U.S. patent number 3,839,072 [Application Number 05/166,233] was granted by the patent office on 1974-10-01 for carbon fibre tow.
This patent grant is currently assigned to National Research Development Corporation. Invention is credited to Hugh Arthur Kearsey.
United States Patent |
3,839,072 |
Kearsey |
October 1, 1974 |
CARBON FIBRE TOW
Abstract
The degree of alignment of carbon fibres in a continuous carbon
fibre tow is improved by applying a resin solution to the tow at a
point where the tow is still travelling under the same tension and
in the same direction as that in which it travelled through the
furnace. Application of the resin, e.g., polyvinyl alcohol in a
volatile organic solvent, may be effected by means of a porous,
e.g., felt, spreader without substantially altering the direction
of travel of the tow.
Inventors: |
Kearsey; Hugh Arthur (London,
EN) |
Assignee: |
National Research Development
Corporation (London, EN)
|
Family
ID: |
10387434 |
Appl.
No.: |
05/166,233 |
Filed: |
July 26, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Jul 27, 1970 [GB] |
|
|
36360/70 |
|
Current U.S.
Class: |
427/172; 8/115.6;
264/290.5; 427/175; 428/367; 428/477.7; 428/522; 264/289.6;
423/448; 427/227; 428/394; 428/413; 428/480 |
Current CPC
Class: |
D01F
11/14 (20130101); D01F 11/122 (20130101); Y10T
428/2967 (20150115); Y10T 428/2918 (20150115); Y10T
428/31765 (20150401); Y10T 428/31935 (20150401); Y10T
428/31511 (20150401); Y10T 428/31786 (20150401) |
Current International
Class: |
D01F
11/14 (20060101); D01F 11/00 (20060101); D01F
11/12 (20060101); B44d 003/12 () |
Field of
Search: |
;117/46CB,46CC,7
;8/115.6 ;118/47 ;423/447,448 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Bell; Janyce A.
Attorney, Agent or Firm: Wenderoth, Lind & Donack
Claims
1. A method of producing a carbon fiber tow which comprises
continuously drawing a carbonizable fiber tow unidirectionally and
substantially linearly under tension through a carbonizing furnace
to carbonize said fiber, drawing the carbon fiber tow from said
furnace so that the fiber travels in substantially the same linear
direction in which it travelled through the furnace, applying a
resin solution to the tow and allowing said resin to substantially
set while the tow is still under tension and travelling in
substantially the said linear direction so as to preserve the
alignment of the carbon fibers in the tow substantially as it
emerges
2. A method as claimed in claim 1, wherein the carbonizable fiber
tow is a
3. A method according to claim 2, wherein the carbonizable
polycrylonitrile fiber tow is subjected to a preliminary oxidation
treatment before
4. A method according to claim 2, wherein the carbonizable
polyacrylonitrile tow is subjected to an oxidation treatment
after
5. A method as claimed in claim 1, wherein the carbon fiber tow is
subjected to a graphitization treatment by being drawn without any
alteration in direction through the treatment zone or zones prior
to the
6. A method according to claim 5, wherein the carbon fiber tow is
also subjected to a surface oxidation treatment by being drawn
without any alteration in direction through the treatment zones
prior to the resin
7. A method as claimed in claim 1, wherein the resin solution is
applied to
8. A method as claimed in claim 1, wherein the resin is applied in
solution
9. A method as claimed in claim 11, wherein the resin is polyvinyl
alcohol,
10. A method as claimed in claim 11, wherein the amount of resin
applied is
11. A method as claimed in claim 11, wherein the resin is applied
in the form of a solution containing from 0.1 to 5 percent by
weight of the
12. A method according to claim 1 wherein the carbon fiber tow is
subjected to a surface oxidation treatment by being drawn without
any alteration in direction through the treatment zone or zones
prior to the resin application.
Description
This invention relates to the production of carbon fibre tows. As
is well known, the standard procedure starts with a
polyacrylonitrile fibre tow, and comprises the following steps:
1. An optional oxidation at a temperature in the range 200.degree.C
to 275.degree.C.
2. Carbonisation at a temperature of the order of 1,000.degree.C to
1,500.degree.C.
3. An optional graphitisation at a temperature in the range
2,250.degree.C to 275.degree.C.
4. An optional surface oxidation treatment. The present invention
relates to a continuous process for the production of carbon fibres
on a relatively large scale. It will be apparent that it is
desirable to produce the carbon fibres in long lengths, and indeed,
for the manufacture of artefacts from the carbon fibres, the longer
the length the better. It is therefore desirable to use as a
starting material long lengths of PAN fibre. Similarly, for the
sake of cheapness, it is desirable to use a commercially available
form of PAN fibre rather than to use a special fibre which, it will
be understood, would inevitably be more expensive. Finally, our
tests have shown that taking into account the inevitable shrinkage
in diameter of the carbon fibres as compared with the precursor
material, it is desirable to make use of a precursor material of
about 1.5-denier.
In order to use carbon fibres, the present practice is normally to
use them as a reinforcement in a matrix, and for many purposes it
is extremely desirable that the carbon fibres should be available
in the form of a tape or band some 4 in. wide, since this form
enables the carbon fibres to be surface-treated if necessary and
then to be preimpregnated with the matrix material. It is
relatively simple thereafter to split the wide tape up into
narrower tapes should this be desirable.
The normal manufacture of PAN fibres for conventional textile
purposes results in two possible forms of fibre, namely straight
fibre and crimped fibre which is produced by forcing the tow
through a heated stuffing box. In practice we have found that
straight filament fibre has a false twist which encourages fibre
entanglement so that it is extremely difficult to spread the
initially circular tow into an even tape of fibres. On the other
hand, with crimped fibre, due to the final crimping stage which is
carried out in the form of a wide band, the fibres naturally fall
into the necessary tape form and therefore we prefer to use crimped
fibres in the process of forming carbon fibres. However, it is
necessary to remove the crimp before the fibres are oxidised, and
also in practice we find that the crimped fibres are normally
provided as 3-denier or thicker fibres and so must be reduced in
thickness before they form the most desirable carbon fibres.
In the process described in British Pat. Specification No. 1110791,
it is taught that at least a part of the operation is performed
with the tow under tension in order to increase the ultimate
tensile strength and Youngs modulus of the product. Tension is
generally applied by means of a roller assembly.
When the emerging carbon fibres reach the outlet rollers, two
factors operate to spoil the alignment of individual fibres within
the tow. Firstly, in those cases where the tow is wrapped around
part of the periphery of a roller, the tow has thickness so that
some fibres pass around the roller at a greater radius than others.
Secondly, it is not practicable to apply much tension to the fibres
for winding up for storage, so that on the outlet side of the
tensioning rollers, tension in the tow is relaxed.
It is an object of the present invention to improve the degree of
alignment of the carbon fibres in the tow as stored.
The present invention provides a method of producing a carbon fibre
tow which method comprises continuously drawing a carbonisable
fibre tow linearly under tension through a carbonising furnace and
applying a resin solution to the carbon fibre tow, at a point where
the tow is still under tension and is still travelling in the
direction in which it travelled through the furnace, so as to
retain the alignment of the carbon fibres in the tow substantially
as it emerged from the furnace.
The carbonisable fibre tow may be a polyacrylonitrile fibre tow
either before or after the optional preliminary oxidation
treatment. As the oxidation treatment is rather slow, it may be
easier to wind up the oxidised tow, rather than to transfer it
direct to the carbonising furnace. The oxidised fibres retain some
elasticity, and the oxidised tow can be wound up without excessive
loss of alignment of the individual fibres.
When a graphitisation and/or surface oxidation treatment is carried
out after carbonisation, the tow is drawn successively without any
alteration in direction through the various treatment zones prior
to the resin application.
The resin solution may be applied to the carbon fibre tow by any
convenient method which does not involve loss of alignment of the
individual fibres. Spraying of the resin solution and application
by means of a porous, e.g., felt, spreader are suitable methods,
the latter being preferred. Passage of the tow through a trough of
the resin solution is not a suitable method if it involves loss of
alignment of the individual fibres on passage round a roller.
The solvent of the resin solution is preferably rapidly volatile.
Conventional organic solvents appropriate to the resin chosen,
e.g., acetone or ether, are generally suitable.
The nature of the resin is not critical to this invention. In
general, the resin will be chosen with regard for the matrix which
the carbon fibre tow is to reinforce. Polyvinyl alcohol, being
water-soluble, is suitable for fibre intended for a further stage
of wet surface treatment or for metal composites. Epoxy resins,
polyvinyl acetate systems, polyester and polyamide resins are
suitable for other applications of the fibres. Further possible
resins will be readily apparent to the reader.
The purpose of the resin application is to prevent or reduce
accidental breakage and loss of the fibres, which are delicate and
slippery, during normal handling. A relatively small amount of
resin, e.g. from 1 to 5 percent, preferably about 2.5 percent by
weight on the weight of the carbon fibre, is sufficient for this
purpose. The resin coating also greatly improves the grip between
the fibres and the rollers.
The concentration of the resin solution is not critical. As the
amount of resin used is small, it may be convenient to use a rather
dilute solution, e.g. from 0.1 percent to 5 percent by weight, of
the resin.
The present invention also provides apparatus for producing a
carbon fibre tow, which apparatus comprises a carbonising furnace,
means for continuously drawing a carbonisable fibre tow linearly
therethrough under tension, and means for applying a liquid to the
tow, without substantially altering its direction of travel, at a
point between the carbonising furnace and the drawing means. The
tension is not critical; we find it convenient to use a tension of
from 2 to 16 Kg, e.g., 8 Kg, for a 160,000 3-denier filament
tow.
A specific embodiment of the invention will now be described with
reference to the accompanying drawing, which is a diagrammatic
representation of apparatus according to the invention.
The apparatus comprises a carbonisation furnace 10, a
graphitisation furnace 11, and a gaseous surface treatment zone 12
in succession, separated from each other and from the atmosphere by
gas locks 13. Adjacent the final gas lock is a felt spreader 14,
supplied with a 2 percent solution of polyvinyl alcohol in acetone
from a reservoir 15. An extraction hood 17 is positioned next to
the felt spreader 14.
In operation a tow of previously oxidised polyacrylonitrile fibres
18 is drawn by means of a pair of driven rollers 22 and 23 from a
supply (not shown) through the nip between rollers 19 and 20, which
are braked to provide the desired degree of tension in the tow
between rollers 19, 20 and rollers 22, 23. The tow passes
successively through furnaces 10 and 11 and treatment zone 12; past
the felt spreader 14 where it picks up approximately its own weight
of the resin solution; past the extraction hood 17, where the
acetone is evaporated off and the polyvinyl alcohol sets and causes
the individual carbon fibres in the tow to adhere lightly together;
around the freely rotating roller 21 which is fitted with a
revolution counter (not shown) to measure the quantity of fibre
passing; through the nip between driven rollers 22 and 23, where
the tension on the tow is relaxed; and finally on to a drum 25,
where it is rolled up interleaved with paper from a supply 26.
Although the felt spreader 14 is illustrated as being above the tow
18, and the extraction hood 17 below it, it may be found more
convenient to apply the resin solution to the tow 18 from below and
to extract volatile solvent from above.
The carbon fibres are slippery and difficult to handle, and it is
not easy to impart a controlled tension to the tow by means of a
pair of conventional driven pinch rollers, even when they are
surfaced with a non-slip material. In the roller combination, 22,
23, which is used in the embodiment of this invention, the roller
22 swings on a pivot 24. Also the tow, in addition to passing
through the nip between the two rollers 22 and 23, passes round a
substantial portion of the circumference of each. Thus the tension
in the tow increases the pressure (and hence grip) between the
rollers.
* * * * *