween, for example 5, 7, 9, 11, 13, 15,
17, and 19
-weight percerit,-or axiy ainount therebetween.-By-the term "chain
extenderitis-xneant-a-
difunctional, low-molecular, multi-functional compound, which is reactive
towards
isocyanates. A suitable chain extender may have an equivalent weight between
about 45
and about 400, or any amount therebetween, for example 70, 100, 130, 160, 190,
220,
250, 280, 310, 340, and 370 or any amount therebetween, and an hydroxyl
functionality
of at least 2. Preferably the chain extender employed in the resin comprises
1,4 -
butanediol.
[0074] The aromatic or aliphatic thermosetting polyurethane resin utilized by
the present
invention may also include known additives used in polyurethane technology,
for
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CA 02595201 2007-07-18
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example, but not limited to, fillers, pigments, plasticizers, curing
catalysts, UV
stabilizers, antioxidants, microbiocides, algicides, dehydrators, thixotropic
agents,
wetting agents, flow modifiers, matting agents, deaerators, extenders,
molecular sieves
for moisture control and desired colour, UV absorber, light stabilizer, fire
retardants or
mixtures thereof. As hereinbefore describe in more detail, an aliphatic
isocyanate
polyarethane resin has superior resistance to W rays. The UV stability can be
further
enhanced by addition of a UV stabilizer, a UV absorber, an antioxidant or a
mixture
thereof. Pot life of the resin can be adjusted by inclusion of a suitable
catalyst, for
example, but not limited to, a tin catalyst, bismuth catalyst, zinc catalyst,
titanium catalyst
or a mixture thereof.
[0075] One method of manufacture of the composite article of the present
invention
utilizes filament winding. However, other methods may be used to produce the
composite article of the present invention, for example pultrusion.
[0076] A typical filament winding set-up is described in CA 2,444,324 and CA
2,274,328 (which is incorporated herein by reference). In the method of
filament
winding, fibrous reinforcement, for example, but not limited to glass, carbon,
or aramid,
is impregnated with resin, and wound onto an elongated mandrel of
predeterniined shape.
The winding process can be done directly on a substrate that can act as a
mandrel, or it
can be done using a mandrel that is removable or dissolvable after the part is
cured. The
later type of mandrels may be used to produce large structures, for example,
utility poles.
[0077] The resin impregnated fibrous material is typically wound onto the
mandrel in a
predetermined sequence. This sequence may involve winding layers of fibres at
a series
of angles rangig between 0 and 87relative to the mandrel axis. The direction
that the
fibrous reinforcement is laid onto the mandrel may effect the eventual
strength and
stiffness of the finished composite article. Other factors that may effect the
structural
properties of the manufactured composite article include the fibrous
reinforcement to
resin ratio, the wrapping sequence, the wall thickness, the type of fibrous
reinforcement
(such as glass, carbon, aramid and the like) and the type of resin used.
[0078] In accordance with one embodiment of the present invention, filament
winding is
used to produce the composite article of the present invention using at least
two different
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CA 02595201 2007-07-18
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resins compositions in the filament winding process. In this embodiment a
first resin, for
example, but not limited to, a polyester, an epoxy, a vinylester, a
polyurethane, or
mixtures thereof, is used to impregnate fibrous reinforcement which is then
wound
around the length of the mandrel for one or more than one full pass to obtain
a thiclcness
of from about 50% to about 98%, or any amount therebetween, of the final
thiclcness of
the fmished composite material. The resin bath or other impregnation structure
is then
charged with an aliphatic isocyanate polyurethane resin composition comprising
an
aliphatic isocyanate component and a polyol component. Fibrous reinforcement
is
impregnated with the aliphatic isocyanate resin composition and wound on top
of the first
resin impregnated fibers for one or more than one fu11 pass to obtain a
thickness of from
about 2% to about 50%, or any aniount therebetween, of the fmal thickness of
the
finished composite material. Multiple layers of aliphatic isocyanate resin
impregnated
fibers may be wound onto the mandrel. The resin is allowed to cure and the
mandrel may
be removed or dissolved as would be apparent to one of skill in the art.
[0079] The finished composite article may comprise between about 5 and about
301ayers
(preferably between about 10 and about 15 layers) of resin impregnated fibrous
reinforcement, or any amount therebetween. The inner core comprising fibrous
reinforcement impregnated with the first resin may comprises between about 4
and about
28 layers (preferably between about 9 and about 14 layers) of the composite
article, or
any amount therebetween, and the outer aliphatic isocyanate resin impregnated
fibers may
comprises between about 1 and about 10 layers (preferably between about I and
about 5
layers), or any amount therebetween of the composite article.
[080]~'exemay-he_a_delay-between -wiudingo-f-the-first r-esi-n-impregnated-
fibers-onta
the mandrel and winding of the aliphatic isocyanate resin impregnated fibers,
to allow the
first resin to cure or set to produce a pre-formed composite material core
(first composite
material). This can be done by placing the mandrel in an oven. Alternatively,
the
winding of the aliphatic isocyanate resin impregnated fibers may be carried
out
substantially consecutively with winding of the first resin impregnated fibers
onto the
mandrel, and the aliphatic isocyanate resin impregnated reinforcement wound
immediately, or after a partial curing of the first composite material, for
example after
reaching from about 30 to about 90%, or any amount therebetween of its final
hardness.
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CA 02595201 2007-07-18
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[0081] The first resin may comprise a non-aliphatic polyurethane resin and
preferably
comprises an aromatic isocyanate polyurethane resin comprising an aromatic
isocyanate
and a polyol. A plurality of different resin compositions may be used in the
filament
winding process to produce a composite article having layers of different
composite
material, provided the outside layer or layers comprises an aliphatic
isocyanate
polyurethane composite material comprising fiom about 20 to about 100 weight
percent,
or any amount therebetween, aliphatic isocyanate polyurethane resin.
[0082] The composite article of the present invention may be a utility pole,
however, the
composite article is not limited to a utility pole and may include other
structural articles,
for example, posts, scaffolding, fencing materials, building materials and the
like. In the
case of a utility pole, it is preferred that the pole be made by filament
winding
substantially as described herein.
[0083] As disclosed in the examples, a utility pole comprising an aliphatic
isocyanate
composite outer layer may be subjected to prolonged sand blasting and UV
exposure
without showing any significant degradation of physical and mechanical
properties
indicating UV stability and abrasion resistance. Furthermore, the Interlaminar
Shear
Strength results indicate that the top or outer layer of aliphatic composite
material
remains fully bound and integral with the inner core layers of the pole
following
prolonged sand blasting and UV exposure.
[0084] According to an alternative embodiment of the present invention, there
is
provided a composite module configured for use in a modular pole assembly, the
composite module comprising one or more than one inner layers of a first resin
composite
material (preferably an aromatic isocyanate polyurethane composite material)
and one or
more than one outer layers of a second composite material (an aliphatic
isocyanate
polyurethane composite material). The composite module of the present
invention may
further include one or more than one intermediate layers of at least one
further resin
composite material different from the first resin composite material. The
composite
module of the present invention is preferably made using filament winding.
[0085] The composite module of the present invention maybe a hollow tapered
tubular
pole section (e.g. 50, Figure 8) having an open base (or first) end (e.g. 52,
Figure 8) and
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CA 02595201 2007-07-18
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an opposed tip (or second) end (e.g. 54, Figure 8), the diameter of the tip
end being less
than the diameter of the base end. Two or more composite modules of the
present
invention may be stacked one on top of the other such that the top end of one
slips into,
or matingly engages with, the base of another to a predetermined length to
provide a
modular pole assembly (e.g. see Figures 1-5 and 8). When the modules are
stacked
together they behave as a single structure able to resist forces, for example
but not limited
to lateral and compression forces, to a predetermined level. The height of the
structure
can be varied simply by adding or removing modules from the stack. The overall
strength
of the structure can be altered for the same height condition simply by
removing a higher
module from the top of the stack and replacing the length by adding a larger,
stronger
module at the base of the stack. In this way the structure can be engineered
to vary not
only strength but also stiffness characteristics for any desired height.
[0086] Accordingly there is further provided by the present invention, a
modular pole
assembly comprising a plurality of composite modules matingly engaged to form
a
vertical structure of selected height, wherein the base end of an overlying
module is
mated with the tip end of an underlying module.
[0087] The module pole assembly of the present invention comprising a
plurality of
staked composite modules having an oi.uter layer of predominantly an aliphatic
isocyanate
polyurethane composite material advantageously has UV stability and superior
abrasion
resistance than a pole comprised of an aromatic isocyanate composite material,
while
being less expensive to produce than a module pole assembly having modules
made
purely from aliphatic isocyanate polyarethane composite material throughout.
This is
particularly advanta eous foxmodule_pole-assemblies-that ar-e-to-be-utilized-
outsid-efor-
long periods of time, such as, but not limited to, utility poles.
[0088] The modular pole assembly provides a solution for use in the electrical
utility
industry which has traditionally used steel and wood as distribution and
transmission
poles. For this application, a pole has to be of a defined height and have a
specified
minimum breaking strength and usually a defined deflection under a specified
load
condition. Poles can be specified to carrypower lines across a terrain and
accommodate
any topography and structural forces resulting from effects such as wind and
ice loading.
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[0089] The electrical utility industry typically uses poles in lengths of 25
ft to 150 ft.
These poles vary in length and in their strength requirements. As range of
pole sizes and
pole classes are required to meet these needs, the amount of inventory
required is a
multiple of these two parameters. In situations where flexibility to meet a
desired need is
warranted, large stocks of poles are required. The composite module of the
present
invention is configured for staking in a modular pole assembly and
advantageously
provides a lightweight structure that displays superior strength and
durability when
compared to the strength and durability associated with wood or steel poles.
The
composite modules of the present invention do not iust like steel and they do
not rot or
suffer microbiological or insect attack as is common in wood structures.
Furthermore,
fibre reinforced composite structures, in contrast to natural products (such
as wood), are
designed so the consistency and service life can be closely determined and
predicted.
[0090] The composite module of the present invention may be constructed so
that the
dimensions allow the tip of the tapered section to fit inside the base of the
ascending
module. In the same way the base of the module may be constiucted so it will
fit onto the
tip of the descending module. The overlaps of these joint areas may be
predetermined so
that adequate load transfer can take place from one module and the next. This
overlap
may vary throughout the structure generally getting longer as the modules
descend in
order to maintain sufficient load transfer when reacting against increasing
levels of
bending moment.
[0091] The joints are designed so they will affect sufficient load transfer
without the use
of additional fasteners, for example press fit connections, bolts, metal
banding and the
like. However, a fastener may be used sometimes in situations-where-the-staek-
of--
modules is subjected to a tensile (upward force) rather than the more usual
compressive
(downwards force) or flexural loading.
[0092] Figure 1 shows a series of composite modules stacked together to form a
pole.
Modules 1 to 5 are 15 ft long plus an allowance for the overlap length.
Therefore, joining
modules 1 and 2 results in a 30 ft pole. Joining modules 1, 2 and 3 results in
a 45 ft pole.
As each successive module is added the pole can increase in height at 15 ft
intervals.
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[0093] In cases where the stack does not begin with module 1, the resultant
length
includes the additional length of the overlap. For example. Modules 2, 3 and 4
would
result in a pole like structure that would measure 45 ft plus the additional
overlap length
at the tip of module 2. If desired, the additional length can be simply cut
off so the pole
meets with height requirements.
[0094] The composite modules of the present invention may be designed so that
a
smaller module for example but not limited to module 1, 2, 3, 4 of Figure 6,
fits inside a
larger module for example but not limited to module 5, 6, 7 (Figure 6), as
shown in
Figure 7. This offers tremendous advantages when handling and transporting
modules
due not only to the compactness and space saving, but also to the
significantly reduced
weight when compared to wood, steel or concrete. Modules can be nested
together in
small stacks. For example, modules 1, 2 and 3 can be nested together which
when
assembled will form a 45 ft pole like structure with the strength
characteristics as
indicated in Figure 2. Similarly modules 2, 3 and 4 can be nested together for
transportation. When erected this will form a 45 ft pole like structure with
higher
strength characteristics as shown in Figure 2. The modules required to stack
together to
form a 90 ft pole class 2 pole, can be subdivided to form other constructions.
In the
example of 90 ft class 2 pole, five modules are required (modules 2, 3, 4, 5
and 6). From
this set of modules further structures can be assembled. For example, modules
2, 3 and 4
can be stacked to form a 45 ft class 1 or 2 pole. Modules 3, 4 and 5 can be
stacked to
form a 45 ft class Hl or H2 pole (see Figure 2). Modules 5 and 6 can be
stacked to form
a 45 ft class H3 or H4 pole. Similarly, modules 2, 3, 4 and 5 can be assembled
to form a
60 ft pole like structure with the strength capabilities corresponding to
class 1 or 2.
Modules 4,_5_and_6-can-a-1so be-assembled to produce a 60 ft pole like
structure with a
strength capability corresponding to Hl or H2 class. These are shown in Figure
3. In the
same way, modules 3, 4, 5 and 6 can be stacked to form a 75 ft pole like
structure with a
strength capability corresponding to class 1 or Hl.
[0095] In essence, a stack of 7 modules has the capability of being erected in
many ways.
In this embodiment with just 7 modules, 19 variations of pole like structures
can be
assembled in heights from 30 ft to 90 ft and displaying a variety of strength
and stiffness
properties. It must be emphasized that this embodiment has used 30 ft - 90 ft
structures
for illustration purposes constructed from 15 ft and 30 ft modules. The system
is not
27
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limited to a minimum of 30 ft or indeed a maximum of 90 ft or 7 modules. The
size of
the modules are also not limited to those shown for illustration purposes. The
complete
system in either part or whole allows for flexibility and ease of erection. If
a shorter pole
is required, the module may be cut at the desired height. Similarly, if a pole
taller than 90
ft is required, then the appropriate composite modules may be designed and
matingly
fitted together as described herein.
[0096] Referring to Figure 8, a top cap 60 may be placed over top end 54 of an
uppermost of the modules, thereby preventing entry of debris or moisture from
above. A
bottom plug 62 may also be placed into bottom end 52 of a lowermost of the
modules,
thereby preventing entry of debris or moisture from below. One significant
advantage
attained from adding a bottom plug is to increase the stability of the
foundation and
prevent the hollow pole like structure from being depressed into the ground
under
compressive loading. In many instances a hole 64 is made in bottom plug 62 to
allow any
moisture from within the stack to drain away.
[0097] The present invention will be further illustrated in the following
examples.
However, it is to be understood that these examples are for illustrative
purposes only, and
should not be used to limit the scope of the present invention in any manner.
EXAMPLES
[0098] In the Examples that follow all percentages given are percentages by
weight
unless indicated otherwise.
[0099] The following materials were used in the Examples:
POLYISOCYANATE A: A HDI Hexane, 1,6-diisocyanato-, homopolymer
polyisocyanate having an NCO content of 23% and a viscosity ranging between
900 -
1500cps, which is commercially available from Rhodia under the name Tolonate
HDT-LVTM
POLYISOCYANATE B: A HDI Hexane, 1,6-diisocyanato-, homopolymer
polyisocyanate having an NCO content of 23% and a viscosity ranging between
450 -
750cps, which is commercially available from Rhodia under the name Tolonate
HDT-
LV2Tm
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POLYISOCYANATE C: A mixture of polyisocyanate, polymeric hexamethylene
diisocyanate, and less than 5% monomeric 1, 6 Hexamethylene Diidocyanate based
Polyisocyanate, having an NCO content of 23% and a viscosity of about 1200cps,
which is commercially available from Bayer material Science LLC under the name
of
Desmodur N3600TM
POLYISOCYANATE D: A polymeric MDI, Polymethylene polyphenyl isocayante
containg 4,4'-Methylene bisphenyl isocyanate, having an NCO content of at
least 32%
and a viscosity of about 200cps, which is commercially available from Dow
Chemicals under the name of PAPI 27 TM
POLYOL A: A polyether polyol having an equivalent weight of about 86 and a
functionality of 3.0 which is commercially available from Arch under the name
PolyG
76-635TM
POLYOL B: A polyether polyol having an equivalent weight of about 100 and
functionality of 4.0 which is commercially available from BASF under the name
Pluracol PEP 450TM
POLYOL C: A polyether polyol having an equivalent weight of about 212 and a
functionality of 2.0 which is commercially available from Arch under the name
PPG
20-265TM
POLYOL D: A polyester polyol having an equivalent weight of about 142 and a
functionali of 2.0 whilus_aommer-ciall-y-available-from Stephan~Company under
the
name Stepanpol PS-4002TM
POLYOL E: A polyester polyol having an equivalent weight of about 288 and a
functionality of about 2.0 which is commercially available from Stephan
Company
under the name Stepanpol PS 20-200A TM
CATALYST A: A tin catalyst which is commercially available from Goldschmidt
Industrial Chemicals under the name Tegokat 21 STM
CHAIN EXTENDER A: 1,4 Butanediol, available from BASF.
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UV SYSTEM A: A liquid light stabilizer system comprising a synergistic blend
of a
light stabilizer, a light absorber and an antioxidant, commercially available
from
CIBA under the name Tinuvin B75TM
UV SYSTEM B: A blend of a liquid hindered light stabilizer commercially
available
from CIBA under the name Tinuvin 765TM and a liquid benzotriazole light
absorber
commercially available from CIBA under the name Tinuvin 571 TM
COLOUR A: Grey colorant commercially available from POLYONE under the name
STANTONE HCCTM Gray
COLOUR B: Blend of 50 % by weight of COLOUR A with the remainder comprising
a 1:1 ratio mixture of Rebus Dark grey 2180TM (available from REBUS) and
Colormatch Metal LDRTM (available from Plasticolor).
COLOUR C: Brown colorant commercially available from POLYONE under the
name STANTONE HCC TM Brown
MOLECULAR SIEVE A: Purmol 3ST TM (available from ZEOCHEM)
REINFORCEMENT A: Glass fibers commercially available from FGI under the name
FLEXISTRAND 250 LYPP 700 TM
Aliphatic isocyanate polyurethane resin composition A
_[00100]_An_aliphatic iso.c_yanate-pal-yur-ethane-r-e&in-ca -m- position
(composition-A-)-was-
made up by mixing polyol component A and POLYISOCYANATE C in a weight ratio of
1:1.7, wherein polyol component A had the following composition:
Polyol component A:
79 parts by weight of POLYOL B
15 parts by weight of POLYOL C
3 parts by weight of MOLECULAR SIEVE A
CA 02595201 2007-07-18
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2 parts by weight of COLOR B
1 part by weight of UV SYSTEM A
0.2 parts by weight CATALYST A
Total: 100parts
[00101] Resin composition A had a pot life of about 65 minutes when started at
25 C
and gave a 15 minute working time when started at 40 C. However, by adjusting
the
catalyst level, the pot life could be adjusted between 5 minutes to 3 hours.
AliRhatic isocyanate polyurethane resin composition B
[00102] An aliphatic isocyanate polyurethane resin composition (composition B)
was
made up by mixing polyol component B and POLYISOCYANATE B in a weight ratio of
1:2.44, wherein polyol component B had the following composition:
Polyol component B:
65 parts by weight of POLYOL A
18 parts by weight of CHAIN EXTENDER A
11 parts by weight of POLYOL D
2 parts by weight of COLOR A
3 parts by weight of MOLECULAR SIEVE A
1 part by weight of UV SYSTEM B
0.2 parts by weight of CATALYST A
Total: 100parts
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Composition B had a pot life of about 50 minutes when started at 25 C.
However, it
will be evident to a person slcilled in the art that the composition may be
modified and
refined in various ways.
Aliphatic isocyanate polyurethane resin composition C
[00103] An aliphatic isocyanate polyurethane resin composition (composition C)
was
made up by mixing polyol component C and POLYISOCYANATE A in a weight ratio of
1:1.72, wherein polyol component C had the following composition:
Polyol component C
65 parts by weight of POLYOL A
18 parts by weight of POLYOL C
11 parts by weight of POLYOL E
2 parts by weight of COLOR C
3 parts by weight of MOLECULAR SIEVE A
1 part by weight of UV SYSTEM B
0.2 parts by weight of CATALYST A
Total: 100parts
[00104] Composition C had a pot life of about 50 minutes when started at 25C.
However, it will be evident to a person skilled in the art that the pot life
may be modified
and refmed in various ways by adjusting the amount of catalyst.
Manufacture and testing of aliphatic isocyanate composite material
[00105] Resin composition C was used to produce an aliphatic ioscyanate
composite
material. About 75% REINFORCEMENT A was impregnated with about 25% resin
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composition C and wound onto a mandrel using a filament winding process
substantially
as hereinbefore described in more detail. The resin impregnated fibers were
allowed to
cure to hardness and the resulting aliphatic iosoyanate composite material had
the
following properties:
Glass fibre content 75%
Specific gravity 2.0
Interlaminar Shear Strength (ASTM D 2344 6500 psi
4 ASTM D 2344 is the standard test method for short-beam strength of polymer
matrix composite
materials and their laminates
[00106] Interlaminar Shear Strength test is a good indicator of the quality of
the fiber-
resin interfacial bond, and hence the quality of the composite material.
Abrasion resistance testing of aliphatic top layered composite poles
[00107] Aliphatic top layered composite poles having 9 inner layers of an
aromatic
isocyanate resin composite material and 3 outer layers of an aliphatic
isocyanate resin
composite material were produced using filament winding process substantially
as
hereinbefore described in more detail.
[00108] The aromatic isocyanate resin composite material inner layers
comprised about
70% by weight REINFORCEMENT A impregnated with about 30% by weight aromatic
-20 isocyanate pz~lyiuethane resm composition A. Aromatic isocyanate
polyurethane resin
composition A was made by mixing polyol component D with POLYISOCYANATE D
in a ratio of 1: 1.15, wherein polyol component D had the following
composition:
Polyol component D:
60 parts by weight of POLYOL A
20 parts by weight of POLYOL C
17 parts by weight of POLYOL E
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3 parts by weight of MOLECULAR SIEVE A
0.02 parts CATALYST A
Total: 100 parts
[00109] Aromatic isocyanate polyurethane resin composition A had a pot life of
about 36
minutes when started at 25C. However, it will be evident to a person skilled
in the art that
the pot life may be modified and refined in various ways by adjusting the
amount of
catalyst.
[00110] The aliphatic isocyanate resin composite material outer layers
comprised about
70% by weight REINFORCEMENT A impregnated with about 30% by weight aliphatic
isocyanate polyurethane resin composition C.
[00111] The aliphatic top layered composite poles were subjected to blown sand
testing
using equipment designed for military applications in harsh climates. The
United States
Military Environmental Testing Specification, blowing sand test MIL-STD-810,
was
performed by Dayton T. Brown (NY) Laboratories, USA using the following test
conditions:
Test Conditions
Air Speed 801cm/h (50 mph)
Temperature 60 C (140 F)
Relative Humidity < 2 %
Sand Concentration 2.15 g/m3
Test duration 90 minutes
[00112] The aliphatic top layered composite poles exposed to the blown sand
testing
were dulled, but showed no indication of abrasion wear. Minute particles of
sand were
lodged in the surface causing slight discoloration on the surface. Light
buffing of the
surface recovered some of the gloss and returned the surface to its original
colour. Table
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CA 02595201 2007-07-18
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1 shows a comparison of properties of the pole samples before and after the
test.
Table 1. Properties of aliphatic top-layered composite pole samples before and
after blowing sand test.
Flexural Strength3 Flexural Modulus3 Interiaminar Shear
(MPa) (GPa) Strength4 (MPa)
Actual StDev Actual StDev Actual StDev
Before Test 435 43 13.5 0.9 39.9 2.9
After Test 428 67 14.0 1.5 41.5 1.1
3 Tested using ASTM D 790 which is the standard test method for flexural
properties of plastics
Tested using ASTM D 2344 which is the standard test method for short-beam
strength ofpolymer matrix
composite materials and their laminates
[00113] These results indicate that there was no degradation of physical and
mechanical
properties in the tested aliphatic top-layered composite pole samples. A post-
test visual
inspection of the aliphatic top layered pole samples revealed no indication of
abrasion
except slight dulling of the exposed surfaces. Light buffmg of the exposed
surface
recovered some of its original gloss. The Interlaminar Shear Strength test
results
indicated that there was good bonding between the fiber-resin interfacial bond
and hence
the quality of the composite material.
UV resistance testing of aliphatic top lay-er_ed co-mposite-polcs
[00114] Aliphatic top layered composite poles were produced as previously
described.
UV exposure test, ASTM G154, was performed by Q-Lab Weathering Research
Service
in Florida, USA. The poles were exposed to UV light for 4088 hours using a
lamp setting
of 0.77 W/m2. Table 2 shows a comparison of properties of the pole samples
before and
after the test, observed by Q-Lab Weathering Research Service.
Table 2. Comparison of visual appearance and mechanical properties of
aliphatic top layered pole before and after UV exposure
CA 02595201 2007-07-18
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Property Non-exposed sample Exposed sample
(pre- test) (post- test)
Challc 5 10 10
Flake 5 10 10
Blister 5 10 10
Crack 5 10 10
Checlc 5 10 10
Interlaniinar shear strength 40.1 41.5
(ASTM D2344M 4), MPa
Flexural modulus (ASTM D790 3), 16.7 18.8
Gpa
Flexural Strength (ASTM D790 3), 593 584
Mpa
3 ASTM D 790 is the standard test method for flexural properties of plastics
4 ASTM D 2344 is the standard test method for short-beam strength of polymer
matrix composite
materials and their laminates
The "visual inspection report" from Q-Lab rated appearance of the composite
pole out of ten, with ten
5 being excellent condition indicating no change which is equivalent to zero
of ISO.
[00115] The visual inspection report from Q-lab indicates that there was no
change in
appearance of the aliphatic top layered pole following prolonged UV exposure.
These
results also indicate that there was no degradation of physical and mechanical
properties
in the tested aliphatic top-layered composite pole samples following prolonged
UV
exposure.
[00116] All references are herein incorporated by reference.
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[00117] In this patent document, the word "comprising" is used in its non-
limiting sense
to mean that items following the word are included, but items not specifically
mentioned
are not excluded, in other words the term "comprising" is substantially
equivalent to the
phrase "including but not limited to", and the word "comprises" has a
corresponding
meaning. A reference to an element by the indefinite article "a" does not
exclude the
possibility that more than one of the element is present, unless the context
clearly requires
that there be one and only one of the elements.
[00118] The present invention has been described with regard to preferred
embodiments.
However, it will be obvious to persons skilled in the art that a number of
variations and
modifications can be made without departing from the scope of the invention as
described
herein. Citation of references is not an admission that such references are
prior art to the
present invention.
37
