U.S. patent number 3,716,331 [Application Number 05/028,167] was granted by the patent office on 1973-02-13 for process for producing carbon fibers having a high young's modulus of elasticity.
This patent grant is currently assigned to Union Carbide Corporation. Invention is credited to Roger Bacon, Wesley A. Schalamon.
United States Patent |
3,716,331 |
Schalamon , et al. |
February 13, 1973 |
PROCESS FOR PRODUCING CARBON FIBERS HAVING A HIGH YOUNG'S MODULUS
OF ELASTICITY
Abstract
Carbon fibers having a high Young's modulus are produced by a
process which comprises longitudinally stressing partially
carbonized cellulosic base fibers by means of an applied tensional
force while concurrently subjecting them to a carbonizing
treatment. The resultant stress carbonized fibers can then be
subjected to a stress graphitizing treatment, if desired.
Inventors: |
Schalamon; Wesley A. (Elyria,
OH), Bacon; Roger (Olmstead Falls, OH) |
Assignee: |
Union Carbide Corporation (New
York, NY)
|
Family
ID: |
21841946 |
Appl.
No.: |
05/028,167 |
Filed: |
April 10, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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610789 |
Jan 23, 1967 |
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Current U.S.
Class: |
423/447.5;
423/447.9 |
Current CPC
Class: |
D01F
9/16 (20130101) |
Current International
Class: |
D01F
9/16 (20060101); D01F 9/14 (20060101); C01b
031/07 () |
Field of
Search: |
;23/209.1,209.2,209.4,209.3 ;264/29 ;8/116 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
McCreight "Ceramic and Graphite Fibers" copyright 1965, Academic
Press, pages 55-60.
|
Primary Examiner: Meros; Edward J.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of application Ser. No. 610,789,
filed Jan. 23, 1967, now abandoned.
Claims
What is claimed is:
1. A process for producing a high Young's modulus of elasticity
non-graphitic carbon fiber which comprises:
a. heating a partially carbonized carbonaceous fiber at a
temperature of from about 250.degree.C. to about 900.degree.C. to
substantially completely carbonize said fiber , said partially
carbonized carbonaceous fiber having been produced by the heat
treatment of a cellulosic fiber at a temperature in the range of
from about 100.degree.C. to about 350.degree.C. until the fiber has
undergone an approximate weight loss based on the starting
cellulosic material in the range of from about 20 percent to about
50 percent, while;
b. concurrently stretching said fiber by means of an applied
tensional force an amount sufficient to achieve a percent effective
stretch of at least 5 percent.
2. The process of claim 1 wherein said partially carbonized
carbonaceous fiber is substantially completely carbonized in an
inert atmosphere.
3. The process of claim 1 wherein said partially carbonized
carbonaceous fiber is produced by heating a cellulosic fiber at a
temperature in the range of from about 150 to about
350.degree.C.
4. The process of claim 1 wherein said partially carbonized
carbonaceous fiber is produced by heating a cellulosic fiber which
has been treated with phosphoric acid to a temperature in the range
of from about 100.degree. to about 350.degree.C.
5. The process of claim 1 wherein said non-graphitic carbon fiber
is graphitized by heating it to a temperature in excess of
2000.degree.C.
6. The process of claim 1 wherein said non-graphitic carbon fiber
is stress graphitized by heating said fiber to a temperature of
about 2800.degree.C. while applying a stressing force thereto
sufficient to permanently stretch said fiber.
7. The process of claim 1 wherein said partially carbonized
carbonaceous fiber is in yarn form.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved process for producing
carbon fibers from cellulosic materials and to the fibers so
produced. As used herein and in the appended claims, carbon is
intended to include both the non-graphitic and graphitic forms of
carbon.
2. Description of the Prior Art
Carbon is an element which possesses many interesting and useful
chemical and physical properties. It is a material which both can
be found in nature and produced synthetically. Carbon is a readily
processible material and can be fashioned into almost any intricate
shape or pattern. Today, the uses of carbon in commerce and
industry are myriad.
Presently, most of the carbon articles used in industry are
produced by a process which comprises mixing non-graphitic carbon
particles with a carbonizable binder, extruding or molding the
so-produced mixture into the desired shape or article and,
subsequently, heating it to a temperature sufficient to carbonize
the binder phase. If, during this heating the maximum temperature
which the resultant article experiences is of the order of
700.degree.-900.degree.C., it is said to be a non-graphitic all
carbon article. However, if the article is further heated to a
temperature of the order of 2000.degree.-2500.degree.C. and higher,
it is said to be converted to a graphitic form of carbon and is
generally called graphite.
Recently, there has been introduced to the carbon art carbon in the
form of a textile. This form of carbon is unique in that it
possesses the flexibility of a textile while at the same time is
characterized by the electrical and chemical properties associated
with conventionally formed carbon articles.
U.S. Pat. No. 3,011,981 which issued Dec. 5, 1961 to W.T. Soltes
describes and claims a method for manufacturing carbon in a textile
form. Briefly, the process disclosed therein comprises heating a
cellulosic textile in an inert atmosphere at a progressively higher
temperature until substantial carbonization of the textile occurs.
The resultant product possesses the chemical and physical
attributes exhibited by conventionally formed carbon articles while
at the same time it retains the flexibility and other physical
characteristics associated with the textile starting material, such
as hand and drape.
A textile form of fibrous graphite is disclosed and claimed in U.S.
Pat. No. 3,107,152, which issued to C.E. Ford and C.V. Mitchell on
Oct. 15, 1963. Broadly stated, the process for producing fibrous
graphite disclosed therein comprises heating a cellulosic starting
material in an inert atmosphere at progressively higher
temperatures for various times until a temperature of about
900.degree.C. is achieved followed by further heating in a suitable
protective atmosphere at higher temperatures until substantial
graphitization occurs. The product produced by this process
exhibits the chemical and physical properties generally associated
with conventionally fabricated graphite while, at the same time, it
retains the textile characteristics of the starting material.
Recently, a high modulus, high strength form of graphite fiber has
become commercially available. Briefly, this material is produced
by a process which comprises stretching a substantially all carbon
fiber while it is being heated to graphitizing temperatures.
Although this improved form of graphite fiber possesses properties
which are unobtained in graphite fibers produced via the methods
disclosed by both Soltes and Ford, et al, the method of producing
it suffers from at least one serious processing difficulty. Namely,
the high force necessary to achieve both maximum strength and a
high Young's modulus is a limiting factor during the stress
graphitization of the already carbonized fiber. That is, in order
to obtain optimum strength and modulus values, the amount of stress
required is dangerously close to the breaking stress of the carbon
fiber. Needless to say, such close limits are not conducive to a
successful commercial operation.
SUMMARY
Briefly, the subject invention is accomplished by a process which
comprises concurrently longitudinally stressing a partially
carbonized cellulosic base fiber while subjecting it to a
carbonizing temperature in the range of from about 250.degree. to
900.degree.C. so that a given length of the resultant, stretched
fiber is at least 5 percent longer than it would have been had it
been carbonized in a stress-free manner. The so-produced
non-graphitic carbon fiber exhibits a higher Young's modulus of
elasticity than heretofore obtainable in non-graphitic carbon
fibers produced by conventional techniques. In addition, the
non-graphitic carbon fiber so-produced is especially amenable to
conventional stress graphitizing treatments. For example,
non-graphitic carbon fibers stress carbonized by the technique of
the instant invention which were subsequently stress graphitized at
a force of 400 grams per two ply exhibited a Young's modulus and
breaking strength of 52 .times. 10.sup.6 lb/in.sup.2 and 280,000
lb/in.sup.2, respectively, while fibers produced by the practice of
the prior art, i.e., by stress graphitizing a conventionally
carbonized fiber, required a force of 1300 grams per 2 ply to
duplicate these physical properties.
DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
Fibers suitable for the practice of the invention are those which
upon carbonization do not melt or fuse but which when so heat
treated tend to lose their inherent orientation. Specifically,
fibers suitable for the practice of the invention are fibers of
either natural or regenerated cellulosic origin which have been
subjected to a pre-heat treatment to convert them to partially
carbonized carbonaceous fibers. This is accomplished by first
heating the raw cellulosic base fibers in either an inert or
oxidizing atmosphere to a temperature in the range of from about
100.degree. to about 350.degree.C. for fibers which have been
treated with a carbonizing aid, such as phosphoric acid, or from
about 150.degree. to about 350.degree.C. for fibers which are
untreated, until the fibers have undergone an approximate weight
loss based on the starting cellulosic material in the range of from
about 20 percent to about 50 percent. Both of these techniques are
described in detail in Ser. No. 224,989, filed Sept. 20, 1962, now
U. S. Pat. No. 3,305,313, issued Feb. 21, 1967, which has been
assigned to the same assignee as the instant application.
The present invention will now be described in greater detail in
the following examples.
EXAMPLE I
An apparatus was constructed for stretching carbonaceous fibers,
preferably in yarn form, at elevated temperatures. This apparatus
consisted of a vertically positioned, electric resistance heated
hollow tube furnace having a length of approximately 2 feet and a
diameter of 2 inches; a graphite rod positioned across the top of
the tube furnace; and an atmosphere control system for regulating
the atmosphere in the hot zone of the furnace. A partially
pre-carbonized yarn prepared by heating a 1650 denier, 720
filament, 1 ply rayon yarn to a temperature of about 250.degree.C.
was doubled over the support rod and passed through the apparatus.
The yarn was joined together at the two ends and the desired weight
(see Table 1) was attached thereto which thereby put the yarn under
a longitudinally applied tension or stress. The fibers in the
furnace were then gradually heated to carbonizing temperatures. The
heating schedule was 600.degree.C./hr. from room temperature to
900.degree.C. followed by an immediate cooling at an initial rate
of approximately 400.degree.C./hr. The 400.degree.C./hr. cool-off
rate rapidly decayed so that the approximate time from
900.degree.C. to room temperature was about 16 hours. An argon
atmosphere was maintained in the furnace both while the yarn was
being heated and cooled. The amount of stretch which the yarn
experienced during the stress carbonization was measured with a
precision cathetometer.
It should be noted here that the partially carbonized cellulosic
starting material inherently shrinks while it is being completely
carbonized. Accordingly, the per cent of effective stretch reported
in Table 1 below is determined by measuring the difference in
length between a unit length of stress carbonized material and a
similar unit length of material carbonized in a stress-free manner
and dividing that value by the length of the stress-free carbonized
material followed by multiplying the obtained value by 100. The
foregoing is the meaning to be applied to the term "percent
effective stretch" when used herein and in the appended claims.
Table 1 presents data which illustrates the resultant properties of
carbon fibers stress carbonized by the foregoing technique.
Table 1
Force on Percent Young's Tensile Sample Fibers Effective Modulus
Strength No. (gm/2 ply) Stretch (10.sup.6 lb/in.sup.2)
(lb/in.sup.2)
__________________________________________________________________________
1 5 0.05 5.8 73,000 2 250 20 8.0 62,000 3 400 35 10.1 83,000 4 500
50 10.4 71,000
__________________________________________________________________________
Although not included in Table 1 additional experimental data
indicates that an effective stretch of at least 5 percent must be
achieved during the stress carbonizing procedure to insure that
so-treated fibers will exhibit significantly improved properties.
An effective stretch of 5 percent has been found to produce fibers
which have a Young's modulus of elasticity of at least 6.2 .times.
10.sup.6 lb/in.sup.2.
EXAMPLE II
Using the same technique, apparatus and type of starting fiber as
described in Example 1, fibers were stress carbonized by applying a
tensional force of 400 gm/2 ply while concurrently heating them to
a temperature of approximately 900.degree.C. These stress
carbonized fibers were then graphitized by heating them to
2800.degree.C. under essentially no load conditions. The properties
of the fibers so-produced are presented in Table II. In order to
produce graphite fibers exhibiting similar properties by
conventional stress graphitizing techniques, it was necessary to
employ a stressing force which was twice as great as that required
by the stress carbonizing method. For comparison, properties of
fibers produced by the technique of the instant invention and by
the prior art method are presented in Table II.
Table II
Effective Force on temp. range Young's fibers over which force
Modulus Tensile Method (gm/2 ply) was applied (.degree.C) (10.sup.6
lb/in.sup.2) Strength
__________________________________________________________________________
Stress Carbonizing 400 250-900 23.4 180,000 (followed by stress
free graphitization to 2800.degree.C.) Stress Graphitizing 800
100-2800 23.0 175,000 (prior art)
__________________________________________________________________________
From the foregoing data, it is clear that the instant invention
provides a method for producing high modulus fibers without
requiring that they be subjected to high stresses during their
subsequent graphitization.
EXAMPLE III
Using the same apparatus, technique and type of starting fiber as
described in Example 1, fibers were stress carbonized by applying a
tensional force of 450 gm/2 ply while concurrently heating them to
a temperature of approximately 900.degree.C. These stress
carbonized fibers were then stress graphitized by applying a
tensional force of 400 gm/2 ply while concurrently heating them to
a temperature of approximately 2900.degree.C. The properties of
fibers so-produced are presented in Table III. For comparison, the
properties of graphite fibers produced by conventional stress
graphitizing techniques are also reported in Table III.
Table III
Effective temp. range Force on over which Young's Tensile fibers
force was Modulus Strength Method gm/2 ply applied (10.sup.6 lb
/in.sup.2) (lb /in.sup.2) (.degree.C.)
__________________________________________________________________________
Stress Carbonized 450 250-900 (and subsequently) Stress Graphitized
400 900-2900 52 280,000 Stress Graphitized (prior art) 1300
1000-2800 55 290,000
__________________________________________________________________________
From a review of the date presented in Table III, it is seen that
stress carbonizing reduces the amount of stressing required to
produce high modulus, high strength, fibers by stress graphitizing
already carbonized fibers.
* * * * *