U.S. patent number 3,903,248 [Application Number 05/461,201] was granted by the patent office on 1975-09-02 for process for the production of large denier carbon fibers.
This patent grant is currently assigned to Celanese Corporation. Invention is credited to Ilmar L. Kalnin, Edward J. Powers.
United States Patent |
3,903,248 |
Kalnin , et al. |
September 2, 1975 |
Process for the production of large denier carbon fibers
Abstract
An improved process is provided for the expeditious formation of
large denier carbon fibers, i.e. carbon fibers having a single
filament denier of at least 30. A fibrous polybenzimidazole
starting material of relatively large denier is initially converted
to a polybenzimidazonium salt by contact with a solution of certain
acids at an elevated temperature, and the resulting fibrous
material sequentially is heated in oxygen-containing and
non-oxidizing gaseous atmospheres at successively elevated
temperatures. The resulting carbonaceous fibrous material contains
at least 90 percent carbon by weight and particularly is suited for
use as a reinforcing medium in a matrix material, e.g. either a
polymeric or metallic matrix material.
Inventors: |
Kalnin; Ilmar L. (Millington,
NJ), Powers; Edward J. (Gillette, NJ) |
Assignee: |
Celanese Corporation (New York,
NY)
|
Family
ID: |
23831610 |
Appl.
No.: |
05/461,201 |
Filed: |
April 15, 1974 |
Current U.S.
Class: |
423/447.4;
423/447.6 |
Current CPC
Class: |
D01F
9/24 (20130101) |
Current International
Class: |
D01F
9/24 (20060101); D01F 9/14 (20060101); C01b
031/07 () |
Field of
Search: |
;423/447 ;264/29 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Meros; Edward J.
Claims
We claim:
1. An improved process for the formation of a large denier
carbonaceous fibrous material comprising:
a. contacting a polybenzimidazole fibrous material having a denier
per filament of about 50 to 600 with a solution of an acid having a
pK.sub.A value below about 4.5 while at an elevated temperature to
transform said polybenzimidazole to a polybenzimidazonium salt
wherein the anion of said salt is derived from said acid,
b. heating said fibrous material following contact with said acid
in an oxygen-containing gaseous atmosphere at a temperature of
about 300.degree. to 530.degree.C. to render said fibrous material
capable of undergoing carbonization while retaining the original
fibrous configuration substantially intact, and
c. heating said resulting fibrous material in a non-oxidizing
gaseous atmosphere at a temperature of at least 1000.degree.C.
until a carbonaceous fibrous material is formed which contains at
least 90 percent carbon by weight and retains the original fibrous
configuration substantially intact.
2. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said polybenzimidazole fibrous material consists essentially of
recurring units of the formula: ##EQU3## wherein R is a tetravalent
aromatic nucleus, with the nitrogen atoms forming the benzimidazole
rings paired upon adjacent carbon atoms of said aromatic nucleus,
and R' is selected from the group consisting of (1) an aromatic
ring, (2) an alkylene group having from 4 to 8 carbon atoms, and
(3) a heterocyclic ring selected from the group consisting of (a)
pyridine, (b) pyrazine, (c) furan, (d) quinoline, (e) thiophene,
and (f) pyran.
3. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said polybenzimidazole fibrous material is
poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole.
4. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said polybenzimidazole fibrous material has denier per filament of
about 100 to 500.
5. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said acid is selected from the group consisting essentially of
sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid,
and acetic acid.
6. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said solution of said acid utilized in step (a) is provided at a
temperature of about 50.degree. to 100.degree.C. when contacted
with said fibrous material.
7. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 6 wherein
said contact is conducted for about 2 to 50 minutes.
8. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said oxygen-containing gaseous atmosphere is air.
9. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said fibrous material following contact with said acid is heated in
said oxygen-containing atmosphere of step (b) for about 1 to 30
minutes.
10. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said non-oxidizing gaseous atmosphere of step (c) is selected from
the group consisting essentially of nitrogen, argon, and
helium.
11. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 1 wherein
said resulting fibrous material is heated in said non-oxidizing
gaseous atmosphere of step (c) for about 2 to 20 minutes.
12. An improved process for the formation of a large denier
carbonaceous fibrous material comprising:
a. contacting a poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole
fibrous material having a denier per filament of about 100 to 500
with an aqueous solution of an acid selected from the group
consisting essentially of sulfamic acid, phosphoric acid, sulfuric
acid, hydrochloric acid and acetic acid, while at a temperature of
about 50.degree. to 100.degree.C. for a residence time of about 2
to 50 minutes to transform said
poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole to a
polybenzimidazonium salt wherein the anion of said salt is derived
from said acid,
b. heating said resulting fibrous material following contact with
said acid in an oxygen-containing gaseous atmosphere at a
temperature of about 300.degree. to 530.degree.C. for a residence
time of about 1 to 30 minutes to render said fibrous material
capable of undergoing carbonization while retaining the original
fibrous configuration substantially intact, and
c. heating said resulting fibrous material at a temperature of at
least 1000.degree.C. in a non-oxidizing gaseous atmosphere selected
from the group consisting essentially of nitrogen, argon, and
helium for a residence time of about 2 to 20 minutes until a
carbonaceous fibrous material is formed which contains at least 90
percent carbon by weight and retains the original fibrous
configuration substantially intact.
13. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 12 wherein
said fibrous material is a continuous length of a multifilament
yarn.
14. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 12 wherein
said fibrous material is a continuous length of a multifilament
tow.
15. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 12 wherein
said aqueous solution of said acid additionally includes a swelling
agent for said fibrous material.
16. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 15 wherein
said swelling agent is benzyl alcohol.
17. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 15 wherein
said oxygen-containing gaseous atmosphere of step (b) is air.
18. An improved process for the formation of a large denier
carbonaceous fibrous material in accordance with claim 15 wherein
said non-oxidizing gaseous atmosphere of step (c) is nitrogen.
Description
BACKGROUND OF THE INVENTION
In the search for high performance materials, considerable interest
has been focused upon carbon fibers. The term "carbon fibers" is
used herein in its generic sense and includes 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.
As is well known to those skilled in the art, carbon fibers
commonly have been formed by the thermal stabilization of a variety
of polymeric fibrous materials, and the subsequent carbonization or
carbonization and graphitization of the same in an inert
atmosphere. Representative U.S. patents disclosing the production
of carbon fibers from an acrylic fibrous precursor include: U.S.
Pat. Nos. 2,913,802; 3,285,696; 3,539,295; 3,592,595; 3,647,770;
3,650,668; 3,656,882; 3,656,883; 3,708,326; and 3,729,549.
Representative U.S. patents disclosing the production of carbon
fibers from a polybenzimidazole fibrous material include: U.S. Pat.
Nos. 3,449,077; 3,528,774; 3,634,035; and 3,635,675.
Heretofore, the carbon fibers produced in the prior art have tended
to have a relatively small denier per filament, e.g. about 0.5 to
2.0 denier per filament corresponding to an average filament
diameter of about 0.0003 to 0.0005 inches. Whenever attempts have
been made to produce carbon fibers of relative large denier per
filament, e.g. 30 to 400 or more, and a filament diameter of 0.001
inch or more special problems have been presented particularly
during the stabilization portion of the process. It has been
recognized that unless the polymeric fibrous precursor is
adequately stabilized (e.g. by heating in air or other oxidizing
atmosphere), it cannot be satisfactorily carbonized or carbonized
and graphitized. During the stabilization portion of the process it
has been found that an oxidized surface layer tends initially to
form upon the fiber surface which tends to impede oxygen diffusion
into the fiber and to retard the further stabilization thereof.
Accordingly extremely long stabilization periods have been required
when the fibrous precursor is a relatively large denier per
filament. Additionally, the subsequent carbonization treatment of
the resulting stabilized fibrous material has tended to be
slow.
Commonly assigned U.S. Ser. No. 296,725, filed Oct. 11, 1972, now
abandoned, of John W. Soehngen discloses an approach for lessening
the time required for the stabilization of an acrylic fibrous
precursor of larger than usual diameter.
Industrial high performance materials of the future are projected
to make substantial utilization of fiber reinforced composites
wherein carbon fibers are incorporated in a resinous or metallic
matrix. 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. Graphite is
one of the very few known materials whose tensile strength
increases with temperature. Uses for carbon fiber reinforced
composites include recreational equipment, such as golf club
shafts, aerospace structural components, rocket motor casings,
deep-submergence vessels, ablative materials for heat shields on
re-entry vehicles, etc.
There has remained a need for improved techniques to produce carbon
fibers of a relatively large denier which are derived from a
polymeric fibrous material of relatively large denier. Such large
denier carbon fibers are capable, inter alia, of forming composite
articles exhibiting an enhanced compressive strength to tensile
strength ratio. Also, such large denier carbon fibers are
particularly suited for use as fibrous reinforcement in a metallic
matrix. When one attempts to incorporate a relatively small
diameter carbon filament in a metallic matrix, it has been observed
that the outer portion of the filament tends to react with the
matrix during composite fabrication which results in a loss of most
of the filament strength. Accordingly, commercially practicable
processes for producing large denier carbon filaments are in
demand, but have proven to be an elusive goal.
It is an object of the invention to provide an improved process for
the production of large denier carbon fibers.
It is an object of the invention to provide an improved process for
the production of large denier carbon fibers beginning with large
denier polybenzimidazole fibrous precursors.
It is an object of the invention to provide a process for the
production of large denier carbon fibers beginning with a large
denier polybenzimidazole fibrous precursor wherein the
stabilization portion thereof is carried out on an expeditious
basis without the necessity to employ extremely long residence
times as commonly required in the prior art thereby yielding
improved production efficiency.
It is another object of the invention to provide large denier
carbon filaments which may be readily substituted for boron
filaments as reinforcement in a metallic matrix.
It is another object of the invention to provide large denier
carbon filaments which may be used as a substrate for receiving the
vapor deposition of boron to form a boron-carbon composite fiber
suitable for incorporation in a metallic matrix.
It is a further object of the invention to provide an improved
process for the production of large denier carbon fibers in which
the various thermal processing steps thereof expeditiously may be
carried out in an in-line continuous manner.
These and other objects, as well as, the scope, nature, and
utilization of the process will be apparent to those skilled in the
art from the following description and appended claims.
SUMMARY OF THE INVENTION
It has been found that an improved process for the formation of a
large denier carbonaceous fibrous material comprises:
a. contacting a polybenzimidazole fibrous material having a denier
per filament of about 50 to 600 with a solution of an acid having a
pK.sub.A value below about 4.5 while at an elevated temperature to
transform said polybenzimidazole to a polybenzimidazonium salt
wherein the anion of the salt is derived from the acid,
b. heating the fibrous material following contact with the acid in
an oxygen-containing gaseous atmosphere at a temperature of about
300.degree. to 530.degree.C. to render the fibrous material capable
of undergoing carbonization while retaining the original fibrous
configuration substantially intact, and
c. heating the resulting fibrous material in a non-oxidizing
gaseous atmosphere at a temperature of at least 1000.degree.C.
until a carbonaceous fibrous material is formed which contains at
least 90 percent carbon by weight and retains the original fibrous
configuration substantially intact.
The resulting large denier carbonaceous fibrous material
particularly is suited for use as a reinforcing medium in a matrix
material, e.g. a polymeric or metallic matrix material.
DESCRIPTION OF PREFERRED EMBODIMENTS
The Starting Material
The large denier polybenzimidazole fibrous material which serves as
the starting material has a denier per filament of about 50 to 600
and an average filament diameter of about 0.003 to 0.010 inch. In a
preferred embodiment of the process the large denier
polybenzimidazole fibrous material has a denier per filament of
about 100 to 500 and a filament diameter of about 0.004 to 0.009
inch.
Polybenzimidazoles are a known class of heterocyclic polymers.
Typical polymers of this class and their preparation are more fully
described in U.S. Pat. No. 2,895,948, U.S. Pat. No. Re. 26,065, and
in the Journal of Polymer Science, Vol. 50, pages 511-539 (1961)
which are herein incorporated by reference. The polybenzimidazoles
consist essentially of recurring units of the following Formulas I
and II. Formula I is: ##EQU1## wherein R is a tetravalent aromatic
nucleus, preferably symmetrically substituted, with the nitrogen
atoms forming the benzimidazole rings being paired upon adjacent
carbon atoms, i.e. ortho carbon atoms, of the aromatic nucleus, and
R' is a member of the class consisting of (1) an aromatic ring, (2)
an alkylene group (preferably those having 4 to 8 carbon atoms),
and (3) a heterocyclic ring from the class consisting of (a)
pyridine, (b) pyrazine, (c) furan, (d) quinoline, (e) thiophene,
and (f) pyran.
Formula II is: ##EQU2## wherein Z is an aromatic nucleus having the
nitrogen atoms forming the benzimidazole ring paired upon adjacent
carbon atoms of the aromatic nucleus.
Preferably, aromatic polybenzimidazoles are selected, e.g.,
polymers consisting essentially of the recurring units of Formulas
I and II wherein R' is at least one aromatic ring or a heterocyclic
ring.
As set forth in U.S. Pat. No. Re. 26,065, the aromatic
polybenzimidazoles having the recurring units of Formula II may be
prepared by self-condensing a trifunctional aromatic compound
containing only a single set of ortho disposed diamino substituents
and an aromatic, preferably phenyl, carboxylate ester substituent.
Exemplary of polymers of this type is poly-2,5(6)-benzimidazole
prepared by the autocondensation of phenyl-3,4-diaminobenzoate.
As also set forth in the above-mentioned patent, the aromatic
polybenzimidazoles having the recurring units of Formula I may be
prepared by condensing an aromatic tetraamine compound containing a
pair of orthodiamino substituents on the aromatic nucleus with a
dicarboxyl compound selected from the class consisting of (a) the
diphenyl ester of an aromatic dicarboxylic acid, (b) the diphenyl
ester of a heterocyclic dicarboxylic acid wherein the carboxyl
groups are substituents upon a carbon in a ring compound selected
from the class consisting of pyridine, pyrazine, furan, quinoline,
thiophene and pyran and (c) an anhydride of an aromatic
dicarboxylic acid.
Examples of polybenzimidazoles which have the recurring structure
of Formula I are as follows:
poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole;
poly-2,2'-(pyridylene-3",5")-5,5'-bibenzimidazole;
poly-2,2'-(furylene-2",5")-5,5'-bibenzimidazole;
poly-2,2'-(naphthalene-1",6")-5,5'-bibenzimidazole;
poly-2,2'-(biphenylene-4",4")-5,5'-bibenzimidazole;
poly-2,2'-amylene-5,5'-bibenzimidazole;
poly-2,2'-octamethylene-5,5'-bibenzimidazole;
poly-2,6-(m-phenylene)-diimidazobenzene;
poly-2,2'-cyclohexeneyl-5,5'-bibenzimidazole;
poly-2,2'-(m-phenylene)-5,5'-di(benzimidazole) ether;
poly-2,2'-(m-phenylene)-5,5'-di(benzimidazole) sulfide:
poly-2,2'(m-phenylene)-5,5'-di(benzimidazole) sulfone;
poly-2,2'-(m-phenylene)-5,5'-di(benzimidazole) methane;
poly-2',2"-(m-phenylene)-5',5"-di(benzimidazole)propane-2,2;
and
poly-2',2"-(m-phenylene)-5',5"-di(benzimidazole)ethylene-1,2
where the double bonds of the ethylene groups are intact in the
final polymer.
The preferred polybenzimidazole for use in the present process is
one prepared from poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole, the
recurring unit of which is: ##SPC1##
Any polymerization process known to those skilled in the art may be
employed to prepare the polybenzimidazole which may then be formed
into a continuous length of fibrous material. Representative
techniques for preparing the polybenzimidazole are disclosed in
U.S. Pat. Nos. 3,509,108; 3,549,603; and 3,551,389, which are
assigned to the assignee of the present invention and are herein
incorporated by reference.
With respect to aromatic polybenzimidazoles, preferably equimolar
quantities of the monomeric tetraamine and dicarboxyl compound are
introduced into a first stage melt polymerization reaction zone and
heated therein at a temperature above about 200.degree.C.,
preferably at least 250.degree.C., and more preferably from about
270.degree. to 300.degree.C. The reaction is conducted in a
substantially oxygen-free atmosphere, i.e., below about 20 ppm
oxygen and preferably below about 8 ppm oxygen, until a foamed
prepolymer is formed having an inherent viscosity, expressed as
deciliters per gram, of at least 0.1 and preferably from about 0.13
to 0.3, the inherent viscosity (I.V.) as used herein being
determined from a solution of 0.4 grams of the polymer in 100 ml.
of 97 percent H.sub.2 SO.sub.4 at 25.degree.C.
After the conclusion of the first stage reaction, which normally
takes at least 0.5 hour and preferably 1 to 3 hours, the foamed
prepolymer is cooled and then powdered or pulverized in any
convenient manner. The resulting prepolymer powder is then
introduced into a second stage polymerization reaction zone wherein
it is heated under substantially oxygen-free conditions, as
described above, to yield a polybenzimidazole polymer product,
desirably having an I.V., as measured above, of at least 0.6, e.g.,
0.80 to 1.1 or more.
The temperature employed in the second stage is at least
250.degree.C., preferably at least 325.degree.C., and more
preferably from about 350.degree. to 425.degree.C. The second stage
reaction generally takes at least 0.5 hour, and preferably from
about 1 to 4 hours or more.
A particularly preferred method for preparing the polybenzimidazole
is disclosed in the aforesaid U.S. Pat. No. 3,509,108. As disclosed
therein aromatic polybenzimidazoles may be prepared by initially
reacting the monomer in a melt phase polymerization at a
temperature above about 200.degree.C. and a pressure above 50 psi
(e.g., 300 to 600 psi) and then heating the resulting reaction
product in a solid state polymerization at a temperature above
about 300.degree.C. (e.g. 350.degree. to 500.degree.C.) to yield
the final product.
The term polybenzimidazole "fibrous material" as used herein
includes monofilaments, as well as multifilament fibrous materials,
such as yarn, strand, cable, tow, or other continuous or
discontinuous fibrous assemblage. In a preferred embodiment of the
process the polybenzimidazole fibrous material is a multifilament
yarn or a multifilament tow.
As is known in the art, polybenzimidazoles are generally formed
into continuous lengths of fibrous materials by solution spinning,
that is, by dry or wet spinning a solution of the polymer in an
appropriate solvent such as N,N-dimethylacetamide,
N,N-dimethylformamide, dimethylsulfoxide or sulfuric acid (used
only in wet spinning) through an opening of predetermined shape
into an evaporative atmosphere for the solvent in which most of the
solvent is evaporated (dry) or into a coagulation bath (wet),
resulting in the polymer having the desired filamentary shape.
The polymer solutions may be prepared in accordance with known
procedures. For example, sufficient polybenzimidazole may be
dissolved in the solvent to yield a final solution suitable for
extrusion containing from about 10 to 45 percent by weight of the
polymer, based on the total weight of the solution, preferably from
about 20 to 30 percent by weight.
One suitable means for dissolving the polymer in the solvent is by
mixing the materials at a temperature above the atmospheric boiling
point of the solvent, for example 25.degree. to 120.degree.C. above
such boiling point and at a pressure of 2 to 15 atmospheres for a
period of 1 to 5 hours.
Preferably, the polymer solutions, after suitable filtration to
remove any undissolved portions, are dry spun. For example, the
solutions may be extruded through a spinneret into a conventional
type downdraft spinning column containing a circulating inert gas
such as nitrogen, noble gasses, combustion gasses, or superheated
steam. Conveniently, the spinneret face is at a temperature of from
about 100.degree. to 170.degree.C., the top of the column from
about 120.degree. to 220.degree.C., the middle of the column from
about 140.degree. to 250.degree.C., and the bottom of the column
from about 160.degree. to 320.degree.C. After leaving the spinning
column, the continuous filamentary materials are taken up, for
example, at a speed within the range of about 50 to 350 meters or
more per minute. If the continuous filamentary materials are to be
washed while wound on bobbins, the resulting "as-spun" materials
may be subjected to a slight steam drawing treatment at a draw
ratio of from about 1.05:1 to 1.5:1 in order to prevent the fibers
from relaxing and falling off the bobbin during the subsequent
washing step. Further details with respect to a method for
dry-spinning a continuous length of a polybenzimidazole fibrous
material are shown in U.S. Pat. No. 3,502,756 to Bohrer et al.
which is assigned to the same assignee as the present invention and
is herein incorporated by reference.
The continuous length of polybenzimidazole fibrous material is next
washed so as to remove at least the major portion of residual
spinning solvent, e.g., so that the washed materials contain less
than about 1 percent by weight solvent based on the weight of the
continuous filamentary material, and preferably so as to obtain an
essentially spinning solvent-free fibrous material (i.e., a fibrous
material containing less than about 0.1 percent solvent by weight).
Typically, a simple water wash is employed; however, if desired,
other wash materials such as acetone, methanol, methylethyl ketone
and similar solvent-miscible and volatile organic solvents may be
used in place of or in combination with the water. The washing
operation may be conducted by collecting the polybenzimidazole
fibrous material on perforated rolls or bobbins, immersing the
rolls in the liquid wash bath and pressure washing the fibrous
material, for example, for about 2 to 48 hours or more.
Alternatively, the continuous length of polybenzimidazole fibrous
material may be washed on a continuous basis by passing the fibrous
material in the direction of its length through one or more liquid
wash baths (e.g., for 1 to 10 minutes). Any wash technique known to
those skilled in the art may be selected.
The continuous length of polybenzimidazole fibrous material may
next be dried to remove the liquid wash bath by any convenient
technique. For instance, the drying operation for bobbins of yarn
may be conducted at a temperature of about 150.degree. to
300.degree.C. for about 2 to 100 hours or more. Alternatively, the
continuous length of polybenzimidazole fibrous material may be
dried on a continuous basis by passing the fibrous material in the
direction of its length through an appropriate drying zone (e.g.,
an oven provided at 300.degree. to 400.degree.C. for 1 to 2
minutes). If drying is employed, preferably the drying temperature
does not exceed about 250.degree.C. for several hours or
400.degree.C. for more than 1 minute, as above these limits
degradation of the fiber may occur.
The polybenzimidazole fibrous material preferably next is hot drawn
at a draw ratio of about 2:1 to 5:1 in order to enhance its
orientation. Representative draw procedures are disclosed in
commonly assigned U.S. Pat. No. 3,622,660, and Ser. No. 297,511,
filed Oct. 13, 1972 which issued as U.S. Pat. No. 3,849,529.
The Formation of a Polybenzimidazonium Salt
The large denier polybenzimidazole fibrous material is contacted
with a solution of an acid having a pK.sub.A below about 4.5
(preferably below about 3.5) while at an elevated temperature to
transform the polybenzimidazole to a polybenzimidazonium salt
wherein the anion of the salt is derived from the acid.
The acid selected may be organic or inorganic in nature and
preferably is relatively non-volatile and incapable of
decomposition at the treatment temperature selected. The pK.sub.A
value of a given acid conveniently may be ascertained by
determining the negative logarithm of the K.sub.A for acid in a
0.1M aqueous solution at 25.degree.C. Those acids having a pK.sub.A
value much above about 4.5 possess insufficient strength to be
useful in the production of the desired salt. Suitable acids
include the mineral acids, monobasic acid and dibasic carboxylic
acids, and sulfonic acids.
Representative inorganic acids include: sulfamic acid, sulfuric
acid, hydrochloric acid, phosphoric acid, perchloric acid,
hydrobromic acid, hydrofluoric acid, hydriodic acid, etc.
Representative carboxylic acids include: acetic acid, oxalic acid,
monochloroacetic acid, dichloroacetic acid, trichloroacetic acid,
monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid,
substituted benzoic acids, salicylic acid, etc.
Representative sulfonic acids include: benzene sulfonic acid,
6-toluene sulfonic acid, m-toluene sulfonic acid, p-toluene
sulfonic acid, 2,4-xylene sulfonic acid, toluene-2,4-disulfonic
acid, 2-naphthalene sulfonic acid, bisphenol disulfonic acid,
chlorosulfonic acid, methane sulfonic acid, trifluoromethane
sulfonic acid, etc.
The particularly preferred acids for use in the process are
sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid
and acetic acid.
The solvent utilized to form the solution of the acid preferably is
aqueous in nature; however, other solvents such as N-propanol,
ethyleneglycolmonomethyl ether, methylene chloride, methanol, etc.,
may alternatively be employed.
The acid preferably may be provided in the solvent in a
concentration of about 1 to 10 percent by weight based upon the
total weight of the solution, and most preferably in a
concentration of about 2 to 5 percent by weight. The acid solution
preferably is provided in a quantity such that its weight exceeds
that of the polybenzimidazole fibrous material undergoing treatment
by about 10 to 40 times. Also the acid preferably is provided in a
quantity such that at least 1 equivalent of acid (e.g. 1 to 2
equivalents of acid) reacts with each repeat unit of the polymer to
form the polybenzimidazonium salt. An aqueous solution of the acid
optionally may include a swelling agent for the polybenzimidazole
dissolved or dispersed therein in order to aid in the uniform
production of the polybenzimidazonium salt throughout the fibrous
material. Representative swelling agents include: benzyl alcohol,
2-phenoxyethanol, or other partially soluble solvents having a
solubility parameter in water between 11 and 13. The swelling agent
preferably is provided in a concentration of about 3 to 20 percent
by weight based upon the total weight of the solution, and most
preferably in a concentration of about 5 to 10 percent by weight.
The particularly preferred swelling agent for use in the process is
benzyl alcohol.
The solution of the acid preferably is provided at a temperature of
about 50.degree. to 100.degree.C. (e.g. about 90.degree. to
98.degree.C.) when contacted with the polybenzimidazole fibrous
material. It is recommended that the fibrous material be immersed
in the solution of the acid in such a manner that direct contact
with the solution throughout the fibrous material is maximized. For
instance, a continuous length of the fibrous material while wound
upon a frame or support to a limited thickness may be positioned in
the solution. Alternatively, a continuous length of the fibrous
material may be continuously passed through the solution in the
direction of its length while substantially suspended therein.
Suitable residence times for the formation of the
polybenzimidazonium salt commonly range from about 2 to 50 minutes
(e.g. 20 to 40 minutes) while in contact with the solution of acid.
Longer residence times may be selected without commensurate
advantage.
Alternatively, the polybenzimidazonium salt may be formed by
contact of the swollen as-spun polybenzimidazole fibrous material
with the solution of acid as described.
After the acid treatment the fibrous material preferably is washed,
(i.e. rinsed) with water to remove excess acid, and is dried (e.g.
at 100 to 200.degree.C. for 15 minutes in a circulating air
oven).
The formation of the polybenzimidazonium salt surprisingly has been
found to render the fibrous material capable of undergoing
stabilization in an oxidizing atmosphere on a more expeditious
basis thereby effectively overcoming stabilization difficulties
commonly associated with large denier polybenzimidazole fibrous
materials.
The formation of a polybenzimidazonium sulfate salt upon reaction
of poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole with sulfuric acid
is illustrative of the salt formation reaction and can be
represented by the following equation: ##SPC2## As indicated
previously, it is not essential that 2 equivalents of acid react
with each repeat unit of the polymer to form the
polybenzimidazonium salt.
Once the salt formation reaction is complete the fibrous material
continues to exhibit its original fibrous configuration, but
exhibits substantially different properties. For instance, the
tendency for the fibrous material to shrink in length when heated
in an unrestrained state in an incandescent flame at about
500.degree.C. is commonly reduced from about 80 percent to 4 or 5
percent. Shifts in uv absorption maxima commonly are observed, e.g.
when sulfuric acid is used to form the salt a thin polymer film on
quartz may exhibit a value of 252,340 nm while the control of
untreated poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole film
exhibits a value of 258,357 nm. Solubility changes and thermal
stability changes may be observed.
Density changes may be observed. For instance when fibers of
poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole are treated in aqueous
solutions of 3 percent acid and 6 percent benzyl alcohol swelling
agent for 40 minutes at 95.degree.C. the following densities were
recorded for the resulting fibers.
______________________________________ Acid Utilized Density of
Fiber (gm./c.c.) ______________________________________ Sulfuric
acid 1.39 Phosphoric acid 1.40 Sulfamic acid 1.38 Hydrochloric acid
1.31 P-toluene sulfonic acid 1.33 Acetic acid 1.29 Trifluoroacetic
acid 1.32 Oxalic acid 1.35 Salicylic acid 1.30 Untreated control
1.27 Control subjected to benzyl alcohol and water only 1.29
______________________________________
Also, crystallinity changes may be apparent.
Poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole fibers generally
exhibit two broad equitorial scattering areas indicating an
amorphous somewhat oriented structure. After the acid treatment to
form the polybenzimidazonium salt two somewhat sharper arcs appear,
one on the equator [A] representing aromatic layer packing, and the
other on the meridian [B] indicating order in the fiber direction.
The crytallite sizes (in Angstroms) of representative acidified
materials in the two directions are as follows:
Acid Utilized [A] [B] ______________________________________
Sulfuric acid 16 19 Hydrofluoric acid 16 15 Phosphoric acid 20 18
Perchloric acid 22 32 Sulfamic acid 19 19
______________________________________
The Thermal Stabilization
The fibrous material following the formation of the
polybenzimidazonium salt is heated for a relatively brief residence
time in a molecular oxygen-containing gaseous atmosphere at a
temperature of about 300.degree. to 530.degree.C. to oxidize the
fibers and to render the same capable of undergoing carbonization
while retaining the original fibrous configuration substantially
intact. The preferred oxygen-containing gaseous atmosphere is air;
however, other gaseous atmospheres containing a greater or lesser
concentration of oxygen produce equally satisfactory results.
The stabilization treatment may be carried out on either a batch or
a continuous basis with the large denier fibrous material being
either (1) statically positioned within the stabilization zone, or
(2) continuously passed through the stabilization zone in the
direction of its length. When the process is carried out on a batch
basis, a continuous length of the fibrous material may be wound
upon a support (e.g. a stainless steel bobbin) and placed in the
stabilization zone. The stabilization treatment is preferably
carried out while the fibrous material is maintained at a
substantially constant length.
Suitable residence times for the stabilization reaction commonly
range from about 1 to 30 minutes. Longer residence times may be
utilized without commensurate advantage.
The period of time required to complete the stabilization reaction
within the gaseous atmosphere generally is inversely related to the
temperature of the gaseous atmosphere, and also is influenced to
some degree by the denier of the fibrous material. During the
stabilization reaction it may be desirable that the fibrous
material be gradually raised to the maximum stabilization
temperature if the resulting product is to exhibit optimum physical
properties. A representative heating profile which is particularly
advantageous when the polybenzimidazonium salt was formed with the
aid of sulfuric acid, or sulfamic acid, is as follows: heat at
300.degree.C. for 10 minutes, at 400.degree.C. for 10 minutes, and
at 465.degree.C. for 5 minutes. When the polybenzimidazonium salt
is formed with the aid of an acid such as phosphoric acid or acetic
acid, the entire stabilization reaction may be carried out at a
relatively constant temperature of about 465.degree.C. for 5
minutes. The exact stabilization heating conditions for optimum
results within the range of about 300.degree. to 530.degree.C. may
be determined by simple experimentation.
The stabilized fibrous material formed in accordance with the
present process is black in appearance which is usually accompanied
by a purple tinge, retains it original fibrous configuration
substantially intact, and is capable of undergoing carbonization
when heated in an inert gaseous atmosphere (e.g. at a temperature
of 1000.degree.C.) without loss of its configuration (e.g. through
coalescence or melting). Also, the fiber can be tensioned upon
continuous carbonization in the absence of breakage. Additionally
the stabilized fibrous material commonly exhibits a bound oxygen
content of about 2-8 percent by weight as determined by the
Unterzaucher, or other suitable analysis.
The theory whereby the initial conversion of the large denier
polybenzimidazole fibrous material to a polybenzimidazonium salt is
capable of expediting the subsequent stabilization reaction so that
the desired stabilization can be accomplished in minutes rather
than hours is considered complex and incapable of simple
explanation when compared with the residence times required in the
prior art for the same fibers. The results achieved are considered
to be surprising and unexpected.
The Formation of a Large Denier Carbon Fiber
The resulting stabilized fibrous material is heated in a
non-oxidizing gaseous atmosphere at a temperature of at least
1000.degree.C. until a carbonaceous fibrous material is formed
which contains at least 90 percent carbon by weight (preferably at
least 95 percent carbon by weight) and retains the original fibrous
configuration substantially intact. Carbonization or carbonization
and graphitization may be accomplished in accordance with
conventional techniques, e.g. the utilization of induction
furnaces, resistance heated furnaces, or reducing flames as
disclosed in commonly assigned U.S. Pat. No. 3,449,077.
In a preferred embodiment of the process the non-oxidizing gaseous
atmosphere is an inert gaseous atmosphere selected from the group
consisting of nitrogen, argon and helium. The particularly
preferred gaseous atmosphere is nitrogen.
The higher the temperature of the non-oxidizing gaseous atmosphere
the greater the degree of graphitic carbon formed within the fiber
and the greater the Young's modulus of the fiber. Temperature
profiles may be utilized wherein the fiber is heated in a
non-oxidizing gaseous atmosphere having a temperature up to about
3000.degree.C. Residence times at a temperature of at least
1000.degree.C. commonly range from about 2 to 20 minutes. Lesser
residence times may be utilized if the resulting stabilized fibrous
material is heated in a reducing flame.
The carbonization or carbonization and graphitization may be
carried out on a batch or continuous basis. Since comparable
residence times are required for the stabilization treatment and
the carbonization treatment, these steps of the process optionally
may be carried out in tandem with a continous length of fibrous
material being passed in the direction of its length through the
appropriate heating zones.
Commonly the carbon fibers formed in the present process have a
denier per filament of about 30 to 400 (e.g. 70 to 350), and an
average diameter of about 0.002 to 0.008 inch. The diameter of the
carbon fiber product is largely determined by the diameter of the
starting material but is generally less than that of the starting
material due to loss of non-carbon atoms during the carbonization
treatment and possible stretching during stabilization and
carbonization.
The large denier carbon fibers formed in the present process may be
incorporated in a matrix material (e.g. a polymeric or metallic
matrix) to form a composite article having an enhanced compressive
strength to tensile strength ratio. The large denier carbon fibers
are particularly suited for incorporation in a metallic matrix,
e.g. a matrix of manganese, aluminum, or copper. If desired, a
protective coating, such as silicon or chromium, may be applied to
the fibers prior to incorporation in a metallic matrix rather than
incorporating the fibers directly in the matrix. Also, the large
denier carbon fibers may be substituted for a tungsten fiber prior
to the application of a coating boron to yield a fiber suitable for
incorporation in a composite article having a lesser density than a
common boron fiber.
The following examples are given 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.
EXAMPLE I
A polybenzimidazole monofilament, namely
poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole, is selected as the
examplary polybenzimidazole for use in carrying out the process of
this invention. The monofilament has a denier per filament of 400
and a fiber diameter of 0.008 inch. The monofilament is formed in
accordance with the procedure described in commonly assigned U.S.
Pat. No. 3,526,693 of R. N. Rulison and J. P. Riggs and has been
hot drawn at a draw ratio of 2.5:1.
The monofilament was wrapped about a mandrel and immersed for 30
minutes in a solution consisting of 2 percent by weight sulfuric
acid, 6 percent by weight benzyl alcohol swelling agent, 0.06
percent by weight of an anionic surfactant (i.e. a sodium salt of a
complex phosphate ester sold under the designation GAFAC MC-470
surfactant), and 91.94 percent by weight water provided at a
temperature of 95.degree.C. to form a polybenzimidazonium salt
having a sulfate anion. The monofilament is next washed in water to
remove excess acid and is dried in air at 200.degree.C. for 15
minutes. The formation of the salt is evidenced by changes in
solubility, fiber color, density, uv absorption, crystallinity and
the presence of 5.3 percent by weight sulfur therein as determined
by x-ray fluorescence. Following the salt formation reaction the
monofilament retains its original fibrous configuration intact and
exhibits a brighter appearance.
The monofilament while wrapped on a suitable mandrel is thermally
stabilized by heating in a circulating air oven in accordance with
the following heating schedule: 10 minutes at 300.degree.C., 10
minutes at 400.degree.C. and 5 minutes at 465.degree.C. The
stabilized monofilament is black in appearance, and retains its
original fibrous configuration intact.
The stabilized monofilament while in a holder is carbonized in a
tube furnace containing a circulating nitrogen atmosphere. The
monofilament over a period of 3 minutes gradually was inserted in
the furnace which was preheated to 1100.degree.C., retained therein
for 15 minutes while at 1100.degree.C., and subsequently withdrawn.
The resulting large denier carbonaceous fibrous material contains
in excess of 90 percent carbon by weight, retains its original
fibrous configuration intact, has a mean denier of 280 and a mean
fiber diameter of about 0.007 inch, a filament strength of 61,000
psi, a break elongation of 0.42 percent, a tensile modulus of 14.5
million psi, a density of 1.39 gm./c.c., and is suited for use as
fibrous reinforcement in a polymeric or metallic matrix
material.
EXAMPLE II
Example I is repeated with the exception that sulfamic acid is
substituted for sulfuric acid in the polybenzimidazonium salt
formation reaction to form a salt having a H.sub.2 N--SO.sub.2
O.sup.- anion. Also, the processing conditions are modified as
indicated. The thermal stabilization solely is conducted in air for
5 minutes at 465.degree.C. During carbonization the fibrous
material is maintained for 3 minutes at 1100.degree.C. The
resulting carbon filament has a mean denier of 279, a tensile
strength of 60,000 psi, a break elongation of 0.75 percent, a
tensile modulus of 8 million psi, and a density of 1.38
gr./c.c.
EXAMPLE III
Example I is repeated with the exception that phosphoric acid is
substituted for sulfuric acid in the polybenzimidazonium salt
formation reaction to form a salt having a phosphate anion. Also,
the processing conditions are modified as indicated. The thermal
stabilization solely is conducted in air for 5 minutes at
465.degree.C. During carbonization the fibrous material is
maintained for 2 minutes at 1100.degree.C. The resulting carbon
filament has a mean denier of 255, a tensile strength of 80,000
psi, a break elongation of 0.41 percent, a tensile modulus of 19
million psi, and a density of 1.40 gm./c.c.
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 (e.g. the process could be carried out on a
continuous basis, etc.). Such variations and modifications are to
be considered within the purview and scope of the claims appended
hereto.
* * * * *