U.S. patent number 3,818,082 [Application Number 05/112,189] was granted by the patent office on 1974-06-18 for process for the production of carbonaceous tapes.
This patent grant is currently assigned to Celanese Corporation. Invention is credited to Kenneth S. Burns, George R. Ferment, Roger C. Waugh.
United States Patent |
3,818,082 |
Burns , et al. |
June 18, 1974 |
PROCESS FOR THE PRODUCTION OF CARBONACEOUS TAPES
Abstract
An improved process is provided for the simultaneous conversion
of a plurality of adjoining parallel ends of an organic polymeric
fibrous material to a carbonaceous fibrous material. The parallel
warp ends are provided and maintained during at least a portion of
the conversion process an an integral tape possessing a high degree
of structural integrity by the presence of a weft pick interlaced
therewith in a sateen weave construction which floats a substantial
number of the parallel warp ends as described. When the resulting
carbonaceous tape is incorporated in a matrix material to form a
composite article, the presence of the weft pick therein produces
no substantial diminution in the composite properties.
Inventors: |
Burns; Kenneth S. (Basking
Ridge, NJ), Ferment; George R. (Dover, NJ), Waugh; Roger
C. (Rock Mart, GA) |
Assignee: |
Celanese Corporation (New York,
NY)
|
Family
ID: |
22342548 |
Appl.
No.: |
05/112,189 |
Filed: |
February 3, 1971 |
Current U.S.
Class: |
264/345;
264/DIG.19; 139/420R |
Current CPC
Class: |
D03D
15/00 (20130101); D03D 3/005 (20130101); D03J
1/00 (20130101); D01F 9/22 (20130101); B29C
70/04 (20130101); D10B 2101/12 (20130101); D10B
2401/063 (20130101); Y10S 264/19 (20130101); D03J
2700/02 (20130101); D10B 2321/10 (20130101); D10B
2505/02 (20130101); B29K 2307/00 (20130101); D10B
2505/00 (20130101) |
Current International
Class: |
D01F
9/22 (20060101); D03J 1/00 (20060101); D03D
15/00 (20060101); D01F 9/14 (20060101); B29c
025/00 () |
Field of
Search: |
;139/42R ;8/115.5,116
;23/29.1F ;264/29 ;423/447 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Jaudon; Henry S.
Claims
We claim:
1. In a process for the simultaneous conversion of a plurality of
adjoining ends of a multifilament acrylic fibrous material capable
of undergoing conversion to a carbonaceous fibrous material
selected from the group consisting essentially of an acrylonitrile
homopolymer and an acrylonitrile copolymer containing at least
about 85 mol per cent of acrylonitrile units and up to about 15 mol
per cent of one or more monovinyl units copolymerized therewith,
while in the form of a tape to a carbonaceous fibrous material
wherein said ends are continuously passed in the direction of their
length through a series of heating zones while substantially
suspended therein to form a fibrous product which contains at least
90 per cent carbon by weight, the improvement which comprises
providing said fibrous material during at least the stabilization
portion of the said conversion process in the form of a tape of
sateen weave construction consisting of at least 32 adjoining
substantially parallel linear multifilament warp ends of fibrous
material essentially coextensive with the length of said tape and a
weft pick which initially is provided prior to stabilization as a
multifilament acrylic yarn having a total denier below about 400
interlaced therewith at a plurality of points capable of
maintaining and substantially parallel relationship of said warp
ends which substantially floats at least 4 of said warp ends prior
to each additional interlacing point in the main body of said tape
as said warp ends are traversed, said weft pick being provided
under a tension sufficient that said linear configuration of said
warp ends is substantially unimparied and at a frequency of about
0.1 to 8 picks per inch of said tape.
2. An improved process according to claim 1 wherein said warp ends
are an acrylonitrile homopolymer.
3. An improved process according to claim 1 wherein the composition
of said weft pick is substantially identical to that of said warp
ends.
4. An improved process according to claim 1 wherein said fibrous
material is provided in the form of said tape of sateen weave
construction while being passed through a stabilization zone and a
carbonization zone.
5. An improved process according to claim 1 wherein said fibrous
material is provided in the form of said tape of sateen weave
construction while being passed through a stabilization zone, a
carbonization zone, and a graphitization zone.
6. An improved process according to claim 1 wherein said fibrous
material is provided in the form of said tape of sateen weave
construction while being passed through a stabilization zone, a
carbonization zone, and a surface treatment zone.
7. An improved process according to claim 1 wherein said warp ends
are continuous multifilament yarns exhibiting a twist of about 0.1
to 5 turns per inch.
8. An improved process according to claim 7 wherein said weft pick
possesses a twist of about 0.5 turn per inch.
9. An improved process according to claim 1 wherein said tape of
sateen weave construction includes 32 to 500 adjoining
substantially parallel linear warp ends.
10. An improved process according to claim 1 wherein the total
denier of said weft pick is equal to or less than that of each of
said warp ends.
11. An improved process according to claim 1 wherein said weft pick
possesses a twist of about 0.1 to 3 turns per inch.
12. An improved process according to claim 1 wherein said weft pick
substantially floats from about 4 to 16 of said warp ends prior to
each additional interlacing point in the main body of said tape as
said warp ends are traversed.
13. An improved process according to claim 1 wherein said weft pick
is provided at a frequency of about 1 to 3 picks per inch of said
tape.
Description
BACKGROUND OF THE INVENTION
In the search for high performance materials, considerable interest
has been focused upon carbon fibers. The terms "carbon" fibers or
"carbonaceous" fibers are used herein the generic sense and include
graphite fibers as well as amorphous carbon fibers. Graphite fibers
are defined herein as fibers which consist essentially of carbon
and have a predominant x-ray diffraction pattern characteristic of
graphite. Amorphous carbon fibers, on the other hand, are defined
as fibers in which the bulk of the fiber weight can be attributed
to carbon and which exhibit an essentially amorphous x-ray
diffraction pattern. Graphite fibers generally have a higher
Young's modulus than do amorphous carbon fibers and in addition are
more highly electrically and thermally conductive.
Industrial high performance materials of the future are projected
to make substantial utilization of fiber reinforced composites, and
graphitic carbon fibers theoretically have among the best
properties of any fiber for use as high strength reinforcement.
Among these desirable properties are corrosion and high temperature
resistance, low density, high tensile strength, and high modulus.
Uses for carbon fiber reinforced composites include aerospace
structural components, rocket motor casings, deep-submergence
vessels and ablative materials for heat shields on re-entry
vehicles.
As is known in the art, numerous procedures have been proposed in
the past for the conversion of various organic polymeric fibrous
materials to a carbonaceous form while retaining the original
fibrous configuration essentially intact. Such procedures have in
common the thermal treatment of the fibrous precursor in an
appropriate atmosphere or atmoshpheres which is commonly conducted
in a plurality of heating zones, or alternatively in a single
heating zone wherein the fibrous material is subjected to
progressively increasing temperatures. Both batch and continuous
processing techniques have been proposed. From the commerical
standpoint those processes which are capable of functioning on a
continuous basis are generally considered to be the most
attractive. However, many of the prior art continuous conversion
techniques have been inherently limited to the processing of a
single end of fibrous precursor at a given time. Such techniques
while offering the advantages of possible automation, still suffer
the disadvantage of limited productivity.
Additionally, techniques have been proposed wherein a plurality of
ends of a fibrous precursor may be simultaneously processed. See
for instant the process of commonly assigned U.S. Ser. Nos.
865,332, filed Oct. 10, 1969, of Kenneth S. Burns and William M.
Cooper (now abandoned) wherein a multiplicity of strands of
polymeric fibrous material are simultaneously stabilized prior to
subsequent carbonization; and 874,731, filed Nov. 7, 1969, (now
U.S. Pat. No. 3,723,157), of Melvin L. Druin wherein a plurality of
multifilament bundles capable of undergoing graphitization are
simultaneously graphitized and subsequently coated. While such
generically defined processes offer substantial advantages over
prior art batch and continuous processes, fiber handling
difficulties may occasionally arise. For example, if one of the
fibrous ends undergoing treatment should be defective, the breakage
of the same while being passed through one of the heating zones
frequently results in catastrophic failure of the process. The
operation of the process must be terminated, the oven or ovens
cooled, and the broken end re-united or replaced. Also, precise
handling of the plurality of ends is essential if substantial end
cross-overs are to be eliminated and a uniform width of the
plurality of the ends maintained.
One technique heretofore proposed for the simultaneous conversion
of a substantial number of fibrous ends to a carbonaceous form has
involved the thermal treatment of a fibrous precursor while in the
form of a woven cloth. See, for instance, Belgian Pat. Nos. 720,947
and 726,761, as well as U.S. Pat. No. 3,541,582 for representative
disclosures of the processing of cloth precursors. While fibrous
assemblages in cloth form commonly offer advantages with respect to
the maintenance of structural integrity throughout the thermal
treatment, a permanent crimp is commonly imparted to the filaments
and the single filament tensile properties of the fibers present
within the cloth have tended to be adversely influenced.
Additionally a high degree of fiber loading within a composite
article is commonly impossible because of the inability of the
cloth to form compact plys within the same. The weft threads in the
cloth further appear to produce an overall reduction in the
composite physical properties.
It is an object of the invention to provide an improved process for
the simultaneous conversion of a plurality of adjoining ends of an
organic polymeric fibrous material while in the form of a tape to a
carbonaceous fibrous material.
It is an object of the invention to provide an improved process for
the simultaneous conversion of a plurality of adjoining ends of an
organic polymeric fibrous material to a carbonaceous fibrous
material while in the form of a tape of enhanced structural
integrity.
It is an object of the invention to provide an improved process for
the simultaneous conversion of a plurality of adjoining ends of an
organic polymeric fibrous material to a carbonaceous fibrous
material wherein catastrophic process failure resulting from the
breakage of an end is effectively eliminated.
It is an object of the invention to provide an improved process for
the simultaneous conversion of a plurality of adjoining ends of an
organic polymeric fibrous material to a carbonaceous fibrous
material while in the form of a tape wherein splits and cross-overs
are substantially eliminated.
It is another object of the invention to provide an improved
process for the simultaneous conversion of a plurality of adjoining
ends of an organic polymeric fibrous material wherein the warp ends
are maintained in position by at least one weft pick in the
substantial absence of the impairment of the linear configuration
and tensile properties of the warp ends.
It is another object of the invention to provide an improved
process for the conversion of a plurality of adjoining ends of an
organic polymeric fibrous material to an integral carbonaceous tape
which is capable of a high degree of compaction and fiber loading
when utilized as a reinforcing medium in a composite article.
It is another object of the invention to provide an improved
process for producing a woven carbonaceous tape which when utilized
as a reinforcing medium yields a composite article of enhanced
physical properties.
It is a further object of the invention to provide in a preferred
embodiment an improved process for producing carbonaceous tapes
from a fibrous acrylic precursor.
These and other objects, as well as the scope, nature, and
utilization of the invention will be apparent from the detailed
description which follows, and the appended claims.
SUMMARY OF THE INVENTION
It has been found in a process for the simultaneous conversion of a
plurality of adjoining ends of an organic polymeric fibrous
material capable of undergoing conversion to a carbonaceous fibrous
material while in the form of a tape to a carbonaceous fibrous
material wherein the ends are continuously passed in the direction
of their length through a series of heating zones while
substantially suspending therein to form a fibrous product which
contains at least 90 per cent carbon by weight, that improved
results are achieved by providing the fibrous material during at
least a portion of the conversion process in the form of a tape of
sateen weave construction consisting of at least 32 adjoining
substantially parallel linear warp ends capable of undergoing
conversion to a carbonaceous fibrous material essentially
coextensive with the length of the tape and a weft pick interlaced
therewith at a plurality of points capable of maintaining the
substantially parallel relationship of the warp ends which
substantially floats at least four of the warp ends prior to each
additional interlacing point in the main body of the tape as the
warp ends are traversed, the weft pick being provided at a tension
sufficient that the linear configuration of the warp ends is
substantially unimpaired and at a frequency of about 0.1 to 8 picks
per inch of the tape.
The preferred organic polymeric fibrous material is an acrylic
polymer comprising at least about 85 mol per cent of acrylonitrile
units and up to about 15 mol per cent of one or more monovinyl
units copolymerized therewith. In a preferred embodiment of the
process the organic polymeric tape is provided in the sateen weave
construction throughout the conversion process.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is an enlarged plan view of a portion of precursor tape of a
4 .times. 4 sateen weave construction suitable for use in the
present process.
FIG. 2 is the numerical weaving pattern for the tape of FIG. 1.
FIG. 3 is an enlarged plan view of a portion of precursor tape of
an 8 .times. 8 sateen weave construction suitable for use in the
present process.
FIG. 4 is the numerical weaving pattern for the tape of FIG. 3.
FIG. 5 is an enlarged plan view of a portion of precursor tape of a
16 .times. 16 sateen weave construction suitable for use in the
present process.
FIG. 6 is the numerical weaving pattern for the tape of FIG. 5.
FIG. 7 is an enlarged plan view of a portion of precursor tape
having a weave construction not in accordance with that employed in
the present process and is presented for comparative purposes.
FIG. 8 is the numerical weaving pattern for the tape of FIG. 7 and
is presented for comparative purposes only.
DESCRIPTION OF PREFERRED EMBODIMENTS
The tape which is converted to a carbonaceous fibrous material
possesses a sateen weave construction (as described in detail
hereafter) during at least a portion of the conversion process
which includes at least 32 adjoining substantially parallel linear
warp ends.
The warp ends are composed of an organic polymeric fibrous material
capable of conversion to a carbonaceous fibrous material. The warp
ends may be conveniently selected from those fibrous materials
which are recognized as being suitable for thermal conversion to a
carbonaceous fibrous material. For instance, the warp ends may be
derived from organic polymers such as an acrylic polymer, a
cellulosic polymer, a polyamide, a polybenzimidole, polyvinyl
alcohol, pitch, etc. As discussed hereafter, acrylic polymeric
materials are particularly suited for use in the formation of the
warp ends employed in the present process. Illustrative examples of
suitable cellulosic materials include the natural and regenerated
forms of cellulose, e.g. rayon. Illusttative examples of suitable
polyamide materials include the aromatic polyamides, such as nylon
6T, which is formed by the condensation of hexamethylenediamine and
terephthalic acid. An illustrative example of a suitable
polybenzimidazole is
poly-2,2'-m-phenylene-5,5'-bibenzimidazole.
An acrylic polymeric material prior to thermal stabilization may be
formed primarily of recurring acrylonitrile units. For instance,
the acrylic polymer should contain not less than about 85 mol per
cent of acrylonitrile units with not more than about 15 mol per
cent of monovinyl compound which is copolymerizable with
acrylonitrile such as styrene, methyl acrylate, methyl
methacrylate, vinyl acetate, vinyl chloride vinylidene chloride,
vinyl pyridine, and the like, or a plurality of such monomers. A
particularly preferred acrylic polymeric material is an
acrylonitrile homopolymer, or a closely relate acrylonitrile
copolymer (i.e. contains at least about 95 mol per cent of
acrylonitrile units and up to about 5 mol per cent of one or more
monovinyl compouds copolymerized with acrylonitrile.
The warp ends may be provided in a variety of physical
configurations. For instance, the warp ends may assume the
configuration of continuous lengths of multifilament yarns, tows,
strands, cables, or similar fibrous assemblages. In a preferred
embodiment of the process the warp ends are a continuous
multifilament yarn.
The warp ends may optionally be provided with a twist which tends
to improve the handling characteristics. For instance, a twist of
about 0.1 to 5 tpi. and preferably about 0.3 to 1.0 tpi, may be
utilized Also, a false twist may be used instead of or in addition
to a real twist Alternatively, one may select bundles of fibrous
material which possess essentially no twist.
The warp ends may be drawn in accordance with conventional
techniques in order to improve their orientation. For instance,
acrylic warp ends may be preliminarily drawn by stretching before
or after incorporaton in the tape while in contact with a hot shoe
at about 140.degree. to 160.degree.C. Additional representative
drawing techniques are disclosed in U.S. Pat. Nos. 2,455,173;
2,948,581; and 3,122,412. It is recommended that acrylic warp ends
selected for use in the process be initially drawn to a single
filament tenacity of at least about 3 grams per denier. If desired,
however, the warp ends may be more highly oriented, e.g. drawn up
to a single filament tenacity of about 7.5 to 8 grams per denier,
or more.
The weft pick is preferably also composed of an organic polymeric
fibrous material which is capable of undergoing carbonization
without the destruction of its original fibrous configuration. If
desired, however, the weft pick may be initially provided as a
previously stabilized organic polymeric fibrous material, a
carbonaceous fibrous material, or other fibrous material capable of
withstanding the carbonization temperatures. Alternatively, a weft
pick may be selected which is incapable of withstanding the highly
elevated temperatures required to complete carbonization and/or
graphitization of the warp ends. For instance, the weft pick may be
formed from a cellulosic material such as cotton which will impart
dimensional stability to the warp ends through the stabilization
step, but which is incapable of withstanding a subsequent heat
treatment step.
The weft pick may be provided in a variety of physical
configurations. For instance, the weft pick may assume the
configuration of a multifilament yarn, tow, strand, cable, or
similar fibrous assemblage. In a preferred embodiment of the
process the weft pick is a continuous multifilament yarn having a
total denier equal to or less than that of the continuous
multifilament yarn warp ends. Preferably the total denier of a
multifilament acrylic yarn weft pick prior to thermal stabilization
is below about 400, e.g. about 100 to 300, total denier. In a
particularly preferred embodiment of the process the total denier
of the weft pick is about 0.2 to 0.5 times the total denier of a
warp end. A minor amount of twist may be beneficially provided in a
multifilament yarn weft pick which improves the handling
characteristics during weaving. For instance, the weft pick may be
provided with a twist of about 0.1 to 5 tpi (preferably 0.1 to 3
tpi), and most preferably about 0.2 to 0.7 tpi. If a twist is
utilized in the warp ends it is recommended that any twist employed
in the weft pick be to a lessor degree so that the weft pick may
readily assume a more flatened configuration when in contact with
warp ends.
It is essential that the weft pick utilized in the formation of the
tape lacks a tendency to undergo excessive shrinkage during heat
treatment (described hereafter) which imparts a pucker to the warp
ends and thereby interferes with the flat configuration of the
tape. In a preferred embodiment of the process the weft pick is hot
drawn at least about 3 times its as-spun length to increase its
orientation and is subsequently relaxed (e.g. 5 to 40 per cent of
drawn length) prior to incorporation in the precursor tape so that
its tendency to undergo shrinkage is minimized.
The fibrous material utilized as the warp ends and weft pick may
optionally be provided in intimate association with one or more
catalytic agents capable of enhancing the rate of the thermal
conversion to a carbonaceous fibrous material.
The fibrous organic polymeric tape utilized as the procursor in the
process of the present invention during at least a portion of its
thermal conversion to a carbonized form is provided in a highly
unbalanced sateen weave construction. A "sateen weave construction"
is defined as a woven construction possessing a substantial number
of floats which run fillingwise (i.e. weftwise). The tern "float"
is used in its usual sense and indicates that a plurality of
substantially perpendicular strands present within the construction
are being passed over or skipped in the absence of interlacement.
The tape is unbalanced in the sense that the numerical proportion
of warp ends to filling picks per square inch present within the
same is substantially greater than 1:1, e.g. about 4:1 to 100:1, or
more, and preferably about 15:1 to 30:1. The tape comprises at
least 32 adjoining substantially parallel linear warp ends.
Commonly, the tape comprises about 32 to 500 adjoining warp ends;
however, even a substantially larger number of warp ends can be
employed, e.g. 1,000 or more. The warp ends are essentially
coextensive with the length of the tape. The weft pick present
within the tape of sateen weave construction is provided at a
frequency of about 0.1 to 8 picks per inch of said tape, and
preferably at a frequency of about 1 to 3 picks per inch of said
tape. Since the weft pick is provided at a relatively low
frequency, and preferably as a continuous length, it may intersect
the edge of the tape at an angle other than exactly ninety degrees
unlike common woven fabrics. The exact angle of intersection with
the edge of the tape is influenced by the pick frequency, and the
width of the tape (i.e. number and total denier of the warp
ends).
The sateen weave construction of the tape is such that the weft
pick is interlaced with the warp ends at a plurality of points
capable of maintaining the substantially parallel relationship of
the warp ends which are in an adjoining relationship in the form of
a flat tape with contact being made between contiguous warp ends.
The weft pick is provided under a tension sufficient that the
linear configuration of the warp ends present within the tape is
substantially unimpaired. Additionally, any crimp which is present
in the tape components should be present in the weft pick and not
in the warp ends.
The weft pick is interlaced with the warp ends in such a manner
that it substantially floats at least four of the warp ends prior
to each additional interlacing point in the main body of the tape,
i.e. the central portion of the tape with the possible exclusion of
the selvage. More specifically, the weft pick floats from about
four to 16, or more, of the warp ends prior to each additional
interlacing point in the main body of the tape as the warp ends are
traversed. As the weft pick passes between adjoining warp ends in
the main body of the tape at an interlacing point, an additional
float preferably of like length is begun on the opposite face of
the tape. Accordingly, floats of at least four warp ends are
substantially present upon each face of the main tape body. Such
floats maintain the warp ends as an integral tape of controlled
lateral integrity. In the particularly preferred embodiment of the
process the weft pick floats about eight of the warp ends prior to
the next interlacing point. While standard weaving equipment is
commonly incapable of producing a sateen weave construction wherein
more than 16 warp ends are floated, this fact should not limit the
maximum float utilized in the process to 16 warp ends. It should be
recognized, however, that the structural integrity of the tape
tends to be reduced if the float greatly exceeds 16 warp ends, e.g.
up to about 50 warp ends.
The lengths of the floats utilized in the sateen weave construction
in the main body of the tape need not be identical provided at
least four of the substantially parallel linear warp ends are
skipped prior to each additional point of interlacement. It is
preferred, however, that floats of substantially uniform length
(i.e. naturally balanced in weft direction) be used throughout a
given sateen weave construction. Such substantially uniform float
lengths aid in imparting transverse symmetry to the resulting tape
which enhances its ability to maintain a flat configuration as the
carbonization reaction progresses. The intersection points are
preferably varied between successive weft interlacements.
Accordingly, as will be apparent to those skilled in weaving
technology, the counter (i.e. step or move) of the sateen weave
construction may commonly be from about one to 10, or more, and is
preferably one.
The tape of sateen weave construction utilized in the present
process can be formed by conventional weaving techniques as will be
apparent to those skilled in weaving technology. For instance, the
warp ends may be beamed, and the weft pick subsequently inserted at
appropriate intervals utilizing a narrow fabric loom. Care, of
course, must be taken to insure that the tension exerted upon the
weft pick is insufficient to impair the substantially linear
configuration of the warp ends.
In a preferred embodiment of the process the tape of sateen weave
construction (as previously described) is provided with a selvage
which is capable of aiding the structural integrity of the weave.
Such selvage may be positioned upon each edge of the main body of
the tape and is of a relatively narrow width. For instance, the
selvage may be formed by converting the sateen weave construction
created by the weft pick to a plain weave construction as the pair
of warp ends at each edge of the tape are traversed. Such a selvage
of relatively narrow width has been found helpful in retaining the
weft pick at substantially the same location as initially woven,
and does not deleteriously influence composite properties to any
significant degree.
The heating temperatures, heating atmospheres, and residence times
utilized in the present process to produce carbon fibers may be in
accordance with thermal conversion techniques heretofore known in
the art. The plurality of adjoining ends of an organic polymeric
fibrous material while in the form of a tape are converted to a
carbonaceous fibrous material by continuous passage in the
direction of their length through a series of heating zones while
substantially suspended therein to form a fibrous product which
contains at least 90 per cent carbon by weight. The organic
polymeric fibrous tape during at least a portion of its thermal
conversion to a carbonaceous fibrous material is provided in the
form of a highly unbalanced tape of a sateen weave configuration
(as heretofore described). In a preferred embodiment of the process
the organic polymeric fibrous tape is provided in the sateen weave
configuration throughout its thermal conversion to a carbonaceous
fibrous material. Alternatively, the sateen weave tape
configuration may be formed subsequent to an initial thermal
stabilization treatment. Additionally, the sateen weave tape
configuration may be optionally retained while the tape is passed
through any or all of the following (1) a graphitization zone, (2)
a surface treatment zone wherein the surface characteristics of the
fibrous product are modified so as to enchance its bonding
characteristics to a matrix material, and (3) a resin impregnation
zone.
The stabilization heating zone is commonly provided at a
temperature of about 200.degree. to 400.degree.C. depending upon
the composition of the tape. As will be apparent to those skilled
in the art, the atmosphere provided in the stabilization heating
zone may be varied. For instance, a cellulosic precursor is
commonly stabilized in (1) an oxygen-containing atmosphere or (2)
in an inert or non-oxidizing atmosphere, such as nitrogen, helium,
argon, etc. Additionally, precursors such as an acrylic polymer, a
polyamide, a polybenzimidazole, or polyvinyl alcohol are commonly
stabilized in an oxygen-containing atmosphere. Air may be
conveniently selected as the oxygen-containing atmosphere for use
in the process. When the stabilization treatment is conducted in an
oxygen-containing atmosphere, it is commonly termed a
"preoxidation" treatment.
The stabilization heating zone is substantially closed in order to
facilitate the confinement and withdrawal of off gases and/or the
maintenance of an appropriate atmosphere. When a non-oxidizing
atmosphere is desired within the heat treatment chamber, the
strands may pass through a seal as they continuously enter and
leave the heat treatment chamber in order to exclude oxygen.
The stabilization of fibers of acrylonitrile homopolymers and
copolymers in an oxygen-containing atmosphere involves (1) an
oxidative cross-linking reaction of adjoining molecules as well as
(2) a cyclization reaction of pendant nitrile groups to a condensed
dihydropyridine structure. While the reaction mechanism is complex
and not readily explainable, it is believed that these two
reactions occur concurrently, or are to some extent competing
reactions.
The cyclization reaction involving pendant nitrile groups which
occurs upon exposure of an acrylic fibrous material to heat is
generally highly exothermic and, if uncontrolled, results in the
destruction of the fibrous configuration of the starting material.
In some instances this exothermic reaction will occur with
explosive violence and result in the fibrous material being
consumed by flame. More commonly, however, the fibrous material
will simply rupture, disintegrate and/or coalesce when the critical
temperature is reached. As the quantity of comonomer present in an
acrylonitrile copolymer is increased, a fibrous material consisting
of the same tends to soften at a progressively lower temperature
and the possible destruction of the original fibrous configuration
through coalescence of adjoining fibers becomes a factor of
increasing importance. The "critical temperature" referred to
herein is defined as the temperature at which the fibrous
configuration of a given sample of acrylic fibrous starting
material will be destroyed in the absence of prior
stabilization.
In a preferred embodiment of the invention the acrylic starting
material exhibits a critical temperature of at least about
300.degree.C., e.g. about 300.degree. to 330.degree.C. In addition
to visual observation, the detection of the critical temperature of
a given acrylic fibrous material may be aided by the use of
thermoanalytical methods, such as differential scanning calorimeter
techniques, whereby the location and magnitude of the exethermic
reaction can be measured quantitatively.
The stabilized acrylic warp ends (1) retain essentially the same
fibrous configuration as the starting material, (2) are capable of
undergoing carbonization, (3) are black in appearance, (4) are
non-burning when subjected to an ordinary match flame, and (5)
commonly contain a bound oxygen content of at least about 7 percent
by weight as determined by the Unterzaucher analysis.
In a preferred embodiment of the process the sateen tape
(heretofore described) is stabilized in accordance with the
processing conditions of commonly assigned U.S. Ser. Nos. 749,957,
filed Aug. 8, 1968, and 865,332, filed Oct. 10, 1969 (now
abandoned) which are herein incorporated by reference.
The carbonization heating zone is commonly provided with an inert
or non-oxidizing atmosphere at a temperature of at least about
900.degree.C. (e.g. 900.degree. to 1,600.degree.C.). Suitable inert
atmospheres include nitrogen, argon, helium, etc. During the
carbonization reaction elements present in the continuous length of
fibrous material other than carbon, e.g. nitrogen, hydrogen and
oxygen are substantially expelled until the warp ends contain at
least 90 per cent carbon by weight, and preferably at least 95 per
cent carbon by weight.
An optional graphitization zone is commonly provided with an inert
or non-oxidizing atmosphere at a more highly elevated temperature
of about 2,000.degree. to 3,100.degree.C.
A longitudinal tension may optionally be applied to the tape while
passing through the carbonization and/or graphitization heating
zones in accordance with techniques known in the art.
In a preferred embodiment of the process the carbonization and
graphitization of a stabilized acrylic sateen tape may be conducted
by the continuous passage of the same through a single heating
apparatus, such as the susceptor of an induction furnace, provided
with a temperature gradient in accordance with the teachings of
commonly assigned U.S. Ser. No. 777,275, filed Nov. 20, 1968 (now
abandoned), which is herein incorporated by reference. A partially
preferred susceptor for use in the production of carbonaceous
fibrous materials while in tape form is disclosed in commonly
assigned U.S. Ser. No. 46,675, filed June 16, 1970 (now U.S. Pat.
No. 3,656,910), which is herein incorporated by reference.
The carbonaceous tape, whether formed of amorphous or graphitic
carbon, can next optionally be passed through a surface treatment
zone wherein its ability to bond to a matrix material is enhanced.
Any conventional surface treatment technique may be selected.
Additionally, the tape (preferably following surface treatment) can
optionally be passed through a coating zone wherein it is
impregnated with a resinous matrix-forming material, e.g. an epoxy
resin.
During the stabilization and carbonization steps of the present
process it is common for the width of the tape to diminish due to
controlled shrinkage as elements other than carbon are expelled. A
flat tape configuration is nevertheless retained.
The tape undergoing treatment in the present process is
continuously passed in the direction of its length through each of
the heating zones (e.g. a stabilization zone and a carbonization
zone). If desired, the forward movement of the tape may be
terminated between heating zones and the tape collected upon a
support where it is stored prior to additional processing. It is
recommended, however, that the heating zones be aligned in close
proximity and the tape continuously passed from one zone to another
without termination of the forward movement. Various rolls, or
other guides may be employed to direct the movement of the tape as
will be apparent to those skilled in fiber technology.
The following examples are provided as specific illustrations of
the invention. It should be understood, however, that the invention
is not limited to the specific details set forth in the
examples.
In the examples tapes of various sateen weave constructions in
accordance with the present invention were continuously passed in
the direction of their length through (1) a pretreatment zone, (2)
a stabilization zone, (3) a heating zone provided with a
temperature gradient wherein both carbonization and graphitization
were carried out, (4) and a surface treatment zone. Following resin
impregnation composite articles incorporating the resulting
graphite tape as fibrous reinforcement were formed.
Each tape was produced by initially beaming 200 warp ends of a dry
spun acrylonitrile homopolymer, and inserting a weft pick by use of
a Fletcher narrow fabric loom. Each warp end consisted of about 385
continuous filaments having a total denier of about 775, and was
provided with a twist of about 0.5 turn per inch. The 200 warp ends
were aligned in adjoining parallel contact to form a flat tape
having a width of 4 inches. Prior to incorporation in the tape the
warp ends had been hot drawn to a single filament tenacity of about
4 grams per denier.
The pretreatment of the acrylonitrile homopolymer tape was
conducted in accordance with the teachings of commonly assigned
U.S. Ser. No. 17,962, filed Mar. 9, 1970 (now abandoned). The tape
was continuously passed through an oven containing circulating air
provided at about 220.degree.C. while under a longitudinal tension
sufficient to permit a 16 per cent reduction in length brought
about by shrinkage for a residence time of about 300 seconds.
The stabilization (i.e. preoxidation) was conducted in accordance
with the teachings of commonly assigned U.S. Ser. No. 865,332,
filed Oct. 10, 1969 (now abandoned). The tape was continuously
passed through an oven containing circulating air maintained at
about 265.degree.C. while under a longitudinal tension sufficient
to maintain a constant length for a residence time of about 175
minutes. The preoxidized tape was black in appearance, retained its
initial fibrous configuration essentially intact, was non-burning
when subjected to an ordinary match flame, and contained a bound
oxygen content of 10 percent by weight as determined by the
Unterzaucher analysis.
The preoxidized tape was continuously passed through a heating zone
of an induction furnace provided with a nitrogen atmosphere and a
temperature gradient in accordance with the teachings of commonly
assigned U.S. Ser. No. 777,275, filed Nov. 20, 1968 (now
abandoned). The hollow graphite susceptor of the induction furnace
was formed in accordance with the teachings of commonly assigned
U.S. Ser. No. 46,675, filed June 16, 1970 (now U.S. Pat. No.
3,656,910). The temperature gradient within the heating zone raised
the tape from room temperature (i.e. about 25.degree.C.) to a
temperature of 800.degree.C. in approximately 50 seconds after
entering the susceptor, from 800.degree. to 1,600.degree.C. in
approximately 25 seconds to produce a carbonized tape, and from
1,600.degree. to 2,750.degree.C. in approximately 50 seconds where
it was maintained .+-.50.degree.C. for about 40 seconds to produce
a graphitized tape. A longitudinal tension of 70 pounds (i.e. about
150 grams per warp end) was exerted upon the tape as it passed
through the heating zone of the induction furnace. The warp ends
and weft picks substantially retained their original fibrous
configuration following carbonization and graphitization and
exhibited a specific gravity of about 2.0. The tape exhibited a
predominant x-ray diffraction pattern characteristic of graphitic
carbon when subjected to x-ray analysis.
The graphite tape was next surface treated to modify its surface
characteristics by continuous passage through a heating zone
provided with an atmosphere of molecular oxygen in an inert carrier
gas. The surface treated tape was collected by winding upon a
package.
Tensile and interlaminar shear strength test bars were formed
employing the surface treated tape as a fibrous reinforcing medium
in a resinous matrix. The tensile test bars had dimensions of 8.5
inches x 0.5 inch .times. 0.03 inch, and the interlaminar shear
strength test bars had dimensions of 8 inches .times. 0.25 inch
.times. 0.125 inch. The composite articles were formed by immersing
strips of the tape in a liquid epoxy resin-hardener mixture
provided at about 70.degree.C., removing excess resin, placing a
plurality of the strips of the impregnated tape in a fixed stop
matched die mold, and curing for 40 minutes at 93.degree.C. with
minimal pressure, 80 minutes at 93.degree.C. at a pressure of 100
psi, and 150 minutes at 200.degree.C. at a pressure of 100 psi,
cooling the resulting bars to room temperature, trimming the same,
and cementing tabs to the ends of the bars for use in an Instron
tester. Twelve plies of the tape were utilized in the tensile test
bars, and 24 plies of the tape were utilized in the interlaminar
shear strength test bars. The resinous matrix material used in the
formation of the composites was provided as a solventless system
which contained 100 parts by weight epoxy resin and 88 parts by
weight of anhydride curing agent.
The tensile strength and the horizontal interlaminar shear strength
of the resulting composites were determined. The tensile strength
was determined employing a modified ASTM D638 procedure utilizing
fiberglass tabs to avoid clamp damage. Precise alignment of the
bars was obtained prior to setting the clamps. The horizontal
interlaminar shear strength of the composite was determined by
short beam testing of the fiber reinforced composite according to
the procedure of ASTM D2344-65T as modified for straight bar
testing with a 4:1 span to depth ratio.
EXAMPLE I
The acrylonitrile homopolymer tape having a double faced 4 float
filling sateen weave construction as illustrated in FIG. 1 was
employed. Representative warp ends are identified at A and
representative weft picks at B. The weft pick was formed from
approximately 200 continuous fils of acrylonitrile homopolymer
having a total denier of about 400 and a twist of 4.5 turns per
inch. The weft pick was provided at a frequency of 4 picks per inch
of tape.
The counter for the weave was one. The weave pattern for the tape
is illustrated in FIG. 2. The appearance of a number within a box
of the weave pattern indicates that the corresponding warp end is
present upon the surface of the woven tape. The absence of a number
within a box of the weave pattern indicates that a weft pick is
present upon the surface of the woven tape. A plain weave
construction was employed when the weft pick traversed the pair of
warp ends adjacent each edge of the tape.
Following stabilization (i.e. preoxidation) the tape width had
decreased to 2.8 inches. Following carbonization and graphitization
the width of the tape had decreased to 2.4 inches. The average
single filament tensile properties (20 breaks tested) of the warp
ends following graphitization and prior to surface treatment were
10 grams per denier tenacity, and 3,250 grams per denier Young's
modulus. The resulting composites exhibited an average tensile
strength of 70,000 psi, and an average horizontal interlaminar
shear strength of 7,300 psi.
EXAMPLE II
The acrylonitrile homopolymer tape having a double faced 8 float
filling sateen weave construction as illustrated in FIG. 3 was
employed. Representative warp ends are identified at A and
representative weft picks at B. The weft pick was formed from
approximately 100 continuous fils of acrylonitrile homopolymer
having a total denier of about 200 and a twist of 0.5 turn per
inch. The weft pick was provided at a frequence of 2 picks per inch
of tape.
The counter for the weave was one. The weave pattern for the tape
is illustrated in FIG. 4. The appearance of a number within a box
of the weave pattern indicates that the corresponding warp end is a
present upon the surface of the woven tape. The absence of a number
within the box of the weave pattern indicates that a weft pick is
present upon the surface of the woven tape. A plain weave
construction was employed when the weft pick traversed the pair of
warp ends adjacent each edge of the tape.
Following stabilization (i.e. preoxidation) the tape width had
decreased to approximately 2.9 inches. Following carbonization and
graphitization the width of the tape had decreased to approximately
2.5 inches. The average single filament tensile properties (20
breaks tested) of the warp ends following graphitization and prior
to surface treatment were 10.2 grams per denier tenacity, and 3,200
grams per denier Young's modulus. The resulting composites
exhibited an average tensile strength of 95,000 psi, and an average
horizontal interlaminar shear strength of 8,700 psi.
EXAMPLE III
The acrylonitrile homopolymer tape having a double faced 8 float
filling sateen weave construction similar to that illustrated in
FIG. 3 was employed. The weft pick was formed from approximately
200 continuous fils of acrylonitrile homopolymer having a total
denier of about 400 and a twist of 4.5 turns per inch. The weft
pick was provided at a frequency of 6 picks per inch of tape.
The counter for the weave was one. The weave pattern for the tape
is illustrated in FIG. 4. The appearance of a number within a box
of the weave pattern indicates that the corresponding warp end is
present upon the surface of the woven tape. The absence of a number
within a box of the weave pattern indicates that a weft pick is
present upon the surface of the woven tape. A plain weave
construction was employed when the weft pick traversed the pair of
warp ends adjacent each edge of the tape.
Following stabilization (i.e. preoxidation) the tape width had
decreased to 2.9 inches. Following carbonization and graphitization
the width of the tape had decreased to 2.5 inches. The average
single filament tensile properties (20 breaks tested) of the warp
ends following graphitization and prior to surface treatment were
10 grams per denier tenacity, and 3,000 grams per denier Young's
modulus. The resulting composite exibited an average tensile
strength of 72,000 psi, and an average horizontal interlaminar
shear strength of 7,700 psi. A comparison of the composite
properties indicates that the tape of Example II is preferred to
that of Example III for utilization in the process of the
invention.
EXAMPLE IV
The acrylonitrile homopolymer tape having a double faced 16 float
filling sateeen weave construction as illustrated in FIG. 5 was
employed. Representative warp ends are identified at A and
representative weft picks at B. The weft pick was formed from
approximately 100 continuous fils of acrylonitrile homopolymer
having a total denier of about 200 and a twist of 0.5 turn per
inch. The weft pick was provided at a frequency of 4 picks per inch
of tape.
The counter for the weave was one. The weave pattern for the tape
is illustrated in FIG. 6. The appearance of a number within a box
of the weave pattern indicates that the corresponding warp end is
present upon the surface of the woven tape. The absence of a number
within a box of the weave pattern indicates that a weft pick is
present upon the surface of the woven tape. A plain weave
construction was employed when the weft pick traversed the pair of
warp ends adjacent each edge of the tape.
Following stabilization (i.e. preoxidation) the tape width had
decreased to approximately 2.9 inches. Following carbonization and
graphitization the width of the tape had decreased to approximately
2.5 inches. The average single filament tensile properties (20
breaks tested) of the warp ends following graphitization and prior
to surface treatment were 10 grams per denier tenacity, and 3,309
grams per denier Young's modulus. The resulting composites
exhibited an average tensile strength of 105,000 psi, and an
average horizontal interlaminar shear strength of 8,400 psi.
For comparative purposes an acrylonitrile homopolymer tape
employing identical warp ends was processed as heretofore described
in the absence of any form of weaving. More specifically, the warp
ends were maintained in parallel in the form of a flat tape which
lacked a weft pick interlaced therewith. The average single
filament tensile properties (20 breaks tested) of the warp ends
following graphitization and prior to surface treatment were 11.5
grams per denier tenacity, and 3,200 grams per denier Young's
modulus. The resulting composites exhibited an average tensile
strength of 90,000 psi, and an average horizontal interlaminar
shear strength of 8,800 psi. A comparison of the composite
properties indicates that the presence of the weft pick within
composites reinforced by carbonized sateen tapes formed in
accordance with the present process results in no substantial
diminution of composite properties. Additionally, the present
process offers significant fiber handling advantages.
For comparative purposes a woven acrylonitrile homopolymer tape was
formed in a plain weave construction and processed as heretofore
described. The warp ends were in adjoining contact throughout the
process. The weave construction is illustrated in FIG. 7.
Representative warp ends are identified at A and representative
weft picks at B. The weft pick was formed from approximately 200
continuous fils of acrylonitrile homopolymer having a total denier
of about 400 and a twist of 4.5 turns per inch. The weft pick was
provided at a frequency of 2 picks per inch of tape. The counter
for the weave was one. The weave pattern for the tape is
illustrated in FIG. 8. The appearance of a number within a box of
the weave pattern indicates that the corresponding warp end is
present upon the surface of the woven tape. The absence of a number
within a box of the weave pattern indicates that a weft pick is
present upon the surface of the woven tape. Following stabilization
(i.e. preoxidation) the tape width had decreased to 3.15 inches.
Following carbonization and graphitization the width of the tape
had decreased to 2.4 inches. The average single filament tensile
properties (20 breaks tested) of the warp ends following
graphitization and prior to surface treatment were 8.6 grams per
denier tenacity, and 3,300 grams per denier Young's modulus. The
resulting composite exhibited an average tensile strength of 46,000
psi, and an average horizontal interlaminar shear strength of 7,200
psi. A comparison of composite properties indicates a substantial
diminution of composite properties results when the reinforcing
tape is formed in the plain weave construction.
Although the invention has been described with preferred
embodiments, it is to be understood that variations and
modifications may be resorted to as will be apparent to those
skilled in the art. Such variations and modifications are to be
considered within the purview and scope of the claims appended
hereto.
* * * * *