Title of Invention

A COMPOSITION PRODUCT

Abstract A fiber-containing product for use in the manufacture of fiber-reinforced composite articles comprising: (a) a prepreg strand comprising a plurality of substantially linear and substantially electrically non-conductive gathered reinforcing fibers adhered together with a solidified, substantially solvent-free chemical treatment comprising a thermoplastic film-forming polymer; wherein said chemical treatment is disposed between and forms a substantially continuous coating on the surface of substantially all of the gathered fibers; and (b) a thermoplastic coating substantially encasing the prepreg strand.
Full Text FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION
The invention relates to applying a chemical treatment to fibers which are
suitable for processing into a composite. More particularly, the invention relates to
applying a chemical treatment to fibers where the chemical treatment has a low viscosity
and is substantially free of an unreactable solvent Even more particularly, the invention
relates to using heat energy to lower the viscosity and improve the wetting ability of a
chemical treatment after being applied to the fibers and/or to increase the molecular weight
of or cure the applied chemical treatment with very little, if any, generation of volatile
organic carbon (VOC).
The present invention also generally relates to the manufacture of fiber-
reinforced composite articles, in particular, to wire-coated fiber/polymer composite strands
used in molding fiber-reinforced composite articles. More particularly, the invention
relates to thermoplastic encased fiber/polymer composite threads and pellets moldable into
fiber-reinforced thermoplastic composite articles.
BACKGROUND OF THE INVENTION
Fibers or fibrous materials are often used as reinforcements in composite
materials. Glass and other ceramic fibers are commonly manufactured by supplying the
ceramic in molten form to a bushing, drawing fibers from the bushing, applying a chemical
treatment, such as a size, to the drawn ceramic fibers and then gathering the sized fibers
into a tow or strand. There are basically three known general types of chemical treatraents-
-solvent-based systems, melt-based systems and radiation cure-based systems.
In a broad sense, the solvent-based chemical treatments include organic
materials that are in aqueous solutions (i.e., dissolved, suspended, or otherwise dispersed in
water), as well as those that are dissolved in organic solvents. U.S. Patents Nos. 5,055,119,
5,034,276 and 3,473,950 disclose examples of such chemical treatments. The solvent (i.e.,
water, organic solvent, or other suitable solvent) is used to lower the viscosity of the
chemical treatment to facilitate wetting of the glass fibers. The solvent is substantially
unreactable with the other constituents of the chemical treatment and is driven out of the

cnemical treatment after the wetting of the glass fibers. In each process for applying
solvent-based chemical treatments, an external source of heat or some other device external
to the fibers is used to evaporate or otherwise remove the water or other solvent from the
applied chemical treatment, leaving a coating of organic material on the glass fibers. One
drawback to a solvent-based process is mat the added step of removing the solvent
increases production costs. In addition, some organic solvents ate very flammable in vapor
form and pose a fire hazard. Another problem with solvent-based systems is that it is very
difficult, if not impossible, to remove all of the solvent from the applied chemical
treatment Therefore, solvent-based chemical treatments are limited, as a practical matter,
to those systems where any residual solvent left behind in the coating of organic material
remaining on the fibers will not have a significantly adverse affect.
With prior melt-based chemical treatments, thermoplastic-type organic
solids are melted and applied to the glass fibers. U.S. Patents Nos. 4,567,102,4,537,610,
3,783,001 and 3,473,950 disclose examples of such chemical treatments. One disadvantage
of prior melt-based processes is the energy costs associated with melting the chemical
treatments. The organic solids used with prior melt-based systems are melted at relatively
high temperatures in order for the melted organic solids to be applied to the glass fibers.
The high temperatures are needed because the organic solids used in the past have relatively
high molecular weights. Such high melt temperatures also pose the risk to workers of being
burned by the equipment used to melt the plastic material and by the molten plastic material
itself. In addition, specialized equipment is typically needed to apply and otherwise handle
the high-temperature molten plastic material.
The radiation cure-based chemical treatments are typically acrylate-based
organic chemicals, either with or without a solvent, which are cured with ultraviolet
radiation via a photoinitiator. U.S. Patents Nos. 5,171,634 and 5,011,523 disclose
examples of such chemical treatments. A major disadvantage to processes using such
chemical treatments is that the radiation used, such as ultraviolet radiation, and the
chemical treatment used, such as acrylates, are relatively hazardous, often requiring special
handling and safety precautions. Some of these processes, such as that disclosed in U.S.
Patent No. 5,171,634, require the radiation curing to be repeated a number of times to
obtain the maximum benefit. Each additional radiation-curing step increases the risks
involved and adds additional cost to the process. Furthermore, radiation-curable thcrmoset

plastics, and their requisite photoinitiators, represent a highly specialized area of thermoset
chemistry. As a consequence, such radiation-cured chemical treatments are expensive and
not generally compatible with various classes of matrix resins.
In order to fabricate composite parts, the strands of glass fibers are often
further chemically treated in an off-line impregnation process with a polymeric resin. The
resin can be a thermoset, either one- or two-part, or a thermoplastic. In one example,
previously formed and sized continuous glass fibers are impregnated with a thermosetting
resin and then pulled through a heated pultrusion die to cure the resin and make the
composite article, such as ladder rails. In such an off-line process, the continuous glass
fibers must be separated in some manner to allow impregnation of the resin between the
fibers and then recombined. This requirement almost always results in the use of additional
hardware such as spreader bars, impregnation baths, and drying or curing ovens. These
types of processes have the disadvantage that they add cost and complexity to the process.
In addition, the resultant extra handling of the glass fibers can cause breakage of the
individual glass filaments, and thereby a degradation in the properties of the composite
article. Therefore, while such off-line processes may be effective, they are time-consuming
and inefficient (e.g., requiring additional process steps) and, thus, expensive.
Accordingly, there is a need in the art for a safer, more efficient and more
cost-effective process for applying a chemical treatment to glass fibers, where the viscosity
of the chemical treatment is low enough to sufficiently wet the glass fibers without the need
for a solvent, where the chemical treatment does not require radiation curing and the
viscosity of the applied chemical treatment increases with very little, if any, generation of
water, volatile organic carbon (VOC) or other solvent vapor, and where the resulting
chemically treated glass fibers are. suitable for subsequent processing into a composite
article. There is also a need for an in-line process for forming a preimpregnated glass
composite strand from a plurality of continuously formed glass fibers which are chemically
treated in this manner, where the resulting prepreg strand is suitable for subsequent in-line
or off-line processing into a composite article.
The use of composites having fiber-reinforced polymeric matrices is
widespread. Fiber-reinforced polymeric composite products have been manufactured using
a variety of processes and materials. As referred to above, one such process involves
impregnating one or more strands or bundles of reinforcing fibers (e.g., glass fibers,

synthetic fibers or some other reinforcing fibers) with a thermoplastic material, and using
the resulting composite strands to mold a composite article. These composite strands have
been used in the form of continuous threads (i.e., long lengths of strand) and discrete pellets
(i.e.; short lengths of strand). The fibers from the composite strands provide the
reinforcement and the thermoplastic material forms at least part of the matrix for the
composite article.
It is desirable for each fiber strand to be fully impregnated with the
thermoplastic matrix material, that is, for the thermoplastic material essentially to be evenly
distributed throughout each bundle of fibers and between the fibers. Because all of the
fibers start out surrounded by matrix material, the fully impregnated fiber strands can be
molded less expensively and more efficiently and the corresponding composite article can
exhibit improved properties. However, it is difficult and time-consuming to fully
impregnate fiber strands with typical thermoplastic matrix materials (e.g., engineering
thermoplastics). Fully impregnating strands at high throughput rates has been particularly
difficult, especially at the throughput rates typically experienced during the production of
continuously formed glass reinforcing fibers.
In an effort to fully impregnate continuously formed glass fiber strands, the
number of fibers used to form each strand (i.e., fiber density) has been reduced from a
typical density of about 2000 fibers/strand to 1200 fibers/strand or less, to reduce the time it
takes to impregnate each fiber strand. However, by reducing the number of fibers in each
strand being processed at a given time, the production output and cost efficiency of the
process can be adversely impacted. In addition, fully impregnating even such lower density
strands is still sufficiently time-consuming to prevent even the lower density strands from
being fully impregnated and processed at the higher throughput rates typically approached
in the production of continuous glass reinforcing fibers.
In an effort to obtain higher throughputs, one prior process only partially
impregnates the fiber strand and coats the strand in a uniform layer of thermoplastic matrix
material, leaving a central core of fibers not impregnated with the thermoplastic. This
coating and partial impregnation of the strand is accomplished by pulling the strand through
what has been referred to as a "wire-coating" device. Wire-coating devices, such as that
disclosed in U.S. Patent No. 5,451,355, typically include an extruder for supplying molten
thermoplastic matrix material and a die having an entrance orifice, an exit orifice and a

coating chamber disposed therebetween. The extruder supplies molten thermoplastic
material to the coating chamber. The strand is coated and partially impregnated with the
thermoplastic matrix material as it passes through the coating chamber, and the coating is
formed into a uniform layer when the coated strand passes through the exit orifice of the
die. The resulting coated strand is either used in the form of a thread (e.g., in compression-
molding applications) or cut into discrete pellets (e.g., in injection-molding applications).
Because the strand is only partially impregnated with the thermoplastic matrix material, the
strand can be processed at relatively high throughputs.
However, these partially impregnated wire-coated strands also exhibit a
number of problems because of their central core of unimpregnated fibers. When in pellet
form, the fibers in the central unimpregnated core tend to fall out of the thermoplastic
coating. When the strand is in the form of a thread, the core fibers are less likely to fall out,
but the core of these wire-coated threads must still be impregnated at some point to
optimize the properties of the resulting composite article. Impregnating the central core of
such wire-coated threads during the molding operation can be difficult and time-consuming,
if not impossible as a practical matter. Thus, molding with such wire-coated threads can
cause a reduction in the overall production rates, rather than an increase as desired.
Therefore, there is a need for a way to produce fully impregnated fiber
strands at throushput rates, even when each strand has a relatively high fiber density,
where the resulting composite strands, either in thread or pellet form, are suitable for
molding fiber-reinforced thermoplastic articles.
SUMMARY OF THE INVENTION
An object of the invention is to attain a chemical treatment for fibers, such as
glass tibers, mat is substantially free of unreactable solvent. Another object is to achieve a
solvent-free chemical treatment mat is substantially non-photosetting. An additional object
of the invention is to provide such a chemical treatment that has an enhanced wetting
ability. A further object is to provide a solvent-free chemical treatment that may be cured
of have its viscosity reduced through application of heat energy to the chemical treatment
coated on fibers. Another object of the invention is to provide an advantageous process for
applying a chemical treatment to fibers, so that the coated fibers may be made into
composite strands useful for forming into composite articles. An additional object is to
provide such a process that yields fibers thoroughly impregnated with chemical treatment.

Such objects are Achieved via, inter alia, a method of making a composite
product, such as a composite stand or a molded article prepared from such a strand
product, the method generally comprising preparing a thermoplastic-encased composite
strand material for disposing in a matrix material. The thermoplastic-encased composite is
prepared by steps, comprising: applying a chemical treatment in an amount sufficient to
coat substantially all of a pluralky of fibers comprising reinforcing fibers to form
preknpregnated fibers, wherein me chemical treatment is compatible with the matrix
material; gathering the prehnpragnated fibers into a preimpregnated strand having the
chemical treatment disposed between substantially all of the plurality of fibers; and
encasing the preimpregnated strand by a process including wire-coating the preimpregnated
strand with a thermoplastic material to form a thermoplastic coating and forming the
thermoplastic coating into a thermoplastic sheath to form a thermoplastic-encased
composite strand. In a preferred embodiment, the thermoplastic-encased composite strand
is cut into lengths to form a plurality of pellets. Alternatively, the thermoplastic-encased
composite strand may be packaged as a thread. In one embodiment, the reinforcing fibers
include preformed reinforcing fibers. The plurality of fibers may also comprise matrix
fibers. The method may also further comprise steps such as preparing the reinforcing fibers
by a process including continuously forming reinforcement fibers from molten glass or
preforming matrix fibers from a polymeric material. Optionally, the method may comprise
preparing the reinforcing fibers in-line by a process including continuously forming
reinforcement fibers from a molten glass material. The chemical treatment used in such a
method may comprise water and an organic material in an amount providing the
preimpregnated strand with an organic material content of from about 2% to about 25% by
weight, with substantially all of the water in the chemical treatment being evaporated before
the gathering step. The organic material may be a solid or a liquid dispersed or emulsified
in the water. More preferably, the organic material content is from about 2% to about 15%
by weight, and the evaporating step comprises heating the chemical treatment after the
applying step, and even more preferably the organic material content is from about 6% to
about 7% by weight, and the heating comprises supplying heat energy to the chemical
treatment from an external source or from the plurality of fibers. In one embodiment, the
chemical treatment is thermosetting, and the preparing of the thermoplastic-encased
composite strand material further comprises the step of at least partially curing the chemical

treatment after the applying step. The chemical treatment is preferably substantially
solvent-free and substantially non-photosetting, and the organic material comprises a film
former and a coupling agent. In one embodiment, the chemical treatment is thermoplastic,
the film former includes a low molecular weight thermoplastic polymer, and the coupling
agent includes a functionalized organic substrate. In another embodiment, the chemical
treatment is thermosetting, the film former includes at least one of a multi-functional
monomer and a low molecular weight mono-functional monomer, and the coupling agent
includes a functionalized organic substrate. The method may further comprise combining
the thermoplastic-encased composite strand with the matrix material to form a composite
formulation, and molding the composite formulation. Furthermore, the method may
comprise forming the thermoplastic-encased composite strand into pellets, and molding the
pellets combined with a resinous matrix material to form a fiber-reinforced composite
article. The invention is also directed to products made according to such methods.
Additionally, the invention relates to a composite product comprising a
plurality of thermoplastic-encased composite strands useful in forming a fiber-reinforced
composite article containing a matrix material, each thermoplastic-encased composite
strand comprising a preimpregnated strand comprising a plurality of gathered fibers
including reinforcing fibers substantially coated with a thermoplastic or thermosetting
chemical treatment compatible with the matrix material. In one embodiment, the composite
product comprises pellets cut from the composite strands, with the chemical treatment
keeping the plurality of gathered fibers together in the pellets. Alternatively, the composite
strands may be packaged in thread form. Preferably, the plurality of gathered fibers
numbers in the range of from about 1,500 to about 10,000, more preferably, from about
2,000 to about 4,000. The plurality of gathered fibers may optionally include matrix fibers
made from a thermoplastic material. In one embodiment, the chemical treatment comprises
an organic material, and each preimpregnated strand has an organic material content of
from about 2% to about 25% by weight, more preferably, from about 2% to about 15% by
weight, and even more preferably, from about 6% to about 7% by weight. The chemical
treatment may be thermoplastic, substantially solvent-free, and substantially non-
photosetting, and comprise a (i) film former containing a low molecular weight
thermoplastic polymer material and (ii) a coupling agent containing a functionalized
organic substrate. Alternatively, the chemical treatment may be thermosetting,

substantially solvent-free, and substantially non-photosetting, and comprise (i) a film
fonner containing at least one of a multi-functional monomer and a low molecular weight
mono-functional monomer and (ii) a coupling agent containing a functionalized organic
substrate. The plurality of composite strands may be molded with a matrix material.
The invention further relates to a method for preparing a composite product,
the method comprising the steps of: applying a thermosetting or thermoplastic chemical
treatment to a plurality of fibers including glass or synthetic reinforcing fibers to form
fibers coated with applied chemical treatment, the chemical treatment being substantially
solvent-free and substantially non-photosetting; and heating the applied chemical treatment
so as to lower the viscosity of at least a portion of the applied chemical treatment or cure at
least partially the applied chemical treatment, or both, to form coated fibers. The chemical
treatment may be applied in an amount of from about 0.1% to about 1% by weight to size
the plurality of fibers, or in an amount of from about 2% to about 25% by weight to
preimpregnate the plurality of fibers. The fibers may further include polymeric matrix
fibers. In one preferred embodiment, the reinforcing fibers include glass reinforcing fibers
and the heating step comprises supplying heat energy to the applied chemical treatment
emanating from the glass reinforcing fibers, with the glass reinforcing fibers being at a
temperature preferably of from about 150°C to about 350°C, more preferably of from about
200°C to about 300°C, during the applying step. The reinforcing fibers may include
preformed reinforcing fibers, with the method further comprising the step of pre-hcating the
preformed reinforcing fibers. Also, the reinforcing fibers may include glass fibers, with the
method further comprising the step of forming the glass fibers from a source of molten
glass reinforcing material, where the heating step includes supplying heat energy retained in
the glass reinforcing fibers from the forming step to the applied chemical treatment. The
heating step may include supplying to the applied chemical treatment heat energy from a
source external to the plurality of fibers. In one preferred embodiment, the chemical
treatment is thermosetting and the heating step cures at least partially a portion of the
applied chemical treatment Alternatively, the chemical treatment is thermoplastic and the
heating step lowers the viscosity of at least a portion of the applied chemical treatment.
The method may further comprise a step of gathering the coated fibers together into a
composite strand, and the heating step may occur after the gathering step. The chemical
treatment may contain an organic material, with the composite strand having an organic

material content of from about 2% to about 25% by weight The method may also include
the step of forming the composite strand into a composite article having the plurality of
fibers disposed in a matrix formed at least in part by the applied chemical treatment. The
plurality of fibers optionally includes polymeric matrix fibers forming at least part of the
matrix of the composite article. The forming step may be performed in-line with the
gathering step. Additionally, the reinforcing fibers and matrix fibers may be commingled
to provide the plurality of fibers. The applying step may involve simultaneously coating
the reinforcing fibers and the matrix fibers with the chemical treatment.
Additionally, the invention relates to apparatus for carrying out the above
methods.
The invention also relates to a chemical treatment for applying to fibers for
processing into a composite strand useful for disposing in a matrix material to form a fiber-
reinforced composite article, the chemical treatment comprising: a film former comprising
at least one of a multi-functional monomer and a low molecular weight mono-functional
monomer, and a coupling agent comprising a functionalized organic substrate. The
chemical treatment is thermosetting, at least partially heat curable, substantially solvent-
free, and substantially non-photosetting. Optionally, the treatment may include a
processing aid, e.g., an epoxy-runctional viscosity modifier or butoxyethylstearate. In a
preferred embodiment, the chemical treatment is heat-curable at a temperature of from
about 150°C to about 350°C. The film former may comprise a monomer selected from
polyester alkyds, epoxy resins, and compounds containing glycidyl ether functional groups.
The film former may also comprise at least one member selected from methanes, vinyl
esters, amic acid, Diels Alder reactive species, and Cope-rearranging compounds.
Preferably, the chemical treatment has a viscosity of up to about 300 centipoise (cps) at a
temperature in the range of from about 93°C to about 110°C.
Furthermore, the invention relates to a chemical treatment for applying to
fibers for processing into a composite strand useful for disposing in a matrix material to
form a fiber-reinforced composite article, the chemical treatment comprising a film former
comprising at least one low molecular weight thermoplastic polymer material and a
coupling agent comprising a functionalized organic substrate, wherein the chemical
treatment is thermoplastic, substantially solvent-free, and substantially non-photosetting.
Optionally, the treatment may comprise a processing aid. The low molecular weight

thermoplastic polymer may include a cracked polyester or polyamide, with the polyester or
polyamide preferably selected from polyethylene terephthalate, polybutylene terephthalate,
and nylon. In a preferred embodiment, the treatment comprises a processing aid including a
monomer equivalent selected from di-n-butyl terephthalate, dibenzoate ester of 1,4-
butanediol, diethyl terephthalate, dibenzoate ester of ethylene glycol, caprolactone, adduct
of adipoylchloride and n-aminohexane, and adduct of 1,6-hexanediamine and
hexanoylchloride. Preferably, the chemical treatment has a viscosity of up to about 300 cps
at a temperature In the range of from about 93 "C to about 110oC.
Other objects, features, and advantages of the various aspects of the present
invention will become apparent from the detailed description of the invention and its
preferred embodiments in conjunction with the appended drawings.
BRIEF DESCRIPTION OF ACCOMPANYING RAWINGS
Figure 1 is a perspective view of one embodiment of an apparatus for
chemically treating fibers continuously formed from a molten material and suitable for
making a composite article.
Figure 2 is a perspective view of another embodiment of a system for
chemically treating fibers, where a heat retainer is disposed between a fiber-forming
mechanism and a chemical-treatment applicator.
Figure 3 is a perspective view of an additional embodiment of an apparatus
for chemically treating fibers continue usly formed from a molten material and preformed
fibers pulled from packages.
Figure 4 is a perspective view of one embodiment of an apparatus for
making and then chopping a thermoplastic-encased composite strand of preimpregnated
reinforcing fibers into a plurality of pellets suitable for being molded into a fiber-reinforced
thermoplastic composite article.
Figure 5 is a plan view of a winder device for winding a thermoplastic-
encased composite strand into a package of thread suitable for being molded into a fiber-
reinforced thermoplastic composite article.
Figure 6 is a perspective view of another embodiment of an apparatus for
making and then chopping a thermoplastic-encased composite strand of preimpregnated
fibers into a plurality of pellets suitable for being molded into a fiber-reinforced
thermoplastic composite article.

DETAILED DESCRIPTION AND
SOVENT-FREE-CHEMICAL TREATMENTS
One general aspect of the invention relates to essentially solvent-free
chemical treatments for applying to fibers to be processed into composite articles. One or
more-chemical treatments can be applied to the fibers, such as with one or more
conventional applicators, so as to size and/or preimpregnate a sufficient number of the
reinforcing fibers to obtain the composite properties desired.
More particularly, fibers or filaments are sized and/or preimpregnated with a
chemical treatment The chemical treatment has a low viscosity, is substantially free of an
unreactable solvent, and is not cured by actinic radiation. The low viscosity may be
obtained by choosing relatively low molecular weight constituents for the chemical
treatment
Heat energy may be used to lower the viscosity and improve the wetting
ability of the chemical treatment after the treatment is applied to the fibers. Additionally or
alternatively, heat energy may be used to increase the molecular weight of, or otherwise
cure (i.e., crosslink or otherwise increase the molecular weight of), the applied chemical
treatment Alternatively, no heat energy may be supplied to the applied chemical treatment
Regardless of whether heating is employed, there is little, if any, generation of water vapor,
volatile organic carbon (VOC) vapor, or other solvent vapor.
The resulting chemically treated fibers are suitable for forming a composite
strand, e.g., a preimpregnated strand ("prepreg"). The composite strand may be
subsequently processed in-line or off-line into a composite article having reinforcing fibers
disposed in a polymeric matrix material.
An apparatus suitable for making one or more composite strands in thread or
pellet form suitable for being molded into a fiber-reinforced thermoplastic composite article
includes a source of reinforcing fibers and, optionally, a source of one or more other types
of fibers. One such source is a bushing of molten reinforcing material (e.g., glass) from
which continuous reinforcing fibers can be drawn in sufficient numbers to form at least a
portion, if not all, of the strand. It may also be desirable for the source of reinforcing fibers
to be one or more spools or other packages of preformed reinforcing fibers. A source of
preformed reinforcing fibers may be used in combination with a source of continuously

formed reinforcing fibers. The source of fibers can also include matrix fibers that are
continuously produced, tot example, from a bushing or spinner and/or are preformed and
provided in suitable packaging, such as spools.
Where glass reinforcing fibers are being formed, the fiber-forming
mechanism forms the fibers from a source of molten glass fiber material, such as a
conventional glass fiber-forming bushing. The fiber-forming operation may be conducted
off-lirie-from or in-line with the balance of the apparatus. When the fibers being formed are
glass reinforcing fibers, the fiber-forming mechanism forms the fibers from a source of
molten glass reinforcing fiber material. In one embodiment, the fiber-forming mechanism
forms the fibers such that they emanate heat energy for a time after being formed.
An applicator is used for applying the chemical treatment to substantially all
of the fibers. The applicator can be of a conventional or any other construction suitable for
applying the desired type and amount of chemical treatment. The applicator may be
disposed in-line with the fiber-forming mechanism for applying a chemical treatment to the
fibers to form a plurality of coated fibers. The applicator applies the chemical treatment,
which is substantially free of solvent and substantially non-photosetting.
One embodiment of the apparatus includes an applicator system that applies
the chemical treatment when the fibers are at a higher temperature than that of the applied
chemical treatment. When the chemical treatment is applied, the fibers are at a sufficiently
higher temperature to provide enough heat energy to cause the applied chemical treatment
to lower its viscosity or heat cure at least partially (e.g., if the chemical treatment is a
thenhoset), or both. The temperature of the fibers when the chemical treatment is applied,
however, is not sufficient to cause significant decomposition of the applied chemical
treatment. The difference in the temperatures of the applied chemical treatment and the
fibers on which the treatment is being applied may be obtained by including a heat retainer
as part of the applicator system. This difference in temperatures may also be obtained by
disposing the applicator close enough (e.g., adjacent) to the fiber-forming mechanism so
that the fibers are at a sufficiently higher temperature than the chemical treatment when it is
applied. Such an applicator system may include a heat retainer disposed so as to help
maintain the temperature of the fibers, or at least reduce the rate of temperature drop, during
and/or after the chemical treatment is applied.

A gathering shoe or some other gatherer or bundler is used to gather the
treated fibers together into at least one strand. The strand may then be coated or encased
with a suitable polymeric material, preferably a thermoplastic, and formed into the desired
composite article.
The material used to coat or encase the chemically treated strand can be
provided from a source of molten thermoplastic material, such as from an extruder. To coat
the treated strand and form an encased composite strand, the treated strand may be pulled or
otherwise passed through a suitable coating device. For example, encased composite
strands can be formed by pulling or otherwise passing a number of the strands through a
corresponding number of dies, with each die having at least one exit orifice sized to form
the coating into a thermoplastic sheath of the desired thickness (e.g., that yielding a
thermoplastic-to-glass weight ratio of from about 30:70 to about 70:30),
Preferably, a wire coater is used to encase the strands. A wire coater is a
device or group of devices capable of coating one or more strands with a plastic material so
as to form a sheath of relatively uniform thickness on each strand. Preferably, the wire
coater includes some form of a die that shapes the sheath to the desired uniform thickness
and/or cross-section.
The strand is fed or passed through the coating device using a suitable
device. For example, a puller may be used to pull the strand through the wire coater. This
puller can be separate from or part of the wire coater. A chopper may be adapted to also
function as a puller or aid the puller in pulling the strand through the wire coater.
The resulting coated or encased composite strand can be cut or otherwise
separated into discrete lengths to form a plurality of encased composite pellets, or wound or
otherwise packaged to form an encased composite thread. The chemical treatment helps
keep the fibers together in each polymer-encased composite pellet or thread.
A composite article can be made by molding one or more of the encased
composite strands form at least part, and may form all, of the matrix of the composite
article to be molded. Exemplary molding processes used to form the composite article
include injection molding, compression molding, and other suitable molding teclmiques.

Figs. 1-3 illustrate a preferred embodiment for chemically treating a plurality
of fibers 10 suitable for making a composite article. A typical composite article comprises
a plurality of reinforcing fibers 12 disposed in a matrix of polymeric material.
In addition to reinforcing fiben.12, the fibers 10 may also include other
types of fibers suitable for making a composite article, such as matrix fibers 13. The matrix
fibers 13 are preferably made from a polymeric matrix material and form at least part of the
matrix. The reinforcing fibers 12 may be glass, which may be continuously drawn from a
source of molten glass reinforcing material (e.g., a conventional glass fiber-forming
bushing as shown in Figs. 1 and 2). Continuously formed glass reinforcing fibers are
especially advantageous since heat energy remaining in the glass fibers from the forming
process may be employed to efficiently provide heat to the applied chemical treatment. In
addition to or instead of using continuously formed glass fibers, the reinforcing fibers 12
may include preformed reinforcing fibers made from glass and/or synthetic reinforcing
materials.
The term "preformed" refers to fibers that arc formed off-line before being
supplied, or provided with a chemical treatment in accordance with the present invention.
The term "glass" means an inorganic product of fusion that solidifies to a rigid,
noncrystalline condition upon cooling, and is intended to include common silicate glasses
as well as glassy mineral materials suitable for making reinforcing fibers, such as
borosilicate glass, glass wool, rock wool, slag wool, and mineral wool. Contrastingly,
"synthetic" reinforcing materials are non-glass materials, such as Kevlar®, carbon or
graphite, silicon carbide (SiC), and other non-glass materials having suitable reinforcing
characteristics. When fibers made from different materials are used, it is contemplated that
the same or a different chemical treatment can be used for each type of fiber.
In one embodiment, the chemical treatment is applied according to methods
and using apparatus which use heat energy to effect at least one of two changes in the
applied chemical. Heat energy may be used to lower the viscosity, which improves the
wetting ability of a chemical treatment that has been applied to the fibers. Alternatively or
additionally, heat energy may be used to increase the molecular weight of, or otherwise
cure, the applied chemical treatment. Figs. 1 and 2 depict exemplary embodiments of
apparatus and methods for applying the chemical treatments.

The chemical treatment used to coat fibers 10 has a relatively low molecular
weight and viscosity compared to the matrix material, and is also substantially free of an
unreadable solvent. An "unreactable solvent" (e.g., water and certain organic solvents) is a
solvent that evaporates out of the chemical treatment in the presence of heat energy rather
than reacts with a constituent of the chemical treatment or the matrix material. The
chemical treatment is substantially "solvent-free"-i.e., essentially free of such a
substantially unreactable solvent Thus, there may be traces of an unreactable solvent in the
chemical treatment, but the amount of the solvent present is not enough, by itself, to
significantly lower the viscosity of the chemical treatment (i.e., affect the ability of the
chemical treatment to wet the fibers). In addition, the applied chemical treatment is
sufficiently free of any unreactable solvents such that no substantial amount of water vapor,
VOC vapor, or other solvent vapor is generated when the chemical treatment is heated,
including during molding of the composite article. By being solvent-free, the present
chemical treatment can have its viscosity reduced and/or be heat-cured without
experiencing a substantial drop in mass. Thus, most of the chemical treatment that is
applied to the fibers 10 remains on the fibers.
That the chemical treatment is solvent-free, however, does not preclude the
use of one or more additives in the chemical treatment that are soluble or compatible with
the other ingredients (e.g., the coupling agent). For example, a compatible viscosity
modifier, such as a HELOXY® (epoxy functional modifier) product available from Shell
Chemical Company, e.g., a digtycidyl ether of 1,4-butanediol (HELOXY Modifier 67) or a
polyglycidyl ether of castor oil (HELOXY Modifier 505), can be used in a film-former
system to interact or react one or more other ingredients to lower the viscosity of the
chemical treatment, instead of being driven off in the form of a vapor when in the presence
of heatenergy.-
The chemical treatment is also not curable by actinic radiation (i.e., is non-
photosetting) to any substantial degree. That is, the chemical treatment does not
photochemically react to cure or significantly increase in viscosity due to the effect of
actinic radiation.
The chemical treatment, which may be thermosetting or thermoplastic in
nature, is used for sizing and/or preimpregnating the number of reinforcing fibers 12 needed
to obtain the composite properties desired. The chemical treatment may also be used for

sizing and/or preimpregnating other types of fibers 10, such as fibers 13 made from a
polymeric matrix material.
Matrix fibers may be either continuously formed in-line or preformed, and
are subsequently used to form part or all of the matrix of the composite article. Where
matrix fibers are used, the step of applying the chemical treatment can include sizing and/or
preimpregnating the matrix fibers with the same or a different chemical treatment than that
applied to the reinforcing fibers.
In most cases preimpregnation as well as sizing is desired, and therefore it is
preferable for the same chemical treatment to be used for both sizing and preimpregnating
the fibers 10. Optionally, however, one chemical treatment may be used to size the
reinforcing and/or matrix fibers, and another chemical treatment may be used to
preimpregnate the reinforcing and/or matrix fibers. If different types of matrix fibers are
used, it may be preferable for a different chemical treatment to be applied to each type of
matrix fiber.
Sizing fibers involves applying at least a monolayer of the chemical
treatment onto the surface of each fiber. Glass reinforcing fibers 12 are generally
considered sized when a chemical treatment content of from 0.1% to 1%, e.g., on the order
of about 0.5%, by weight based on the total weight of the treated fibers, is applied onto the
fibers 12. Preimpregnating involves coating or otherwise applying a sufficient amount of
the chemical treatment to a plurality of fibers to substantially fill in the spaces between the
fibers when the fibers 10 are formed into a bundle or strand 14. A bundle or strand 14 of
glass reinforcing fibers 12 is generally considered preimpregnated when the strand 14 has a
chemical treatment content of from about 2% to about 25% by weight.
The fibers may be sized without being preimpregnated at the same time, for
example, when the chemical treatment is applied in a low quantity and/or when it has a
sufficiently low viscosity. The viscosity of a chemical treatment may be adjusted by
adjusting its temperature. For example, the viscosity of the treatment may be suitably
adjusted after it is applied by employing the heat present in the fiber.
Preferably at least the reinforcing fibers 12 of the strand fibers 10 are coated
with a chemical treatment in an amount of from about 2% to about 15% by weight, more
preferably from about 5% to about 15% by weight, and even more preferably with about
8% by weight (based on the weight of the treated fibers). A conventional loss on ignition

(LOI) method can be used to determine how much of the applied chemical treatment is on
the fibers 12, which ate preferably glass.
A preferred LOI range or value is the one that gives the desired composite
strand properties at the lowest cost At an LOI value of 8%, sample strands 14 have been
found to be well impregnated but not wet to the touch. LOI values that are too low may
cause fuzzing of the strand 14 (i.e., breakage of a number of individual glass fibers in the
strand) in subsequent in-line or off-line processing and handling. But the more chemical
treatment added, the more the final product will cost. Higher LOI values may also bleed
low viscosity components but of the strand 14. In any event, an LOI value of from about
25% to about 40% by weight is preferred for making a composite article with all the matrix
polymer being provided by the composite strand 14.
Thus, fibers 10 can be chemically treated in accordance with the present
invention to form aprepreg (preimpregnated composite strand) 14, or a composite strand 14
that contains only sized fibers 10. One or more of the composite strands 14 can be
subsequently processed, in-line or off-line, into a variety of composite articles. For
example, the step of forming the composite strand may be accomplished in-line with a
gathering step. Exemplary composite articles into which a strand 14 may be formed
include a mat, fabric, sheet, panel, filament-wound pipe, pultruded article (pultrusion), or
spray-up article (gun roving). The strands 14 may also be chopped into lengths or pellets
suitable for use in injection or other molding processes to form composite articles.
Generally, a chemical treatment according to the present invention
comprises a film former and a coupling agent. The film former forms a layer of polymeric
material around each fiber coated with the chemical treatment. The coupling agent helps
bond or otherwise couple the film former to at least the reinforcing fiber. The coupling
agent, if appropriate, can also be chosen to help the film former react or interact with the
polymeric matrix material.
The applied chemical treatment behaves as a thcrmosct or a thermoplastic.
Also, the treatment can have both thermosetting and thermoplastic components--e.g., the
treatment may contain a substantially thermoplastic polymer with reactive end groups that
can participate in a thermosetting/curing reaction. The film former used in either type of
chemical treatment may be the same polymeric material as that used for the composite
matrix.

A thermosetting-type chemical treatment is partially or fully heat-curable
and substantially non-photosetting, and may be used with a polymeric matrix material that
is either a thcrmoset or is thermoplastic. If the chemical treatment behaves as a thermoset,
applied heat energy may at least partially cure and cause an increase in the viscosity of at
least the portion of the applied chemical treatment being cured. A preferred chemical
treatment is heat-curable at temperatures of about 350°C (66"2°F) and below.
"In-exemplary thermosetdng-type chemical treatments, the film former
preferably comprises eitherone or more relatively low molecular weight mono-functional
monomers, one or more relatively low or high molecular weight multi-functional
monomers, or a combination thereof. A mono-functional monomer has one reaction site
per molecule, while a multi-functional monomer has two or more reaction sites per
molecule. The monomer is heat-curable without generating a substantial amount of water
vapor, volatile organic carbon vapor, or other solvent vapor. For example, the film former
used in a thermosetting-type chemical treatment may include at least one low molecular
weight functional monomer from the group including, e.g.. a polyester alkyd, an epoxy
resin, and a combination of glycidyl ether functional groups sufficient to form a film on
each fiber yet not constitute an epoxy resin. Other suitable functional monomers for use as
all or part of a film former include urethane, vinyl ester, amic acid, Diels Alder reactive
species (such as dienes or dieneophiles), and molecules that can undergo Cope
rearrangement. The molecular weight of the functional monomers is suitably low
compared to the matrix material to obtain a chemical treatment having a low viscosity.
In exemplary thermoplastic-type chemical treatments, the film former
preferably comprises at least one low molecular weight thermoplastic polymeric material
which has a relatively low viscosity at elevated temperatures. Thermoplastics usually have
relativelyhigh molecular weights, and thus high viscosities, compared to typical uncured
thermosets. However, such high molecular weight thermoplastics may still be used in the
film former of a thermoplastic-type chemical treatment if cracked or otherwise processed to
a sufficiently low molecular weight High molecular weight thermoplastics, for example,
polyethylene terephthalatc (PET), polybutylene terephthalate (PBT), other polyesters, and
polyamides such as nylon may be adequately cracked for this purpose.
Some thermoplastics even when cracked may have an undesirably high
viscosity. In such cases, a processing aid or a viscosity modifier may be used in the film-

former system. For instance, a monomer equivalent of the thermoplastic material, or a
mixture of a monomer equivalent and an oligomer (e.g., a cracked thermoplastic material),
may be used as a processing aid with a high molecular weight thermoplastic. Exemplary
thermoplastic monomer equivalents include di-n-butyl terephthalate and the di-benzoate
ester of 1,4-butanediol for PBTs; diethyl terephthalate and the dibenzoate ester of ethylene
glycol for PETs; and caprolactone, the adduct of adipoylchloride and n-aminohexane, and
the adduct of 1,6-hexanediamine and hexanoylchloride for nylons. In these examples, the
monomer equivalent molecules may act as processing aids to allow high molecular weight
thermoplastics such as PBT, PET, and nylon to form at least part of the film former in the
chemical treatment.
The above exemplary monomer-equivalent processing aids may be used
with other thermoplastics, and/or they may be made reactive and used with thermosets or
thermoplastics. Satisfactory results have been obtained using butoxyethylstearate (BES) as
a processing aid in the BES-containing chemical treatments described in the examples
below for thermoset matrices. Preferably, such processing aids contain the same kinds of
functional groups as the matrix polymer. There may be myriad molecules and/or
combinations of molecules that may be useful as monomer equivalent processing aids.
If the chemical treatment behaves as a thermoset, a step of heating is
preferably used to at least partially cure the applied chemical treatment and cause an
increase in the viscosity of at least the portion of the applied chemical treatment being
cured (i.e., the part most directly exposed to the heat). This increase in viscosity can be
caused by an increase in molecular weight as the thermoset-type chemical treatment cures.
The thcrmosctting-type film former is heat-curable without generating a substantial amount
of solvent vapor when heated. Preferably, the functional monomers used for the film
former are heat-curable at temperatures of about 350°C (662°F) and below, because the risk v
of permanent degradation increases to an undesirable degree for many chemical treatments
at temperatures of above about 350°C (662°F).
If the applied chemical treatment behaves as a thermoplastic, the heating can
cause a decrease in the viscosity of at least the portion of the applied chemical treatment
most directly exposed to the heat (e.g., adjacent to a hot fiber). If the viscosity is lowered
during the heating step, preferably there is enough of a drop in viscosity to improve as
desired the ability of the applied thermoplastic-type chemical treatment to wet the fibers 10

(to coat the fibers and interact with the fiber surface). The wetting of the applied chemical
treatment on the fibers 10 is more likely to improve when a drop in viscosity occurs for at
least the portion of the applied chemical treatment located adjacent to the fiber surface. To
reduce the chance of permanent degradation while being heated, it is also preferable for the
thermoplastic-type film former in particular, and for the thermoplastic-type chemical
treatment as a whole, to exhibit a sufficiently low viscosity at temperatures of about 3 50°C
(662°F) and below.
The viscosity of either type of chemical treatment is low enough to at least
partially, if not fully, wet the fibers 10 when the chemical treatment is initially applied. To
be able to apply the chemical treatment using conventional equipment (e.g., with a standard
single- or dual-roll applicator 26) without causing the fibers 10, in particular glass fibers, to
break in oignifionntly high numbow, tho chemical treatment preferably has a viscosity of
about 1000 cps or less before being applied. The lower me viscosity of the chemical
treatment being applied, the faster the fibers 10 can be processed without causing
significant fiber breakage. Thus, more preferably the chemical treatment before being
applied has a viscosity of about 300 cps or less. In a preferred embodiment for
advantageous processing of the fibers 10, the chemical treatment as it is applied has a
viscosity on the order of about 50 cps, more preferably of about 10 cps, as measured by a
conventional viscometer (e.g., a Brookfield or ICI viscometer).
The following are specific examples of film formers divided into two main
categories: liquid and meltable. In the "liquid" category, there are three examples of
maleate-based film formers that have been synthesized. In addition, there are twelve
epoxy-based film formers prepared from commercially available ingredients. There is
another liquid film former (allyl propoxylate urethane) which can be used in either a
-type or a thermoplastic-type chemical treatment. In the "meltable" category
the-two film-former systems, each prepared from a commercially available
polycploectone and one of the liquid film formers. The exemplary polycaprolactone
system is a..solid polymer at room temperature. These exemplary film formers are all
processable in accordance with the present invention.
Examples 1- 6: Liquid Film Formers
Example 1--Propyleneglycal-Fumarate;

A conventional ten-gallon (38 L) stainless steel reactor was charged with
17.02 kg of propylene glycol (available from Ashland Chemical Company of Columbus,
Ohio) and 12.98 kg of fumaric acid (available from Huntsman Specialty Chemical of Salt
Lake City, Utah). For stability, 3.62 g (120 ppm) of toluhydroquinone (THQ) (available
from Aldrich Chemical Company of Milwaukee, Wisconsin) was added into the reactor.
The molar ratio of the charge was 2:1 propylene glycol (PG) to fumaric acid (FA). The
mixture was heated under a nitrogen atmosphere at 380°F (193°C) for five hours. The
cndpoiut of the reaction was determined by the viscosity of the PG-FA product, which was
360 to 450 cps at 120°F (49°C) as determined by a cone-and-plate viscometer, such as that
made by ICI of Wilmington, Delaware. The acid value at the reaction endpoint is typically
observed to be 10 to 36 Meq KOH/g of alkyd (milliequivalcnt of potassium hydroxide per
gram of alkyd). This material may be used directly as a film former.
Example 2--Propoxylated Bisphenol-A-Maleate:
A 50-gallon (189 L) stainless steel reactor was charged with 159.68 kg of
propoxylated bisphenol-A (available from Milliken Chemical oflnman, South Carolina)
and 20.33 kg of maleic anhydride (available from Huntsman Specialty Chemical). For
stability, 18 g (100 ppm) of hydroquinone (HQ) (available from Aldrich Chemical
Company) was added to the reactor. The mixture was heated under a nitrogen atmosphere
at 175°F (79°C) for 2.5 hours, then at 275°F (135°C) for 3.5 hours. The endpoint of this
reaction was determined by acid value-the reaction was considered to be complete when
the acid value reached a level of 63.6 Meq KOH/g of alkyd and no more maleic anhydride
was observed by infrared spectroscopy. The viscosity of this product ranges from 100 to
130 cps at a temperature of 200oF (93°C) as measured by an ICI cone-and-plate viscometer.
This material may be used directly as a film former.
Example 3-Propoxlated AHyl Alcohol-Maleate:
A 15-gallon (57 L) stainless steel reactor was charged with 15.49 kg of
propoxylated allyl alcohol (available from Arco Chemical Company of New Town Square,
Pennsylvania) and 9.88 kg of maleic anhydride (available from Huntsman Specialty
Chemical). For stability, 2.53 g (100 ppm) of HQ was added to the reactor. The mixture
was heated under a nitrogen atmosphere at 250-300cF (121 -149°C) for four hours. The
reaction endpoint was when the acid value reached a level of 263.4 Meq KOH/g of alkyd
ind no more maleic anhydride was observed by infrared spectroscopy. The viscosity of this

product ranges from 100-130 cps at a temperature of 200°F (9.1 °C) as measured by an ICl
cone-and-plate viscometer. This material may be used directly as a film former.
Examples 4A-K--Low-Viscosity Epoxy Systems:
A typical epoxy-based film former contains one or more cpoxies that are
available from Shell Chemical Company, e.g., EPON Resin 8121, EPON Resin SU-2.5,
EPON Resin 160, HELOXY Modifier 62 (cresyl glycidyl ether), HELOXV Modifier 67
(diglycidyl ether of 1,4-butanediol), and HELOXY Modifier 505 (polyglycidyl ether of
castor oil). All of the epoxy-based film-former systems listed below have a viscosity below
50 cps at room temperature. The specified percentages are in weight percent (all
percentages and ratios given throughout this specification are by weight, unless indicated
otherwise).
(A) 100% HELOXY Modifier 67
(B) 98% HELOXY Modifier 67,2% HELOXY Modifier 62
(C) 90% HELOXY Modifier 67,10% HELOXY Modifier 62
(D) 98% HELOXY Modifier 67,2% EPON Resin 160
(E) 90% HELOXY Modifier 67, 10% EPON Resin 160
(F) 98% HELOXY Modifier 67,2% EPON Resin SU-2.5
(G) 90% HELOXY Modifier 67, 10% EPON Resin SU-2.5
(1-1) 97% HELOXY Modifier 67, 3% HELOXY Modifier 505
(I) 100% HELOXY Modifier 62
(J) 70% HELOXY Modifier 62, 30% EPON Resin 8121
(K) 65% HELOXY Modifier 62,30% EPON Resin 8121, 5% EPON Resin SU- 2.5
Example 5--High-Viscositv Epoxy:
In addition to the above-noted epoxy systems, an exemplary higher
temperature, higher viscosity epoxy film-former system is a one-to-one mixture of DER
337 epoxy resin (available from Dow Chemical) and Araldite GT7031 (available from
Ciba Gcigy Corp. of Switzerland). This film former has a viscosity of 350-450 cps at
?00°F (93°C) as determined using a Brookfield viscometer.
Example 6-Allyl Propoxylate Urethane:
A 12-Hter three-neck, round-bottom glass reactor equipped with a heating
mujitic, a Freidrieh condenser, a 1-liter addition fiuuiei, an electric overhead stirrer, and a
thermocouple temperature probe was charged with 3.63 kg (21.6 mol) of Desmodur H

(hexamethylenediisocyanate, available from Bayer Chemical of Pittsburgh, Pennsylvania).
To this was added 0.5 g (50 pprh) of dibutyl tin dilaurate (available from Aldrich Chemical
Company). Next, 6.37 kg (43.6 mol) of ARCAL Allyl Proproxylate 1375 (propoxylated
allyl alcohol, available from Arco Chemical Company) was added via the addition funnel,
the allyl propoxylate was added dropwise and the temperature was maintained at 80°C by
varying the addition rate and the temperature of the healing mantle. When the addition was
complete, the temperature of the reactor contents was maintained at 80°C for three (3) hours
or for a time until the 2200 wave number peak in the infrared spectrum of the reaction
mixture, corresponding to the isocyanate groups of the Desmodur H, disappeared. This
film former may be used directly without any purification or further manipulation.
Examples 7 and 8: Meltable Film Formers
Example 7--Propoxlated Bisphenol-A Maleate/TONE 0260
The propoxylated bisphenol-A maleate from Example 2 was mixed with
TONE 0260 (a polycaprolactone polymer available from Union Carbide) in a weight ratio
of one-to-one. This mixture is a solid at room temperature, but has a viscosity of 50-250
cps at a temperature of200-230°F (93 - 110°C).
Example 8-Propoxlated Allyl Alcohol Maleate/TONE 0260
The propoxylated allyl alcohol maleate from Example 3 was mixed with
TONE 0260 in a weight ratio of 1:1. This mixture is a solid at room temperature, but has a
viscosity of 50-250 cps at a temperature of 200-230°F (93-110°C).
Optional Ingredients
In addition to or instead of other viscosity modifiers such as those mentioned
above, n-butyl amic acid may also be used as a modifier where it is suitably reaclive with
either thermoplastic or thermosetting materials to lower the viscosity of the film former and
the overall chemical treatment. A preferred amic-acid reactive modifier was prepared as
follows:
A 2-liter three-neck, round-bottom glass reactor equipped with a heating
mantle, a Freidrich condenser, a 1-liter addition funnel, an electric overhead stirrer, and a
thermocouple temperature probe was charged with 150 g (1.53 mol) of mnleic anhydride
(available from Huntsman Specialty Chemical) and 0.02 g of hydroquinone (available from
Aldrich Chemical Co.). These solids were dissolved by the addition of 350 ml of acetone
(high-purity grade available from Aldrich Chemical). The solution of maleic anhydride and

hydroquinone was stirred in the reactor. A solution of 111 g (1.51 mol) of n-butyl amine
(available from Aldrich Chemical) in 150 ml of acetone was added to the reactor. The n-
butyl amine solution was added dropwise, and the (temperature was maintained at 55 °C by
varying the addition rate and the temperature of the heating mantle. Once the addition was
complete, the temperature of the reactor and contents was maintained at 60°C for three
hours. The acetone was then removed at reduced pressure and 60°C by rotary evaporation.
The solid n-butyl amic acid product was removed from the reactor as a liquid at 90°C,
which may be used directly without further purificttion or manipulation. A small portion
of the n-butyl amic acid produced was recrystallizad from acetone. The melting point of
the recrystallized material was 74.9°C by differential scanning calorimetry (DSC).
Coupling Agents
For either a thermosetting or thermoplastic chemical treatment, the coupling
agent comprises a functionalized organic substrate (i.e., at least one organic functional
group bonded to an organic substrate). Exemplary types of functionalized organic
substrates include alcohols, amines, esters, ethers, hydrocarbons, siloxaucs, silazaiies,
silar.es, lactams, lactones, anhydrides, cavbenes. nitrenes, orthoestcrs, imides, diamines,
imines, amides, imides, and olefins. The functionalized organic substrate is capable of
interacting and/or reacting with the surface of the fibers at elevated temperatures
(preferably, of from about 100°C (2I2°F) to about 350°C (662°F)) so as to produce
sufficient coupling or bonding between the reinforcing fibers and matrix material to achieve
the desired properties. Interaction involves bonding resulting from an attracting force, such
as hydrogen bonding or Van der Waals bonding. Reacting involves chemical bonding,
which is typically covalent bonding. The functionalized organic substrate can also be
interactive or reactive with the matrix material. Exemplary coupling agents include silanes
such as gamma-aminopropyltriethoxysilane (A-l 100), gamma-methacryloxy-
propyltrimclhoxysilane (A-174), and gamma-glycidoxypropyltrimethoxysilane (A-187),
which are all available from Witco Chemical Company of Chicago, Illinois. Non-silane
coupling agents may also be used. By choosing one or more suitable functionalized organic
substrates for the coupling-agent system, the desired mechnnicnl properties between the
reinforcing fibers and the matrix material in the composite article can be obtained.
While not intending to be limited to any theory regarding the chemical
treatments, a possible explanation of how the treatments may operate is provided below.

Silane-type coupling agents are typically found in aqueous-based chemical treatments.
Under a current view, with a conventional silane-type coupling agent the alkoxysilnne
portion of the molecule undergoes hydrolysis to become a hydroxysilane or si land to
water-solubilize the coupling agent. One end of the molecule reacts or interacts with the
glass surface and the other end of the molecule reacts or interacts with the matrix material.
More particularly, coupling agents that have typically been used in the glass industry are
organosilanes, which have an organic portion thought to react or interact with the matrix
polymer and a silane portion, or more specifically a silanol portion, thought to react or
interact wiUi the glass surface. Also, in some cases, it is generally accepted that the organic
portion of an organosilane is capable of reacting (e.g., covalent or ionic bonding) or
interacting (e.g., hydrogen or Van der Waals bonding) with the glass surface. In general,
hydrogen bonding and other associations arc thought to be thermodynamic (reversible
under mild reaction conditions) processes. In some cases, such as when silanols bond to a
glass surface, chemical bonding is considered a thermodynamic process. Thus, with
previous coupling-agent technology, the bonding of aqueous-based chemical treatments to
the glass occurs as a thermodynamic process. This is because conventional processes are
usually conducted under relatively mild conditions and are usually reversible to a
substantial degree. In a conventional process, after the glass fibers are coaled with an
aqueous-based chemical treatment, the coated fibers are packaged and dried in an oven.
While in the oven there is a potential for some of the organic functional groups of the
coupling agent to react irreversibly with some of the organic functional groups in the film
former. This does not happen to any great extent, however, because the oven temperatures
typically being used, about 150-190°F (66-88°C), are not high enough.
Contrastingly, with the solvent-free chemical treatments according to the
present invention, the bonding or coupling process becomes more kinetic in nature. That is,
the bonding may occur under relatively harsh conditions (e.g., at higher temperatures) and
may involve a substantially irreversible reaction. Moreover, in addition to a coupling agent
bonding to the fiber surface, an interphase region can now be formed between the
reinforcing fibers and the matrix material of the composite article. The inteiphase region is
formed, at least in part, by the applied chemical treatment. The interphase region may also
include, in whole or in part, a region around the fiber where the chemical treatment and the

matrix material have interacted and/or reacted with one another. The chemical treatment
may also become completely dispersed or dissolved in the surrounding matrix material.
Although conventional silane coupling agents may be used in the present
chemical treatments, it is believed that the mechanism of their interaction or reaction with
the glass surface differs from that which occurs in prior processes. Since there is essentially
no water present during the present processing, the alkoxysilanes react directly with the
glass surface to give a siloxane linkage and liberate alcohol. Indeed, there is experimental
evidence (proton NMR data) that suggests that the alkoxysilanes do not hydrolyze in the
present chemical treatments under the conditions to which they are exposed when processed
in accordance with the invention. It is believed that the alkoxysilane group of the coupling
agent used in the present chemical treatments is reacting or interacting with the glass
surface in a kinetic fashion to form a siloxane linkage and liberate alcohol. Thus, the
present process is kinetic, rather than thermodynamic, as evidenced by the observation that
good composite properties have been obtained for both thermoset and thermoplastic
composites when alkoxysilane coupling agents were present in the chemical treatments
according to the invention, whereas less desirable composite properties have been obtained
for both thermoset and thermoplastic composites when alkoxysilane coupling agents were
not present in the chemical treatments.
If an alkoxysilane coupling agent in a present chemical treatment reacts or
interacts with a newly formed glass or other reinforcing fiber surface via some kinetic
process, then other types of molecules containing sufficiently reactive functional groups,
such as those noted above, will also react or interact with a glass or other reinforcing fiber
surface via a kinetic process. Further, these same functional groups that react or interact
with the glass or other fiber surface via a kinetic process may react or interact with the rest
of the organic material in the chemical treatment and/or the matrix material via a kinetic
process as well. This may then serve to build an interphase region at or very near the glass
or other fiber surface, and may also serve to increase the average molecular weight of the
chemical treatment, thereby imparting desirable physical characteristics to the resulting
glass strand product. Thus, advantages of the present invention include the flexibility to
use a wider variety of coupling agents and to build an interphase region between the fiber
and the matrix.

For the composite article to exhibit desirable mechanical properties between
the reinforcing fibers and the matrix material, the chemical treatment is preferably
compatible with the matrix material of the composite article. In general, a chemical
treatment is considered compatible with the matrix material if it is capable of interacting
with and/or reacting with the matrix material. The film former of cither type of applied
chemical treatment may comprise the same polymeric material as the matrix material and
be provided in an amount sufficient to form part or all of the matrix of the composite
article.
The chemical treatments may be misciblc in the matrix material, in whole or
in part, and/or may form a separate phase from the matrix material. If a separate phase, the
chemical treatment disposed around each fiber may form a plurality of separate phase
regions dispersed in the matrix material and/or a single, separate phase region surrounding
its corresponding fiber.
When it is desirable for the composite article to be made with one type of
chemical treatment and a different type of matrix material, a thcrmoselling-typc chemical
treatment is preferably used with a thermoplastic matrix. A low molecular weight
thermosetting-type chemical treatment can cure during thermoplastic processing and/or
may react with the chain ends of the thermoplastic matrix material. Consequently, such
types of molecules will not readily plasticize the thermoplastic matrix material. In
choosing an appropriate chemical treatment, one should note that some low molecular
weight thermoplastic materials can plasticize thermoplastic matrix resins when the chemical
structure of the thermoplastic matrix resin and the low molecular weight thermoplastic
material arc very different. An example of such different thermoplastic materials is
dibutylterephthalate as part of the chemical treatment and polypropylene as the matrix
material.
Optionally, the chemical treatment may further comprise a compatibilizer for
improving the interaction and/or reaction between the chemical treatment and the matrix
material, thereby making otherwise non-compatible or less compatible polymeric
components or ingredients of the treatment more compatible (e.g., more miscible) in the
matrix material. When a thermosetting or thermoplastic chemical treatment is used with a
thermoplastic matrix material, exemplary compatibilizers include the PBT monomer
equivalents di-n-butyl terephthalate and dibenzoate ester of 1,4-butanediol; the PET

monomer equivalents diethyl terephthalate and dibenzoate ester of ethylene glycol; and the
nylon monomer equivalents caprolactone, the adduct of adipoylchloride and n-
aminohexane, and the adduct of 1,6-hexanediarnine and hexanoylchloridc.
When either type of chemical treatment is used with a thermosetting matrix
material, it is preferable to use a more reactive campatibilizer. For example, for a polyester
or vinylester thermoset, a suitable compatibiliaer is glycidyl methacrylate end-capped
diacids and esters of the trimellitlc anhydride system. Specific examples of suitable
compatibilizers for polyester and vinylester thennosets include diallylphthalate (DAP,
which is commercially available), glycidylmetbacrylate-capped isophthalic acid, trimellitic-
anhydride-dodecinate, bis-allylalcohol adduct of terephthalic acid and
CH3CH2(OCH2CH2)n(CH2)mCO2H, where n is an integer from 3 to 7 and m is 16 (e.g.,
CBA-60, available from Witco Chemical of Chicago, Illinois). For epoxy-based
thermosets, esters based on glycidol may be suitable compatibilizers, such as
glycidylmethacrylate by itself, diglycidylcster of adipic acid, and triglycidylisocyanurate
(TGIC).
The chemical treatment may also include one or more processing aids to
facilitate the use of the chemical treatment at some point during the manufacturing process
and/or to optimize the properties of the resulting composite article. For a thermosetting-
type chemical treatment, the processing aid can Include, e.g., a viscosity reducer for
reducing the viscosity of the thermosetting-type chemical treatment before it is applied to
the fibers. The viscosity reducer is substantially solvent-free and preferably aids the curing
of a thermosetting film former. The processing aids used in the thermosetting-type
chemical treatment can include, e.g., styrene and peroxide. Styrenes are preferably used to
thin the film former and participate in the thermoset reaction. Peroxides preferably function
as a catalyst or curing agent
Optionally, non-aqueous versions of other types of additives typically used
to size glass fibers may also be employed as processing aids in the present chemical
treatments. For example, processing aids or additives may be employed to help control the
lubricity of the glass tow or strand, control the relative amount of static generated, or
control the handleability of the glass strand or tow product. Lubricity may be modified by
adding processing aids or lubricating agents, for example, a polyethylencglycol ester
emulsion in mineral oil (e.g., Emeriube 7440, available from Henkel Textile Technologies

of Charlotte, North Carolina); polyethyleooglycols, e.g., PEG-400-MO (polyethylene glycol
monooleate) and PEG-400-monoisoatoarale (available from the Henkcl Corporation); and
butoxyethylstearate (BES). These lubricating agents serve to enhance the runability of the
glass by acting as lubricants, and when used judiciously should have little, if any, adverse
affect on the properties of the finished composite article. Static generation may be
controlled by adding processing aids such as polyethyleneimines, for example Emery 6760-
0 and Emery 6760-U (available from Henkel Corporation). Handleability may be
enhanced with processing aids such as polyvinyl pyrrolidone (e.g., PVP K90, available
from GAF Corporation of Wayne, New Jersey), which can provide good strand integrity
and cohesiveness, and wetting agents or surfactants such as Pluronic Li01 and Pluronic
PI 05 (both available from BASF Corporation), which can improve the ability of the matrix
material to wet the fibers. Any ingredient present, however, has a formulation and is added
in an amount such that the chemical treatment remains solvent-free.
Preferred embodiments of methods and apparatus for applying the inventive
chemical treatments will now be further described in reference to the drawings. Fig. 1
illustrates one embodiment of an apparatus 20 for applying a chemical treatment to fibers
10 used in making a composite article, and includes a fiber-forming mechanism 22, such as
a conventional glass fiber-forming bushing 24, which is operatively adapted according to
well known practice for continuously forming a plurality of glass reinforcing fibers 12 from
a source of molten glass material in a melter above the bushing 24. In this exemplary
process, die glass reinforcing fibers 12 emanate heat energy for a time after being formed.
One or more applicators 26, such as a standard single- or dual-roll style applicator 28 and
pan 30, can be used to apply one of the above-described exemplary chemical treatments to
the reinforcing fibers 12 in order to form a plurality of coated fibers 32. For the process to
continue to run after the chemical treatment is applied, i.e., without having a substantial
number of the. fibers 10 break, the viscosity of the chemical treatment is made to be
sufficiently low before being applied or to drop a sufficient amount after being applied as
discussed above.
Two alternative processes for applying chemical treatment to newly formed
glass fibers 12 are described below. Exemplary Process 1 is used when the viscosity of the
chemical treatment is relatively low at relatively low temperatures (e.g., viscosities of 150
cps or less at temperatures of 150°F (66°C) or less). Exemplary Process 2 is employed with

higher-viscosity chemical treatments. Chemical treatments which include one of the film
formers from the above Examples M(K) and 6 may be used in Process 1. Chemical
' treatments which include one of the film formers from Examples 5,7 and 8 may be used
witty Process 2. Any chemical treatment used in Process 1 can also be used in Process 2.
Any chemical treatment that can be used in either Process 1 or Process 2 may also be used
in Process 3, which is another exemplary system.
Process 1:
This process for applying a chemical treatment employs conventional glass
reinforcing fiber-forming equipment modified in the area around applicator 26 such that the
position of the applicator 26 is adjustable in a plane perpendicular to the stream of the glass
fibers 12 (i.e., the flow of fibers 10) as well as the plane containing the fibers 10. The
applicator 26 is fixed to a wheeled cart by means of a cantilever arm. The cart is on rails so
that it may be easily positioned along the axis perpendicular to the direction of flow of the
fibers. The top of the cart is connected to the main body of the cart by a scissors jack and
worm gear arrangement This allows the applicator 26 to be raised or lowered relative to
the bushing 24. The position of the applicator 26 can be adjusted along both axes while the
process is running. The chemical treatment is stored in a metal pail, such as a 5-gallon
(19 L) bucket
Heating of the chemical treatment is optional. To heat the chemical
treatment, the bucket may be placed on a hot plate and/or wrapped with a bucket heater,
such as a Model 5 available from OHMTEMP Corporation of Oarden City, Michigan. The
temperature of the chemical treatment is maintained at the desired level by means of a
variable AC thermocouple-based heating controller, such as those which are available from
major scientific supply houses such as Fisher Scientific or VWR Scientific. The chemical
treatment is pumped to and from the applicator pan 30 by means of a peristaltic pump, such
as a Masterflex model # 7529-8 equipped with a Masterflex pump controller model #7549-
50 and Masterflex tubing part #6402-73, all available from Barnant Company (a division of
Cole-Parmer, in Barrington, Illinois). The applicator 26 is of a standard design for a glass
fiber-forming process, and consists of a metal pan 30 supporting a single graphite roller 28
that is 3.0 inches (7.6 cm) in diameter and driven by an electric motor at speeds ranging
Tom 3 to 20 feet (0.9 to 6.1 m) per minute. An alternative pump can be used to replace the
)eristaltic pump, such as a Zenith pump model #60-20000-0939-4, available from Parker

Hannifin Corporation, Zenith Pump Division, Sanford, NC. This alternative pump is a
gear-type pump equipped with a heated feed and return hose assembly, and generally has
the following features: Teflon-lined, high-pressure, 0.222" (0.564 cm) inside diameter x
72" (183 cm) long, 12,000 psi (83 MPs) burst, 3000 psi (21 MPa) operating pressure,
stainless steel, 7/16-20 thread JIC female swivel fittings, 120 volts, 300 watts, 100 ohm
platinum RTD, 72" (183 cm) long cord with Amphenol #3106A-14S-06P plug, available
from The Conrad Company, Inc., of Columbus, Ohio (the heated hose assembly is a
difference between the two alternative (peristaltic vs. gear-type) pumping systems).
Process 2:
In another exemplary process, a dual-roll applicator is used for applying
high-viscosity, elevated-temperature chemical treatments in non-aqueous form. The dual-
roll applicator is fixed in position relative to the glass-forming apparatus. The position of
the dual-roll applicator is essentially the same as that found in a standard glass fiber-
forming process, which is approximately 50 inches (127 cm) from the bushing. The heating
system and pumping system used for the chemical treatment in this process ore the same as
described above for Process 1.
The dual-roll applicator includes a secondary applicator roll, which is the
larger of the two rolls, for transferring and metering the chemical treatment to a smaller,
primary applicator roll. The primary roll is used to directly apply the chemical treatment to
the fibers. The relatively small diameter of the primary roll reduces the drag between the
roll and the fibers by providing a reduced contact area therebetween. Tension in the fibers
is also reduced due to the reduction in drag. The thickness of the applied chemical
treatment may be metered by controlling the gap between the primary and secondary rolls
and by providing a doctor blade on the smaller roll. Such a dual-roll applicator is disclosed
in U.S. Patent No. 3,817,728 to Petersen and U.S. Patent No. 3,506,419 to Smith et al., the
disclosures of which are herein incorporated by reference.
Process 3:
In this preferred embodiment, a dual-roll applicator of Process 2 and the
positional adjustment capability of Process 1 are used together, along with the above-
described heating and pumping systems for the chemical treatment. The coated fibers 32
are gathered together into a strand 14 using a gathering mechanism 34, such as a
conventional gathering shoe. A pulling mechanism 36, such as a conventional pair of

opposing pull wheels, is used to continuously draw the fibers 12 from the bushing 24 in a
manner well known in the art. The strand 14 can be wound on a package (not shown) or
chopped into segments of desired length and stored for subsequent processing off-line into
a composite article. Alternatively, the composite strand 14 can be processed directly into a
composite article in-line with the gathering step.
In addition to the continuously formed reinforcing fibers 12, the fibers 10
can further compose a plurality of matrix fibers 13 made from a suitable matrix material. If
matrix fibers 15 are used, the step of applying the chemical treatment can include sizing
and/or preimpregnatingthe matrix fibers 13 with the same or a different chemical treatment
than that applied to the reinforcing fibers 12. If different types of matrix fibers 13 are used,
it may also be preferable for a different chemical treatment to be applied to each type of
matrix fiber 13. Likewise, if different types of reinforcing fibers 12 are used, it may be
preferable for a different chemical treatment to be applied to each type of reinforcing fiber
12. The same techniques and equipment may be used to chemically treat each type of
reinforcing fiber and matrix fiber, whether they are continuously formed or preformed.
Chemical Treatment Examples
Provided below arc examples of chemical treatments for applying to glass
reinforcing fibers and various matrix fibers, and suitable for use with PBT, nylon, and
polypropylene matrix resins. The various matrix fibers are made from the same material as
the corresponding matrix resin. The designations "HEAT" and "NO HEAT" indicate that
the listed chemical treatments are heated to a significant degree or not, respectively, after
being applied to their corresponding fibers. The chemical treatments below for
reinforcement fibers with "NO HEAT" may also be used on matrix fibers made from the
corresponding matrix resin. When continuously formed glass fibers reach the applicator at
a conventional location (e.g., the applicator being a significant distance from the source of
molten glass), the glass fibers are still giving off some residual heat. At this distance from
the bushing, however, the amount of heat emanating from the fibers may not be enough to
have any significant affect on some of the applied chemical treatments. The designation
"NO HEAT" therefore covers such a situation.
Example A
Composite matrix resin: PBT.

Formulation for reinforcement fibers:
(1) For HEAT: *83% HELOXY Modifier 67,10% EPON SU-2.5, 5%
maleic anhydride, and 2% A-l 100;
(2) For NO HEAT: 95% HELOXY Modifier 67, 3% HELOXY Modifier
505, and 2% A-l 100.
Formulation for matrix fibers:
(1) For HEAT: 83% HELOXY Modifier 67,10% EPON 160, and 7%
DICY;
(2) For NO-HEAT: 83% HELOXY Modifier 67,10% HELOXY Modifier
62. and 7% TGIC.
Example B
Composite matrix resin: nylon.
Formulation for reinforcement fibers:
(1) For HEAT: 44.5% FG-fumarate with hydroxy terminal groups, 44.5%
TONE 0260, 5% DESMODUR N-100,5% BES, and 1% A-l 100;
(2) For NO HEAT: (a) 47% propoxylated bis-A maleate, 47% TONE
0260, 5% BES, and 1% A-l 100; or (b) 99% allylpropoxylate urethane and 1% A-l 100.
Formulation for,matrix fibers:
(1) For HEAT: (a) 90% allylpropoxylate urethane and 10% amic acid; or
(b) 90% allylpropoxylate urethane, 5% PG-rumarate (hydroxy-terminated), and 5%
DESMODUR N-100;
(2) For NO-HEAT: 47.5% propoxylated bis-A maleate, 47.5% TONE
0260, and 5% BES.
Example C
Composite matrix resin: polypropylene.
Formulation for reinforcement fibers:
(1) For HEAT: (a) 68% PG-fumarate, 20% propoxylated allylalcohol, 5%
maleic anhydride, 5% TBPB,'and 2% A-l 100 or A-174; or (b) 83% PG-fumarate
(hydroxy-terminated), 5% DESMODUR N-100, 5% maleic anhydride, 5% TBPB, and 2%
A-l 100 or A-174;

(2) For NO-HEAT: (a) 88% allylpropoxykte urethane, 10%EPON 8121,
and 2% A-I100; or (b) 90% allylpropoxylate urethane, 5% diallylphthalate, 2% maleic
anhydride, 2% BPO, and 1% A-1100.
Formulation for matrix fibers:
(1) For HEAT: 91% allylpropoxylate urcthanc, 5% diallylphthalate, 2%
maleic anhydride, and 2% TBPB;
(2) For NO-HEAT: (a) 90% allylpropoxylate urethane and 10%EPON
8121; or (b) 91% allylpropoxylate urethane, 5% diallylphthalate, 2% maleic anhydride, and
2% BPO.
The abbreviation DICY stands for dicyandiimide, which is a high-
temperature amine-based curing agent for epoxy resins. Both the DICY curing agent and
the reactive modifier diallylphthalate (for lowering viscosity) are available from the Aldrich
Chemical Company. DESMODURN-100 is a polyisocyanatc available from Witco
Chemical Company. The PG-furaarate, propoxylated bis-A maleate (propoxylated
bisphenol-A maleate), allylpropoxylate-uiethane, propoxylated ally alcohol, and amic acid
(i.e., n-butyl amic acid) can all be prepared as described above. BBS represents
butoxyethylstearate, which may be replaced tn the above chemical treatments, in whole or
in part, by compounds such as the adduct of adipoylchloride and n-aminohexane or the
adduct of 1,6-diaminohcxane and hexanoylchloride, caprolactone (available from the
Aldrich Chemical Co.), and amic acids, such as the n-butyl amic acid, and these alternative
compounds may perform other functions in addition to that provided by the BES. TPBP
and BPO are the peroxides t-butylperoxybenzoate and benzoyl peroxide, respectively, and
are available from Akzo-Nobel Chemical Company of Chicago, Illinois. EPON 8121 is a
bisphenol-A type epoxy resin available from Shell Chemical Company.
The chemical treatment of 99% allylpropoxylate-urethane and 1% Al 100
was applied to glass fibers, the coated fibers were formed into a composite strand, the
composite strand was wire coated or encased with a sheath of nylon thermoplastic matrix
material, the encased composite strand was chopped into pellets, and the pellets were
injection molded into composite test specimens. The encased composite pellets were
formed using the inventive wire-coating process described further below. The glass fibers
in these composite test specimens were not completely dispersed in the matrix material.
This lack of complete dispersion of the glass fibers from individual strands in the finished

composite article indicates that at least a portion of the chemical treatment reacted enough,
at some point during the manufacturing process, to prevent the fibers from separating and
dispersing into the molten matrix material during die molding of the composite article (i.e.,
to maintain strand cohesion). To reduce its reactivity (i.e., to reduce fiber cohesion in each
composite strand during the composite-article molding process) and thereby obtain more
dispersion of the reinforcing fibers In the matrix material, the aUylpropoxylate-urethane
may be diluted with another film fonner-e.g., for a nylon system, TONE 0260 (a
polycaprolactone, available from Union Carbide Corp.) may be used.
The following are further examples of thermoset-type and thermoplastic-
type chemical treatments according to the present invention.
Nylon-Based Chemical Treatment:
An especially preferred nylon-based thermoplastic-type chemical treatment
was prepared by depositing about 9 kg of a polycaprolactone, specifically TONE 0260
(available from Union Carbide Corporation), and about 9 kg of a polyester alkyd,
specifically propoxylated bisphenol-A-maleate, into separate 5-gallon (19 L) metal cans.
Upon the complete melting or liquefying of these two materials, they were combined in a
heated five-gallon (19 L) can and stirred until the mixture became homogeneous. The
temperature was maintained at or above 200°F (93°C) with constant stirring until complete
mixing was achieved (about 30 minutes). The heating was then discontinued and the
mixture was allowed to cool to 190°F (88°C). While the temperature was maintained at
190°F,(88°C), about 360 g of the amine silanc coupling agent A-l 100 (gamma-
aminopropyltriethoxysilane) was added to the mixture with constant stirring. The resulting
chemical treatment contained, by weight, 49-49.5% TONE 0260,49-49.5% propoxylated
bisphenol-A-maleate, and 1-2% A-l 100. This chemical treatment was solid at about 25CC
and had a viscosity of 660 cps at 75°C, 260 cps at 100°C, 120 cps at 125°C, and 60 cps at
150°C.
The chemical treatment was then transferred with its container to a bucket
heater described in Process 2 above, and pumped to a suitable applicator. Glass fibers 12
were attenuated and allowed to contact the applicator roll 28. The chemical treatment, at a
temperature of about 115°C, was then transferred onto the glass fibers 12. The fibers 12
were gathered at a conventional shoe 34 and wound onto a collet, making a square-edged
package, and allowed to cool.

The resulting package is stable and shippable, and the roving runs out well.
The resulting composite strand 14 may be wire coated and chopped into pellets for eventual
use in injection-molding applications.
PBT-Based Chemical T-Based Chamical Treatment:
An especially preferred PBT-based thermoplastic-type chemical treatment
was prepared by depositing 17.28 kg of diglycidyl ether of 1,4-butanediol (HELOXY 67)
into a five-gallon (19 L) metal can. To this was added 540 g of polyglycidyl ether of castor
oil (HELOXY 505). To this mixture was added 180 g of A-l 100 (gamma-
aminopropyltriethoxysllane) as a coupling agent. The resulting chemical treatment
contained, by weight, 96% HELOXY 67,3% HELOXY 505, and 1% A-l 100. This
mixture was stirred until it became homogeneous. Then it was transferred with its
container to a bucket heater, such as that of Process 1 (although it is not necessary to heat
this chemical treatment to process it). For applying this chemical treatment, the applicator
26 is raised to within 8-10 inches (20.32-25.4 cm) from the bushing 24.
Polyester- or VinvlesteT-Based Chemical Treatment:
An especially preferred polyester- or vinylestcr-based thermoset-type
chemical treatments is prepared by depositing 6.75 kg of DER 337 epoxy (a bisphenol-A
epoxy resin, available from Dow Chemical Company) into a five-gallon (19 L) metal can.
This material is heated to 220°F (104°C) and stirred until all of the solids completely
liquefy. To this liquid is added 6.75 kg of Araldite GT7013 epoxy (a bisphcnol A epoxy
resin, available from Ciba Oeigy Corporation). The Araldite is added slowly with a great
deal of agitation over a period of two hours. Upon complete dissolution of the Araldite
epoxy, the mixture is allowed to cool in air to 200QF (93°C), and 0.76 kg of Pluronic L101
(an ethylene oxide/propylcne oxide copolymer surfactant, available from BASF) and 2.21
kg of Pluronic P105 (an ethylene oxide/propylene oxide copolymer surfactant, also
available from BASF) are added. Also added at this time is 1 kg of PEG 400 MO
(polyethylene glycol monooleate, available from Henkcl Corporation) and 0.5 kg of
butoxyethylstearate (BES) (available from Stepan Company of Northfield, Illinois). The
mixture is allowed to cool further with continued stirring to a temperature of 160- 170°F
(71-77°C), at which point 2 kg of A-l 74 (gamma-metnacryloxypropyltrimethoxysilane,
available from Witco Chemical Corporation) is added. Finally, 20 g of Uvitex OB (a
fluorescent brightening agent available from Ciba-Geigy of Hawthorne, New York) is

added to the mixture with agitation to facilitate good dispersion. The resulting chemical
treatment contains, by weight;33.78% DER 337 epoxy, 33.78% Araldite GT7013 cpoxy,
3.79% Pluronic L101,11.05% Pluronic P105,5% PEG 400 MO, 2.5% BES, 0.10% Uvitex
OB, and 10% A-174. The chemical treatment is then transferred with its container to a
bucket heater as described in Process 2.
Epoxv-Bascd Chemical Treatment;
The formulation for this example of a thermoset-type chemical treatment is
as described above for polyester- and vinylestcr-based thermoset-type chemical treatments,
except that A-187 (gamma-glycidoxypropyltrimethoxysilane, available from Witco
Chemical Company) is used in place of A-174.
Two-Silane. Polyester- or Vinylestcr-Based Chemical Treatment:
The formulation for this example of a thermoset-type treatment, which lias
multi-compatibility (compatibility with polyester, vinylester or epoxy), is as described for
the polyester- or vinylester-based thermoset-type chemical treatment described above,
except that the silane coupling system consists of 1.25 kg (5% by weight) A-187 and 1.25
kg (5% by weight) A-174, in place of the A-174 alone.
In the preferred embodiment shown in Fig. 3, matrix fibers 13 are preformed
and then commingled with the reinforcing fibers 12 before being gathered into a composite
strand 14. Alternatively, the matrix fibers 13 may be continuously formed in-line with the
reinforcing fibers 12. The matrix fibers 13 ultimately form part or all of the matrix of a
resulting composite article. The fibers 10 may comprise both continuously formed and
preformed reinforcing fibers 12 or only preformed reinforcing fibers. If preformed
reinforcing fibers 12 are used, they can be processed directly into a strand 14 containing
only the preformed reinforcing fibers 12. Such preformed reinforcing fibers 12 can also be
commingled with any other types of fibers in the same, or a similar, manner as the
preformed matrix fibers 13 shown in Fig. 3. While only two spools or.packages of
preformed fibers are shown, it is understood that any suitable number of packages of
preformed fibers can be supplied in the illustrated manner or another suitable manner.
The same applicator 26 can be used to chemically treat both the preformed
fibers (e.g., the preformed matrix fibers indicated by the phantom lines 13') and the
continuously formed fibers (e.g., the continuously formed reinforcing fibers 12) before the
fibers are gathered into a strand 14. Alternatively, a separate applicator 26' can be used to

chemically treat the preformed fibers (e.g., the preformed matrix fibers 13). If a separate
applicator 26' is used, the gathering mechanism 34 may include a bar or roller 39 to help
commingle the fibers 12 and 13 together before being gathered into a strand 14. Preformed
fibers and continuously formed fibers may be chemically treated either together using the
same applicator or separately using different applicators, e.g., as described in U.S. Patent
Application Serial No. 08/527,601, filed September 13, 1995, the disclosure of which is
incorporated by reference. Alternatively, some of the fibers 10, e.g., matrix fibers 13, may
be gathered together with the coated fibers 32 without a chemical treatment first being
applied.
The applied chemical treatment may be heated before, during, and/or after
the step of gathering the fibers. If it behaves as a thermoset, the applied chemical treatment
can be partially or fully heat cured at some point during the formation of the composite
strand 14. How much and when an applied thermosetting-type chemical treatment is heat-
cured depend on the type of composite article being made from the strand 14. For example,
a composite strand 14, with full, partial, or no heat-curing of the applied chemical
treatment, can be chopped into a plurality of short discrete lengths, mixed into a molding
compound, and injection molded into a composite article.
For chopped lengths of strand 14, an applied chemical treatment is cured
enough, if at all, to ensure that the short lengths of the composite strand 14 remain cohesive
(i.e., that fibers 10 stay together) during subsequent processing. Where it behaves as a
thermoset or is otherwise heat-curable, the applied chemical treatment on the coated fibers
is preferably only partially cured during the forming of the composite strand 14. Curing of
the applied chemical treatment is preferably completed in subsequent in-line or off-line
processing (e.g., pultrusion, filament winding, transfer injection molding, compression
molding, etc.) of the composite strand 14 into a composite article. A thermosetting-type
chemical treatment preferably remains only partially cured until the forming of the
composite article, because if the molecular weight of the chemical treatment approaches
infinity (i.e., is maximized) during the forming of the composite strand 14, then the strand
14 may not be further processable in downstream composite-forming applications. Such
partial curing may be accomplished by choosing ingredients which will not fully react with
one another under the conditions present during me composite strand-forming process. It
may also be accomplished by choosing the relative amounts of the reactive ingredients of

the chemical treatment so that at least one of the thermosetting constituents in the chemical
treatment (e.g., a resin) remains only partially reacted or cured until the forming of the
composite article (e.g., by controlling the stoichiometry of the chemical treatment). An
exemplary chemical treatment having at least one reactive constituent that can remain only
partially reacted or curjed during the strand-forming process comprises about 85% by
weight PG-fumarate, about 10% by weight styrene, and about 5% by weight t-butylperoxy-
benzoate.
In the chemical treatments listed in Examples A-C above, there are several
reactive species represented. While in most cases it is preferable for some unreacted
chemical species to remain on the strand 14 at the end of the strand-forming process, it may
be preferable in some cases, for example, in the above-listed chemical treatments that
contain isocyanates or amic acids, for the chemical species to be fully reacted when in the
strand form. With the isocyanates, if there is a diol present and in sufficient quantity (e.g.,
about 20 times the number of isocyanate groups) and if the chemical treatment is applied at
a high enough fiber surface temperature, the isocyanate groups will be fully reacted in the
composite strand 14. Likewise, if the reaction conditions are right (e.g., high temperature
and relatively low concentration), the amic acid in a chemical treatment will likely be
completely converted to imide.
A chemical treatment can be prepared that comprises about 45% by weight
PG-tumarate, about 50% by weight styrene, and about 5% by weight t-butylpcroxy-
benzoatc. This represents a polyester resin formulation that may be applied to glass fibers
using applicator equipment as described above in Processes 1-3 and that may cure to a hard
mass on a glass fiber strand 14 upon the addition of heat emanating from newly formed
glass fibers. By removing about 90% of the styrene, this polyester resin chemical treatment
may be rendered only partially curable when applied to the fibers. An additional chemical
treatment can be prepared that comprises about 35% by weight of the. epoxy resin Epon
828, available from Shell Chemical Company, about 35% by weight of the reactive epoxy
modifier HELOXY 505, about 28% by weight maleic anhydride, and about 2% by weight
Al 100. This epoxy resin formulation may be applied to glass fibers using any of the
applicator equipment described above, and cures to a hard mass on a glass fiber strand 14
upon the addition of heat emanating from newly formed glass fibers. By removing about

90% to all of the maleic anhydride, this epoxy-resin chemical treatment may be rendered
only partially curable when applied to the fibers.
By raising the applicator 26 to a position closer to the heat emanating from
the molten glass (e.g., bushing 24), the viscosity of a thermoplastic-type chemical treatment
on the surface of the applicator roll 28 (Let* where the roll 28 comes in contact with the
glass fibers 10) has been observed to drop, as well as that on the surface of the glass fibers
12. A thermosetting-type chemical treatment which behaves like a thermoplastic at this
stage of the process will also experience such a lowering of its viscosity. Gradients in the
viscosity of the chemical treatment have been observed along the surface of the applicator
roll 28. The viscosity has been found to be the lowest behind the fan of glass fibers 10, and
appears to increase toward either end of the roller 28.
For the Fig. 1 embodiment of apparatus 20, the applicator 26 is positioned
adjacent or otherwise close enough to the bushing 24 that the chemical treatment is applied
when the fibers 12 are at a high enough temperature (i.e., the fibers 12 emanate enough heat
energy) to cause the desired drop in the viscosity and/or the desired degree of heat curing
by crosslinking or otherwise increasing the molecular weight of the applied chemical
treatment. At the same time, the applicator 26 is proforably positioned far enough away
from the bushing 24 so that the chemical treatment is applied while the fibers 12 are at a
temperature which will not cause significant damage to the chemical treatment (e.g.,
decomposition of any organic chemicals or compounds). In this way, the resulting strand
14 can be provided with the properties desired for subsequent processing into a composite
article.
Exemplary fiber temperatures for applying the chemical treatments are
temperatures of up to about 350°C (662°F), with it possible to apply some treatments at
even higher temperatures, without being significantly degraded or otherwise damaged.
Fiber temperatures as low as about 150oC (302°F), or even lower, may be used. To protect
the applied chemical treatment and cause at least one of the above two desired changes to
occur in the applied chemical treatment, preferably the fibers 12 are at a temperature of
from about 200°C (392°F) to about 300°C (572°F). Satisfactory results have been obtained
when the viscosity of the chemical treatment of either type drops down to from about 200
cps to about.400 cps at a temperature of from about 200°C to about 300°C.

For glass reinforcing fibers 12 drawn from a conventional bushing 24 having
a normal throughput, the applicator 28 is preferably disposed so that the-chemical treatment
is applied to the glass fibers 12 at a minimum of at least about 3 inches (7.62 cm), and
typically about 6 inches (15.24 cm), or more from the bushing 24 (i.e., from where the
fibers 12 exit the bushing). The chemical treatment may be applied to the glass reinforcing
fibers 12 at a distance of from about 8 inches to about 10 inches (20.32 cm to 25.4 cm)
from the bushing 24. The exact location of the applicator 26 relative to the bushing 24
depends, for example, on the type of bushing 24 used (e.g., the number of fibers being
drawn from the bushing), the temperature of the molten glass material, the type of chemical
treatment being applied, the desired properties of the interphase region around the
reinforcing fibers 12, and the properties desired for the resulting strand 14 and ultimately
for the composite article.
Referring to the alternate embodiment depicted in Fig. 2, an apparatus 38
includes the components of the previously described apparatus 20 and a heat retainer 40.
Accordingly, components of apparatus 38 the same or similar to those of apparatus 20 have
been designated with the same reference numerals. The heat retainer 40 is disposed,
partially or completely, at least around the fibers 12 and is adapted using conventional
techniques to maintain the heat energy emanating from the surface of the fibers 12 for a
longer period of time and a farther distance from the fiber-forming mechanism 22.
Satisfactory results have been obtained with a low-throughput glass fiber bushing 24 using
an exemplary heat retainer 40 made from sheet metal formed into an open-ended
rectangular box shape having a length of about 15 inches (38.1 cm), a width of about 3
inches (7.62 cm), and a height of about 16 inches (40.64 cm). A low-tliroughput glass fiber
bushing 24 typically forms glass reinforcing fibers 12 at a rate of less than or equal to about
30-40 lbs./hr (13.62-18.16 kg/hr). The box-shaped heat retainer 40 is disposed between the
fiber-forming mechanism 22 and the applicator 26 So that at least the fibers 12 are drawn
through its open ends 42 and 44. Preferably the heat retainer 40 is sufficiently insulative to
keep the surface of each fiber 12 at a temperature of from about 150°C (302°F) to about
350°C (662°F) by the time the applicator 26 applies the chemical treatment to the fibers 12.
The use of such a heat retainer 40 is particularly advantageous when a low-
throughput continuous glass fiber forming bushing 24 is being used. The amount of heat
energy being stored by the fibers 12 formed using a low-throughput bushing 24 is less than

that stored by fibers 12 formed using a normal- or high-throughput bushing. Thus, the heat
retainer 40 allows fibers 12 formed using a low-throughput bushing to be maintained at the
temperature needed to cause the desired reaction (drop in viscosity and/or at least partial
heat curing) in the applied chemical tmttnent. The heat retainer 40 may be modified to be
disposed up to or even farther downline beyond the applicator 26 in order to maintain the
fibers 12 at a desired elevated surface temperature at a point up to or downline from the
applicator 26. For example, another heat retainer similar in structure to heat retainer 40
could be disposed, partially or completely, around the coated fibers 32 and between the
applicator 26 and the gathering mcchaniam 34. The use of such an additional heat retainer
may be desirable when additional curing of the chemical treatment is needed before the
strand 14 is collected, for example on a spool, or otherwise subsequently processed. An
example of a means that may be useful as such a heat retainer in the present invention, in
particular, after the chemical treatment is applied to the fibers, is described in U.S. Patent
No. 5,055,119, the disclosure of which is incorporated by reference herein.
The energy used in heating the applied chemical treatment can be at least
partially, if not completely, provided by heat energy emanating from the coated fibers 32.
For example, residual heat emanating from, or remaining in, the continuously formed glass
fibers can provide a substantial amount of the heat energy. Residual heat emanating from
continuously formed polymeric matrix fibers 13 may similarly be used to effect desired
changes in an applied chemical treatment.
If residual heat from the fiber-forming process is not available or is
insufficient, such as when the fibers 10 are preformed, have cooled off, or otherwise are not
at the desired temperature, the fibers 10 can be pre-heated to impart the heat energy desired
for the applied the chemical treatment. Such pre-heating can be accomplished by the use of
a conventional heating system. For example, referring to Fig. 2, a conventional open-ended
furnace (not shown) can be used in place of the heat retainer 40 to pre-heat at least the
fibers 12 to the desired temperature before the chemical treatment is applied.
By using heat energy emanating from the fibers 32 to supply at least part of
the necessary heat energy, the applied chemical treatment has its viscosity reduced and/or is
at least partially heat-cured from the surface of the coated fibers 32 outwardly through at
least part of the applied chemical treatment. Heating from the fiber surface outwardly is
especially preferred and efficient way to heat the applied chemical treatment and to help

optimize bonding between, the chemical treatment and the surface of the coated fibers 32.
In addition, heating from the surface of the coated fibers 32 outwardly allows for greater
versatility in engineering the interphase region formed by the applied chemical treatment,
between each of the coated fibers 32 and the matrix material of the composite article.
For example, heating an applied thermoplastic-type chemical treatment from
the inside out helps to insure that its viscosity at the surface of the fibers will be low enough
to obtain adequate wetting of the fiber surface. In addition, heating an applied heat-curable
chemical treatment in this manner allows for the applied chemical treatment to be fully
cured only at its interface with the fiber surface, thereby retaining an outer region of only
partially cured or uncured chemical treatment, which can be fully cured when and where it
is desired during subsequent processing. For instance, it may be desirable for this outer
region to be partially cured or uncured to facilitate bonding between the chemical treatment
and a subsequently applied matrix material or between the contacting layers of the applied
chemical treatment on adjoining fibers.
Preferably, heat emanating from the fibers 12 is used to heat the applied
chemical treatment. Optionally, the energy used to heat the applied chemical treatment
may be partially, substantially, or completely provided by heat energy emanating from a
source external to the coated fibers. For example, after the chemical treatment is applied,
the coated fibers 32 can be passed through a conventional open-ended furnace (not shown)
either before, during, or after the coated fibers 32 are gathered into the strand 14. The
applied treatment can also be heated externally during the forming of the strand 14 into a
composite article. By heating it externally, the applied treatment has its viscosity reduced
and/or is at least partially heat cured from its outer surface into the applied chemical
treatment toward the surface of the coated fibers 32. Thus, it is also contemplated that the
energy used to heat the applied chemical treatment may be provided by a combination of
heat emanating from the coated fibers 32 and one or more external heat sources disposed so
as to heat at least the reinforcing fibers 12 before and/or after the chemical treatment is
applied.
The chemical treatment may be kept cool before it is applied to the fibers 12
to permit the use of very reactive ingredients and to help reduce the risk of heat-caused
degradation of the chemical treatment. The temperature of the chemical treatment before
being applied may be kept at less than or equal to about room temperature for the same

means. For example, a cooling coil (not shown) can be submerged within the chemical
treatment. When continuously formed glass fibers are being formed, the apparatus may
also be adapted so as to surround the glass fibers 12 with an inert atmosphere before the
chemical treatment is applied. The inert atmosphere should help prevent moisture from
accumulating on the surface of the fibers 12, thereby inhibiting moisture-induced cracking
and moisture-caused passivation of potential reactive species on the glass fiber surface. An
inert atmosphere may not be desired when a high-output bushing is used or any other time
the temperature of the glass fibers is sufficiently high. The glass fibers 12 can be
surrounded with an inert atmosphere by using the heat retainer 40 (see Fig. 2) or similar
structure to surround the glass fibers, with piping of the inert atmosphere into the heat
retainer 40 as the fibers 12 pass therethrough. Suitable inert atmospheres include, for
example, one or a combination of nitrogen and argon gases.
An advantage of the inventive chemical treatments is that they may be
processed using known fiber, strand, and composite-article forming equipment. In a
preferred embodiment, the solvent-free chemical treatments are advantageously employed
in a wire-coating system described below.
PREPARATION OF ENCASED STRANDS
Another general aspect of the invention relates to a method and apparatus for
making one or more plastic-encased composite strands that are moldable into a composite
article having a polymeric or resinous matrix reinforced with fibers made from a suitable
reinforcing material, such as a glass material, a synthetic or polymeric material, or another
suitable non-glass material. The encased composite strands may be in thread form (i.e.,
long lengths) or pellet form (i.e., short lengths).
More particularly, each encased composite strand has a plurality of fibers,
including at least reinforcing fibers and optionally fibers made of the thermoplastic matrix
material to be used in the composite article. The fibers are processed into a strand or
bundle, with each strand preferably containing from about 1,500 to about 10,000 fibers,
more preferably from about 2000 to about 4,000 fibers. The strand is preimpregnated with
a chemical treatment before the strand is formed.
The preimpregnated composite strand is encased in a sheath of thermoplastic
material. When the encased composite strand is to be formed into pellets, the chemical

treatment is applied in a sufficient amount and between enough of the fibers to keep the
fibers from falling out of the pallet When the encased composite strand is to be formed
into thread, the chemical treatment is disposed between substantially all of the fibers.
In a preferred embodiment, the chemical treatment is a thermoplastic-type
polymeric material. Alternatively, the chemical treatment impregnating the composite
strand may be a thermoset-typc polymeric material that is in a fully cured, partially cured,
or uncured state. The strand of fibers optionally may be fully impregnated with an
engineering thermoplastic matrix material, such as that used to encase or coat the composite
strand. Although some engineering thermoplastic materials have relatively high melting
points and high viscosities that can make it very difficult or impractical to apply the
engineering thermoplastic to the fibers using conventional applicators, the artisan may
appropriately modify such engineering thermoplastics for use as a chemical treatment in the
invention.
Preferably, the sheath encasing the composite strand is made from the same
thermoplastic material as that used to form the matrix of the composite article. The
thermoplastic sheath material may form a portion or all of the matrix of the composite
article, depending on the thickness of the sheath. Preferably the chemical treatment
sufficiently bonds.or otherwise helps the sheath keep the fibers together in the
preimpregnated strand, at least until the molding of the composite article. In addition, the
chemical treatment is at least compatible with the thermoplastic matrix material of the
composite article.
According to a preferred process for making one or more of the
thermoplastic-encased composite strands, a wire-coating or extrusion-coating process is
used. The process comprises the steps of: providing a plurality of fibers comprising at
least reinforcing fibers; applying a chemical treatment so as to coat substantially all of the
fibers and thereby form preimpregnated fibers; gathering or otherwise combining the coated
fibers together into at least one preimpregnated strand having the chemical treatment
disposed between substantially all of the fibers forming the preimpregnated strand; coating
at least the outside of the preimpregnated strand with a thermoplastic material to form at
least one coated strand; and forming the coated strand into at least one wire-coated or
otherwise, encased composite strand.

The fibers can be provided using an in-line process that includes
continuously forming the reinforcing fibers from a source of molten reinforcing material,
such as glass. In addition to continuously formed reinforcing fibers, the fibers being
provided may include preformed reinforcing fibers, preformed matrix fibers, continuously
formed matrix fibers, or combinations thereof. When it is an aqueous system, the applied
chemical treatment on the fibers is1 heated to evaporate a substantial amount of the moisture
therein before the coated fibers are gathered together into a preimpregnated strand. When it
is a thermoset-type, the chemical treatment is applied to the fibers either in an uncured or
partially cured state. The uncured or partially cured chemical treatment that ends up
impregnating the encased composite strand may be processed (e.g., by heating) to induce
additional partial or full curing, depending on the desired condition of the encased
composite strand during the molding of the composite article. In a preferred embodiment, a
solvent-free chemical treatment as described above is used. Alternatively, a two-part non-
aqueous chemical treatment may be used as set out in U.S. Patent Application Serial No.
08/487,948, filed June 7,1995, the disclosure of which is hereby incorporated by reference.
Exemplary systems for forming polymer-encased strands are illustrated in
the drawings, particularly in Figs. 4-6. Fig. 4 shows one embodiment of an apparatus 110,
including a source 112 of fibers 113, which in this embodiment consist of reinforcing fibers
114, One exemplary source 112 is a conventional bushing 115 of molten reinforcing
material (e.g., glass) from which the continuous reinforcing fibers 114 are drawn.
An applicator 116 applies a chemical treatment onto substantially all of the
fibers 114. In an exemplary embodiment, the chemical treatment being applied is aqueous,
and the applicator 116 is a conventional type suitable for applying aqueous-based chemical
treatments. The exemplary applicator 116 includes a rear-facing applicator roller 118,
which applies the chemical treatment to the reinforcing fibers 114, thereby forming
preimpregnated or coated fibers 120. The chemical treatment is applied as the fibers 114
come in contact with the roller 118 when passing thereover. A trough 122 containing the
chemical treatment is positioned below the roller 118. The roller 118 extends into the
trough 122, and transfers the chemical treatment from the trough 122 to the fibers 114 as
the roller 118 is rotated by a conventional drive device, such as a motor (not shown). Other
suitable devices or techniques used for applying si2e or other chemical treatments may be

used in place of the applicator roll assembly 116 to apply the chemical treatment to the
reinforcing fibers 114.
The aqueous-based chemical treatment applied on the preimpregnated or
coated fibers 120 is heated to evaporate a substantial amount of the moisture therein, and
then the coated fibers 120 are gathered together into a preimpregnated composite strand
124. The moisture can be driven out of the applied aqueous-based chemical treatment
using any suitable heating device 125. For example, the coated fibers 120 can be passed
over and brought into contact with a heating device 125 substantially similar to either of the
heating plates described in U.S. Patent Applications Serial Nos. 08/291,801, filed August
17,1994, and 08/311,817, filed September 26,1994, the disclosures of which arc
incorporated by reference herein.
A conventional gathering shoe or some other form of gatherer 127 can be
used to gather together the dried fibers 120 into at least one preimpregnated strand 124.
The preimpregnated strand 124 is coated or encased with a layer of polymer materia! and
thereby formed into an encased composite strand 126 by pulling or otherwise passing the
preimpregnated strand 124 through a wire coater 128. A wire coater is a device or devices
capable of, or means for, coating one or more preimpregnated fiber strands with a polymer
material so as to form a polymeric sheath on each preimpregnated strand 124. Preferably,
each strand contains from about 1,500 to about 10,000 fibers, more preferably, from about
2,000 to about 4,000 fibers.
The fibers 113 used in forming an encased composite strand 126 can be
made using an in-line process, like the one shown in Fig. 4, where reinforcing fibers 114
are continuously drawn from a bushing 115 of molten reinforcing material, such as glass.
In addition to or instead of continuously formed reinforcing fibers 114, the fibers 113 may
comprise preformed reinforcing fibers. Also, the fibers 113 may include preformed matrix
fibers, and even continuously formed matrix fibers; or combinations thereof. An exemplary
system for applying an aqueous chemical treatment to continuous and preformed fibers to
form a preimpregnated strand is disclosed in the above-incorporated U.S. Patent
Application Serial No. 08/311,817.
The matrix fibers ultimately form part or all of the matrix of the resulting
composite article or product, such as pellets 132. Examples of suitable polymeric materials
for the matrix fibers include polyesters, polyamides, polypropylenes, and polyphenylene

sulfides. The continuous and preformed reinforcing fibers may be glass fibers, synthetic
fibers, and/or any other suitable reinforcing fibers, e.g., fibers of traditional silicate glass,
rock wool, slag wool, carbon, etc. When various fibers made from different materials are
used, the same or a different chemical treatment may be used for each type of fiber.
Preferably, the wire coater 128 includes a source of molten polymeric
material, such as a conventional extruder, for providing the material used to encase the
preimpreghated strand 124. The wire coater 128 also preferably includes a die or other
suitable means having at4east one outlet or exit opening for shaping the sheath into a
desired thickness and/or cross-section, preferably into a thickness and cross-section that are
maintained relatively uniformly along its length. An exemplary wire coater 128 is
manufactured by Killion of Cedar Grove, New Jersey, which includes a KN200 2-inch
(5 cm) extruder equipped with a cross-head coating die. One or more encased composite
strands 126 can be formed by pulling or otherwise passing one or more of the coated
strands 124 through one or more such dies. The sheath material is preferably thermoplastic
and may form a portion or all of the matrix of the composite article, e.g., depending on the
thickness of the sheath. In a preferred embodiment, the sheath encasing the composite
strand 124 is made from the same thermoplastic material as that used to form the matrix of
the composite article.
When it is desired for the encased composite strand 126 to be in short
lengths, the apparatus 110 can include means such as a chopper 130 for cutting or otherwise
separating the encased composite strand 126 into a plurality of encased composite pellets
132. An exemplary chopper 130 is the model 204T Chopper manufactured by Conair-Jettro
of Bay City, Michigan. When pellets 132 are being formed, the chemical treatment helps
keep together the fibers 114 in each encased composite pellet 132 (helps keep a significant
number of the fibers 114 from falling out of a pellet 132).
The encased composite pellets preferably have lengths of from about 3/16
inch (0.476 cm) to about 1 1/2 inches (3.8 cm), although they can be longer or shorter as
appropriate. In an exemplary embodiment, the pellets have lengths of approximately 0.5
inches (1.27 cm). Of course, the length of a pellet may vary from one application to
another. Moreover, the form of the encased composite strand may vary to suit the particular
application.

which functions, e.g., to draw the reinforcing fibers 114 from the bushing 115 and pull the
preimpregnated strand 124 through the wire coater 128. An exemplary puller 134 which
has been used successfully in-line with the above-described Killion wire coater 128 is a
4/24 High Speed Puller, also manufactured by Killion. Alternatively, the wire coater 128
and/or the chopper 130 may be adapted to perform the function of the puller or to aid the
puller in pulling the preimpregnated strand 124 through the wire coater 128.
When it is desired for the encased composite strand product to be in thread
form, the chopper 130 may be replaced by a winder device 136 for drawing the reinforcing
fibers 114 from the bushing 115, pulling the preimpregnated strand 124 through the wire
coater 128, and winding the encased composite strand 126 into a spool or other package
138 of encased composite thread 140. When in thread form, the strand 124 is at least
substantially, if not fully, impregnated with the applied chemical treatment. That is, the
strand 24 is impregnated enough to produce satisfactory properties in the composite article
formed thereby.
Optionally, the winder device 136 may include a puller to help draw the
fibers 114 and/or pull the strand 124. The exemplary winder device 136 illustrated in Fig. 5
comprises a rotatable member or a collet 142, upon which is provided a removable large-
diameter spool 144. The winder device 136 also includes a traversing mechanism 146 to
distribute the continuous composite strand 126 along the length of the spool 144 to form a
package 138. An air supply device (not shown) may be provided for supplying streams of
air which impinge upon the strand 126 to cool it before winding.
Exemplary winding means 136 which may be used in conjunction with an
off-line wire coating operation combines a Hall Capstan Machine #634 (a puller) and a Hall
Winder Machine #633, both of which are manufactured by Hall Industries of Branford,
Connecticut. In such an off-line wire coating operation, the preimpregnated strand 124 is
first formed andpackaged, then the packaged strand 124 is subsequently unwound off-line
and pulled through the wire coater 128, and the resulting encased composite strand 126 is
rewound into a package. If appropriate, the above-mentioned Hall wire-winding device can
be adapted using techniques known in the wire- and cable-handling industry to handle the
high processing speeds associated with an in-line wire coating process. For example, die

spool 144 on which the encased composite thread 140 is wound can be made with a larger
diameter.
An exemplary setup procedure for the apparatus 110, and generally for a
wire coater 128, includes threading or otherwise passing the free end of the preimpregnated
strand 124 through the wire coater 128 and pulling enough of the strand 124 therethrough to
allow the process to proceed on its own (e.g., to allow the strand to be pulled
automatically). Such a setup procedure may include temporarily pulling a free end of the
preimpregnated strand 124 (indicated by phantom line \2A% such as with a pair of
conventional pull wheels 137 positioned apart from the wire coater 128, until a sufficient
length of the preimpregnated strand 124 is available for passing through the wire coater
128. This length of the preimpregnated strand 124 is then passed through the wire coater
128 and pulled therethrough by the puller 134, chopper 130, winder 136, or a combination
thereof. With the above-described wire coater 128 a feeder line is preferably used to thread
the free end of the preimpregnated strand 124 through the wire coating die. Such a feeder
line has an end capable of being secured to the free end of the strand 124. For example, a
length of wire with a hook at one end can be used as the feeder line. The feeder line can be
pre-positioned through the wire-coater die and the free end of the strand 124 doubled over,
hooked by the feeder line, and then drawn through the wire coater 128. It is preferable to
break-out (i.e., a strand of fibers breaking).
Preferably, the die used in the wire coater 128 has an openablc or "clam-
shell" configuration that allows the preimpregnated strand 124 to be laid into the die from
one end to the other, rather than requiring threading longitudinally through the die. Such an
openable die can eliminate the need for the above-described feeder line. An exemplary
clam-shell die comprises two die halves which can be mated using guide posts or pins
disposed through matching holes formed through opposing faces of the die halves.
Alternatively, the two die halves can be hinged along adjoining edges and adapted to be
fastened together along the opposite edges when the halves are hinged closed. The face of
each die half defines half of the die cavity through which the preimpregnuted strand is
pulled. With the die halves mated together, the die cavity has and entrance opening and an
exit opening. It is preferable for the entrance to be oversized to minimize fiber abrasion and

for the exit to be sized so as to define the desired final diameter, and sheath thickness, of the
encased composite strand 126.
With the die halves separated, the strand 124 can be quickly disposed
between the die halves and the strand 124 trapped therebetween in the die cavity by closing
the dio halves. A high-temperature gasket may be disposed between the opposing faces of
the two die halves along the length of the die cavity. Each die half has one or more gates
(i.e., through-holes) through which one or more streams of the molten thermoplastic
encasing material, for example, from the extruder, are delivered into the die cavity so as to
encase the preimpregnated strand 124 as it is pulled therethrough. Each die half can be
adapted to accept a variety of inserts tailored widi different die cavities to vary the cross-
sectional profile (e.g., round, rectangular, oval, irregular, etc.) of the encased strand 126.
With such replaceable inserts, the same die can handle a variety of fiber diameters with less
down-time caused by having to replace the entire die.
Preferably, the chemical treatment is selected to bond or otherwise help die
sheath keep the fibers 113 together in the encased composite strand 126, at least until the
molding of the composite article. To help ensure that the composite article exhibits optimal
mechanical properties between its reinforcing fibers and its matrix, the chemical treatment
should be compatible with the thermoplastic matrix material of the composite article. A
chemical treatment is considered compatible with the matrix material if it does not cause
important properties, such as tensile strength, tensile modulus, flexural strength, or flexural
modulus, of the resulting composite article to be inadequate. Such compatibility may be
accomplished by formulating the chemical treatment so as to be capable of interacting with
and/or reacting with the thermoplastic matrix material. The interaction and/or reaction
between the chemical treatment (e.g., thermoplastic- or thermoset-type) and the matrix
material may occur during the making of the encased composite strand, during the molding
of the composite article, or during both processes.
The chemical treatments may be miscible in me matrix material, in whole or
in part, and/or may form a separate phase from the matrix material. Where a separate phase
is formed, the chemical treatment disposed around each fiber may form a plurality of
separate phase regions dispersed in the matrix material and/or a single separate phase region
surrounding its corresponding fiber. A chemical treatment, such as one of those discussed
below, may be selected to enhance the properties of the composite article.

Aqueous Chemical Treatments
The aqueous chemical treatment applied, e.g., using the apparatus 110, may
comprise one or more polymeric film formers in the form of a solid powder or other
particles dispersed in a water medium. The particulate Him former may be a thermoplastic-
type polymer, a thermoset-type polymer, or a combination of both. Low and/or high
molecular weight solid thermoplastic and thermoset polymers may be used to form a
particulate film former. The aqueous chemical treatment may also include one or more
binders dispersed in the water medium along with the particles of me film former. The
binder may include a thermoplastic and/or thermoset liquid, low melting point
thermoplastic particles, or a combination thereof.
Preferably, the binder prevents the solid particles of the film former from
falling out of the encased composite strand, as well as prevents the fibers from falling out of
the composite strand, even when the strand is in the form of a pellet. To accomplish this,
the thermoplastic binder particles are at least partially molten or fusible by the heat energy
used to evaporate the water out of the chemical treatment. In addition, the liquid binder has
the necessary degree of tackiness or adhesiveness to sufficiently maintain the cohesiveness
of the film former particles and the fibers. Preferably, a higher melting point thermoplastic
film former powder is modified or combined with a lower melting point thermoplastic
binder powder, such as particles of polyvinyl acetate (PVAc), aqueous urethane, etc.
The aqueous chemical treatment may also contain a liquid film former
dispersed in the water medium (e.g., as an emulsion). The liquid film former may comprise
one or more low molecular weight thermoplastic polymers, one or more thermoset
polymers, or a combination thereof. Preferably, with an aqueous chemical treatment
emulsion, a liquid film former also functions as the binder. The aqueous chemical
treatment may also be a combination of a liquid-solid dispersion and a liquid-liquid
emulsion.
The thermoset-type film formers and binders used in the aqueous chemical
treatments are preferably applied to the fibers in an uncured state, although they may also
be applied in a partially cured state. The amount of set or cure of a thermoset-type
chemical treatment may be controlled by choosing a thermosetting material, with an
appropriate curing temperature, that will cure to the degree desired at the temperatures seen
during processing according to the present invention. The uncured or partially cured

thennoset-typc chemical treatment impregnating the encased composite strand may be
processed (e.g., by heating) to induce additional curing or full curing, depending on the
desired condition of the encased composite strand during the chopping operation, the
winding operation, or the molding of the composite article. The degree to which an applied
thermoset-type chemical treatment is cured, regardless of whether it is aqueous or not, may
be controlled by using a heating device (e.g., heater 125).
Therefore, the thermoset-type chemical treatment may be tailored to allow
only enough curing, if any, to maintain the cohesivencss and/or degree of impregnation of
the encased composite strand until the molding of the composite article. The individual
fibers forming the strand do not have to separate in the thermoplastic matrix material to
form a desired composite article. The thermoset-type chemical treatment may then be
adapted to fully cure so that the fibers essentially remain permanently together, even during
the molding of the composite article.
The aqueous solution treatment contains an amount of one or more chemical
treatment polymers or other organic compounds or materials (e.g., film formers, binders) to
sufficiently preimpregnate the fibers. For example, the aqueous chemical treatment
contains enough of the film former and, if present, binder polymers to impregnate the fibers
to the degree desired. It is preferable for the aqueous chemical treatment to contain one or
more film formers, binder polymers, and/or other organic material in sufficient
concentrations to provide the preimpregnated strand with an organic material content of up
to about 25% by weight, more preferably of up to about 15% by weight, and even more
preferably of approximately 6-7% by weight, based on the total weight of the chemical
treatment plus fibers, after the desired amount of moisture has been removed from the
applied chemical treatment. This degree of organic material loading may also be useful for
non-aqueous chemical treatments discussed herein. A loss on ignition (LOI) method can be
used to determine the amount of applied chemical treatment loaded onto the fibers.
Satisfactory results have been obtained with a chemical treatment solution having an
organic material content of about 30% by weight. Such an organic material concentration
attains strands preimpregnated with 5-15% by weight of die organic compounds present in
the chemical treatment.
A suitable organic material concentration of the aqueous chemical treatment
can generally be selected independently of the form of the chemical treatment (i.e.,

dispersion, emulsion, or the like). In addition, the concentration of organic materials in the
preimpregnated strand, for a given concentration, can vary depending on a number of
factors, such as how fast the fibers are moving, the temperature of the heating device, the
temperature of the chemical treatment when applied, the tendency of the chemical treatment
to remain impregnated in the strand (e.g., its viscosity), the speed (rpm's) of the applicator
roller, and whether prepad water sprays are used.
The following are specific examples of aqueous chemical treatments which
may be applied, e.g., using the apparatus 110, to preimpregnate fibers.
Example I
Six thousand grams (6000 g) of chemical treatment was formed by the
following procedure. Fifteen g (0.25 % weight percent as received) of amine silane
coupling agent A-1100 was added to 2345 g of deionized water. This was stirred for
several minutes. Then 1875 g (31.25%) of film former Covinax 201 and 1500 g (25.0%) of
film former Covinax 225 were combined in a two-gallon pail. The silane solution was then
mixed with the mixture of film formers using moderate agitation. Next, 480 g (fi.0%) of
Maldene 286 was added to the mixture of silane and film formers. Finally, 200 g (3.3%) of
BES homogenate (the fatty acid ester KESSCO BES that has been emulsified into a
homogenate) was added under continuous stirring. The organic compound concentration of
the resulting chemical treatment solution was 30% by weight The resulting chemical
treatment is appropriate for applying to polyamide fibers as well as glass fibers.
Example II
Six thousand grams (6000 g) of chemical treatment was formed as follows.
Fifteen g (0.25%) of A-l 100 silane was added to 1870 g of deionized water. This was
stirred for several minutes. Then 3450 g (57.5%) of film former Synthemul 97903-00 was
poured into a two-gallon pail (7.6 L). The silane solution was then mixed with the film
former using moderate agitation. Next, 480 g (8.0%) of Maldene 286 was added to the
mixture of silane and film former. Finally, 200 g (3.3%) of BES homogenate was added
under continuous stirring. The organic compound concentration of the resulting chemical
treatment solution was 30%. The resulting chemical treatment is suitable for applying to
polyamide fibers as well as glass fibers.

Six thousand grams (6000 g) of chemical treatment was formed by the
following procedure. Fifteen g (0.25%) of A-l 100 was added to 2325 g of deionized water.
This was allowed to stir for several minutes. Then 1875 g (31.25%) of Covinax 201 and
1500 g (25.0%) of Covinax 225 were combined in a two-gallon pail (7.6 L). The silane
solution was then mixed with the mixture of Covinax film formers using moderate
agitation. A terephthalic acid solution was prepared by dissolving 30 g (0.5%) of
terephthalic acid in 30 ml of concentrated ammonium hydroxide. The terephthalic acid
solution was added to the mixture of silane and film formers. Then, 300 g (5.0%) of
Polyemulsion 43N40 was added to the mixture. Finally, 200 g (3.3%) of BES homogenate
was added under continuous stirring. The organic compound concentration of the resulting
chemical treatment solution was 30%. The resulting chemical treatment is suitable for
applying to polypropylene libers as well as glass fibers.
Example IV
Six thousand grams (6000 g) of chemical treatment was formed by the
following procedure. Fifteen g (0.25%) of A-l 100 (silane) was added to 2020 g of
deionized water. This was stirred for several minutes. Next, 3450 g (57.5%) of Synthemul
97903-00 (film former) was poured into a two-gallon pail (7.6 L). The silane solution was
then mixed with the film former using moderate agitation. A terephthalic acid solution was
prepared by dissolving 30 g (0.5%) of terephthalic acid in 30 ml of concentrated
ammonium hydroxide. The terephthalic acid solution was added to the mixture of silane
and film former. Then, 300 g (5.0%) of Polyemulsion 43N40 was added to the mixture.
Finally, 200 g (3.3%) of BES homogenate was added under continuous stirring. The
organic compound concentration of the resulting chemical treatment solution was 30%.
The resulting chemical treatment may be applied to polypropylene fibers as well as glass
fibers.
Example V
Six thousand grams (6000 g) of chemical treatment was formed by the
following procedure. Fifteen g (0.25%) of A-l 100 was added to 1870 g of deionized water.
This was stirred for several minutes. Next, 3450 g (57.5%) of Synthemul 97903-00 was
poured into a two-gallon pail (7.6 L). The silane solution was then mixed with the film
former using moderate agitation. Finally, 200 g (3.3%) of BES homogenate was added
under continuous stirring. The organic compound concentration of the resulting chemical

treatment solution was 30%. The resulting chemical treatment may be applied to fibers
made from a wide variety of materials, including polyphenylene sulfide and inorganic
fibers.
Example VI
Six thousand grams (6000 g) of chemical treatment was prepared by the
following procedure, Fifteen 15 g (0.25%) of A-1100 was added to 2345 g of deionized
water. Itds was allowed to stir for several minutes. Then, 1875 g (31.25%) of Covinax
201 and 1500 g (25.0%)-of Covinax 225 were combined in a two-gallon pail (7.6 L). The
silaoe solution was then mixed with the mixture of film formers using moderate agitation.
Finally, 200 g (3.3%) of BES homogenate was added under continuous stirring. The
organic compound concentration of the resulting chemical treatment solution was 30%.
The resulting chemical treatment may be applied to fibers made from a wide variety of
materials, including polyphenylene sulfide and inorganic fibers.
In reference to the above Examples I-VI, Covinax 201 and Covinax 225 are
thermoplastic vinyl acrylics which function as film formers and are commercially available
from Franklin International, located in Columbus, Ohio. Synthemul 97903-00 is a
thermoplastic urethane film former and is commercially available from Reichold Chemicals
Inc., located in Research Triangle Park, North Carolina. Epoxies, polyvinyl acetates, and
polyesters may also be used as film formers. A-l 3 00 is a silane-based coupling agent
commercially available from Witco Chemical Company of Chicago, Illinois. KESSCO
BES is a fatty acid ester which functions as a lubricant and is commercially available from
the Stepan Co., of Nortbiield, Illinois. Another lubricant that may be used is a mixture of
stearic acid and acetic acid commercially available from Owens Coming under the product
name K12. Polyemulsion 43N40 is a maleic anhydride modified polypropylene wax
dispersed in water, which is commercially available from the Chemical Corporation of
America, of East Rutherford, New Jersey. Polyemulsion 43N40 functions as an interphase
modifier to improve the interphase region (adhesion) between glass fibers and a
polypropylene matrix material by chemically reacting with the coupling agent. The
terephthalic acid is commercially available from the Aldrich Chemical Company of
Milwaukee, Wisconsin, and also functions as an interphase modifier to improve adhesion
between glass and the polypropylene matrix material by inducing the polypropylene to
crystallize close to the glass surface. Maidenc 286 is a partial ammonium salt of butadiene-

maleic acid copolymer commercially available from Lindau Chemical Inc., of Columbia,
South Carolina. Maldene 286 functions as an interphase modifier to improve adhesion
between glass fibers and nylon matrix material.
Solvent-Free Chemical Treatments
Solvent-free chemical treatments, such as those described above, may also
be used to prepare encased strands. The use of such chemical treatments has advantages,
e.g., no substantial amounts of water vapor, volatile organic carbon, or other solvent vapor
are generated when processed (e.g., heated) according to the above-described wire-coating
method, including during the molding of the composite article. By being substantially
solvent-free, the chemical treatment may have its viscosity reduced and/or be heat-cured
without experiencing a substantial drop in mass, thereby allowing for most of the chemical
treatment that is applied to the fibers to remain on the fibers. Such chemical treatment is
preferably also substantially non-photosetting.
Illustrated in Fig. 6 is an embodiment of an apparatus 150 which is capable
of making one or more polymer-encased composite strands 126 using solvent-free chemical
treatments. The resulting encased composite strands 126, which may be formed into pellets
or threads, are also suitable for molding into a fiber-reinforced composite articles.
Structural elements and components of the apparatus 150 which are identical or similar to
those of the previously described apparatus 110 are indicated by the same reference
numerals used above. The exemplary apparatus 150 includes an applicator 116 having a
front-facing applicator roller 118 which applies the chemical treatment to the reinforcing
fibers 114, thereby forming coated fibers 120. A conventional dual-roller applicator may
also be used in place of the single-roller 118.
When it is desired for the applied chemical treatment on the fibers to be
heated before the gathering of the fibers 113, an exemplary apparatus 150 has applicator
116 positioned adjacent to the underside of the bushing 115. The applicator 116 is
positioned such that the chemical treatment is applied when the fibers 114 are at a high
enough temperature (e.g., the fibers 114 emanate enough heat energy) to cause the desired
drop in viscosity and/or a desired degree of heat-curing (crosslinking or otherwise
increasing the molecular weight) of the applied chemical treatment, depending on the type
being applied. At the same time, the applicator 116 is positioned far enough away from the
bushing 115 so that the chemical treatment is applied while the fibers 114 are at a

temperature which will not cause significant damage to the chemical treatment (e.g.,
decomposition of any organic chemicals or compounds). In this way, the resulting strand
126 can be provided with the properties desired for subsequent processing into a composite
article.
For glass reinforcing fibers 114 drawn from a conventional bushing 115
having a normal throughput, the applicator 116 is preferably disposed so that the chemical
treatment is applied to the glass fibers 114 at a minimum of about 3 inches (7.62 cm),
preferably, about 6 inches (15.24 cm), from the bushing 115 (from where the fibers exit the
bushing). Satisfactory results may be obtained when the chemical treatment is applied to
the glass reinforcing fibers 114 in the range from about 8 inches to about 10 inches (20.32
cm to 25.4 cm) from the bushing 115. The optimal location of the applicator 116 relative to
the bushing 115 depends, for example, on the type of bushing used (e.g., the number of
fibers being drawn from the bushing 115), the temperature of the molten glass material, the
type of chemical treatment being applied, the desired properties of the interphase region
around at least the reinforcing fibers 14 and the properties desired for the resulting strand
124 and the ultimate composite article.
It may be desirable for the chemical treatment to be kept cool before it is
applied to the fibers 14 to allow very reactive ingredients to be used in the chemical
treatment and to help reduce the risk of heat-caused degradation of the chemical treatment.
It may also be desirable for the temperature of the chemical treatment, before it is applied,
to be kept at less than or equal to about room temperature for the same reasons. The
chemical treatment can be kept at the desired temperature by suitable means. For example,
a cooling coil may be submerged within the chemical treatment. When continuously
formed glass fibers are being formed, it may also be desirable for the apparatus to be
adapted so as to surround the glass fibers 114 with an inert atmosphere before the chemical
treatment is applied. The inert atmosphere should help prevent moisture from accumulating
on the surface of the fibers 114, thereby inhibiting moisture-induced cracking and moisture-
caused passivation of potential reactive species on the fiber surface, as discussed above. An
inert atmosphere is preferably not employed, however, when a high-output bushing is used
or any other time the temperature of the glass fibers is sufficiently high.
As with the aqueous-based system depicted in Fig. 4, the fibers 113 being
coated with the solvent-free chemical treatment may include fibers other than the

continuously drawn reinforcing fibers 114. The fibers 113 may include preformed
reinforcing and/or matrix fibers 152. As shown in Fig. 6, the preformed fibers 152 are
pulled from spools or other packages and then commingled with the continuously formed
reinforcing fibers 114 before all the fibers 113 are gathered into a composite strand 124.
The fibers 113 may also include matrix fibers that are continuously produced, for example,
from a bushing or spinner, and commingled in-line with the reinforcing fibers 114. Before
being commingled, the preformed fibers 152 may be coated with the same or a different
chemical treatment than that applied to the reinforcing fibers 114. Depending on the type
of fibers 152, a chemical treatment may not be applied to the fibers 152 before the fibers
113 are commingled. The same techniques and equipment may be used to chemically treat
each type of reinforcing fiber and matrix fiber, whether they are continuously formed or
preformed.
The same applicator 116 can be used to chemically treat both the preformed
fibers 152 and the continuously formed fibers 114 before the fibers 113 are gathered into a
strand 124. Alternatively, a separate applicator 116' can be used to chemically treat the
preformed fibers 152 (as indicated by phantom lines 152'). If a separate applicator 116' is
used, the gathering mechanism 127 may include a bar or roller 154 to help commingle the
fibers 114 and 152 together before being gathered into the strand 124. The above-
incorporated U.S. Patent Application Serial No. 08/527,601 describes other methods, and
apparatus for chemically treating preformed fibers and continuously formed fibers together
using the same applicator or separately using different applicators. Alternatively, some of
the fibers 113, such as matrix fibers 152, may be gathered with the coated fibers 120
without a chemical treatment first being applied.
A composite article may then be made using conventional techniques, such
as by molding one or more encased composite strands 126, in the form of pellets 132,
threads 140, or both. The resulting composite article may be formed by using injection
molding, compression molding, transfer molding, or any other suitable molding technique.
The encased composite threads 140 may be formed into a fabric, for example, by an
intennediate weaving or knitting process, and then compression- or transfer-molded into the
desired composite article. An example of such a fabric-forming method and apparatus is
described in U.S. Patent Application Serial No. 08/527,601, filed September 13, 1995, the
disclosure of which is hereby incorporated by reference.

Through consideration of the above description and practice of the
invention, appropriate modifications of the present invention will be apparent to those
skilled in the art Thus, thescope of the invention is intended not to be limited by the
foregoing detailed description or depiction of preferred embodiments, but to be defined by
the following claims and equivalents thereof.

WE CLAIM:
1. A fiber-containing product for use in the manufacture of fiber-reinforced
composite articles comprising:
a) a prepreg strand comprising a plurality of substantially linear and
substantially electrically non-conductive gathered reinforcing fibers
adhered together with a solidified, substantially solvent-free
chemical treatment comprising a thermoplastic film-forming
polymer; wherein said chemical treatment is disposed between and
forms a substantially continuous coating on the surface of
substantially all of the gathered fibers; and
b) a thermoplastic coating substantially encasing the prepreg strand.
2. The fiber-containing product as claimed in claim 1, in the form of pellets
having a length of from about 3/16 to 1 1/2 inches.
3. The fiber-containing product as claimed in claim 1, wherein said plurality
of substantially linear and substantially electrically non-conductive
J^yy gathered reinforcing fibers numbers in the range of from a&eu* 1,500 to
ajfeeut 10,000 fibers.

4. The fiber-containing product as claimed in claim 1, wherein said plurality
of substantially linear and substantially electrically non-conductive
g
athered reinforcing fibers numbers in the range of from 2,000 to
4,000 fibers.
5. The fiber-containing product as claimed in claim 1, wherein said chemical
treatment further comprises a coupling agent.
6. The fiber-containing product as claimed in claim 5, wherein said chemical
treatment comprises a molten, low molecular weight thermoplastic film-
forming polymer and a functionalized organic substrate as the coupling
agent.
7. The fiber-containing product as claimed in claim 6, wherein the low
molecular weight thermoplastic film-forming polymer is derived from a high
molecular weight thermoplastic that has been cracked or otherwise
processed to a low molecular weight.
8. The fiber-containing product as claimed in claim 1, wherein the chemical
treatment has a viscosity of up to 300 cPs at a temperature in the
range of from 93°C to 110°C.

9. The fiber-containing product as claimed in claim 1, wherein the chemical
treatment further comprises one or more compounds selected from the
group consisting of processing aids, lubricants, viscosity-modifiers and
surfactants.

A fiber-containing product for use in the manufacture of fiber-reinforced
composite articles comprising: (a) a prepreg strand comprising a plurality of
substantially linear and substantially electrically non-conductive gathered
reinforcing fibers adhered together with a solidified, substantially solvent-free
chemical treatment comprising a thermoplastic film-forming polymer; wherein
said chemical treatment is disposed between and forms a substantially
continuous coating on the surface of substantially all of the gathered fibers; and
(b) a thermoplastic coating substantially encasing the prepreg strand.
Fig. 1

Documents:

163-KOL-2004-CORRESPONDENCE.pdf

163-KOL-2004-FORM-27.pdf

163-kol-2004-granted-abstract.pdf

163-kol-2004-granted-assignment.pdf

163-kol-2004-granted-claims.pdf

163-kol-2004-granted-correspondence.pdf

163-kol-2004-granted-description (complete).pdf

163-kol-2004-granted-drawings.pdf

163-kol-2004-granted-examination report.pdf

163-kol-2004-granted-form 1.pdf

163-kol-2004-granted-form 18.pdf

163-kol-2004-granted-form 2.pdf

163-kol-2004-granted-form 3.pdf

163-kol-2004-granted-form 5.pdf

163-kol-2004-granted-others.pdf

163-kol-2004-granted-pa.pdf

163-kol-2004-granted-reply to examination report.pdf

163-KOL-2004-OTHERS.pdf


Patent Number 231386
Indian Patent Application Number 163/KOL/2004
PG Journal Number 10/2009
Publication Date 06-Mar-2009
Grant Date 04-Mar-2009
Date of Filing 02-Apr-2004
Name of Patentee OWENS CORNING
Applicant Address ONE OWEN CORNING PARKWAY, TOLEDO, OHIO
Inventors:
# Inventor's Name Inventor's Address
1 ANDREW B. WOODSIDE 7760 TUMWATER COURT, PICKERINGTON, OHIO 43147
PCT International Classification Number C03C 25/10
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 08/695,909 1996-08-12 U.S.A.