JP4450928B2 - Method for producing porous composite material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a porous material having voids and / or pores, and particularly relates to a porous material in which voids and / or pores are filled and / or covered with ceramics and a method for producing the same.
[0002]
[Prior art]
Using a so-called inorganic solid material or metal as a matrix, ceramic is applied to the inside of voids and / or pores of a porous material having voids and / or pores, and is filled with ceramics or coated with ceramics. Yes. The chemical vapor infiltration method (CVI method) applying the chemical vapor phase method (CVD method) is used for supplying ceramics to the voids and the like. The CVI method is a method in which a gas raw material for producing ceramics is introduced into a void or the like, and the gas raw material is reacted with heat or the like inside the void or the like to produce and deposit ceramic on the inner surface of the void or the like. As a result of such a ceramic formation reaction from the source gas being repeated inside the voids, a ceramic film can be formed on the inner surface of the voids, or the voids can be filled with ceramics.
[0003]
[Problems to be solved by the invention]
In carrying out the CVI method, it is first necessary to discharge the initial gas from the beginning into the voids of the porous material. However, exhausting residual gas has been very difficult. This is because the porous material has a large surface area and a large amount of adhering gas, so that the adhering gas cannot be completely separated even if exhausted.
Due to the residual gas in the pores, the pressure in the pores becomes higher than the outside of the porous material, and the gas raw material cannot be diffused or penetrated to a deep part such as a void. This problem is common in that even when two or more kinds of gas raw materials are used, the previously used gas raw material remains, and the gas raw material to be used next cannot be diffused.
[0004]
Then, an object of this invention is to provide the manufacturing method of the porous composite material by which ceramic is provided also in the space | gap and / or hole of the deep part of a porous material. It is another object of the present invention to provide an apparatus for applying ceramics to voids and / or pores of a porous material.
[0005]
[Means for Solving the Problems]
As means for solving the above-described problems, the present invention provides the following means.
That is, the present invention provides a porous composite material in which a gas raw material that generates ceramics by a chemical reaction is supplied to voids and / or pores of a porous material, and ceramics are applied to the inside of the voids and / or pores. A method of manufacturing
In a state where one side and the other side of the porous material are partitioned through the porous material, the gas raw material is forcibly passed from the one side to the other side, and the voids and / or pores A method is provided in which a gaseous raw material is supplied to the inside of the container.
According to this method, the gas raw material is forced to pass through the porous material, so that the gas raw material is suppressed from staying in the voids and / or pores of the porous material, and remains from the beginning. Gas can be discharged from the hole. For this reason, ceramics are also generated inside the deep voids and / or pores of the porous material.
[0006]
Preferably, the method further comprises a step of forcibly passing the gaseous material from the one side to the other side and a step of forcibly passing the gaseous material from the other side to the one side. According to this, ceramics can be more uniformly generated on the entire outer surface of the porous material and the entire inner surface of the voids and / or the pores.
[0007]
In this manufacturing method, preferably, the gas raw material is two or more kinds, and includes a step of supplying a first gas raw material and a step of supplying a second gas raw material. A step of discharging the first gas material from a section on the supply side of the one gas material. If it does in this way, it can prevent that the 1st gaseous raw material stagnates in the said upstream. For this reason, it can prevent that the 1st and 2nd gaseous raw material mixes in the said upstream.
[0008]
The present invention also provides a porous composite material in which a gas raw material that generates ceramics by a chemical reaction is supplied to the voids and / or pores of the porous material, and the ceramics are applied to the inside of the voids and / or pores. An apparatus for manufacturing
It has a cavity that is divided into one side and the other side of the porous material through the porous material, and is formed so that the gaseous material can be forcibly passed from the one side to the other side of the cavity. Providing the device.
[0009]
Moreover, it is preferable that the gas raw material is an apparatus that is formed so as to be able to be forcibly passed from the one side to the other side and to be forcibly passed from the other side to the one side. Moreover, the gaseous raw material channel | path which the said one side and the said other side are connected However, it is formed to be openable and closable so as to allow the gas material to pass through the opening only when the passage resistance in the porous material is increased. It is preferable. Furthermore, it is preferable to provide two or more cavities. Moreover, it is preferable that one cavity is divided into three or more through each of two or more porous materials.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
The production method and apparatus of the present invention are a method for producing a porous composite material using a so-called CVI method and an apparatus used for the CVI method.
In the production method of the present invention, a gas material that generates ceramics by a chemical reaction is supplied to voids and / or pores of a porous material to produce a composite material in which ceramics are applied in the voids and / or pores. In the method, the gas raw material supplying step to the inside of the void and / or the hole is performed in a state where one side and the other side of the porous material are partitioned through the porous material. This is achieved by forcibly passing the filter from the one side to the other side.
The voids and / or pores of the porous composite material obtained by the method of the present invention are coated or filled with ceramics. In particular, the voids and / or holes in the deep part are evenly coated or filled with ceramics.
The apparatus of the present invention has a cavity partitioned into one side and the other side of the porous material via the porous material so that the gaseous material supply step can be achieved, It is formed so that it can be forcibly passed from the one side to the other side.
[0011]
The porous material in the present invention is not particularly limited as long as it is a material having a large number of voids and / or pores. Since ceramics are applied by a CVD method, particularly a thermal CVD method, that is, a thermochemical reaction, the material is preferably a material having heat resistance to an extent that allows the method or the thermochemical reaction. For example, inorganic solid materials such as ceramics and porous materials using metals as a matrix can be used.
The form of a space | gap and a hole part is not ask | required. It is preferable to provide a void and / or a hole that is continuous or in communication with the outside.
[0012]
The gas raw material is a compound gas composed of elements constituting the ceramic to be formed. In particular, it is preferable to select a gas raw material from which ceramics are generated by a thermochemical reaction. Ceramics include various forms of ceramics such as oxides, nitrides, and carbides. Further, ceramics are generated from these products by chemical reaction on the surface of the porous material. Ceramics may be formed by any of so-called thermal CVD, plasma CVD, photo-CVD, etc., preferably thermal CVD. Therefore, it is preferable to use a gas raw material that generates ceramics by a thermochemical reaction.
Ceramics are often produced from two or more gaseous raw materials. Various known combinations can be applied to the present invention as the combination of such gas raw materials and the ceramics to be produced. For example, the following can be exemplified.
(Gas source) → Examples of ceramics
(SiH ₂ Cl ₂ + C ₂ H ₂ ) → SiC
(SiCl _Four + CH _Four ) → SiC
In addition, you may use only the gaseous raw material which produces | generates 1 type of ceramics, and may use it combining a gaseous raw material so that 2 or more types of ceramics may be produced | generated.
[0013]
(First embodiment)
In the present embodiment, an example of the manufacturing method and manufacturing apparatus of the present invention will be described with reference to FIGS.
FIG. 1 shows a schematic configuration of a manufacturing apparatus 2 used in the present embodiment. FIG. 2 shows a gas source supply step in the present embodiment.
[0014]
The production apparatus of the present invention basically includes a cavity (furnace) 2 having cavities 10 and 14 that are divided into one side and the other side of a porous material through a porous material 4. Is formed. Pipes 18, 20, and 22 are connected to the cavity 10 so that the gas source A and the gas source B can be supplied into the furnace 2. Each of these pipes 18, 20, and 22 is provided with a valve. That is, the pipes 18 and 20 are connected to the supply sources of the gas raw materials A and B, respectively, and the pipes 18 and 20 are connected to the pipe 22 connected to the furnace 2.
Further, a pipe 24 is connected to the cavity 14 so that the gas in the furnace 2 can be exhausted (sucked). As a result, the furnace 2 is formed so that the gas raw materials A and B can be forcibly passed from the cavity 10 to the cavity 14.
[0015]
In the furnace 2, the porous material 4 constitutes at least a part of an inner wall (partition wall) that divides the cavities 10 and 14. In portions other than the porous material 4, the cavities 10 and 14 are partitioned by an appropriate member, and both the cavities 10 and 14 are blocked. In particular, in the furnace 2, the partition wall 12 supports the porous material 4 and also blocks the cavities 10 and 14.
Although the whole furnace 2 may be formed so that it can be heated from the outside, it is preferable that only the porous material 4 inside the furnace 2 can be heated. A plurality of furnaces 2 may be formed. In that case, it can arrange | position in series with respect to the passage direction of a gaseous raw material, and can also arrange | position in parallel.
[0016]
Next, a method for generating ceramics in the voids and / or pores of the porous material 4 in the furnace 2 will be described based on the gas raw material supply step illustrated in FIG.
First, the porous material 4 is arranged at a predetermined position in the furnace 2, and the one side and the other side are partitioned through the porous material 4. Next, the furnace 2 is heated to a predetermined temperature.
In the first step, the air in the furnace 2 is discharged (sucked) by the pipe 24 in a state where the predetermined temperature is maintained. In the second step, the gaseous raw material A is supplied to the cavity 10 via the pipes 18 and 22 for a certain period while maintaining the suction.
[0017]
As a result, the gaseous material A is forcibly passed from one side of the porous material 4 to the other side, that is, from the cavity 10 to the cavity 14. Thereby, the gaseous raw material A can pass through the voids and / or pores of the porous material 4 from the cavity 10 side to the cavity 14 side without staying in the voids or the like. For this reason, the gaseous raw material A is uniformly supplied not only on the surface layer side (cavity 10 side) of the heated porous material 4 but also inside the voids and / or holes on the deep side (cavity 14 side). As a result, the product of the gaseous raw material A is uniformly generated on the inner surface such as the voids.
[0018]
In the third step, after the supply of the gas raw material A is stopped, only the suction from the pipe 24 is performed for a certain period, and the gas raw material A staying in the furnace 2 is removed. Then, in the fourth step, the suction state is maintained, and another kind of gas raw material B is supplied to the cavity 10 via the pipes 20 and 22 to forcibly pass the porous material 4.
That is, when supplying two or more kinds of gaseous raw materials, as shown in FIG. 2, after the supply of the one kind of gaseous raw materials is stopped, preferably at a predetermined interval, only suction from the cavity 14 side is performed, Supply other gaseous raw materials. That is, it is preferable to supply each gaseous raw material discontinuously through the exhaust process of the gaseous raw material used previously. As a result, the porous material 4 and the gas raw material in the previous process staying in the furnace 2 are removed, and the gas raw material is mixed in the furnace 2 other than the porous material 4 to prevent an undesirable reaction from occurring. . Further, it is possible to promptly penetrate the porous material 4 of the next gas source to be supplied.
[0019]
According to this embodiment, since the furnace 2 is always sucked from the pipe 24, the gaseous raw material does not stay in the furnace 2. Therefore, the gas raw material can be forced to pass continuously. Also, two or more kinds of gas materials can be supplied substantially continuously while switching each gas material.
[0020]
In this way, a ceramic film is uniformly formed in the entire interior of the voids and / or pores of the porous material 4, and the porous material 4 in which the ceramics are combined can be obtained.
Such a porous material 4 can uniformly impart desired characteristics to the entire inner surface because the entire inner surface of the material 4 is uniformly filled or coated with ceramics. Such a composite material is particularly preferably used for a separation material (membrane).
[0021]
(Second Embodiment)
The second embodiment is a modification of the first embodiment. The apparatus of this embodiment is different only in that the furnace 2 of the first embodiment is further provided with a pipe 26 and a pipe 28, and a valve is provided in each of the pipes 26 and 28. The pipe 26 is branched from the pipe 22 that can supply the gas raw materials A and B, and is connected to the cavity 14. That is, the gas raw materials A and B are changed from the cavity 14 side to the cavity 10 side through the pipe 26 in a direction (opposite direction) different from the first embodiment by the valve switching operation. Can be supplied.
At the same time, the pipe 28 is branched from the pipe 22 and connected to the exhaust pipe 24 so that the inside of the furnace 2 can be sucked from the cavity 10 side by a valve switching operation. That is, in the first embodiment, the inside of the furnace 2 can be exhausted only from the cavity 14 side, but in this apparatus, the inside of the furnace 2 can also be exhausted from the cavity 10 side.
[0022]
By using such an apparatus, the direction of passage of the gas raw material can be switched between the direction from one side of the porous material 4 to the other side and the direction from the other side to the one side as necessary. .
When the gas raw material is continuously passed in one direction at all times, in the porous material 4, ceramics are generated in the void and / or hole on the gas raw material supply side, and the void and / or hole on the side gradually increases. There is a tendency to become smaller. For this reason, there is a tendency that the gaseous raw material does not easily reach the gaseous raw material discharge side of the porous material 4, and ceramics are hardly generated on the discharge side. However, according to the apparatus of this embodiment, since the gas raw material passage direction can be switched as appropriate, ceramics are uniformly generated in the voids and / or pores in the porous material 4 regardless of the gas raw material passage direction. be able to.
Further, it is possible to avoid an increase in the passage resistance of the gas raw material in the porous material 4 and obtain a good state of passage of the gas raw material and a contact state to the inner surface of the porous material 4.
[0023]
According to such an apparatus, for example, the gas raw material A and the gas raw material B can be supplied to the porous material 4 from different directions. Alternatively, the gas materials A and B can be sequentially supplied from the same side, and then the gas materials A and B can be sequentially supplied from the opposite side.
Further, as will be described later, according to the present apparatus, since the inside of the furnace 2 can be exhausted from the cavity 10 side, the gaseous raw material staying from the cavity 10 can be discharged after the gaseous raw material is supplied from the cavity 10 side. . Similarly, after supplying the gas source from the cavity 14, the gas source staying there can be discharged from the cavity 14.
[0024]
(Third embodiment)
In the present embodiment, the apparatus shown in FIG. 4 is used. This apparatus is a modification of the apparatus of the first embodiment shown in FIG. 1 and differs only in that the furnace 2 is further provided with a pipe 30. The pipe 30 is connected so that the furnace 2 can be exhausted (suctioned) from the cavity 10 side. In this embodiment, the exhaust pipe 24 is connected via the pipe 22.
By providing such a pipe 30, if necessary, unlike the apparatus of the first embodiment, not only from the downstream side (cavity 14) in the gas material supply direction but also from the supply side (upstream side, cavity 10). ), The inside of the furnace 2 can be sucked and exhausted.
[0025]
By using such an apparatus, for example, the gaseous material supply process shown in FIG. 5 can be performed.
In these steps, as in the step shown in FIG. 2, the state where the pipe 24 is always sucked from the cavity 14 side is maintained (see the lowermost stage in FIG. 5, exhaust (downstream side)).
In the first step, the upstream side, that is, the cavity 10 side is also sucked together (see the second stage from the bottom in FIG. 5, exhaust (upstream side)). After the suction on the upstream side is stopped, the gas raw material A is supplied to the cavity 10 in the second step (see the uppermost stage in FIG. 5, supply of the gas raw material A). The supply of the gaseous raw material A is stopped, and in the third step, the exhaust state is only from the cavity 14 side. By this step, the gaseous raw material A staying on the cavity 14 side in the furnace 2 is sucked and removed. In the fourth step, the cavity 10 side is again sucked and exhausted. Thereby, in particular, the gas raw material A staying on the cavity 10 side can be further removed. The suction from the cavity on the gas raw material supply side is particularly effective when the voids and / or pores of the porous material 4 become smaller due to the generation of ceramics. This is because the gaseous raw material tends to stay in the supply side cavity.
In this way, before the gas source B is supplied next time, the gas source A is removed from the supply side cavity, thereby improving the passage state of the gas source B and the contact state with the inner surface of the porous material 4. be able to. Further, mixing with the remaining gas raw material A can be avoided.
[0026]
(Fourth embodiment)
An apparatus used in this embodiment is shown in FIG. In particular, this apparatus includes a furnace 52 different from the above-described embodiment. The furnace 52 has a cavity defined on one side and the other side of the porous material 4 with the porous material 4 interposed therebetween, but the defined cavities 60 and 64 have a double structure. . A pipe 72 is connected to the cavity 60 so as to be able to communicate with the outside, and a pipe is also connected to the cavity 64 so as to be able to communicate with the outside.
The cavity 60 is formed in a substantially box shape including the porous material 4, the partition wall 76, and the wall surface on which the pipe 72 is formed in the furnace 52. That is, the cavity 60 is configured to exist inside the cavity 64.
[0027]
According to the furnace 52 of the said form, only the porous material 4 can be heated effectively, without heating the furnace 52 whole. That is, only the cavity 60 is heated, or only the porous material 4 is heated from the inside of the cavity 60. For example, the porous material 4 can be locally heated by microwave heating, laser heating, or the like. Thereby, since the entire inner wall of the furnace 52 is not heated, ceramics can be effectively applied to the inner surface of the porous material 4 while avoiding the generation of ceramics on the inner wall portion in the furnace 52 as much as possible. Moreover, ceramics can be applied only to a desired region of the porous material 4.
In this embodiment, in addition to the switching of the gas source supply direction and the switching of the exhaust gas in the above-described embodiment, the formation of the gas source passage to the partition wall, which will be described later, may be applied individually or in combination of two or more. it can.
[0028]
(Fifth embodiment)
FIG. 7 shows an apparatus used in the fifth embodiment. The furnace 82 of this apparatus includes cavities 90 and 94 that are defined by the porous material 4, and the cavities 90 and 94 have pipes 92 and 98 that can supply or suck a gas raw material. Is provided. The partition wall 104 in the furnace 82 is formed so as to partition the inside of the furnace 82 together with the porous material 4.
In this embodiment, a passage 110 through which a gaseous material can pass is provided between the cavities 90 and 94 that are partitioned. The passage 110 may have any form. It may be a pipe that connects the cavities 90 and 94 so as to communicate with each other, or may be an opening provided in at least a part of the partition wall 104 as shown in FIG. The gas raw material passage may always be in an open state, or may be formed to be openable and closable as necessary.
[0029]
By using such an apparatus, for example, the following effects can be obtained. When ceramic formation in the voids and / or pores of the porous material 4 proceeds and the voids and / or pores become smaller, the passage resistance of the porous material 4 increases. As a result, the gaseous raw material tends to stay in the supply side cavity. However, if the gas source passage 110 is provided, even if the passage resistance is increased, the gas source passage is present in a portion other than the porous material 4, so that the retention of the gas source can be prevented. In particular, it is preferable to form the gas source passage 110 so as to be openable and closable so that the gas source passes through the opening 110 only when the passage resistance in the porous material 4 is increased.
In the present embodiment, the switching of the gas raw material supply direction and the exhaust gas direction in the above-described embodiment can be applied individually or in combination.
[0030]
(Sixth embodiment)
The device of this embodiment is shown in FIG. The furnace 112 of this apparatus includes three cavities 120, 122, and 124 that are partitioned in series via two porous materials 4, respectively. Are provided with pipes 132 and 138 capable of supplying or exhausting air. The furnace 112 also includes two partition walls 140 and 142 that partition the cavities 120, 122, and 124 together with the porous material 4.
According to this apparatus, a plurality of porous materials 4 can be processed at a time by supplying the gas raw material.
In the present embodiment, the cavities are arranged in series, but a plurality of porous materials 4 may be collectively processed by arranging the cavities in parallel.
Further, switching of the gas source supply side, switching of the exhaust side, and formation of the opening in the partition wall can be applied to the present embodiment either in combination or in combination of two or more.
[0031]
As described above, the present invention can also take the following forms.
(1) Supplying a gas raw material that generates ceramics by a chemical reaction to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores A way to
There are two or more gaseous raw materials,
In a state where one side and the other side of the porous material are partitioned through the porous material, the first gas raw material is forcibly passed from the one side to the other side, and the gap and / or Supplying a first gaseous material into the hole,
Discharging the first gaseous raw material;
Forcing a second gaseous material from the one side to the other side and supplying the second gaseous material into the voids and / or holes,
A method comprising:
(2) Supplying a gas raw material that generates ceramics by a chemical reaction to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores A way to
There are two or more gaseous raw materials,
Forcibly passing at least one gas source from the one side to the other side in a state where one side and the other side of the porous material are partitioned via the porous material; Forcing a gaseous source of seed from the other side to the one side.
[0032]
(3) Supplying a gas raw material that generates ceramics by a chemical reaction to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores A way to
There are two or more gaseous raw materials,
Forcibly passing at least one gas source from the one side to the other side in a state where one side and the other side of the porous material are partitioned via the porous material; Forcing a gaseous material from the other side to the one side.
(4) A gas material that generates ceramics by a chemical reaction is supplied to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores. A way to
There are two or more gaseous raw materials,
Forcing at least one gas source from the one side to the other side in a state where one side and the other side of the porous material are partitioned via the porous material;
Discharging the one kind of gaseous raw material from the supply side;
Forcing other gaseous materials to pass from the other side to the one side;
Discharging the other gaseous raw material from the supply side;
A method comprising:
[0033]
(5) A gaseous raw material that generates ceramics by a chemical reaction is supplied to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores. A device,
A cavity that is partitioned into one side and the other side of the porous material through the porous material, and is formed so that the gaseous material can be forcibly passed from the one side to the other side of the cavity. The apparatus provided with two or more in series or parallel with respect to the passage direction of a gaseous raw material.
(6) A gaseous raw material that generates ceramics by a chemical reaction is supplied to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores. A device,
A cavity that is partitioned into one side and the other side of the porous material through the porous material, and that is formed so that the gaseous raw material can be forcibly passed from the one side to the other side. An apparatus comprising a cavity partitioned into three or more through a porous material.
(7) Supplying a gas raw material that generates ceramics by a chemical reaction to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores. A device,
A cavity that is partitioned into one side and the other side of the porous material through the porous material, and is formed so that the gaseous material can be forcibly passed from the one side to the other side; Wherein the compartment is substantially surrounded by the other compartment.
(8) A gaseous raw material that generates ceramics by a chemical reaction is supplied to the voids and / or pores of the porous material to produce a porous composite material in which ceramics are applied to the inside of the voids and / or pores. A device,
It has a cavity partitioned into one side and the other side of the porous material through the porous material, and the gaseous material is formed so as to be forcibly passed from the one side to the other side of the cavity,
An apparatus formed so that the cavity can be evacuated from the one side.
(9) The gas source is formed so as to be capable of forcibly passing from the one side to the other side and forcibly passing from the other side to the one side. The device according to any one of the above.
(10) The apparatus according to any one of (5) to (9), further including a gas raw material passage that communicates the one side with the other side.
[0034]
【Example】
Hereinafter, specific examples will be described as examples of the present invention.
In this example, a porous α-alumina cylindrical tube composed of two layers of fine particles on the outside and coarse particles on the inside was used as the porous material, and the surface was modified with γ-alumina. .
This cylindrical tube is formed so that it can be heated from the outside, and a furnace (quartz glass, outer diameter 40 mm, inner diameter 40 mm, inner diameter 40 mm, two openings each formed so as to be able to supply and discharge gaseous raw materials by switching valves) It was installed within a length of 470 mm).
The porous material was installed such that one end of the cylindrical tube was sealed with a dense alumina cap, and the other end was installed such that one of the openings was surrounded by the cylindrical tube. As a result, the inside of the furnace is in a state where one side (inside the cylindrical pipe) and the other side (outside the cylindrical pipe) are partitioned via the cylindrical pipe, and the gaseous material supplied into the furnace must be made of a porous material. It was made to pass through. That is, when supplying a gaseous material from the opening in the cylindrical tube, the gaseous material passes from the inside of the cylindrical tube to the outside, and when supplying a gaseous material from the other opening, the gaseous material is supplied from the outside of the cylindrical tube to the inside. It has come to pass.
[0035]
The porous material in the furnace was heated to 800-900 ° C. with a heater (length 400 mm) outside the furnace and kept constant.
The gas source is hydrogen diluted 10% dichlorosilane gas (SiH ₂ Cl ₂ ) And 10% acetylene gas diluted with hydrogen (C ₂ H ₂ ) Was used. The two types of gaseous raw materials were alternately supplied into the reactor by switching the valve controlled by the computer. Each gas passes through a flow meter and dichlorosilane gas is 2.0 cm per cycle. ^Three Acetylene gas is 2.2 cm ^Three Was fed into the furnace. The supply pattern of the gas raw material was the same as in FIG. That is, since each gaseous raw material is supplied in pulses and immediately exhausted by a rotary pump, the two gaseous raw materials were not mixed in the reaction furnace. In addition, the film thickness can be controlled by controlling the number of cycles.
[0036]
The film forming process will be described in order. In this step, the gas raw material is supplied from the opening inside the cylindrical tube and is always sucked from the other opening. That is, the gas raw material passes from the inside of the cylindrical tube to the outside.
SiH ₂ Cl ₂ Gas was supplied to the furnace through an opening inside the cylindrical tube. SiH ₂ Cl ₂ After the gas supply was stopped, the inside of the furnace was sucked with a rotary pump, and the remaining gas raw material was immediately exhausted out of the furnace. Then C ₂ H ₂ The gas was supplied, and then the inside of the furnace was sucked with a rotary pump, and the remaining gas raw material was exhausted. This was one cycle, and a total of 100 cycles were performed.
When the inner surface of the void of the porous material after 100 cycles was observed, a SiC film having a thickness of about 0.1 μm was formed.
[0037]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the porous composite material by which ceramic is provided also in the space | gap and / or hole of the deep part of a porous material can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram showing a schematic configuration of an apparatus used in a first embodiment of the present invention.
FIG. 2 is a diagram showing a gaseous raw material supply step of the first embodiment of the present invention.
FIG. 3 is a diagram showing a schematic configuration of an apparatus used in a second embodiment of the present invention.
FIG. 4 is a diagram showing a schematic configuration of an apparatus used in a third embodiment of the present invention.
FIG. 5 is a view showing a gaseous material supply process in the third embodiment.
FIG. 6 is a diagram showing a schematic configuration of an apparatus used in a fourth embodiment.
FIG. 7 is a diagram showing a schematic configuration of an apparatus used in a fifth embodiment.
FIG. 8 is a diagram showing a schematic configuration of an apparatus used in a sixth embodiment.
[Explanation of symbols]
2,52,82,112 furnace
4 Porous material
10, 14, 60, 64, 90, 94, 120, 122, 124 cavity

Claims (4)

This is a method for producing a porous composite material in which ceramics are applied to the inside of the voids and / or pores by supplying a gas raw material that generates ceramics by a chemical reaction to the voids and / or pores of the porous material. And
Through said porous material in a state where the one side and the other side of the porous material is partitioned, a step of the gas raw material Ru forced through from the one side to the other side, the said gas material A method in which a gas raw material is supplied to the inside of the void and / or the hole by forcibly passing it from the other side to the one side .   There are two or more gas raw materials, and the method includes a step of supplying a first gas raw material and a step of supplying a second gas raw material. The method of claim 1, comprising discharging the first gaseous feedstock from the compartment. An apparatus for manufacturing a porous composite material in which a gas raw material that generates ceramics by a chemical reaction is supplied to voids and / or pores of a porous material, and ceramics are applied to the inside of the voids and / or pores. And
It has a cavity partitioned into one side and the other side of the porous material through the porous material, and the gas raw material is formed so as to be able to forcibly pass from the one side of the cavity to the other side. In addition, the apparatus is configured to be able to forcibly pass from the other side to the one side . The gas source passage communicating the one side and the other side is formed to be openable and closable so as to allow the gas source to pass through the opening only when passage resistance in the porous material is increased. The device described in 1.

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