U.S. patent number 3,919,387 [Application Number 05/318,483] was granted by the patent office on 1975-11-11 for process for producing high mesophase content pitch fibers.
This patent grant is currently assigned to Union Carbide Corporation. Invention is credited to Leonard S. Singer.
United States Patent |
3,919,387 |
Singer |
November 11, 1975 |
Process for producing high mesophase content pitch fibers
Abstract
An improved process for producing carbon fibers from pitch which
has been transformed, in part, to a liquid crystal or so-called
"mesophase" state. According to the process, the mesophase content
of fibers spun from such pitch is increased before the fibers are
thermoset and carbonized by solvent extraction of the non-mesophase
content of the fibers.
Inventors: |
Singer; Leonard S. (Berea,
OH) |
Assignee: |
Union Carbide Corporation (New
York, NY)
|
Family
ID: |
23238364 |
Appl.
No.: |
05/318,483 |
Filed: |
December 26, 1972 |
Current U.S.
Class: |
264/344;
264/29.2; 423/447.4; 264/DIG.19 |
Current CPC
Class: |
D01F
9/145 (20130101); Y10S 264/19 (20130101) |
Current International
Class: |
D01F
9/145 (20060101); B29c 025/00 () |
Field of
Search: |
;423/447
;264/29,DIG.19,87,233,164,344 ;106/273R ;208/8,45 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Woo; Jay H.
Attorney, Agent or Firm: Piscitello; J. S.
Claims
What is claimed is:
1. A process for producing a pitch fiber having a high mesophase
content which comprises spinning a carbonaceous fiber from a
nonthixotropic carbonaceous pitch containing from 40 percent by
weight to 70 percent by weight mesophase, said mesophase being
present in the form of large, homogeneous, coalesced regions, and
extracting the non-mesophase content of the spun fiber with a
solvent capable of dissolving the non-mesophase portion of the
fiber but in which the mesophase portion is insoluble, so as to
dissolve at least 10 percent by weight of the nonmesophase content
of the fiber and produce a fiber of higher mesophase content.
2. A process as in claim 1 wherein the solvent is pyridine.
3. A process as in claim 1 wherein the solvent is quinoline.
4. A process as in claim 1 wherein extraction is effected at the
refluxing temperature of the solvent.
5. A process as in claim 4 wherein the solvent is pyridine.
6. A process as in claim 4 wherein the solvent is quinoline.
7. A process as in claim 4 wherein extraction is effected in a
Soxhlet extractor.
8. A process as in claim 7 wherein the solvent is pyridine.
9. A process as in claim 7 wherein the solvent is quinoline.
10. A process as in claim 1 wherein extraction is effected by
immersing the fibers in the solvent.
11. A process as in claim 10 wherein the solvent is pyridine.
12. A process as in claim 10 wherein the solvent is quinoline.
13. A process as in claim 10 wherein extraction is effected at the
refluxing temperature of the solvent.
14. A process as in claim 13 wherein the solvent is pyridine.
15. A process as in claim 13 wherein the solvent is quinoline.
16. A process as in claim 1 wherein the pitch contains from 50 per
cent by weight to 65 percent by weight mesophase.
17. A process as in claim 16 wherein the solvent is pyridine.
18. A process as in claim 16 wherein the solvent is quinoline.
19. A process as in claim 16 wherein extraction is effected at the
refluxing temperature of the solvent.
20. A process as in claim 19 wherein the solvent is pyridine.
21. A process as in claim 19 wherein the solvent is quinoline.
22. A process as in claim 19 wherein extraction is effected in a
Soxhlet extractor.
23. A process as in claim 22 wherein the solvent is pyridine.
24. A process as in claim 22 wherein the solvent is quinoline.
25. A process as in claim 16 wherein extraction is effected by
immersing the fibers in the solvent.
26. A process as in claim 25 wherein the solvent is pyridine.
27. A process as in claim 25 wherein the solvent is quinoline.
28. A process as in claim 25 wherein extraction is effected at the
refluxing temperature of the solvent.
29. A process as in claim 28 wherein the solvent is pyridine.
30. A process as in claim 28 wherein the solvent is quinoline.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an improved process for producing carbon
fibers from pitch which has been transformed, in part, to a liquid
crystal or so-called "mesophase" state. More particularly, this
invention relates to an improved process for producing carbon
fibers from pitch of this type wherein the mesophase content of
fibers spun from such pitch is increased before the fibers are
thermoset and carbonized by solvent extraction of the non-mesophase
content of the fibers.
2. Description of the Prior Art
As a result of the rapidly expanding growth of the aircraft, space
and missile industries in recent years, a need was created for
materials exhibiting a unique and extraordinary combination of
physical properties. Thus, materials characterized by high strength
and stiffness, and at the same time of light weight, were required
for use in such applications as the fabrication of aircraft
structures, re-entry vehicles, and space vehicles, as well as in
the preparation of marine deep-submergence pressure vessels and
like structures. Existing technology was incapable of supplying
such materials and the search to satisfy this need centered about
the fabrication of composite articles.
One of the most promising materials suggested for use in composite
form was high strength, high modulus carbon textiles, which were
introduced into the market place at the very time this rapid growth
in the aircraft, space and missile industries was occurring. Such
textiles have been incorporated in both plastic and metal matrices
to produce composites having extraordinary high-strength- and
high-modulus-to-weight ratios and other exceptional properties.
However, the high cost of producing the high strength, high modulus
carbon textiles employed in such composites has been a major
deterrent to their widespread use, in spite of the remarkable
properties exhibited by such composites.
One recently proposed method of providing high modulus, high
strength carbon fibers at low cost is described in copending
application Ser. No. 239,490, entitled "High Modulus, High Strength
Carbon Fibers Produced From Mesophase Pitch". Such method comprises
first spinning a carbonaceous fiber from a carbonaceous pitch which
has been transformed, in part, to a liquid crystal or socalled
"mesophase" state, then thermosetting the fiber soproduced by
heating the fiber in an oxygen-containing atmosphere for a time
sufficient to render it totally infusible, and finally carbonizing
the thermoset fiber by heating in an inert atmosphere to a
temperature sufficiently elevated to remove hydrogen and other
volatiles and produce a substantially all-carbon fiber. The carbon
fibers produced in this manner have a highly oriented structure
characterized by the presence of carbon crystallites preferentially
aligned parallel to the fiber axis, and are graphitizable materials
which when heated to graphitizing temperatues develop the
three-dimensional order characteristic of polycrystalline graphite
and graphitic-like properties associated therewith, such as high
density and low electrical resistivity.
Since carbonaceous fibers drawn from pitches having a high
mesophase content can be thermoset in less time than carbonaceous
fibers drawn from pitches having a lower mesophase content, it is
desirable to employ pitches of high mesophase content in such
process. However, because the spinning of mesophase-containing
pitches becomes increasingly difficult as the mesophase content of
the pitch increases, and must be done at higher and higher
temperatures, the fibers are usually prepared from pitches having a
mesophase content of only from about 40 percent by weight to about
70 percent by weight.
SUMMARY OF THE INVENTION
In accordance with the present invention, it has now been
discovered that pitch fibers having a high mesophase content can be
prepared from pitch fibers of lower mesophase content which have
been spun from pitches of the type described in aforementioned
copending application Ser. No. 239,490, i.e., carbonaceous pitches
which have been transformed, in part, to a liquid crystal or
so-called "mesophase" state, by treating the fibers with a solvent
capable of dissolving the non-mesophase portion of the fiber but in
which the mesophase portion is insoluble; and that the so-treated
fibers can be converted by heat treatment into carbon fibers having
a high Young's modulus of elasticity and high tensile strength. The
invention takes advantage of the differences in solubility between
the mesophase portion of the fiber and the non-mesophase portion to
effect removal of the non-mesophase portion and produce a fibrous
residue of higher mesophase content. Except for certain
non-mesophase insolubles present in the original pitch or which, in
some instances, are produced during development of the mesophase,
the non-mesophase portion of the spun fibers is readily soluble in
organic solvents, such as quinoline and pyridine, while the
mesophase portion is insoluble. Thus, by employing such solvents to
extract the non-mesophase portion of the spun fibers, fibers having
a high mesophase content can be easily produced. This non-mesophase
material can be substantially completely removed by the extraction
or only partially, depending upon the relative amounts of mesophase
and nonmesophase material present in the fibers, the diameter of
the fibers, the particular solvent and the amount of solvent
employed, the temperature of the solvent, and the extraction
time.
The fibers produced in this manner have a high degree of preferred
orientation of their molecules parallel to the fiber axis and can
be converted by heat treatment into carbon fibers having a high
Young's modulus of elasticity and high tensile strength. The carbon
fibers so-produced have a highly oriented structure characterized
by the presence of carbon crystallities preferentially aligned
parallel to the fiber axis, and when heated to graphitizing
temperatures develop the three-dimensional order characteristic of
polycrystalline graphite and graphitic-like properties associated
therewith, such as high density and low electrical resistance. At
all stages of their development from the as-drawn condition to the
graphitized state, the fibers are characterized by the presence of
large oriented graphitizable domains preferentially aligned
parallel to the fiber axis, with the fibers after extraction,
however, containing a lesser amount of non-mesophase material than
before extraction.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
When natural or synthetic pitches having an aromatic base are
heated at a temperature of about 350.degree.C. -450.degree.C.,
either at constant temperature or with gradually increasing
temperature, small insoluble liquid spheres begin to appear in the
pitch and gradually increase in size as heating is continued. When
examined by electron diffraction and polarized light techniques,
these spheres are shown to consist of layers of oriented molecules
aligned in the same direction. As these spheres continue to grow in
size as heating is continued, they come in contact with one another
and gradually coalesce with each other to produce larger masses of
continuous aligned layers. Eventually, substantially the entire
pitch coalesces and takes on the superficial appearance of a mosaic
structure where, however, the transition from one oriented region
to another occurs smoothly and continuously through gradual curving
lamellar regions rather than through sharp boundaries between
uniform areas of orineted lamellae.
The highly oriented, optically anisotropic, insoluble material
produced by treating pitches in this manner has been given the term
"mesophase", and pitches containing such material are known as
"mesophase pitches". Such pitches, when heated above their
softening points, are mixtures of two immiscible liquids, one the
optically anisotropic, oriented mesophase portion in either
spherulite or coalesced form, and the other the isotropic
nonmesophase portion. The term "mesophase" is derived from the
Greek "mesos" or "intermediate" and indicates the
pseudo-crystalline nature of this highly-oriented, optically
anisotropic material.
Carbonaceous pitches having a mesophase content of from about 40
percent by weight to about 70 percent by weight can easily be spun
into fibers which can subsequently be converted by heat treatment
into carbon fibers having a high Young's modulus of elasticity and
high tensile strength. Although fibers can also be spun from
pitches having a mesophase content in excess of about 70 percent by
weight, e.g., up to about 90 per cent by weight, these pitches are
exceedingly difficult to work with because of their high softening
temperatures, and fibers can only be spun from such pitches at
elevated temperatures where the pitches readily undergo
polymerization and/or coking.
In order to obtain highly oriented carbonaceous fibers capable of
being heat treated to produce fibers having the three-dimensional
order characteristic of polycrystalline graphite from carbonaceous
pitches having a mesophase content of from about 40 per cent by
weight to about 90 percent by weight, however, it is not only
necessary that such amount of mesophase be present, but also that
it be present in the form of large, homogeneous, coalesced regions.
Pitched which polymerize very rapidly develop small or stringy
mesophase regions rather than large coalesced regions and are
unsuitable. Likewise, pitches which do not form homogeneous
coalesced regions of mesophase are unsuitable. The latter
phenomenon is caused by the presence of non-mesophase insolubles
(which are either present in the original pitch or which develop on
heating) which are enveloped by the coalescing mesophase and serve
to interrupt the homogeneity and uniformity of the coalesced
domains.
Another requirement is that the pitch be nonthixotropic under the
conditions employed in the spinning of the pitch into fibers, i.e.,
it must exhibit a Newtonian or plastic flow behavior so that the
viscosity coefficient is independent of the shear rate of the pitch
during the spinning process. When such pitches are heated to a
temperature where they exhibit a viscosity of from about 10 poises
to about 200 poises, uniform fibers may be readily spun therefrom.
Thixotropic pitches, on the other hand, which do not exhibit
Newtonian or plastic flow behavior when attempts are made to spin
fibers therefrom, but rather undergo changes in apparent viscosity,
do not permit uniform fibers to be spun therefrom which can be
converted by further heat treatment into fibers capable of
developing the threedimensional order characteristic of
polycrystalline graphite.
Carbonaceous pitches having a mesophase content of from about 40
per cent by weight to about 90 percent by weight can be produced in
accordance with known techniques, as disclosed in aforementioned
copending application Ser. No. 239,490, by heating a carbonaceous
pitch in an inert atmosphere at a temperature above about
350.degree.C. for a time sufficient to produce the desired quantity
of mesophase. By an inert atmosphere is meant an atmosphere which
does not react with the pitch under the heating conditions
employed, such as nitrogen, argon, xenon, helium and the like. The
heating period required to produce the desired mesophase content
varies with the particular pitch and temmperature employed, with
longer heating periods required at lower temperature than at higher
temperatures. At 350.degree.C., the minimum temperature generally
required to produce mesophase, at least one week of heating is
usually necessary to produce a mesophase content of about 40
percent. At temperatures of from about 400.degree.C. to
450.degree.C., conversion to mesophase proceeds more rapidly, and a
50 percent mesophase content can usually be produced at such
temperatures within about 1-40 hours. Such temperatures are
preferred for this reason. Temperatures above about 500.degree.C.
are undesirable, and heating at this temperature should not be
employed for more than about 5 minutes to avoid conversion of the
pitch to coke.
The degree to which the pitch has been converted to mesophase can
readily be determined by polarized light microscopy and solubility
examinations. Except for certain non-mesophase insolubles present
in the original pitch or which, in some instances, develop on
heating, the non-mesophase portion of the pitch is readily soluble
in organic solvents such as quinoline and pyridine, while the
mesophase portion is insoluble. (1) In the case of pitches which do
not develop non-mesophase insolubles when heated, the insoluble
content of the heat treated pitch over and above the insoluble
content of the pitch before it has been heat treated is due to
conversion of the pitch to mesophase. (2) In the case of pitches
which do develop non-mesophase insolubles when heated, the
insoluble content of the heat treated pitch over and above the
insoluble content of the pitch before it has been heat treated is
not solely due to the conversion of the pitch to mesophase, but
also represents non-mesophase insolubles which are produced along
with the mesophase during the heat treatment. Pitches which contain
such non-mesophase insolubles (either present in the original pitch
or developed by heating) in amounts sufficient to prevent the
development of homogeneous coalesced mesophase regions are
unsuitable for use in the present invention, as noted above.
Generally, pitches which contain in excess of about 2 percent by
weight of such materials are unsuitable. The presence or absence of
such homogeneous coalesced mesophase regions, as well as the
presence or absence of non-mesophase insolubles, can be visually
observed by polarized light microscopy examination of the pitch
(see, e.g., Brooks, J. D., and Taylor, G. H., "The Formation of
Some Graphitizing Carbons," Chemistry and Physics of Carbon, Vol.
4, Marcel Dekker, Inc., New York, 1968, pp. 243-268; and Dubois,
J., Agache, C., and White, J. L., "The Carbonaceous Mesophase
Formed in the Pyrolysis of Graphitizable Organic Materials,"
Metallography 3, 337-369, 1970). The amounts of each of these
materials may also be visually estimated in this manner.
Aromatic base carbonaceous pitches having a carbon content of from
about 92 percent by weight to about 96 percent by weight and a
hydrogen content of from about 4 percent by weight to about 8
percent by weight are generally suitable for producing mesophase
pitches which can be employed to produce fibers capable of being
heat treated to produce fibers having the three-dimensional order
characteristic of polycrystalline graphite. Elements other than
carbon and hydrogen, such as oxygen, sulfur and nitrogen, are
undesirable and should not be present in excess of about 4 percent
by weight. The presence of more than such amount of extraneous
elements may disrupt the formation of carbon crystallites during
subsequent heat treatment and prevent the development of a
graphitic-like structure within the fibers produced from these
materials. In addition, the presence of extraneous elements reduces
the carbon content of the pitch and hence the ultimate yield of
carbon fiber. When such extraneous elements are present in amounts
of from about 0.5 percent by weight to about 4 percent by weight,
the pitches generally have a carbon content of from about 92-95
percent by weight, the balance being hydrogen.
Petroleum pitch, coal tar pitch and acenaphthylene pitch, which are
well-graphitizing pitches, are preferred starting materials for
producing the mesophase pitches which are employed to produce the
fibers of the instant invention. Petroleum pitch, of course, is the
residum carbonaceous material obtained from the distillation of
crude oils or the catalytic cracking of petroleum distillates. Coal
tar pitch is similarly obtained by the distillation of coal. Both
of these materials are commercially available natural pitches in
which mesophase can easily be produced, and are preferred for this
reason. Acenaphthylene pitch, on the other hand, is a synthetic
pitch which is preferred because of its ability to produce
excellent fibers. Acenaphthylene pitch can be produced by the
pyrolysis of polymers of acenaphthylene as described by Edstrom, et
al. in U.S. Pat. No. 3,574,653.
Some pitches, such as fluoroanthene pitch, polymerize very rapidly
when heated and fail to develop large coalesced regions of
mesophase, and are, therefore, not suitable precursor materials.
Likewise, pitches having a high non-mesophase insoluble content in
organic solvents such as quinoline or pyridine, or those which
develop a high non-mesophase insoluble content when heated, should
not be employed as starting materials, as explained above, because
these pitches are incapable of developing the homogeneous regions
of coalesced mesophase which are necessary to produce highly
oriented carbonaceous fibers capable of developing the
three-dimensional order characteristic of polycrystalline graphite.
For this reason, pitches having a quinoline-insoluble or
pyridine-insoluble content of more than about 2 percent by weight
(determined as described above) should not be employed, or should
be filtered to remove this material before being heated to produce
mesophase. Preferably, such pitches are filtered when they contain
more than about 1 peprcent by weight of such insoluble material.
Most petroleum pitches and synthetic pitches have a low insoluble
content and can be used directly without such filtration. Most coal
tar pitches, on the other hand, have a high insoluble content and
require filtration before they can be employed.
As the pitch is heated at a temperature between 350.degree.C. and
500.degree.C. to produce mesophase, the pitch will, of course,
pyrolyze to a certain extent and the composition of the pitch will
be altered, depending upon the temperature, the heating time, and
the composition and structure of the starting material. Generally,
however, after heating a carbonaceous pitch for a time sufficient
to produce a mesophase content of from about 40 percent by weight
to about 90 percent by weight, the resulting pitch will contain a
carbon content of from about 94-96 percent by weight and a hydrogen
content of from about 4-6 percent by weight. When such pitches
contain elements other than carbon and hydrogen in amounts of from
about 0.5 percent by weight to about 4 percent by weight, the
mesophase pitch will generally have a carbon content of from aobut
92-95 percent by weight, the balance being hydrogen.
After the desired mesophase pitch has been prepared, it is spun
into fibers by conventional techniques, e.g., by melt spinning,
centrifugal spinning, blow spinning, or in any other known manner.
As noted above, in order to obtain highly oriented carbonaceous
fibers capable of developing the three-dimensional order
characteristic of polycrystalline graphite the pitch must contain
large homogeneous regions of coalesced mesophase and be
nonthixotropic under the conditions employed in the spinning.
The temperature at which the pitch is spun depends, of course, upon
the temperature at which the pitch exhibits a suitable viscosity.
Since the softening temperature of the pitch, and its viscosity at
a given temperature, increases as the mesophase content of the
pitch increases, the mesophase content should not be permitted to
rise to a point which raises the softening point of the pitch to
excessive levels. For this reason, pitches having a mesophase
content of more than about 70 percent are usually not employed.
Pitches containing a mesophase content of about 40 percent by
weight usually have a viscosity of about 200 poises at about
250.degree.C. and about 10 poises at about 300.degree.C., while
pitches containing a mesophase content of about 70 percent by
weight exhibit similar viscosities at about 390.degree.C. and
440.degree.C., respectively. Within this viscosity range, fibers
may be conveniently spun from such pitches at a rate of from about
20 feet per minute to about 100 feet per minute and even up to
about 3000 feet per minute. Preferably, the pitch employed has a
mesophase content of from about 50 percent by weight to aobut 65
percent by weight and exhibits a viscosity of from about 30 poises
to about 60 poises at temperatures of from about 340.degree.C. to
about 380.degree.C. At such viscosity and temperature, uniform
fibers having diameters of from about 10 microns to about 20
microns can be easily spun. As previously mentioned, however, in
order to obtain the desired fibers, it is important that the pitch
be nonthixotropic and exhibit Newtonian or plastic flow behavior so
that the viscosity coefficient is independent of the shear rate of
the pitch during the spinning of the fibers.
The carbonaceous fibers produced in this manner are highly oriented
graphitizable materials having a high degree of preferred
orientation of their molecules parallel to the fiber axis. By
"graphitizable" is meant that these fibers are capable of being
converted thermally (usually by heating to a temperature in excess
of about 2500.degree.C., e.g., from about 2500.degree.C. to about
3000.degree.C.) to a structure having the three-dimensoional order
characteristic of polycrystalline graphite.
The fibers produced in this manner, of course, have the same
chemical composition as the pitch from which they were drawn, and
like such pitch contain from about 40 percent by weight to about 90
percent by weight mesophase. When examined under magnification by
polarized light and scanning electron microscopy techniques, large
fibrillarshaped domains of mesophase interspersed with large
elongated non-mesophase regions can be seen distributed throughout
the fiber, giving the fibers the appearance of a "mini-composite.".
These fibrillar mesophase domains are highly oriented and
preferentially aligned parallel to the fiber axis.
Characteristically, these domains have diametes in excess of 5,000
A, generally from about 10,000 A to about 40,000 A, and because of
their large size are easily observed when examined by conventional
polarized light microscopy techniques at a magnification of 1000.
(The maximum resolving power of a standard polarized light
microscope having a mangification factor of 1000 is only a few
tenths of a micron [1 micron = 10,000 A] and anisotropic domains
having dimensions of 1000 A or less cannot be detected by this
technique.)
After the fibers have been spun, as hereinbefore described, they
are treated with a solvent capable of dissolving the non-mesophase
portion of the fiber but in which the mesophase portion is
insoluble. As previously stated, the invention takes advantage of
the differences in solubility between the mesophase portion of the
fiber and the non-mesophase portion to effect removal of the
non-mesophase portion and produce a fibrous residue of higher
mesophase content. As has been noted, except for certain
nonmesophase insolubles present in the original pitch or which, in
some instances, are produced during development of the mesophase,
the non-mesophase portion of the spun fibers is readily soluble in
organic solvents, such as quinoline and pyridine, while the
mesophase portion is insoluble. Thus, by employing such solvents to
extract the non-mesophase portion of the spun fibers, fibers having
a high mesophase content can be easily produced. This non-mesophase
material can be substantially completely removed by the extraction
or only partially, depending upon the relative amounts of mesophase
and non-mesophase present in the fibers, the diameter of the
fibers, the particular solvent and the amount of solvent employed,
the temperature of the solvent, and the extraction time. The extent
to which non-mesophase has been removed can readily be determined
by the loss in weight which the fibers undergo during
extraction.
Removal of the non-mesophase portion of the fibers can be effected,
for example, by Soxhlet extraction, or simply by immersing the
fibers, in a solvent capable of dissolving the non-mesophase
portion of the fiber but in which the mesophase portion is
insoluble. For convenience, when continuous filaments are being
extracted, the fibers may be wrapped around a spool or similar
object and immersed in the solvent. The fibers should be allowed to
soak in the solvent for a time sufficient to remove as much of the
non-mesophase material from the fibers as desired. The time
required to effect such removal will, of course, vary with such
factors as the relative amounts of mesophase and non-mesophase
material present in the fibers, the diameter of the fibers, the
nature and amount of the solvent, and the temperature of the
solvent. Relatively thick fibers and/or fibers having a relatively
high nonmesophase content require longer extraction times as well
as the use of larger amounts of solvent and/or higher temperatures
to effect this removal than do thinner fibers or fibers having a
lower non-mesophase content. Removal of at least 10 percent by
weight of the non-mesophase content of the fibers can usually be
effected with the use of a an appropriate amount of an appropriate
solvent and temperature within from about 15 minutes to about 1
hour extraction time. Removal of from about 40 percent by weight to
about 60 percent by weight of the non-mesophase content may require
more protracted extraction times, e.g., from about 1 to about 4
hours, while removal of in excess of 70 percent by weight of the
non-mesophase content may require 10 or more hours of
extraction.
The volume of solvent and the temperature employed should be chosen
so as to effect the desired degree of extraction. Increased
quantities of solvent and higher temperatures permit more complete
extraction in shorter periods of time. By employing sufficient
amounts of an appropriate solvent and sufficiently high
temperatures for an appropriate time it is possible to
substantially completely remove the entire non-mesophase content of
the fibers. Generally, the amount of solvent and temperature
employed are such as will dissolve at least 10 percent by weight of
the non-mesophase content of the fibers to in excess of 70 percent
by weight of said non-mesophase content within from about 15
minutes to about 10 hours. The temperature employed can vary from a
temperature just above the freezing point of the solvent to just
below the softening point of the fibers, but is preferably
maintained at from ambient room temperature up to the refluxing
temperature of the solvent. From 200 milliliters of 2000
milliliters of solvent per gram of fibers are usually sufficient to
effect the desired extraction at such temperatures. After
extraction of the fibers, the solvent may be recovered from the
extract by distillation.
Removal of the non-mesophase content of the fibers may similarly be
effected by extraction with a suitable solvent in a Soxhlet
extractor. Extraction in this manner allows continuous use of the
same solvent, so that lesser amounts of solvent are required per
gram of fiber than when extraction is effected by immersion of the
fibers in the solvent, e.g., amounts about 10 percent as large as
those necessary in the immersion technique are sufficient. As in
the case when the fibers are immersed in the solvent, removal of at
least 10 percent by weight of the non-mesophase content of the
fibers to in excess of 70 percent by weight of said non-mesophase
content can generally be effected within from about 15 minutes to
about 10 hours, while removal of from about 40 percent by weight to
about 60 percent by weight of the non-mesophase content can
generally be effected in from about 1 to about 4 hours.
Among the solvents which can be employed to effect removal of
non-mesophase material from the fibers are acetone, benzene,
toluene, xylene, methyl ethyl ketone, quinoline, isoquinoline,
indole, pyridine, quinoxaline, pyrazine, dimethyl formamide,
dimethyl acetamide, dimethylsulfoxide, dimethylsulfone, and the
like, and mixtures thereof. Among these solvents, pyridine and
quinoline are preferred.
After the fibers have been extracted for a time sufficient to
remove the desired amount of non-mesophase material, they are
removed from the presence of the solvent and dried, e.g., by
heating for a short time to volatilize any remaining solvent. The
fibers produced in this manner, like their precursors, are
characterized by the presence of large oriented graphitizable
domains preferentially aligned parallel to the fiber axis, with the
fibers after extraction, however, containing a lesser amount of
non-mesophase material than before extraction. By heat treatment,
these fibers can be converted into carbon fibers having a high
Young's modulus of elasticity and high tensile strength.
While extracted fibers containing in excess of about 85 percent by
weight mesophase are, at times, sufficiently infusible to permit
them to be carbonized without any prior thermosetting treatment,
fibers containing less than about 85 percent by weight mesophase
require some thermosetting before they can be carbonized.
(Evidently, the fibers containing more than 85 per cent by weight
mesophase are sufficiently reinforced by their fibrillar structure
to allow them to be carbonized directly without any prior
thermosetting treatment). In any event, because of the higher ratio
of mesophase to non-mesophase of the extracted fibers compared to
their precursors, they can be thermoset, at any given temperature,
in shorter periods of time than said precursors.
Thermosetting of the fibers is readily effected by heating the
fibers in an oxygen-containing atmosphere for a time sufficient to
render them totally infusible. The oxygen-containing atmosphere
employed may be pure oxygen or an oxygen-rich atmosphere. Most
conveniently, air is employed as the oxidizing atmosphere.
The time required to effect thermosetting of the fibers will, of
course, vary with such factors as the particular oxidizing
atmosphere, the temperature employed, the diameter of the fibers,
the particular pitch from which the fibers are prepared, and the
mesophase content of the fibers. Generally, however, thermosetting
of the fibers can be effected in relatively short periods of time,
usually in from about 4 minutes to about 50 minutes.
The temperature employed to effect thermosetting of the fibers
must, of course, not exceed the temperature at which the fibers
will soften or distort. The maximum temperature which can be
employed will thus depend upon the particular pitch from which the
fibers were spun, and the mesophase content of the fibers. The
higher the mesophase content of the fiber, the higher will be its
softening temperature, and the higher the temperature which can be
employed to effect thermosetting. At higher temperatures, of
course, fibers of a given diameter can be thermoset in less time
than is possible at lower temperatures. Fibers having a lower
mesophase content, on the other hand, require relatively longer
heat treatment at somewhat lower temperatures to render them
infusible.
A minimum temperature of at least 250.degree.C. is generally
necessary to effectively thermoset the extracted fibers produced in
accordance with the invention. Temperatures in excess of
400.degree.C. may cause melting and/or excessive burn-off of the
fibers and should be avoided. Preferably, temperatures of from
about 325.degree.C. to about 390.degree.C. are employed. At such
temperatures, thermosetting can generally be effected within from
about 4 minutes to about 50 minutes. Since it is undesirable to
oxidize the fibers more than necessary to render them totally
infusible, the fibers are generally not heated for longer than
about 50 minutes, or at temperatures in excess of 400.degree.C.
After the fibers have been thermoset, the infusible fibers are
carbonized by heating in an inert atmosphere, such as that
described above, to a temperature sufficiently elevated to remove
hydrogen and other volatiles and produce a substantially all-carbon
fiber. Fibers having a carbon content greater than about 98 percent
by weight can generally be produced by heating to a temperature in
excess of about 1000.degree.C., and at temperatures in excess of
about 1500.degree.C., the fibers are completely carbonized.
Usually, carbonization is effected at a temperature of from about
1000.degree.C. to about 2000.degree.C., preferably from about
1500.degree.C. to about 1900.degree.C. Generally, residence times
of from about 0.5 minute to about 25 minutes, preferably from about
l minute to about 5 minutes, are employed. While more extended
heating times can be employed with good results, such residence
times are uneconomical and, as a practical matter, there is no
advantage in employing such long periods.
In order to ensure that the rate of weight loss of the fibers does
not become so excessive as to disrupt the fiber structure, it is
preferred to heat the fibers for a brief period at a temperature
from about 700.degree.C. to about 900.degree.C. before they are
heated to their final carbonization temperature. Residence times at
these temperatures of from about 30 seconds to about 5 minutes are
usually sufficient. Preferably, the fibers are heated at a
temperature of about 700.degree.C. for about one-half minute and
then at a temperature of about 900.degree.C. for like time. In any
event, the heating rate must be controlled so that the
volatilization does not proceed at an excessive rate.
In a preferred method of heat treatment, continuous filaments of
the fibers are passed through a series of heating zones which are
held at successively higher temperatures. Several arrangements of
apparatus can be utilized in providing the series of heating zones.
Thus, one furnace can be used with the fibers being passed through
the furnace several times and with the temperature being increased
each time. Alternatively, the fibers may be given a single pass
through several furnaces, with each successive furance being
maintained at a higher temperature than that of the previous
furnace. Also, a single furnace with several heating zones
maintained at successively higher temperatures in the direction of
travel of the fibers, can be used.
The carbon fibers produced in this manner have a highly oriented
structure characterized by the presence of carbon crystallites
preferentially aligned parallel to the fiber axis, and are
graphitizable materials which when heated to graphitizing
temperatures develop the three-dimensional order characteristic of
polycrystalline graphite and graphitic-like properties associated
therewith, such as high density and low electrical resistivity.
If desired, the carbonized fibers may be further heated in an inert
atmosphere, as described hereinbefore, to a still higher
temperature in a range of from about 2500.degree.C. to about
3300.degree.C., preferably from about 2800.degree.C. to about
3000.degree.C., to produce fibers having not only a high degree of
preferred orientation of their carbon crystallites parallel to the
fiber axis, but also by a structure characteristic of
polycrystalline graphite. A residence time of about 1 minute is
satisfactory, although both shorter and longer times may be
employed, e.g., from about 10 seconds to about 5 minutes, or
longer. Residence times longer than 5 minutes are uneconomical and
unnecessary, but may be employed if desired.
The fibers produced by heating at a temperature above about
2500.degree.C., preferably above about 2800.degree.C., are
characterized as having the three-dimensional order of
polycrystalline graphite. This three-dimensional order is
established by the X-ray diffraction pattern of the fibers,
specifically by the presence of the 112 cross-lattice line and the
resolution of the 10 band into two distinct lines, 100 and 101. The
short arcs which constitute the 00l) bands of the pattern show the
carbon crystallites of the fibers to be preferentially aligned
parallel to the fiber axis. Microdensitometer scanning of the 002
band of the exposed X-ray film indicate this preferred orientation
to be no more than about 10.degree., usually from about 5.degree.
to about 10.degree. (expressed as the full width at half maximum of
the azimuthal intensity distribution). Apparent layer size L.sub.a
and apparent stack height L.sub.c of the crystallites are in excess
of 1000 A and are thus too large to be measured by X-ray
techniques. The interlayer spacing d of the crystallites,
calculated from the distance between the corresponding 00l)
diffraction arcs, is no more than 3.37 A, usually from 3.36 A to
3.37 A.
EXAMPLE 1
A commercial petroleum pitch was employed to produce a pitch having
a mesophase content of about 73 percent by weight. The precursor
pitch had a density of 1.23 grams/cc., a softening temperature of
120.degree.C. and contained 0.5 percent by weight quinoline
insolubles (Q. I. was determined by quinoline extraction at
75.degree.C.). Chemical analysis showed a carbon content of 93.3%,
a hydrogen content of 5.6%, a sulfur content of 0.9% and 0.04%
ash.
The mesophase pitch was produced by heating the precusor petroleum
pitch at a temperature of about 400.degree.C. for about 20 hours
under a nitrogen atmosphere. After heating, the pitch contained 73
percent by weight pyridine insolubles, indicating that the pitch
had a mesophase content of close to 73 percent.
A portion of this pitch was transferred to an extrusion cylinder
and spun into fiber by applying pressure to the pitch with an argur
while the molten pitch was extruded through a pin-hole orifice
(diameter 0.015 inch) at the bottom of the extruder at a rate of
between 200 to 400 feet/minute. The filament passed through a
nitrogen atmosphere as it left the extruder orifice and was then
taken up by a reel. A considerable quantity of fiber 50-100 microns
in diameter was produced in this manner at a temperature of
400.degree.C.
A portion of the as-drawn fiber was extracted with boiling pyridine
(115.degree.C) for 18 hours in a Soxhlet extractor. The resulting
fibers, after drying in a vacuum oven at 110.degree.C., showed a
loss in weight of about 20 percent as a result of the extraction.
These fibers essentially fully retained the integrity of the
as-drawn fiber after the extraction, and did not melt when further
heated in an argon atmosphere to 700.degree.c. at a rate of
5.degree.C. per minute. The resulting fibers appeared shiny and
showed no serious disruptions in the fiber surface.
EXAMPLE 2
A commercial petroleum pitch was employed to produce a pitch having
a mesophase content of about 52 percent by weight. The prescursor
pitch had a density of 1.23 grams/cc., a softening temperature of
120.degree.C. and contained 0.5 percent by weight quinoline
insolubles (Q. I. was determined by quinoline extraction at
75.degree.C.). Chemical analysis showed a carbon content of 93.3%,
a hydrogen content of 5.6%, a sulfur content of 0.9% and 0.04%
ash.
The mesophase pitch was produced by heating the precursor petroleum
pitch at a temperature of about 400.degree.C. for about 14 hours
under a nitrogen atmosphere. After heating, the pitch contained 52
percent by weight pyridine insolubles, indicating that the pitch
had a mesophase content of close to 52 percent.
A portion of this pitch was transferred to an extrusion cylinder
and spun into fiber by applying pressure to the pitch with an argur
while the molten pitch was extruded through a pin-hole orifice
(diameter 0.015 inch) at the bottom of the extruder at a rate of
between 200 to 400 feet/minute. The filament passed through a
nitrogen atmosphere as it left the extruder orifice and was then
taken up by a reel. A considerable quantity of fiber 30-50 microns
in diameter was produced in this manner at a temperature of
380.degree.C.
A portion of the as-drawn fiber was extracted with boiling pyridine
(115.degree.C). for 18 hours in a Soxhlet extractor. The resulting
fibers, after drying in a vacuum oven at 110.degree.C., showed a
loss in weight of about 48 percent as a result of the extraction,
indicating that these fibers had a mesophase content of about 100
percent. The fibers essentially fully retained the integrity of the
as-drawn fiber after the extraction and showed no serious
disruptions in the fiber surface.
* * * * *