U.S. patent number 3,881,977 [Application Number 05/306,648] was granted by the patent office on 1975-05-06 for treatment of graphite fibers.
This patent grant is currently assigned to United States of America as represented by the Secretary of the Air Force. Invention is credited to Richard J. Dauksys.
United States Patent |
3,881,977 |
Dauksys |
May 6, 1975 |
Treatment of graphite fibers
Abstract
A method of fabricating a composite reinforced with graphite
yarn that coises heating the yarn in an oxidizing atmosphere and
then coating the yarn with a thermoplastic polymer. Thereafter, the
treated yarn is coated with a thermosetting resin prior to
fabrication of composites having greatly enhanced interlaminar
shear strength.
Inventors: |
Dauksys; Richard J. (Bellbrook,
OH) |
Assignee: |
United States of America as
represented by the Secretary of the Air Force (Washington,
DC)
|
Family
ID: |
23186231 |
Appl.
No.: |
05/306,648 |
Filed: |
November 15, 1972 |
Current U.S.
Class: |
156/242; 156/180;
264/137; 273/DIG.23; 427/389.9; 428/375; 428/413 |
Current CPC
Class: |
C08J
5/06 (20130101); Y10T 428/31511 (20150401); Y10T
428/2933 (20150115); Y10S 273/23 (20130101) |
Current International
Class: |
C08J
5/06 (20060101); C08J 5/04 (20060101); B29g
003/00 () |
Field of
Search: |
;117/228,47A,72,46
;156/242,180 ;264/137 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Pianalto; Bernard D.
Attorney, Agent or Firm: Kuhn; Cedric H.
Claims
I claim:
1. A method for treating graphite yarn which comprises heating the
yarn in air at a temperature in the range of 1000.degree. to
4500.degree.F for a period ranging from about 0.10 to 12 seconds;
passing the heated yarn through a solution of a thermoplastic
polymer, thereby coating the yarn with the polymer; and evaporating
solvent from the coating on the graphite yarn.
2. A method according to claim 1 in which the yarn is passed
through an oxidizing gas flame.
3. The method according to claim 2 in which the gas flame is a
propane-generated flame.
4. The method according to claim 1 in which the solution contains
in the range of about 0.5 to 25 weight percent of thermoplastic
polymer.
5. The method according to claim 4 in which the amount of
thermoplastic polymer coated on the graphite yarn is in the range
of about 5 to 30 percent by weight of the yarn.
6. The method according to claim 5 in which the thermoplastic
polymer is selected from the group consisting of a polyhydroxy
ether, a polyphenylene oxide, a polysulfone, a polyarylsulfone, a
polycarbonate and a polyamide.
7. A method for fabricating a composite reinforced with graphite
yarn which comprises heating the yarn in 1000.degree.at a
temperature in the range of 100.degree. to 4500.degree.F for a
period ranging from about 0.10 to 12 seconds; passing the heated
yarn through a solution of a thermoplastic polymer, thereby coating
the yarn with the polymer; evaporating solvent from the coating on
the graphite yarn; passing the coated yarn through a solution of a
thermosetting resin; thereby coating the thermoplastic polymer
coated yarn with thermosetting resin; evaporating solvent from the
coated yarn; and molding portions of the coated yarn under heat and
pressure to form a composite.
8. A method according to claim 7 in which the first mentioned
solution contains in the range of about 0.5 to 25 weight percent of
thermoplastic polymer; the amount of thermoplastic polymer coated
on the graphite yarn is in the range of about 5 to 30 percent by
weight of the yarn; the second mentioned solution contains in the
range of about 30 to 80 weight percent of thermosetting resin; and
the amount of thermosetting resin coated on the thermoplastic
polymer coated yarn is in the range of about 25 to 60 weight
percent, based upon the weight of the thermoplastic polymer coated
yarn.
9. The method according to claim 8 in which the thermoplastic
polymer is selected from the group consisting of a polyhydroxy
ether, a polyphenylene oxide, a polysulfone, a polyarylsulfone, a
polycarbonate and a polyamide and the thermosetting resin is
selected from the group consisting of an epoxy resin, a phenolic
resin, a polyimide resin, a polybenzimidazole resin, and a pyrrone
resin.
10. The method according to claim 9 in which the thermoplastic
polymer is a polyhydroxy ether having the following structural
formula: ##SPC2##
wherein n has a value such that the polymer has a molecular weight
of about 35,000; the thermosetting resin is an epoxy resin; and
stacked plies of the coated yarn are molded at a temperature in the
range of about 175.degree. to 450.degree.F under a pressure of
about 100 to 1000 psi for a period of about 1 to 8 hours.
11. The method according to claim 9 in which the thermosplastic
polymer is poly(2,6-diphenyl-1,4-phenylene oxide); the
thermosetting resin is an epoxy resin; stacked plies of the coated
yarn are molded at a temperature in the range of about 175.degree.
to 450.degree.F under a pressure of about 100 to 1000 psi for a
period of about 1 to 8 hours.
Description
FIELD OF THE INVENTION
This invention relates to the treatment of high modulus graphite
fibers. In one aspect it relates to composites which include the
treated fibers. In another aspect it relates to a method for
fabricating composites.
BACKGROUND OF THE INVENTION
Graphite fibers and yarns derived from a variety of precursors are
described in the literature. Examples of precursors that have been
used include fibers from cellulosic materials, such as cotton,
flax, sisal, and viscose rayon, acrylonitrile polymers,
polybenzimidazoles, polyamides, polyimides and the like. The
graphite fibers are often prepared by initially heating the
precursory fibers in an oxidizing atmosphere at a temperature of
about 450.degree. to 575.degree.F followed by carbonization and
graphitization steps carried out in an inert atmosphere at elevated
temperature. While the properties of the graphite fibers depend to
a substantial degree upon the particular precursory fiber employed,
they generally have a high tensile strength and high modulus of
elasticity.
The above-mentioned properties of graphite fibers render them
particularly suitable for use as reinforcing materials in the
fabrication of composites. Composites prepared by incorporating
reinforcing materials in various matrices, particularly
thermosetting resins, have in recent years been utilized in many
applications, especially in the construction of aerospace
components, such as the leading edges of high speed aircraft, nose
cones, rocket engine components, and the like. While graphite
fibers possessing high tensile strength and high modulus properties
are important in providing satisfactory composites, it is equally
important that a good bond exists between the fibers and matrix.
Otherwise, the composite will have a low interlaminar shear
strength that could result in composite failure.
It is an object of this invention, therefore, to provide graphite
fibers which possess improved bonding characteristics when
incorporated in thermosetting resins.
Another object of the invention is to provide a method for treating
graphite fibers so as to improve their adherence to thermosetting
resins.
A further object of the invention is to provide composites having
an improved interlaminar shear strength.
Still another object of the invention is to provide a method for
fabricating composites having an improved interlaminar shear
strength.
Other objects and advantages of the invention will become apparent
to those skilled in the art upon consideration of the accompanying
disclosure and the drawing which is a schematic illustration of
apparatus that can be used in practicing the method of this
invention.
SUMMARY OF THE INVENTION
Broadly speaking, the present invention resides in a method for
treating graphite fibers so as to improve their adherence to
thermosetting resins. The method for improving the fiber bonding
characteristics comprises the steps of heating the graphite fibers,
generally in the form of a yarn, under oxidizing conditions;
coating the heated fibers with a solution of a thermoplastic
polymer; and heating the coated fibers so as to evaporate solvent
therefrom.
In a more specific embodiment of the invention the fibers, treated
as described above, are immersed in a solution of a thrmosetting
resin so as to form prepreged fibers which are then placed in a
form or shape appropriate for their intended use. For example, the
fibers can be cut to a desired length or they can be wound on a
mandrel preparatory to forming a sheet or tape. After precuring the
thermosetting resin, the resulting B-staged material is arranged in
a mold or press wherein it is heated under pressure to affect a
cure. Thereafter, a cured product having a desired configuration
and structure, e.g., a laminate, is recovered.
Reference is now made to the drawing which illustrates
schematically apparatus suitable for carrying out the method of
this invention. As shown in the drawing, a graphite fiber or yarn
10 is pulled from "take-off" reel 11. Any graphite fiber or yarn,
such as those mentioned hereinbefore, can be employed. From reel 11
the graphite yarn passes under roller 12 and over roller 13 which
are so positioned that the yarn moves substantially in a horizontal
plane. While moving from roller 12 to roller 13, the yarn passes
through an oxidation zone which, as illustrated, is an oxidizing
flame (nonluminous) 14 emanating from flared nozzle 16 of gas
burner 17. Any hydrocarbon gas mixed with air can be used to
produce the oxidizing flame, but it is generally preferred to use
propane or butane or mixtures thereof. In passing through the
oxidation zone, the graphite yarn is subjected to a temperature
ranging from about 1000.degree. to 4500.degree.F. The speed at
which the yarn moves is controlled so that it is present in the
oxidation zone and thereby exposed to the high temperature for a
period ranging from about 0.10 to 12 seconds. It is to be
understood that the higher the temperature the shorter the time
period and vice versa. Although it is generally preferred to
utilize an oxidizing flame, it is within the scope of the invention
to pass the yarn through an induction furnace susceptor in an
oxygen-containing atmosphere such as air. When utilizing such a
furnace, the length of the susceptor and its temperature are such
that the yarn is maintained at a temperature in the above-mentioned
range for the indicated period of time. Another type of heating
means that can be employed, particularly at lower temperatures, is
a tube furnace.
After passing over roller 13, the thermally treated yarn is guided
by rollers 18 and 19 through tank 21 containing a bath of a
solution of a thermoplastic polymer. While thermoplastic polymers
in general can be employed, it is usually preferred to use a
polyhydroxy ether, polyphenylene oxide, polysulfone,
polyarylsulfone, polycarbonate or polyamide. Suitable solvents for
such polymers are well known in the art and include acetone, methyl
ethyl ketone, Carbitol (diethylene glycol ethyl ether), butyl
Carbitol (diethylene glycol butyl ether), Cellosolve (glycol ethyl
ether), Cellosolve acetate (hydroxyethyl acetate), butyl Cellosolve
(glycol butyl ether), dimethylformamide, dimethylsulfoxide,
dimethylacetamide, dioxane, ethoxy triglycol, mesityl oxide,
tetrahydrofuran, benzene, toluene, xylenes, butanol,
tetrachloroethane, methylene chloride, ethylene chloride, and the
like.
The solution in tank 21 contains about 0.5 to 25, preferably 0.75
to 12, weight percent of the thermoplastic polymer, based on the
total weight of the solution. The amount of polymer coated on the
graphite yarn depends upon the polymer concentration of the bath
and the period of time during which the yarn is immersed in the
bath. The yarn-solution contact time in turn depends upon the speed
at which the yarn moves through the bath and the length of the path
that the yarn travels in the bath. Since the speed at which the
yarn moves is determined by the time during which it is in contact
with oxidizing flame 14, in the final analysis the amount of
polymer coating is controlled by varying the polymer concentration
and the length of the path of travel in the bath. In general, these
variables are so controlled that the amount of thermoplastic
polymer coating on the graphite yarn is in the range of about 5 to
30 percent by weight of the yarn.
After leaving tank 21, the yarn is passed through a heating zone
wherein the solvent is evaporated. As depicted in the drawing, an
infrared lamp 22, positioned a short distance above the coated
fiber, provides a source of heat for the heating zone. However, it
will be apparent to those skilled in the art that other heating
means, e.g., a hot air gun, can be utilized. The temperature of the
heating zone is sufficient to cause evaporation of solvent
contained in the thermoplastic polymer coating, and will
necessarily vary with the particular solvent used in preparing the
polymeric coating bath in tank 21. However, the temperature is
usually no greater than about 180.degree.F. Furthermore, when using
solvents having boiling points below room temperature, the heating
zone may be omitted, the solvent being permitted to evaporate under
ambient conditions.
After traveling through the heating zone, the graphite yarn, now
coated with a dried thermoplastic polymer, passes over roller 23
into tank 24. Contained in tank 24 is a solution of a thermosetting
resin which will subsequently function as the matrix in fabricating
composites. Any suitable thermosetting resin, of which there are
many described in the literature, can be utilized. Examples of such
suitable resins or polymers include polyepoxides, such as the
condensation products of bisphenol A (4,4'-isopropylidenephenol)
and epichlorohydrin; phenolic resins prepared by reaction of phenol
and formaldehyde; polyimide resins formed by the condensation of an
aromatic tetrabasic acid anhydride and an aromatic diamine;
polybenzimidazole resins formed by the reaction of an aromatic
tetraamine with an aromatic diacid; pyrrone resins formed by the
condensation of an aromatic dianhydride and an aromatic tetraamine;
and the like. Solvents for a particular thermosetting resin are
well known and include alcohols such as propanol and butanol,
ketones such as acetone and methyl ethyl ketone, dimethylformamide,
dimethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, and the
like. The solution in tank 24 contains in the range of about 30 to
80 percent by weight of the thermosetting resin.
The coated yarn is guided through tank 24 containing the
thermosetting resin solution by means of rollers 26 and 27. In its
passage through the solution, the coated yarn picks up in the range
of about 25 to 60 weight percent of the resin, based upon the
weight of the coated yarn. As in the case of the thermoplastic
polymer coating operation, the amount of thermosetting resin "pick
up" is controlled by varying the resin concentration and the length
of the path of travel in the resin solution. Thus, these variables
are so adjusted that the amount of resin deposited on the coated
yarn is in the aforementioned range.
After leaving tank 24, the graphite yarn, coated with successive
layers of a thermoplastic polymer and a thermosetting resin, is
wound onto "take-up" mandrel or drum 28. The yarn is wound on the
mandrel under tension with filaments parallel to each other and in
a single layer. The mandrel is rotated at a speed such that the
yarn will move through flame 14 at a desired rate. After completion
of the winding operation, solvent is allowed to evaporate from the
prepreg yarn. This can be accomplished by exposing the yarn to the
atmosphere at room temperature for an extended period of time,
e.g., for about 8 to 24 hours, or until the yarn is slightly tacky
to non-tacky. It is also within the scope of the invention to heat
the mandrel, as with an internal heater, so as to evaporate the
solvent. When the drying method is used, the prepreg yarn is
usually heated at a temperature ranging from about 100.degree. to
150.degree.F for a period of about 15 minutes to 1 hour.
Upon completion of the drying step, the prepreg yarn is slit from
the mandrel as a sheet. The sheet can then, if desired, be cut to
form a plurality of plies of tape, or it can be separated into
multiple strands. The prepreg yarn in the form of tape or strands
is then cured under pressure to form a composite of a desired
shape. For example, in fabricating a laminate, a plurality of plies
of tape are stacked in a press or mold and heated to a temperature
in the range of about 175.degree. to 450.degree.F under a pressure
of about 100 to 1000 psi for a period of about 1 to 8 hours. During
the curing operation any residual solvent that may be present is
released from the press or mold. After cooling, generally while
under pressure, the laminate is removed from the press or mold. The
edges of the laminate are then trimmed so as to provide a smooth
uniform product. Subsequent to the curing operation, it is often
desirable to postcure the laminate by heating it in the absence of
oxygen to an elevated temperature over an extended period of time,
e.g., to a temperature ranging from 300.degree. to 750.degree.F
over a period of from about 12 to 72 hours. Thus, the postcuring
can be conducted in a furnace in the presence of an inert gas, such
as nitrogen, argon or helium. It is to be understood that the
actual curing procedure to be followed will depend upon the
particular thermosetting resin employed. In many instances a
supplier of resins recommends curing conditions that should be
used.
A more complete understanding of the invention can be obtained by
referring to the following illustrative examples which are not
intended, however, to be unduly limitative of the invention.
EXAMPLE I
A series of runs was conducted in which a graphite yarn was treated
in accordance with the method of this invention after which the
treated yarn was coated with a thermosetting resin and used in the
fabrication of laminates. Apparatus similar to that shown in the
drawing was utilized in carrying out the runs.
In carrying out the runs, a graphite yarn derived from a cellulosic
precursor was pulled through the nonluminous or oxidizing portion
of a propane-generated flame. The graphite yarn was a product of
Union Carbide sold under the trademark Thornel 50. The yarn was
sized with polyvinyl alcohol and had a modulus of elasticity of 50
.times. 10.sup.6 psi. The temperature of the flame was about
4000.degree.F, and the width of the flame was about 1 inch. The
yarn was pulled at the rate of 4 feet per minute so that the yarn
was in contact with the flame for about 1.25 seconds. Thereafter,
the heated yarn was passed into and through a bath of a solution of
a thermoplastic polymer. After emerging from the bath, the yarn
coated with the thermoplastic polymer, was passed under an infrared
lamp, thereby causing evaporation of solvent. The coated yarn was
next pulled through a bath of a solution containing 60 weight
percent of a thermosetting resin. The thermosetting resin utilized
was an epoxy resin, a product of Union Carbide identified by the
symbol ERL 2256, composed of a mixture of a diglycidylether of
biphenol A diluted with 37.5 weight percent bis
2,3-epoxycyclopentyl ether and containing as the hardener a mixture
of m-phenylene diamine and dimethylaniline. Upon emergence from
this bath, the yarn coated with successive layers of a
thermoplastic polymer and the thermosetting resin was wound on a
mandrel to form a monolayer of a prepreg tape.
After exposure overnight to the atmosphere at room temperature,
solvent had evaporated, leaving a slightly tacky prepreg tape. The
tape was then slit and stripped from the mandrel and cut into
individual pieces corresponding to mold dimensions (21/4 .times.
21/4 inches). In each run 10 plies of the tape were stacked in a
steel mold and molded according to the recommendations of the
supplier of the thermosetting resin. Thus, the mold was first
heated at 180.degree.F for 2 hours followed by heating at
300.degree.F for 4 hours. The mold was cooled to room temperature
between the heating periods, and was maintained at a pressure of
100 psi during the period. The laminate was removed from the mold
and tested to determine its flexural properties and interlaminar
shear strength. Control runs were also carried out in which the
graphite yarn was merely passed through the thermosetting resin
solution prior to fabrication of laminates. The composition of the
solutions of thermoplastic polymers and the results of the tests
are shown below in Table I. ##SPC1##
EXAMPLE II
Another series of runs was carried out as described in Example I
except that the graphite yarn used (Thornel 50) was water sized.
The compositions of the thermoplastic solutions and the results of
the runs are set forth below in Table II.
TABLE II
__________________________________________________________________________
Thermoplastic Flexural Flexural Interlaminar Run Polymer Volume %
Modulus, Strength Shear Strength, No. Solution Yarn
.times.10.sup.2,psi .times.10.sup.3,psi .times.10.sup.3,psi
__________________________________________________________________________
9 Control 64.6 18.2 109.6 3.8 10 0.91 wt % PHE in Cellosolve 65.2
19.6 100.1 5.0 11 2.3 wt % PPO in benzene 57.0 18.5 90.7 7.7
__________________________________________________________________________
EXAMPLE III
Two runs were carried out as described in Example I except that the
graphite yarn used (Thornel 80) had a modulus of elasticity of 80
.times. 10.sup.6 psi. The yarn was sized with polyvinyl alcohol.
The composition of the thermoplastic solution and the results of
the runs are recorded below in Table III.
TABLE III
__________________________________________________________________________
Thermoplastic Flexural Flexural Interlaminar Run Polymer Volume %
Modulus Strength Shear Strength, No. Solution Yarn
.times.10.sup.6,psi .times.10.sup.3,psi .times.10.sup.3,psi
__________________________________________________________________________
12 Control 60 28.0 125.0 2.8 13 2 wt % PHE In 37.5% Cello- solve
acetate and 62.5% methyl ethyl ketone 59.3 28.7 121.0 6.3
__________________________________________________________________________
EXAMPLE IV
Other runs were carried out according to the procedure of this
invention as described in Example I except that in certain runs the
heating step was omitted and in other runs the step of applying the
thermoplastic polymer coating was omitted. The results obtained
demonstrated that no beneficial effects resulted from the use of
only one of the steps. In other words it was found that both of the
steps are required in order to improve the interlaminar shear
strength of the composites.
From the data shown in the foregoing examples, it is seen that the
method of this invention makes it possible to fabricate composites
having interlaminar shear strengths that are from 2 to 3 times
greater than those prepared with untreated high modulus graphite
fibers.
Modifications of the present invention will become apparent to
those skilled in the art after considering the foregoing
disclosure. Such modifications clearly come within the spirit and
scope of the invention.
* * * * *