U.S. patent number 3,669,158 [Application Number 05/017,265] was granted by the patent office on 1972-06-13 for continuous carbon fiber tapes.
This patent grant is currently assigned to Minister of Technology in Her Britannic Majesty's Government of the. Invention is credited to Leslie Nathan Phillips.
United States Patent |
3,669,158 |
Phillips |
June 13, 1972 |
CONTINUOUS CARBON FIBER TAPES
Abstract
Tape containing continuous high strength high modulus carbon
fibers and optionally also glass fibers suitable for use as
pre-impregnated tape in mechanical winding processes is disclosed
wherein there is a light cross-weave of 1-10 filaments of fine
glass fiber at a frequency of about 10-2 threads per inch.
Inventors: |
Phillips; Leslie Nathan
(Farnborough, EN) |
Assignee: |
Minister of Technology in Her
Britannic Majesty's Government of the (London,
EN)
|
Family
ID: |
26249029 |
Appl.
No.: |
05/017,265 |
Filed: |
March 6, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Mar 10, 1969 [GB] |
|
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12,448/69 |
Nov 6, 1969 [GB] |
|
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54,452/69 |
|
Current U.S.
Class: |
139/420R;
139/420C; 138/118; 28/166 |
Current CPC
Class: |
D03D
15/47 (20210101); D03D 3/005 (20130101); D03D
15/267 (20210101); D03D 15/00 (20130101); D03D
13/002 (20130101); D10B 2401/063 (20130101); D10B
2101/06 (20130101); D10B 2101/12 (20130101); D10B
2321/10 (20130101); D10B 2505/02 (20130101) |
Current International
Class: |
D03D
15/00 (20060101); D03d 015/00 () |
Field of
Search: |
;117/161ZB,161P,161LE,161LC,228 ;57/14G ;161/87,88,90,91,92,93
;139/383R,384R,42R,42G ;28/75 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Jaudon; Henry S.
Claims
I claim:
1. A pre-impregnation tape comprising a plurality of warp members
parallel to and contiguous with one another selected from the group
consisting of tow of glass fiber and tow of unidirectional carbon
fibers, at least 10 percent by weight of said warp members
consisting of said tow of carbon fibers, and a continuous weft
thread continuously woven through said warp members at a frequency
of between about 10 and 2 threads per inch, said weft thread being
selected from the group consisting of continuous glass fiber and
continuous carbon fiber.
2. A tape as claimed in claim 1 wherein the warp members are
composed entirely of carbon fiber tow.
3. A tape as claimed in claim 1 wherein the carbon fiber tow
include high modulus carbon fiber having a Young's modulus parallel
to the fiber axis of not less than 16 .times. 10.sup.6 pounds per
square inch.
4. A tape as claimed in claim 1 wherein the weft thread comprises
between 1 and 10 filaments of glass fiber.
5. A tape as claimed in claim 1 wherein the carbon fiber tows have
a surface dressing comprising a resin selected from the group
consisting of epoxy, phenolic, Friedel-Crafts, polyimide and
polyester resin.
6. A tape as claimed in claim 1 and impregnated with resin.
7. A pre-impregnation tape comprising a plurality of warp members
parallel to and contiguous with one another selected from the group
consisting of tow of glass fiber and tow of unidirectional carbon
fibers, at least 10 percent by weight of said warp members
consisting of said tow of carbon fibers, and a continuous weft
thread continuously woven throughout the length of said warp
members and zigzaggedly crossing said warp members at an oblique
angle at a frequency of between about 10 and 2 threads per inch,
said weft thread being selected from the group consisting of
continuous glass fiber and continuous carbon fiber.
8. A method of preparing a cured tape comprising immersing carbon
fiber in a dressing solution of not more than 35 percent by weight
of resin in a volatile organic non-aqueous solvent and drying to
remove said solvent in order to provide a dressing on said carbon
fiber, preparing a plurality of warp members from tow of glass
fiber and tow of unidirectional carbon fiber comprising said
dressed carbon fiber, at least 10 percent by weight of said warp
members consisting of tow of carbon fibers, and weaving a
continuous weft thread through said warp members and continuously
throughout the length thereof at a frequency of between about 10
and about 2 threads per inch whereby said warp members are
maintained parallel to and contiguous with one another during
curing of said tape, said weft thread being selected from the group
consisting of continuous glass fiber and continuous carbon fiber,
and curing said tape.
9. A method as claimed in claim 8 wherein the solvent is selected
from the group consisting of acetone, ethyl acetate, methyl ethyl
ketone, ethylene dichloride and 1,2-dichloroethane.
10. A method as claimed in claim 8 wherein the dressing solution
comprises a 1-5 percent by weight of epoxy resin in acetone.
Description
The present invention relates to tape containing unidirectional
carbon fibers which may be resin impregnated and used to produced
reinforced plastic articles by applying to or winding on a former
followed by curing.
It is well known to produce composite shaped articles by winding a
resin pre-impregnated tape upon a former or mandrel of a suitable
shape and then to place the former and tape in a mould either
without further addition of resin or after further resin has been
impregnated into the tape. However, it has been discovered that the
parallel alignment of the reinforcing fibers in the tape is not
retained in the mould because in the early stages of cure the resin
is liquid and under the influence of the hydrostatic pressure in
the liquid resin the individual reinforcing fibers in the
pre-impregnated tape are forced apart and the phenomenon known as
barrelling takes place. This results in misalignment of the
reinforcing fibers and may lead to failure to realize the full
strength possible of the composite material.
Misalignment of fibers in carbon fiber reinforced articles can
cause weakness because the relatively small extension at break of
carbon fibers means that in a composite in which the fibers are not
properly aligned individual fibers may fail before other fibers in
a different orientation are taking an appreciable proportion of the
load.
In accordance with the present invention, a tape containing
unidirectional carbon fiber comprises a plurality of warp members,
which include carbon fiber tows, and a continuous weft-thread woven
through said warp members at a frequency of between about 10 and 2
threads per inch said weft thread being arranged to maintain the
warp members parallel to and contiguous with one another.
Normally the warp members are not individual filaments but
aggregations of individual filaments and conveniently a warp member
is a tow of carbon fiber of about 10,000 ends or filaments although
for particular purposes the number of ends or filaments in any
given carbon fiber tow warp member may be any number down to about
500 as may be convenient.
The warp members may be entirely carbon tows or a proportion
thereof may be replaced by bundles or tows of glass fiber and up to
90 percent by weight of the total warp may be bundles or tows of
glass fiber.
Tows of carbon fiber and tows of glass fiber may alternate as warp
members or a plurality of adjacent warp members may be of carbon
fibers and/or a plurality of adjacent warp members may be of glass
fiber so that the tape has a banded structure wherein the carbon
and glass fiber are grouped together in the warp. In an extreme
example a single tow of glass fiber or a single tow of carbon
fibers may be interposed between two groups of fiber of the
opposite type. For example if a tape containing both carbon fiber
and glass fiber has to be trimmed at the edges it is more
economical to have the edges to be trimmed off entirely of glass
fiber because of the cost of carbon fiber, so long as this does not
detract from the properties of the finished composite.
Conveniently the tows of glass fiber and tows of carbon fiber are
substantially the same size so that the weave of the finally
produced tape remains even. The sizes may, however, vary quite
markedly if this does not spoil the evenness of the weave of the
finally produced tape or permit misalignment of the carbon fibers
in a finally produced composite such that an appreciable number of
carbon fibers break under strain before substantially all the
carbon fibers are loaded.
Preferably the unidirectional carbon fiber tows of the warp members
are of high strength high modulus carbon fiber manufactured by one
or more of the processes described in the specifications of U.K.
Pat. Nos. 1,110,791, 1,148,874, 1,166,251, 1,166,252, 1,168,619,
1,180,441 and U.K. application No. 28881/66 now U.K. Pat. No.
1,193,263.
The carbon fiber tows of this invention include high strength high
modulus carbon fiber produced by one or more of the processes
described in U.S. Pat. No. 3,412,062.
In U.S. Pat. No. 3,412,062, there is described a method of making
carbon fibers having a Young's modulus parallel to the fiber axis
of not less than 16 .times. 10.sup.6 pounds per square inch
comprising the steps of oxidizing an organic polymer fiber by
simultaneously heating the fiber in an oxidizing atmosphere at a
temperature of from about 200.degree. to 250.degree. C for a time
sufficient to permit substantially complete permeation of oxygen
throughout the core of the fiber while the fiber is held under
longitudinal tension, said tension being sufficient at least to
limit shrinkage of the fibers during heating to not more than about
12 percent of the length of the fiber, and carbonizing the fiber by
heating the oxidized fiber in a non-oxidizing atmosphere to a
temperature of up to about at least 1,000.degree. C. Preferably the
organic polymer fiber is polyacrylonitrile.
It is to be noted that the term polyacrylonitrile fibers is used by
those skilled in this art to include copolymers or terpolymers of
acrylonitrile with other monomers e.g. methyl methacrylate or vinyl
acetate, either alone or to which have been added polymers
compatible with them for example phenolic resins or Friedel-Crafts
condensates. It is in this sense that the term polyacrylonitrile
fibers is used throughout said U.S. Pat. No. 3,412,062.
The high temperature carbonizing is performed under vacuum or in a
non-oxidizing atmosphere such as hydrogen.
The preliminary low temperature oxidizing step which forms part of
said method should not be of too short duration as the fibers are
then left with a soft core and upon subsequent high temperature
heat treatment holes are formed in the resulting fibers.
In a further embodiment according to said U.S. Pat. No. 3,412,062,
a process of producing carbon fibers comprises initially heating
fibers of polyacrylonitrile while held under tension in an
oxidizing atmosphere at from 200.degree.-250.degree.C for
sufficient time to permit substantially complete permeation of
oxygen throughout the individual fibers and subsequent further
heating of the fibers so formed to a carbonizing temperature of at
least 1,000.degree.C under non-oxidizing conditions.
The duration of the initial heating required will depend to a large
extent on the diameter of the fibers concerned but for a
temperature of 220.degree.C complete oxygen permeation of the
fibers takes place after heating for about 24 hours for 21/2 denier
fibers and after about 50 hours for 41/2 denier fibers.
The fibers are tensioned so that longitudinal shrinkage which
normally takes place during this initial heating is reduced,
eliminated or is such as to cause the fibers to elongate.
Further improvements in the characteristics of the fibers produced
are achieved if, subsequent to carbonizing to about 1,000.degree.C
the fibers are further heat treated to above 2,000.degree.C in a
non-oxidizing atmosphere.
The tensioning of fibers may also be maintained during the
subsequent carbonizing and/or heat treatment.
For further details, please refer to the examples of said U.S. Pat.
No. 3,412,062.
The weft is intended to prevent the phenomenon of barrelling
described above and maintain the fibers in alignment and the
material used is selected to be sufficiently strong to achieve this
end although it must also be selected to be compatible with the
unidirectional carbon fiber used as reinforcement, with the plastic
to be reinforced, and with any additive thereto.
The weft thread may be of continuous carbon fiber but this is not
in general successful. Advantageously the weft thread is glass
fiber and it has been found that between 1 and 10 ends or filaments
of fine glass fiber is preferred.
An embodiment of the invention is illustrated in the accompanying
drawing in which A represents warp members which may be tows of
carbon fiber or a mixture of tows of carbon fiber and tows of glass
fiber as described above and B represents the continuous weft
thread, which is woven at a frequency of between about 10 and 2
threads per inch and which is between 1 and 10 filaments of fine
glass fiber. More particularly, as shown in said drawing, B
represents the continuous weft thread, which is continuously woven
throughout the length of said warp members and zigzaggedly crossing
said warp members at an oblique angle at a frequency of between
about 10 and 2 threads per inch.
The tape may be woven by the well known means of the weaving art
and preferably prior to the weaving process the carbon fiber tows
are treated by the process of dressing described in U.K. Pat.
Application Nos. 52,653/67 and 4,711/68, now issued as a single
U.K. Pat. No. 1,195,219 which discloses a dressing for facilitating
the handling and processing of carbon fibers comprising a dilute
solution of not more than 35 percent by weight of resin in a
volatile organic non-aqueous solvent.
The resin may comprise an epoxy, phenolic, Friedel-Crafts,
polyimide or polyester resin.
Suitable solvents are acetone, ethyl acetate, methyl ethyl ketone
and chlorinated hydrocarbons such as ethylene dichloride and 1.2
dichloroethane.
In one example it was found that a solution of 1-5 percent by
weight of epoxy resin in acetone formed a satisfactory
dressing.
Examples of epoxy resins which have been used are Araldite
(Registered Trade Mark) LY 558 and Shell (Registered Trade Mark)
Epikote 828. Other epoxy resins may be used, it being desirable
that they should have a high viscosity and that brittle resins be
avoided. Low viscosity resins of the cycloaliphatic type, such as a
cyclopentadiene based resin, may be blended with other more viscous
resins in order to obtain the overall required viscosity.
It a further example it was found that a solution of 5-20 percent
by weight of polyester resin in methyl ethyl ketone formed a
satisfactory dressing.
It was also found that either a hot or cold setting polyester resin
was satisfactory, e.g. Bakelite (Registered Trade Mark) S.R. 17449
resin an unsaturated polyester made from a glycol, a dicarboxylic
acid and maleic anhydride has been found satisfactory.
Also, according to the present invention a process for rendering
carbon fibers readily handleable comprises impregnating the fibers
with a dressing comprising a weak solution of resin, such as an
epoxy, phenolic, Friedel-Crafts, polyimide or polyester resin in a
volatile organic non-aqueous solvent, and allowing the solvent to
evaporate, evaporation of the solvent leaving the carbon fibers in
a close knit handleable form.
It is to be noted that the term Friedel-Crafts resin means a resin
formed from an aromatic compound with an aromatic linking agent
which has two chloromethyl or methoxymethyl groups attached to an
aromatic nucleus by means of a polycondensation reaction involving
the nuclear hydrogen atoms and may be aided by the presence of a
small amount of Friedel-Craft type catalyst such as stannic
chloride.
Once the tape is obtained it may then be impregnated with an
appropriate resin and converted to a pre-impregnated tape suitable
for use as described above.
Such a process lends itself to the continuous production of thin
carbon fiber reinforced composite material. In an example of such a
process a continuous supply of carbon fibers, as from a process in
which carbon fibers are produced continuously, are drawn in turn
through a bath containing said dressing, a drying region in which
surplus dressing drains from the fiber and that remaining on the
fibers is dried, a second bath containing a heat catalyzed
polyester resin in which the fibers are immersed and between a pair
of rollers between which the composite material comprising the
fibers, dressing which has been softened by the polyester resin and
the resin are flattened to a tape like form. The resin content of
the tape may subsequently be cured by the application of heat.
In one example a non-continuous process for producing a plastics
composite material 80 grams of 10,00 filament tow carbon fibers of
7 microns diameter of the type disclosed in British Pat. No.
1,110,791 and having an ultimate tensile strength of 280 .times.
10.sup.3 lg/sq in. and a Young's modulus of 55 .times. 10.sup.6
lb/sq in. were supported in a glass fiber cloth cradle or sling and
dipped into a tank containing 3 liters of polyester resin solution
comprising 1 part by weight of Bakelite (Registered Trade Mark)
S.R. 17,449 polyester resin and 4 parts by weight of methyl ethyl
ketone.
After immersion for 30 seconds, the cradle supporting the fibers
was removed from the solution and the surplus solution allowed to
drain off. The fibers, with residual dressing adhering to them,
were then suspended vertically for 2 hours at room temperature
until dry. The resulting clumped fibers were then incorporated as a
reinforcement in a matrix comprising 100 parts by weight S.R.
17,449 polyester resin, 2 parts peroxide catalyst and 2 parts
cobalt naphthenate, the fibers comprising approximately 40 percent
by volume of the resulting composite formed when curing of the
resin was complete.
The tape of the present invention may be used advantageously when
it is desired to tension the unidirection carbon fibers while the
moulding process is being carried out. This has the advantage that
individual carbon fibers are aligned substantially parallel during
the curing process and also helps to ensure that the load of the
composite finally produced is evenly distributed among the carbon
fibers. This is important in view of the relatively small extension
at break of carbon fibers which means that in a composite in which
fibers are not properly aligned individual fibers may fail before
other fibers in a different fibers in a different orientation are
taking an appreciable share of the load.
* * * * *