TECHNICAL FIELD
[0001] The present invention relates to an oxidized fiber bundle and a production method
for a carbon fiber bundle. More specifically, the present invention relates to an
oxidized fiber bundle useful for efficient production of an oxidized fiber bundle
having high quality, a production method for a carbon fiber bundle, and an oxidation
furnace.
BACKGROUND ART
[0002] Being high in specific strength, specific elastic modulus, heat resistance, and chemical
resistance, the carbon fiber is useful as a reinforcing material for various materials
and has been used in a wide range of fields such as aerospace applications, leisure
applications, and general industrial applications.
[0003] In a generally known process for producing a carbon fiber bundle from an acryl based
fiber bundle, an acryl based fiber bundle containing several thousands to several
tens of thousands of aligned single fibers of an acrylic polymer is fed to an oxidation
furnace and subjected to heat treatment (oxidation treatment) by exposing it to a
flow of hot oxidizing gas such as hot gas heated at 200°C to 300°C supplied from a
heated gas supply nozzle (hereinafter referred to simply as supply nozzle) installed
in the furnace body, and the resulting oxidized fiber bundle is sent to a carbonization
furnace where it is subjected heat treatment (precarbonization treatment) in an inert
gas atmosphere maintained at 300°C to 1,000°C. Finally, it is subjected to heat treatment
(carbonization treatment) in a carbonization furnace filled with an inert gas atmosphere
at 1,000°C or more. The oxidized fiber bundle obtained as an intermediate material
is so high in fire retardance that it has been also used widely as material for fire
retardant woven fabrics.
[0004] In the carbon fiber bundle production process, the oxidation step is the longest
in treatment time and the largest in energy consumption. In this aspect, productivity
improvement in the oxidation step is the most important point in the production of
a carbon fiber bundle.
[0005] In order to permit prolonged heat treatment in the oxidation step, it is common to
use an oxidation apparatus (hereinafter referred to as oxidation furnace) that has
turn-around rollers disposed outside the furnace body of the oxidation furnace to
allow the acryl based fibers to be turned around and moved to and fro many times in
the horizontal direction in the furnace body of the oxidation furnace. The method
in which hot gas is supplied in a substantially parallel direction to the traveling
direction of the acryl based fiber bundle in the furnace body of such an oxidation
furnace is called the parallel flow method, whereas the method in which hot gas is
supplied in the orthogonal direction to the traveling direction of the acryl based
fiber bundle is called the orthogonal flow method. An apparatus to work according
to the parallel flow method has either an end-to-end (hereinafter simply referred
to ETE) hot gas heating structure in which a supply nozzle is installed at one end
of a parallel flow furnace with a nozzle for discharging gas out of the furnace body
(hereinafter referred to simply as discharge nozzle) installed at the other end or
a center-to-end (hereinafter simply referred to CTE) hot gas heating structure in
which a supply nozzle is installed in the central portion of the parallel flow furnace
with discharge nozzles installed at both ends thereof. It is noted that apparatuses
of the ETE hot gas heating structure is generally is lower in equipment cost than
apparatuses of the CTE hot gas heating structure.
[0006] Among other methods for improving the productivity of an oxidation process, it is
effective to feed a large number of acryl based fiber bundles at the same time to
achieve a higher density of acryl based fiber bundles in the furnace body of the oxidation
furnace. It is also effective to increase the traveling speed of the acryl based fiber
bundle. However, with an increasing mass per unit volume of the acryl based fiber
bundle supplied to the furnace body, an increasing quantity of heat per unit volume
will be required to add heat to or remove heat from the acryl based fiber bundle,
and this makes temperature control difficult and leads to oxidized fibers with deteriorated
quality.
[0007] Furthermore, in the case of increasing the traveling speed of the acryl based fiber
bundle, it will be necessary to increase the size of the oxidation furnace in order
to maintain the same heat treatment rate. In particular, when the size in the height
direction is increased, it will be necessary to divide a building floor into multiple
subfloors or increase the load capacity per unit area of the floor face, which may
lead to an increase in equipment cost. Therefore, to increase the size of the oxidation
furnace while avoiding an increase in equipment cost, it will be effective to reduce
its size in the height direction while increasing the distance of one horizontal pass
(hereinafter referred to as the oxidation furnace length). However, as the oxidation
furnace length is lengthened, the heat treatment length is lengthened accordingly,
which makes it difficult to control the temperature of the acryl based fiber bundle.
In particular, this occurs in a noticeable manner in a furnace of the ETE hot gas
heating structure.
[0008] Therefore, when an attempt is made to improve the productivity of an oxidation process
that uses a furnace of the ETE hot gas heating structure, there occurs the problem
of necessity to improve the efficiency in heating of and heat removal from the acryl
based fiber bundle traveling in the furnace body of the oxidation furnace.
[0009] As a means of solving this problem, Patent document 1 describes a method in which
the discharge faces of the discharge nozzles are provided at a distance from the heat
treatment chamber to allow the hot gas in the heat treatment chamber to be sucked
so that flows are formed in the gaps between the discharge nozzles, thereby facilitating
the heating of and heat removal from the acryl based fiber bundle.
[0010] Furthermore, Patent document 2 describes a heat treatment method in which hot gas
is supplied to the space located between supply nozzles that are installed at the
center of the furnace body of a furnace having the CTE hot gas heating structure so
that the space located between the supply nozzles and the space inside the furnace
body have roughly the same temperature.
[0011] In addition, Patent document 3 describes a method, which was originally designed
to serve as a means of improving the sealing property of an oxidation furnace, that
uses a heating device having a supply face to emit hot gas in order to heat the acryl
based fiber bundle in a flow channel gap through which the acryl based fiber bundle
travels from outside the furnace body of the oxidation furnace into the furnace body.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
SUMMARY OF INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0013] However, findings obtained so far by the present inventors suggest that the control
of the flow formed in the gap between discharge nozzles proposed in Patent document
1 alone cannot serve enough to change the gas flow morphology in the furnace body
of the oxidation furnace and will sometimes fail in sufficiently achieving the heating
of or heat removal from the acryl based fiber bundle. Since the gas flow morphology
(speed and direction of the hot gas flow) near the acryl based fiber bundle in the
oxidation furnace is the dominant factor in the heat transfer to the acryl based fiber
bundle, it is considered that the above gas flow control near the discharge nozzles
can work effectively only in the space between the gas discharge nozzles, leading
to a failure in having an sufficient effect.
[0014] Furthermore, when performing the method proposed in Patent document 2, the supply
of hot gas between the supply nozzles causes gas turbulence as the hot gas moves across
the acryl based fiber bundle, and accordingly, the acryl based fiber bundle will undergo
significant thread sway even at a low gas flow speed, possibly resulting in contact
with an adjacent acryl based fiber bundle, intermingling, breakage, etc. of the acryl
based fiber bundles, or the like. In addition, Patent document 2 only proposes a method
for equalizing the temperature of the gas flow between the supply nozzles and in the
space inside the furnace body and discloses no techniques to control the temperature
of the acryl based fiber bundle inside the furnace body. The parameters required for
controlling the temperature of the acryl based fiber bundle in the furnace body include
the temperature and speed of the hot gas flow. Although there is a description about
the former, i.e. temperature, there is no detailed description about the speed of
the hot gas flow, and accordingly, it is impossible in some cases to control the temperature
of the acryl based fiber bundle. In addition, the document is limited to the CTE hot
gas heating structure based on the parallel flow method, and there is no detailed
description about application to the ETE hot gas heating structure, which is smaller
in equipment cost.
[0015] In Patent document 3, furthermore, the hot gas supply face is located outside the
furnace body of the oxidation furnace, and therefore, it is sometimes impossible to
fully improve the performance in heating of or heat removal from the acryl based fiber
bundle traveling in the furnace body of the oxidation furnace. In addition, since
the method proposed in Patent document 3 is intended to improve the sealing performance
of the oxidation furnace, hot gas is supplied in a direction toward outside the furnace
body so that the hot gas supplied from the supply face is emitted directly out of
the furnace body, and therefore, it is sometimes impossible to form a gas flow in
the space between the nozzles through which the acryl based fiber bundle is traveling.
MEANS OF SOLVING THE PROBLEMS
[0016] To solve the above problems, the production method for an oxidized fiber bundle according
to the present invention is configured as described below. Specifically, it is a production
method for an oxidized fiber bundle comprising a step for heat-treating aligned acryl
based fiber bundles in an oxidizing gas atmosphere while turning them back on guide
rollers installed on both ends outside the furnace body of a hot gas heating type
oxidation furnace wherein: supply nozzles for supplying hot gas into a heat treatment
chamber are installed at an end in the traveling direction of the acryl based fiber
bundles; a fiber bundle traveling passage(s) exists above and/or below each nozzle;
hot gas is supplied from the supply face(s) located above and/or below the acryl based
fiber bundle; and the requirements (1) and (2) are satisfied where Vf is the gas flow
speed in a substantially parallel direction to the traveling direction of the acryl
based fiber bundle in the fiber bundle traveling passage and V is the gas flow speed
in a substantially parallel direction to the traveling direction of the acryl based
fiber bundle in the heat treatment chamber.

[0018] In addition, the method for producing a carbon fiber bundle according to the present
invention is configured as described below. Specifically, it is
a production method for a carbon fiber bundle comprising a step for subjecting an
oxidized fiber bundle produced by the above production method for an oxidized fiber
bundle to precarbonization treatment at a maximum temperature of 300°C to 1,000°C
in an inert gas atmosphere to produce a precarbonized fiber bundle and a subsequent
step for subjecting the precarbonized fiber bundle to carbonization treatment at a
maximum temperature of 1,000°C to 2,000°C in an inert gas atmosphere.
[0019] Here, a "substantially parallel direction to the traveling direction of the acryl
based fiber bundle" referred to for the present invention means a direction within
±0.7°of the reference horizontal line, which connects the tops of a pair of mutually
opposed turn-around rollers located at either end outside the furnace body.
[0020] Here, a "fiber bundle traveling passage" referred to for the present invention means
a space around the acryl based fiber bundle formed along the traveling direction of
the acryl based fiber bundle, and it is actually the space between a supply nozzle
and another supply nozzle that are adjacent to each other in the vertical direction,
the space between the supply nozzle and the upper face of the furnace body, or the
space between the supply nozzle and the bottom face of the furnace body.
[0021] In addition, the oxidation furnace according to the present invention also has the
following features. Specifically, it is
an oxidation furnace designed to perform heat treatment of an acryl based fiber bundle
including:
- (i) a furnace body having slits though which aligned fiber bundles can enter and exit
the furnace body,
- (ii) a plurality of supply nozzles disposed at intervals along a vertical line located
at an end in the traveling direction of the fiber bundles in the heat treatment chamber
so that hot gas is supplied into the furnace body,
- (iii) a plurality of discharge nozzles disposed at intervals along a vertical line
located at the other end in the traveling direction of the fiber bundles in the furnace
body so that the hot gas supplied from the supply nozzles is discharged out of the
heat treatment chamber,
- (iv) at least one gas blowing device designed to circulate hot gas through the supply
nozzles and the discharge nozzles,
- (v) at least one heating device disposed in a flow path of the circulating hot gas,
and
- (vi) guide rollers disposed at both ends outside the furnace body to turn back the
fiber bundles so that they travel to and fro a plurality of times in the heat treatment
chamber while passing through the spaces between mutually adjacent supply nozzles
and between mutually adjacent discharge nozzles, wherein
- (vii) each of the supply nozzles has a supply face(s) at the top and/or bottom so
that a first hot gas stream(s) is supplied to the fiber bundle traveling passage(s)
running above and/or below the supply nozzle and also has an auxiliary supply face
on a side of the supply nozzle facing the interior of the heat treatment chamber so
that a second hot gas stream is supplied, and
- (viii) adjusting devices to adjust the gas flow speed of the first hot gas stream
and the gas flow speed of the second hot gas stream supplied from the supply nozzle.
ADVANTAGEOUS EFFECTS OF THE INVENTION
[0022] The production method for an oxidized fiber bundle according to the present invention
serves to improve the performance in the heating of and heat removal from an acryl
based fiber bundle passing through the furnace body of an oxidation furnace, thereby
achieving efficient production of an oxidized fiber bundle and carbon fiber bundle
having high quality.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023]
[Fig. 1] This is a schematic cross-sectional view of an oxidation furnace used in
an embodiment of the present invention.
[Fig. 2] This is a partial enlarged cross-sectional view of a region extending from
around the supply nozzles to around the discharge nozzles used in an embodiment of
the present invention.
[Fig. 3] This is a schematic view of the gas flow morphology in the region extending
from around the supply nozzles to around the discharge nozzles adopted in an embodiment
of the present invention.
[Fig. 4] This is a partial enlarged cross-sectional view of a region extending from
around the supply nozzles to around the discharge nozzles used in another embodiment
of the present invention.
[Fig. 5] This is a schematic view of the gas flow morphology in the region extending
from around the supply nozzles to around the discharge nozzles in a conventional apparatus.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0024] Embodiments of the present invention are described in detail below with reference
to Fig. 1 to Fig. 4. Fig. 1 is a schematic cross-sectional view of an oxidation furnace
used in an embodiment of the present invention and Fig. 2 is a partial enlarged cross-sectional
view of a region extending from around the supply nozzles to around the discharge
nozzles. In addition, Fig. 4 is a partial enlarged cross-sectional view of a region
extending from around the supply nozzles to around the discharge nozzles in an oxidation
furnace used for another embodiment of the present invention. Fig. 3, furthermore,
is a schematic view of the gas flow morphology in the region extending from around
the supply nozzles to around the discharge nozzles adopted in an embodiment of the
present invention. It should be noted that these figures provide only schematic views
designed for accurate understanding of important points of the present invention and
that they are simplified drawings. There are no specific limitations on the oxidation
furnace to use for the present invention and various embodiments may be modified in
size etc.
[0025] The present invention provides a production method for an oxidized fiber bundle that
is designed to perform heat treatment of an acryl based fiber bundle 2 in an oxidizing
gas atmosphere and it is carried out in an oxidation furnace in which oxidizing gas
is flowing. As shown in Fig. 1, the oxidation furnace 1 has a heat treatment chamber
3 provided with guide rollers 4 positioned outside the furnace body 18, wherein an
acryl based fiber bundle 2 is subjected to oxidation treatment by blowing hot gas
against it as it travels to and fro in multi-stage traveling areas in the furnace
body 18 while turning around on the guide rollers 4. The acryl based fiber bundle
2 is sent into the furnace body 18 through a slit 17 provided in a side wall of the
furnace body 18. Then, after traveling substantially straight in the heat treatment
chamber 3, it is once sent out of the furnace body 18 through a slit 17 provided in
the opposite side wall. Subsequently, it is turned around on a guide roller 4 provided
on either side of the furnace body 18 and sent back into the furnace body 18. In this
way, the acryl based fiber bundle 2 is repeatedly turned around on a plurality of
guide rollers 4 so that it is sent in and out of the heat treatment chamber 3 a plurality
of times. Thus it moves from top to bottom as a whole in the heat treatment chamber
3 while traveling through multi-stage areas as illustrated in Fig. 1. Here, it may
move from bottom to top and the number of times the acryl based fiber bundle 2 is
turned around in the heat treatment chamber 3 is not particularly limited. These features
may be appropriately designed depending on the size of the oxidation furnace 1 etc.
In addition, although the guide rollers 4 are installed outside the furnace body 18
in Fig. 1, the guide rollers 4 may be installed inside the furnace body 18.
[0026] While the acryl based fiber bundle 2 turns around repeatedly and travels to and fro
in the heat treatment chamber 3, it is gradually oxidized as it is heated by hot gas
flowing from the supply nozzles 5 toward the discharge faces 7 of the discharge nozzles
14, finally resulting in an oxidized fiber bundle. As described above, this oxidation
furnace 1 is a parallel flow ETE hot gas heating type oxidation furnace. Here, a plurality
of aligned acryl based fiber bundles 2 are arranged in the perpendicular direction
to the figure plane to form a wide sheet.
[0027] The oxidizing gas flowing in the heat treatment chamber 3, which may be gas for example,
is heated to a desired temperature by a heating device 8 before entering the heat
treatment chamber 3 and supplied into the heat treatment chamber 3 from the supply
faces 6 and/or the auxiliary supply faces 12 of the supply nozzles 5 with its supply
rate controlled by the gas blowing device 9. Here, a supply face 6 of a supply nozzle
5 is a supply face positioned so as to face another supply nozzle 5 located next to
the upper or lower face of the former supply nozzle 5, and the auxiliary supply face
12 of the supply nozzle 5 is a supply face positioned on the side of the supply nozzle
5 that faces the corresponding discharge nozzle 14. Then, the oxidizing gas discharged
out of the heat treatment chamber 3 through the the discharge faces 7 of the discharge
nozzles 14 may be released to the atmosphere after treating unnecessary substances
in an exhaust gas treatment furnace (not shown in figures). However, it is not necessary
to treat the oxidizing gas completely, and part of the untreated oxidizing gas may
be sent through the circulation channel back into the heat treatment chamber 3 from
the supply nozzle 5. Hereinafter, a supply face 6 of a supply nozzle 5 is simply referred
to as supply face 6, the auxiliary supply face 12 of a supply nozzle 5 referred to
as auxiliary supply face 12, and the discharge face 7 of a discharge nozzle 14 referred
to as discharge face 7.
[0028] The heating device 8 used in the oxidation furnace 1 is not particularly limited
as long as it has a desired heating ability, and for example, a known heating device
such as an electric heater may be used. The gas blowing device 9 is not particularly
limited either as long as it has a desired gas blowing ability, and for example, a
known gas blowing device such as an axial fan may be used.
[0029] In addition, the guide rollers 4 can serve to control the traveling speed and tension
of the acryl based fiber bundles 2 when their respective rotation speeds are adjusted
appropriately. They can be adjusted on the basis of the required physical properties
of the oxidized fiber bundles and the required processing rate per unit time.
[0030] Furthermore, the spaces between and the number of the plurality of acryl based fiber
bundles 2 running in parallel can be controlled by engraving an appropriate number
of grooves at appropriate intervals on the surface layers of the guide rollers 4 or
by providing an appropriate number of comb guides (not shown in figures) at appropriate
intervals in the vicinity of the guide rollers 4.
[0031] Conventionally, it has been known that an improved productivity can be achieved by
increasing the traveling speed of the acryl based fiber bundle 2 or increasing the
number of acryl based fiber bundles per unit distance, that is, the thread density,
in the width direction of the oxidation furnace 1. However, if such requirements are
satisfied with the aim of improving the productivity, it causes an increase in the
supply rate of the acryl based fiber bundles 2 into the furnace body 18 relative to
the supply rate of hot gas into the furnace body 18 per unit time. Accordingly, it
leads to a relative decrease in the amount of heat of the hot gas that can be used
for the heating of or heat removal from the acryl based fiber bundles 2. As a result,
the temperature controllability of the acryl based fiber bundles 2 tends to decrease,
possibly leading to deterioration in quality. For this, conceivable solutions include
providing additional heating or heat removal devices and increasing the supply of
heat in order to increase the amount of hot gas available for the heating of or heat
removal from the acryl based fiber bundles 2. However, they are disadvantageous because
they can cause a significant increase in costs due to increased equipment cost and
utilities cost.
[0032] To solve this problem, it is effective to improve the efficiency in heat transfer
between the acryl based fiber bundles 2 and the hot gas and good means thereof include
increasing the flow speed of the hot gas and supplying hot gas in the orthogonal direction
to the traveling direction of the acryl based fiber bundles 2 . Another means is to
loosen the fibers in the acryl based fiber bundles 2 in order to increase the surface
area to improve the heat transfer efficiency. However, if the fibers are loosened,
adjacent acryl based fiber bundles 2 running in parallel tend to be entangled together.
As described above, furthermore, an increase in the flow speed of hot gas causes an
increase in utilities cost and accordingly an increase in running cost, and a change
in the flow direction of hot gas toward the orthogonal direction to the acryl based
fiber bundles 2 causes increased sway of the acryl based fiber bundles 2, allowing
adjacent acryl based fiber bundles 2 running in parallel to be entangled together
more easily. In addition, if the oxidation furnace length is increased in order to
construct a larger ETE heating type oxidation furnace, which requires less equipment
cost, there occur various disadvantages against productivity improvement such as excessive
heat generation from the acryl based fiber bundles 2 in the latter part of each passage,
which makes it impossible to control the temperature of the acryl based fiber bundles
2.
[0033] The production method for an oxidized fiber bundle according to the present invention,
which was developed as a result of intensive studies on the above problems, serves
for efficient production of high-quality oxidized fiber bundles. Specifically, the
present inventors have developed a method that can achieve an improved efficiency
in heat transfer between the acryl based fiber bundles 2 and the hot gas while preventing
an increase in equipment cost and running cost and suppressing the entanglement between
acryl based fiber bundles 2. Described in detail below is the principle of improving
the efficiency in heat transfer between the acryl based fiber bundles 2 traveling
in the heat treatment chamber 3 and the hot gas, which is the most important point
of the present invention.
[0034] First, in order to clarify the difference between the conventional technology and
the present invention, the gas flow morphology in the furnace body 18 constructed
based on the conventional technology will be described with reference to Fig. 5. The
lengths of the arrows showing gas flows in Fig. 5 represent the speeds of the gas
flows.
[0035] In Fig. 5, the hot gas supplied from the first supply face 19 of a supply nozzle
5 installed at one end in the furnace body 18 passes through the fiber bundle traveling
passage 10 between two supply nozzles 5. When it reaches the confluence plane 13 where
the fiber bundle traveling passage 10 and the heat treatment chamber 3 come in contact
with each other, it merges with the hot gas supplied from the second supply face 20
and continues to flow through the heat treatment chamber 3 while gradually narrowing
the difference in speed between them. In this conventional technology, the speed of
the gas flow moving in the fiber bundle direction in the fiber bundle traveling passage
10, which originates in the hot gas supplied from the first supply face 19, is smaller
than the speed of the gas flow that originates in the hot gas supplied from the second
supply face 20. Therefore, the gas flow speed in the vicinity of the acryl based fiber
bundles 2 immediately after passing the confluence plane 13 is accelerated as the
gas flow moves from the fiber bundle traveling passage 10 into the heat treatment
chamber 3 while maintaining its flow speed, and it merges gradually with the gas flow
that originates in the hot gas supplied from the second supply face 20. Then, the
merged gas flow reaches a discharge nozzle 14 installed at the other end in the furnace
body 18 and it is discharged nearly completely through the discharge face 7 while
partly passing between two discharge nozzles 14 and flowing out of the furnace body
18.
[0036] Described below is the temperature of the acryl based fiber bundle 2 in the case
where the thread density of the acryl based fiber bundles 2 is increased (or the traveling
speed of the acryl based fiber bundles 2 is increased) in order to improve the productivity.
The acryl based fiber bundles 2 once exit the furnace body 18 and, after being cooled
by outside air, enters the fiber bundle traveling passage 10 again and is heated again.
If the acryl based fiber bundles 2 have an increased thread density, a larger amount
of heat is required for heat transfer and it becomes more difficult to implement the
heating of or heat removal from the acryl based fiber bundles 2, making it impossible
to heat them sufficiently in the heat treatment chamber 3. In particular, if the gas
flow speed Vf in the fiber bundle traveling passage 10 is too small, the acryl based
fiber bundles 2 will be fed to the heat treatment chamber 3 without being heated sufficiently,
and consequently, the temperature in the heat treatment chamber 3 will drop, making
it all the more difficult to raise the temperature of the acryl based fiber bundles
2. As described above, as the flow speed of the gas flow in the vicinity of the acryl
based fiber bundles 2 has the greatest influence on the heat transfer, the acryl based
fiber bundles 2 near the supply nozzles 5 in the heat treatment chamber 3 will be
largely affected by the flow speed Vf of the hot gas passing through the fiber bundle
traveling passage 10.
[0037] To overcame this disadvantage, in an embodiment of the present invention in which,
as shown in Fig. 3, hot gas is supplied from a supply face 6 of a supply nozzle(s)
5 located above and/or below the acryl based fiber bundle 2, the gas flow morphology
is designed so that the requirements (1) and (2) are satisfied where Vf is the speed
of the gas flow moving in a substantially parallel direction to the traveling direction
of the acryl based fiber bundles 2 in the fiber bundle traveling passage 10 and V
is the speed of the gas flow moving in a substantially parallel direction to the traveling
direction of the acryl based fiber bundles 2 in the heat treatment chamber 3:

and

[0038] Here, the speed Vf of the gas flow moving in a substantially parallel direction
to the traveling direction of the acryl based fiber bundles 2 in the fiber bundle
traveling passage 10 is the average of measurements taken at three points that are
located on the line intersection between the confluence plane 13 and the acryl based
fiber bundles 2 and that are aligned in the width direction and include the width-directional
center of the furnace body 3 and the speed V of the gas flow moving in a substantially
parallel direction to the traveling direction of the acryl based fiber bundles 2 in
the heat treatment chamber 3 is the average of measurements taken at three points
that are located on the line intersection between the acryl based fiber bundles 2
and the cross section of the heat treatment chamber 3 at the center in the traveling
direction of the acryl based fiber bundles 2 and that are aligned in the width direction
and include the width-directional center of the furnace body 3. Here, the above-mentioned
measurement at each of the three points aligned in the width direction including the
width-directional center of the furnace body 3 is the average of 30 measurements taken
at one second intervals using a thermal anemometer. In addition, the line intersection
between the confluence plane 13 and the acryl based fiber bundles 2 referred to above
is the line intersection between the confluence plane 13 and the virtual plane that
contains the plurality of traveling acryl based fiber bundles 2 aligned in parallel
in the machine width direction, and the line intersection between the cross section
of the heat treatment chamber 3 at the traveling-directional center of the acryl based
fiber bundles 2 and the acryl based fiber bundles 2 is the line intersection between
the cross section of the heat treatment chamber 3 at the traveling-directional center
of the acryl based fiber bundles 2 and the virtual plane that contains the plurality
of traveling acryl based fiber bundles 2 aligned in parallel in the machine width
direction. Therefore, the measuring points are included in the virtual plane that
contains the plurality of traveling acryl based fiber bundles 2 aligned in parallel
in the machine width direction. However, Vf and V are indicators representing the
speeds of the gas flows in the vicinity of the acryl based fiber bundles 2 in the
fiber bundle traveling passage 10 and the heat treatment chamber 3, respectively,
and accordingly, the arrows showing Vf and V in Fig. 3 (also in Fig. 5) are in the
vicinity of the acryl based fiber bundles 2, rather than overlapping them.
[0039] When these conditions are met for the acryl based fiber bundles 2, high-speed hot
gas flows come from a supply face 6 that faces a fiber bundle traveling passage 10
and hit the acryl based fiber bundles 2 to strongly promote the heat transfer between
the acryl based fiber bundles 2 and the hot gas. Then, this hot gas turns toward the
parallel direction to the traveling direction of the acryl based fiber bundles 2 and
flows in the vicinity of the acryl based fiber bundles 2 in the fiber bundle traveling
passage 10. Thus, it further accelerates the heat transfer and the temperature of
the acryl based fiber bundles 2 rises rapidly. Subsequently, as the hot gas continues
to flow in the vicinity of the acryl based fiber bundles 2 while maintaining the speed
for the time being even in the heat treatment chamber 3, heat transfer between the
acryl based fiber bundles 2 and the hot gas is promoted, thus enabling highly accurate
control of the temperature of the acryl based fiber bundles 2. Therefore, the temperature
of the acryl based fiber bundles 2 can be controlled even if the speed V of the gas
flow passing through the heat treatment chamber 3 is reduced, making it possible to
decrease the overall volume of hot gas that is circulating in the oxidation furnace
1. As another technique, hot gas that hits the acryl based fiber bundles 2 may be
emitted only from an end portion of the supply nozzle 5 near the guide rollers 4,
that is, in an area where the sag in the acryl based fiber bundles 2 is relatively
small. This serves to increase the heat transfer without a significant increase in
the sway of the acryl based fiber bundles 2.
[0040] Then, after passing through the fiber bundle traveling passage 10, the hot gas reaches
the heat treatment chamber 3 and then continues to flow while spreading in the vertical
direction. At this time, the additional hot gas supplied from the auxiliary supply
face 12 works to reduce gas turbulence that may be caused by the spread of the hot
gas flow, thereby serving to reduce fiber commingling that may result from sway of
the acryl based fiber bundles 2.
[0041] Here, in order to adjust the flow speed of the hot gas supplied from the supply faces
6 and the auxiliary supply face 12, good methods include installing an adjusting valve
such as damper in the circulation flow path that leads to each supply face and providing
flow control plates such as perforated panel and honeycomb core plywood with different
opening ratios at these supply faces.
[0042] Thus, for the oxidation method according to the present invention, it is extremely
important that hot gas flows having high flow speeds be supplied in the orthogonal
direction to the acryl based fiber bundles 2 in the fiber bundle traveling passage
10 and also that the requirements (1) and (2) given above be satisfied where Vf is
the gas flow speed in a substantially parallel direction to the traveling direction
of the acryl based fiber bundles 2 in the fiber bundle traveling passage 10 and V
is the gas flow speed in a substantially parallel direction to the traveling direction
of the acryl based fiber bundles 2 in the heat treatment chamber. These features are
not taken into consideration at all in the conventional technology. In order to maximize
the effect of the invention, it is more preferable that the requirements (3) and (4)
be satisfied where Vf is the gas flow speed in a substantially parallel direction
to the traveling direction of the acryl based fiber bundles 2 in the fiber bundle
traveling passage 10 and V is the gas flow speed in a substantially parallel direction
to the traveling direction of the acryl based fiber bundles 2 in the heat treatment
chamber 3:

and

[0043] To give an example where the requirement (1) or (2) is not satisfied, an gas flow
speed Vf of less than 1.5 m/s may sometimes cause a failure in achieving sufficient
heating of or heat removal from the acryl based fiber bundles 2. If the gas flow speed
Vf is larger than 15 m/s, on the other hand, the acryl based fiber bundles 2 may sometimes
receive an increased drag from the hot gas, which may lead to increased sway.
[0044] If the gas flow speed V is less than 1.5 m/s, furthermore, it may sometimes lead
to a failure in achieving sufficient heating of or heat removal from the acryl based
fiber bundles 2 in the heat treatment chamber 3. If the gas flow speed V is larger
than 10 m/s, on the other hand, the acryl based fiber bundles 2 may sometimes receive
an increased drag from the hot gas, which may lead to increased thread sway. If the
gas flow speed V is larger than 10 m/s, furthermore, it may sometimes cause an increase
in the amount of hot gas that circulates in the oxidation furnace, leading to an increase
in utilities cost.
[0045] In addition, it is more preferable that the requirement (5) be satisfied where Vn
is the gas flow speed in the orthogonal direction to the traveling direction of the
acryl based fiber bundles 2 at a supply face 6. In this case, the efficiency in the
heating of or heat removal from the acryl based fiber bundles 2 can be largely increased
while suppressing their sway caused by the drag that the acryl based fiber bundles
2 may receive from the hot gas. Here, if the gas flow speed Vn is less than 0.1 m/s,
it may sometimes lead to a failure in achieving sufficient heat transfer to the acryl
based fiber bundles 2 and increasing its temperature sufficiently. An gas flow speed
Vn of more than 5 m/s may sometimes lead to an increased thread sway. In addition,
it is more preferable that the gas flow speed Vn be less than 3.5 m/s because this
can maximize the effect of the present invention.

Here, the speed Vn of the gas flow emitted from a supply face 6 in the orthogonal
direction to the traveling direction of the acryl based fiber bundles 2 is the average
of measurements taken at three points on the supply face 6 that are located on a line
orthogonal to the fiber bundle traveling direction and aligned in the width direction
and that include the width-directional center of the furnace body 3. Here, the above-mentioned
measurement at each of the three points aligned in the width direction including the
width-directional center of the furnace body 3 is the average of 30 measurements taken
at one second intervals.
[0046] In addition, if the hot gas supplied from a supply face 6 has a temperature controlled
at 210°C or more and 295°C or less, it serves more remarkably to achieve an improvement
in the heat transfer performance. In this case, the temperatures of the hot gas supplied
from supply faces 6 and auxiliary supply faces 12 may be different from each other,
but they are preferably identical from the viewpoint of temperature controllability
of the acryl based fiber bundles 2 and equipment cost.
[0047] Next, another embodiment of the present invention is described below with reference
to Fig. 4. The disposition position of each supply face 6 in a supply nozzle 5 is
not limited to both surfaces of the supply nozzle 5 but may be disposed only at the
bottom (not shown) or only at the top (not shown) thereof. If a supply face 6 is disposed
only at the top, it serves to support the weight of the acryl based fiber bundles
2 and therefore a reduction in their sway can be expected. On the other hand, if supply
faces 6 are disposed at both surfaces to supply an gas flow with a constant speed
Vf in the fiber bundle traveling passage 10, the gas speed can be reduced by half
and the gas turbulence around the acryl based fiber bundles 2 can be decreased. This
is preferable because their sway can be suppressed.
[0048] In addition, the disposition position of each supply face 6 of a supply nozzle 5
is not limited to a part nearer to the outer wall of the furnace body (Fig. 2), but
may be on a part nearer to the interior of the furnace boy, or may be divided into
several parts that are disposed at different positions, or may cover the entire surface
(Fig. 4).
[0049] Furthermore, the supply nozzle 5 may have no auxiliary supply face 12 but may be
designed to supply hot gas only from supply faces 6. In this case, where there is
no auxiliary supply face 12, a flow control plate 16 may be provided to divide and
minimize the heat treatment chamber 3 to work only around the traveling path of the
acryl based fiber bundles 2 (Fig. 4) in order to prevent gas turbulence from being
caused by the rapid spreading of gas flows that occurs as they move from the fiber
bundle traveling passage 10 into the heat treatment chamber 3.
[0050] In addition, various effects can be created by changing the angle between the main
flow direction of the hot gas supplied from a supply face 6 and the traveling direction
of the acryl based fiber bundles. For example, if the angle is not orthogonal, it
serves to suppress hot gas turbulence that may be caused by collisions between the
acryl based fiber bundles and the supply nozzle 5. Here, if the main flow direction
of the hot gas is inclined toward the heat treatment chamber 3, it serves to allow
part of the hot gas to move more easily into the heat treatment chamber 3, thereby
suppressing its leakage out of the oxidation furnace 1. If the main flow direction
of hot gas is designed to be orthogonal to the traveling direction of the acryl based
fiber bundles, it serves to improve the efficiency in heat transfer to the acryl based
fiber bundles 2. In this way, the main flow direction of hot gas may be set appropriately
taking into account the performance required of the acryl based fiber bundles 2 and
the oxidation furnace.
[0051] Furthermore, it is preferable that the flow rate of the hot gas removed through a
discharge face 7 be larger than the total flow rate of the hot gas supplied from the
supply faces 6 and the auxiliary supply face 12 of a supply nozzle 5. This allows
the hot gas supplied from a supply face 6 to flow easily into the heat treatment chamber
3, making it possible to suppress the leakage of hot gas from the heat treatment chamber
3 and improve the sealing performance.
[0052] Here, the processing rate of the acryl based fiber bundles 2 is preferably 0.14 to
11 kg/min per meter of the width of the oxidation furnace. As the processing rate
increases, a larger heat transfer improving effect can be realized.
[0053] For the production method for an oxidized fiber bundle according to the present invention,
furthermore, it is preferable for the acryl based fiber bundles 2 to have a single
fiber fineness of 0.05 to 0.22 tex, more preferably 0.05 to 0.17 tex. If it is in
the preferable range, it serves to prevent the single fibers in adjacent acryl based
fiber bundles 2 from being entangled when the bundles come into contact with each
other, thereby effectively avoiding the commingling of fibers between acryl based
fiber bundles and it also serves to allow heat to reach the inner single fiber layer
thoroughly in the furnace body of the oxidation furnace, prevent the acryl based fiber
bundles 2 from undergoing fluffing easily, and ensure effective prevention of large-scale
fiber commingling. Accordingly, this ensures that an oxidized fiber bundle with higher
quality will be produced with higher operability. In this way, a higher single fiber
fineness ensures a higher heat transfer efficiency as an effect of the present invention,
thereby allowing heat to reach the inner single fiber layer thoroughly.
[0054] It is preferable that an oxidized fiber bundle produced by the method described above
be precarbonized at a maximum temperature of 300°C to 1,000°C in an inert gas atmosphere
to produce a precarbonized fiber bundle and that it be carbonized at a maximum temperature
of 1,000°C to 2,000°C in an inert gas atmosphere to produce a carbon fiber bundle.
[0055] The maximum temperature of the inert gas atmosphere used for the precarbonization
treatment is more preferably 550°C to 800°C. The adoptable gasses to form such an
inert gas atmosphere that fills the precarbonization furnace include known inert gasses
such as nitrogen, argon, and helium, of which nitrogen is preferable from the viewpoint
of economy.
[0056] The precarbonized fiber produced by the above precarbonization treatment is then
sent to a carbonization furnace where it is subjected to carbonization treatment.
To produce a carbon fiber with improved mechanical properties, it is more preferable
to carry out carbonization treatment at a maximum temperature of 1,200°C to 2,000°C
in an inert gas atmosphere.
[0057] The adoptable gasses to form such an inert gas atmosphere that fills the carbonization
furnace include known inert gasses such as nitrogen, argon, and helium, of which nitrogen
is preferable from the viewpoint of economy.
[0058] The carbon fiber bundle thus obtained may be provided with a sizing agent in order
to improve the handleability, affinity with the matrix resin, etc. The type of the
sizing agent to use is not particularly limited as long as the desired characteristics
can be realized, and good examples thereof include sizing agents containing, as main
component, an epoxy resin, polyether resin, epoxy-modified polyurethane resin, and
polyester resin. A generally known method may be used to apply such a sizing agent.
[0059] In addition, if necessary, the carbon fiber bundle may be subjected to electrolytic
oxidation treatment or surface oxidation treatment in order to improve the affinity
and adhesiveness with the matrix resin to use for producing a fiber-reinforced composite
material.
[0060] For the production method for an oxidized fiber bundle according to the present invention,
the acryl based fiber bundle to use as the fiber bundle to be heat-treated is preferably
made of an acryl fiber containing 100 mol% acrylonitrile or an acrylic copolymer fiber
containing 90 mol% or more acrylonitrile. Preferable copolymerization components for
use in the acrylic copolymer fiber include acrylic acid, methacrylic acid, itaconic
acid, alkali metal salts thereof, ammonium metal salts thereof, acrylamide, and methyl
acrylate. Here, but there are no specific limitations on the chemical properties,
physical properties, size, etc. of the acryl based fiber bundle.
EXAMPLES
[0061] The present invention will be illustrated below in greater detail with reference
to examples, but the invention should not be construed as being limited thereto. Here,
measurements of the gas flow speed and the thread sway used in the examples and comparative
examples were taken by the methods described below.
[0062] (1) Measuring method for single fiber fineness of acryl based fiber bundle A specimen
was taken from an acryl based fiber bundle before feeding it into an oxidation furnace
and measurement was perform according to JIS L 1013 (2010-06-21 revised edition).
(2) Measuring method for gas flow speed
[0063] An Anemomaster Model 6162 high temperature gas flow speed meter, manufactured by
Kanomax Japan Inc., was used as a thermal type anemometer and the average of 30 measurements
of instantaneous gas flow speed taken at one second intervals was adopted. A measuring
probe was inserted through a measuring hole (not shown in figures) provided in the
side wall of a furnace body 18. Then, the average of measurements taken at three points
that were located on the line intersection between the confluence plane 13 and the
acryl based fiber bundles 2 and that were aligned in the width direction and included
the width-directional center was determined as Vf; the average of measurements taken
at three points that were located on the line intersection between the acryl based
fiber bundle 2 and the cross section of the heat treatment chamber 3 at the center
in the traveling direction of the acryl based fiber bundle 2 and that were aligned
in the width direction and included the width-directional center was determined as
V; and the average of measurements taken at three points on a supply face 6 that were
located on a line orthogonal to the traveling direction of the acryl based fiber bundles
2 and that were aligned in the width direction and included the width-directional
center was determined as Vn.
(3) Measuring method for temperature of acryl based fiber bundle
[0064] A K-thermocouple was fastened to a traveling acryl based fiber bundle 2 and the temperature
of the acryl based fiber bundle 2 in the heat treatment chamber 3 was measured at
one second intervals, followed by calculating the thread temperature uniformity I
(%).

[0065] Here, T is the temperature T of the hot gas supplied from a supply nozzle 5, and
I is the arithmetic average of five measurements I(n).
(4) Operability and quality
[0066] The criteria for them were as described below.
(Operability)
[0067] Operation was performed continuously for 10 days and the daily frequency of troubles
such as fiber commingling and fiber bundle breakage was used for the criterion.
Excellent: The average frequency is zero (extremely good level).
Good: The average frequency is about 1 to 9 (sufficiently good level for performing
continuous operation).
Fair: The average frequency is about 10 to 19 (barely satisfactory level for performing
continuous operation).
Poor: The average frequency is 20 or more (unsatisfactory level for performing continuous
operation).
(Quality)
[0068] A 10 m portion of the oxidized fiber bundle was visually observed after leaving the
oxidation process, and the number of 10 mm or more fluff spots detected per meter
of the oxidized fiber bundle was used for the criterion.
Excellent: The average number is 1 or less (the fluffing quality has no influence
at all on the processability in production process or higher-order processability
of the resulting product).
Good: The average number is more than 1 and less than 10 (the fluffing quality has
little influence on the processability in production process or higher-order processability
of the resulting product).
Fair: The average number is 10 or more and less than 20 (the fluffing quality has
influence frequently on the processability in production process or higher-order processability
of the resulting product).
Poor: The average number is 20 or more (the fluffing quality has adverse influence
on the processability in production process or higher-order processability of the
resulting product).
[Example 1]
[0069] The heat treatment furnace according to the present invention shown in Fig. 1 is
used as the oxidation furnace for producing a carbon fiber. At one end of a furnace
body 18, a plurality of supply nozzles 5, which serve as supply sources of hot gas,
are installed above and below acryl based fiber bundles 2 traveling in the furnace
body 18. As illustrated in Fig. 2, supply faces 6 are provided at the top and bottom
of each supply nozzle 5, and an auxiliary supply face 12 is provided to supply hot
gas in the traveling direction of the acryl based fiber bundles 2. A perforated plate
with an opening ratio of 30% is provided on the supply faces 6 and the auxiliary supply
face 12 so that the gas flow speed is maintained uniform in the width direction, and
a damper (not shown in figures) was provided in the circulation flow path that leads
to each supply face in order to control the flow speed of the hot gas supplied from
each supply face.
[0070] Regarding the acryl based fiber bundles 2 traveling in the furnace body, 100 acryl
based fiber bundles 2 containing 20,000 single fibers with a single fiber fineness
of 0.11 dtex were pulled and hannei aligned, and they were heat-treated in the oxidation
furnace 1 to produce oxidized fiber bundles. In addition, guide rollers 4 were installed
at both ends outside the furnace body 18 of the oxidation furnace 1 with horizontal
distance (roller span) L' of 15 m. The guide rollers 4 were grooved rollers with a
groove distance (groove pitch) Wp of 10 mm. At this time, the oxidizing gas in the
heat treatment chamber 3 of the oxidation furnace 1 had a temperature of 240°C to
280°C. The traveling speed of the acryl based fiber bundles 2 was adjusted in the
range of 1 to 15 m/min depending on the oxidation furnace length L to ensure a sufficiently
long oxidation treatment time while the process tension was adjusted in range of 0.5
to 2.5 g/dtex.
[0071] The resulting oxidized fiber bundles were then subjected to stabilization and carbonization
in a precarbonization furnace at a maximum temperature of 700°C, subjected to stabilization
and carbonization in a carbonization furnace at a maximum temperature of 1,400°C.
Then, electrochemical treatment of the fiber surface was carried out and a sizing
agent was applied to provide carbon fiber bundles.
[0072] Results are given in Table 1 and they show that the thread temperature uniformity
was 20% when the gas flow speed Vn on the supply faces 6, the gas flow speed Vf in
the fiber bundle traveling passage 10, and the average gas flow speed V in the heat
treatment chamber 3 were 8.5 m/s, 11.2 m/s, and 7.0 m/s, respectively. Under the above
conditions, the frequencies of fiber intermingling and fiber bundle breakage due to
contact between acryl based fiber bundles were small during the oxidation treatment
of the acryl based fiber bundles 2, serving to produce oxidized fiber bundles with
high operability. In addition, the resulting oxidized fiber bundles were observed
visually, and results showed that they had good quality with little fluffing etc.
[Example 2]
[0073] Except that the gas flow speed Vn on the supply faces, the gas flow speed Vf in the
fiber bundle traveling passage 10, and the average gas flow speed V in the heat treatment
chamber 3 were 6.0 m/s, 3.3 m/s, and 3.0 m/s, respectively, the same procedure as
in Example 1 was carried out. In this test run, the thread temperature uniformity
was 17%. Under the above conditions, the frequencies of fiber intermingling and fiber
bundle breakage due to contact between acryl based fiber bundles were zero during
the oxidation treatment of the acryl based fiber bundles 2, serving to produce oxidized
fiber bundles with extremely high operability. In addition, the resulting oxidized
fiber bundles were observed visually, and results showed that they had good quality
with little fluffing etc.
[Example 3]
[0074] Except that the gas flow speed Vn on the supply faces was 3.3 m/s, the same procedure
as in Example 2 was carried out. In this test run, the thread temperature uniformity
was 16%. Under the above conditions, the frequencies of fiber intermingling and fiber
bundle breakage due to contact between acryl based fiber bundles were zero during
the oxidation treatment of the acryl based fiber bundles 2, serving to produce oxidized
fiber bundles with extremely high operability. In addition, the resulting oxidized
fiber bundles were observed visually, and results showed that they had extremely good
quality without fluffing etc.
[Comparative example 1]
[0075] Except that the gas flow speed Vf in the fiber traveling passage 10 and the average
gas flow speed V in the heat treatment chamber 3 were 1.1 m/s and 6.0 m/s, respectively,
for Comparative example 1, the same procedure as in Example 2 was carried out. In
this test run, the thread temperature uniformity was 8%, and under the above conditions,
fiber intermingling and single fiber breakage due to contact between acryl based fiber
bundles occurred frequently during the oxidation treatment of the acryl based fiber
bundles 2. In addition, the resulting oxidized fiber bundles were observed visually,
and results showed that they had poor quality with significant fluffing etc.
[Table 1]
[0076]
Table 1
|
Example 1 |
Example 2 |
Example 3 |
Comparative example 1 |
Equipment settings |
roller span [m] |
15.0 |
15.0 |
15.0 |
15.0 |
groove pitch [mm] |
10.0 |
10.0 |
10.0 |
10.0 |
Vf [m/s] |
11.2 |
3.3 |
3.3 |
1.1 |
V [m/s] |
7.0 |
3.0 |
3.0 |
6.0 |
Vn [m/s] |
8.5 |
6.0 |
3.3 |
3.3 |
Thread temperature uniformity [%] |
20 |
17 |
16 |
8 |
Operability |
good |
excellent |
excellent |
poor |
Quality |
good |
good |
excellent |
poor |
INDUSTRIAL APPLICABILITY
[0077] The present invention relates to a production method for an oxidized fiber bundle
and a production method for a carbon fiber bundle and can be applied to members of
aircraft, industrial products such as pressure vessels and windmill blade, sporting
goods such as golf shafts, and the like, although its scope of application is not
limited thereto.
EXPLANATION OF NUMERALS
[0078]
1. oxidation furnace
2. acryl based fiber bundle
3. heat treatment chamber
4. guide roller
5. supply nozzle
6. supply face
7. discharge face
8. heating device
9. gas blowing device
10. fiber bundle traveling passage
12. auxiliary supply face
13. confluence plane
14. discharge nozzle
16. flow control plate
17. slit
18. furnace body
19. first supply face
20. second supply face