JP2006176924A - Method for controlling wall thickness of silicon carbide microtube by irradiation under cooling - Google Patents
Method for controlling wall thickness of silicon carbide microtube by irradiation under cooling Download PDFInfo
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- JP2006176924A JP2006176924A JP2004371267A JP2004371267A JP2006176924A JP 2006176924 A JP2006176924 A JP 2006176924A JP 2004371267 A JP2004371267 A JP 2004371267A JP 2004371267 A JP2004371267 A JP 2004371267A JP 2006176924 A JP2006176924 A JP 2006176924A
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 29
- 238000001816 cooling Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 18
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000012510 hollow fiber Substances 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920003257 polycarbosilane Polymers 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000010894 electron beam technology Methods 0.000 description 12
- 230000005855 radiation Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940003953 helium / oxygen Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- Inorganic Fibers (AREA)
Abstract
Description
本発明は、SiCマイクロチューブの壁厚を２〜20μｍの範囲で任意に制御可能な製造方法に関する。 The present invention relates to a manufacturing method capable of arbitrarily controlling the wall thickness of a SiC microtube within a range of 2 to 20 μm.
従来、SiCマイクロチューブの製造方法としては、ケイ素系高分子であるポリカルボシラン繊維を電子線で中空化する方法がある。これは次の工程からなる方法による。
１．ケイ素高分子を紡糸し、直径数十μｍの繊維とする。
Conventionally, as a manufacturing method of an SiC microtube, there is a method of hollowing a polycarbosilane fiber, which is a silicon-based polymer, with an electron beam. This is based on a method comprising the following steps.
1. A silicon polymer is spun into a fiber having a diameter of several tens of μm.
２．室温、空気中で電離放射線を照射して表面のみを酸化する。
３．不活性ガス中で熱処理し、酸化層を架橋て溶媒に不溶化する。
４．繊維内部の未架橋部を有機溶媒で抽出し、中空化する。
2. Irradiate ionizing radiation in air at room temperature to oxidize only the surface.
3. It heat-processes in inert gas, bridge | crosslinks an oxidation layer, and insolubilizes in a solvent.
4). The uncrosslinked portion inside the fiber is extracted with an organic solvent and hollowed out.
５．不活性ガス中、1000℃以上の熱処理でセラミック化する。
しかし、上記方法では、放射線照射における線量率や酸素分圧を変化させることによりチューブの壁厚を制御することは可能であるが、室温における電子線照射では、電子線のエネルギーで試料の温度が上昇するため、チューブの壁厚を10μｍ以下に制御する事が困難である。
5. Ceramicize in an inert gas by heat treatment at 1000 ℃ or higher.
However, in the above method, it is possible to control the wall thickness of the tube by changing the dose rate and oxygen partial pressure in the radiation irradiation. Since it rises, it is difficult to control the wall thickness of the tube to 10 μm or less.
上記方法に関する文献としては次のものが知られている。即ち、ケイ素系ポリマーの放射線照射によるマイクロセラミックチューブの製造法（特許文献１）、シリコン基ポリマーを放射線に曝すことによりマイクロセラミックチューブを製造する方法（特許文献２）、放射線酸化によるポリマー前駆体からの炭化ケイ素マイクロチューブの改良（非特許文献１）、及び電子線の照射効果で実現した炭化ケイ素セラミックスマイクロチューブ（非特許文献２）等である。
上記のように、現状では、壁厚が10μｍ以下の任意の壁厚に制御してSiCマイクロチューブを製造することが困難であり、工業的に量産されている直径15μｍのSiC繊維を、用途に適した任意の壁厚に制御して中空化することは不可能である。 As described above, at present, it is difficult to manufacture SiC microtubes by controlling the wall thickness to an arbitrary wall thickness of 10 μm or less, and industrially mass-produced SiC fibers with a diameter of 15 μm are used for applications. It is impossible to hollow by controlling to an appropriate wall thickness.
本発明は電離放射線の照射条件を制御する事で壁厚が2〜10μｍのSiCマイクロチューブを製造する方法を提供することにある。本発明者は、電離放射線により酸化されるケイ素系高分子の層の厚さが、電離放射線によりケイ素高分子を切断する事により生成する活性点（ラジカル）量と、ケイ素高分子表面から拡散により内部に侵入する酸素量とに関係しており、酸素の拡散量を電離放射線照射時の試料温度により制御可能である点に着目し本発明を完成させた。 An object of the present invention is to provide a method for producing a SiC microtube having a wall thickness of 2 to 10 μm by controlling the irradiation conditions of ionizing radiation. The present inventor believes that the thickness of the silicon polymer layer oxidized by ionizing radiation depends on the amount of active sites (radicals) generated by cutting the silicon polymer by ionizing radiation and diffusion from the surface of the silicon polymer. The present invention has been completed by paying attention to the fact that the amount of oxygen diffused can be controlled by the sample temperature at the time of ionizing radiation irradiation in relation to the amount of oxygen penetrating into the inside.
これは以下の原理による。ケイ素系高分子繊維に空気中で放射線を照射すると、繊維中に均一に生成する活性ラジカルと酸素が反応する。放射線の線量率が大きい場合、表面から繊維内部への酸素の拡散速度よりも繊維表層で活性ラジカルと酸素が反応する速度の方が大きくなるため、繊維の表層のみが酸化される。この際、照射時の試料を冷却するとケイ素高分子中の酸素の拡散速度が小さくなるため、単位時間に拡散により繊維に侵入する酸素量が減少し、より表層に近い部分ですべての酸素が活性ラジカルと反応するため酸化される部分に相当する壁厚が小さくなる。 This is based on the following principle. When the silicon polymer fiber is irradiated with radiation in the air, the active radicals uniformly generated in the fiber react with oxygen. When the dose rate of radiation is large, only the surface layer of the fiber is oxidized because the rate at which active radicals react with oxygen in the fiber surface layer is greater than the diffusion rate of oxygen from the surface to the inside of the fiber. At this time, since the diffusion rate of oxygen in the silicon polymer decreases when the sample at the time of irradiation is cooled, the amount of oxygen that penetrates into the fiber by diffusion per unit time decreases, and all oxygen is activated in a portion closer to the surface layer. Since it reacts with radicals, the wall thickness corresponding to the oxidized portion is reduced.
したがって、特に、本発明は、ケイ素系高分子繊維を-40〜0℃の温度に冷却しながら電離放射線を照射することにより表面のみ酸化し、酸化部分を熱処理により架橋した後、有機溶媒により繊維中心部の未架橋部分を抽出して中空繊維とし、これを不活性ガス中で焼成して、壁厚（チューブの肉厚）SiCが2〜１０μｍの任意の壁厚で炭化ケイ素(SiC)マイクロチューブを製造する方法である。 Therefore, in particular, the present invention oxidizes only the surface by irradiating ionizing radiation while cooling the silicon-based polymer fiber to a temperature of -40 to 0 ° C., and crosslinks the oxidized portion by heat treatment, and then the fiber with an organic solvent. The uncrosslinked part at the center is extracted to form a hollow fiber, which is fired in an inert gas, and has a wall thickness (tube thickness) of silicon carbide (SiC) micro with an arbitrary wall thickness of 2 to 10 μm. A method of manufacturing a tube.
工業的に量産されているケイ素系高分子繊維である外径20μｍのポリカルボシラン繊維を任意の壁厚に制御して外径15μｍのSiCマイクロチューブの製造が可能となる。 It is possible to manufacture SiC microtubes having an outer diameter of 15 μm by controlling the polycarbosilane fiber having an outer diameter of 20 μm, which is a silicon polymer fiber that is industrially mass-produced, to an arbitrary wall thickness.
図１に、本発明の放射線照射を用いたマイクロセラミックチューブの製造工程の一例を示す。原料のケイ素高分子繊維を、-40〜0℃の温度で酸素分圧が0.5〜50kPaとなるように不活性ガスと酸素を混合したガスを流通させ電子線を照射し表層を酸化する。この際、電子線の線量は、ケイ素高分子が酸素により架橋される線量より大きく、かつ繊維中心部が放射線により無酸素で架橋される線量より小さい1〜5MGyの範囲で設定する必要がある。 In FIG. 1, an example of the manufacturing process of the micro ceramic tube using the radiation irradiation of this invention is shown. A raw material silicon polymer fiber is irradiated with an electron beam through a gas mixed with an inert gas and oxygen so that the partial pressure of oxygen is 0.5 to 50 kPa at a temperature of -40 to 0 ° C., and the surface layer is oxidized. At this time, the dose of the electron beam needs to be set in the range of 1 to 5 MGy, which is larger than the dose at which the silicon polymer is cross-linked by oxygen and smaller than the dose at which the fiber center is cross-linked by oxygen-free oxygen.
表層のみ酸化されたケイ素高分子繊維を、アルゴン雰囲気または真空中で熱処理し酸化部分を架橋することで溶媒に不溶化する。この際、繊維の導入された酸素量に対応する適切な温度を230〜300℃の範囲で設定する。中空化処理は、未架橋のケイ素高分子が可溶なシクロヘキサン、THF（テトラヒドロフラン）などの有機溶媒中で保持することで行う。不活性ガス雰囲気で1000℃以上まで加熱することでケイ素高分子をセラミック化してSiCマイクロチューブに転換する。 The silicon polymer fiber oxidized only on the surface layer is heat-treated in an argon atmosphere or vacuum to crosslink the oxidized portion, thereby insolubilizing in the solvent. At this time, an appropriate temperature corresponding to the amount of oxygen introduced into the fiber is set in the range of 230 to 300 ° C. The hollowing treatment is performed by holding in an organic solvent such as cyclohexane or THF (tetrahydrofuran) in which the uncrosslinked silicon polymer is soluble. By heating up to 1000 ° C or higher in an inert gas atmosphere, the silicon polymer is converted into a ceramic and converted to a SiC microtube.
以下、実施例を挙げて本発明を具体的に示す。
SiCセラミックスの原料物質となるケイ素高分子であるポリカルボシラン(PCS)を外径20μｍに繊維化する。この繊維を液化炭酸ガスの気化熱により冷却可能な試料台上に設置し、ガス置換可能な電子線照射容器中に入れ、ヘリウム／酸素の混合ガスを流通させながら2MeVの電子線を0.4〜1.6kGy/secの線量率で2.4MGyまで照射する。照射後、200〜300℃の範囲で不活性ガスまたは真空中で加熱する事で酸化された表面層部分を架橋し、有機溶媒に不溶化する。室温においてシクロヘキサンにより繊維中心部の未架橋部分を抽出し、中空繊維とする。得られた中空繊維をアルゴン中、1000℃で焼成しセラミックチューブ化してSiCマイクロチューブとする。こうして得られたマイクロSiCチューブの外径は約15μｍであり、その壁厚は図２に示すように温度、酸素分圧、電子線の線量率により決まる。室温で照射した場合８μｍが下限である。一方、-20℃で電子線照射した場合、酸素分圧 20kPaでは4〜10μｍ、酸素分圧10kPaでは2〜5μｍの範囲でSiCマイクロチューブの壁厚が制御可能である。
Hereinafter, the present invention will be specifically described with reference to examples.
Polycarbosilane (PCS), a silicon polymer that is a raw material for SiC ceramics, is fiberized to an outer diameter of 20 μm. This fiber is placed on a sample stage that can be cooled by the heat of vaporization of liquefied carbon dioxide gas, placed in an electron beam irradiation container that can be replaced with gas, and a 2 MeV electron beam is passed through a mixed gas of helium / oxygen between 0.4 and 1.6. Irradiate to 2.4MGy at a dose rate of kGy / sec. After irradiation, the oxidized surface layer portion is crosslinked by heating in an inert gas or vacuum in the range of 200 to 300 ° C. and insolubilized in an organic solvent. At room temperature, the uncrosslinked portion at the center of the fiber is extracted with cyclohexane to form a hollow fiber. The obtained hollow fiber is fired at 1000 ° C. in argon to form a ceramic tube to obtain a SiC microtube. The outer diameter of the micro SiC tube thus obtained is about 15 μm, and its wall thickness is determined by temperature, oxygen partial pressure and electron beam dose rate as shown in FIG. 8 μm is the lower limit when irradiated at room temperature. On the other hand, when the electron beam is irradiated at −20 ° C., the wall thickness of the SiC microtube can be controlled within a range of 4 to 10 μm at an oxygen partial pressure of 20 kPa and 2 to 5 μm at an oxygen partial pressure of 10 kPa.
即ち、酸素分圧 20kPaにおいて、室温で電子線照射した場合には、最上段の線グラフに示されるとおり、SiCマイクロチューブの平均壁厚が厚く、しかもその壁厚は８μｍ程度で下限となる。又、酸素分圧 20kPaにおいて、-20℃で電子線照射した場合、中段の線グラフで示されるとおり、 SiCマイクロチューブの平均壁厚は4〜10μｍであり、更に又、酸素分圧10kPaにおいて、-20℃で電子線照射した場合、最下段の線グラフで示されるとおり、SiCマイクロチューブの平均壁厚は２〜５μｍである。 That is, when an electron beam is irradiated at room temperature at an oxygen partial pressure of 20 kPa, as shown in the uppermost line graph, the average wall thickness of the SiC microtube is thick, and the wall thickness is about 8 μm, which is the lower limit. In addition, when an electron beam is irradiated at −20 ° C. at an oxygen partial pressure of 20 kPa, the average wall thickness of the SiC microtube is 4 to 10 μm as shown in the middle line graph. When the electron beam is irradiated at −20 ° C., the average wall thickness of the SiC microtube is 2 to 5 μm as shown in the bottom line graph.
ケイ素系高分子から合成されるSiCはアモルファス構造を呈し、水素ガスを選択透過する機能を有している。SiCマイクロチューブをガス分離フィルターとして応用した場合、その大きな表面積から高効率化が可能であり、熱化学水素製造法などの耐熱・耐蝕性のガス分離フィルターが必至な工程へ応用が期待される。 SiC synthesized from silicon-based polymers has an amorphous structure and has a function of selectively permeating hydrogen gas. When SiC microtubes are applied as gas separation filters, high efficiency is possible due to their large surface area, and application to heat and corrosion resistant gas separation filters such as thermochemical hydrogen production is expected.
Claims (7)
The method according to any one of claims 1 to 5, wherein the cooling temperature is -40 to 0 ° C.
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| JP2004371267A JP4665132B2 (en) | 2004-12-22 | 2004-12-22 | Wall thickness control method by cooling irradiation of silicon carbide microtube |
| US11/274,504 US7964171B2 (en) | 2004-11-16 | 2005-11-16 | Process for producing silicon carbide ceramic micro tube with thin wall |
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| CN101804981A (en) * | 2010-04-01 | 2010-08-18 | 中国科学院山西煤炭化学研究所 | Method for preparing hollow silicon carbide nano material |
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| CN108043437A (en) * | 2017-11-09 | 2018-05-18 | 国家电网公司 | A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst |
| CN108456949A (en) * | 2018-01-23 | 2018-08-28 | 中国科学院宁波材料技术与工程研究所 | A kind of hollow silicon carbide ceramic fiber and preparation method thereof |
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| CN108043437A (en) * | 2017-11-09 | 2018-05-18 | 国家电网公司 | A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst |
| CN108043437B (en) * | 2017-11-09 | 2023-09-22 | 国家电网公司 | Preparation method of hollow SiC support Ir-Ru catalyst |
| CN107779969A (en) * | 2017-11-14 | 2018-03-09 | 中国人民解放军国防科技大学 | Preparation method of hollow ceramic fiber |
| CN108456949A (en) * | 2018-01-23 | 2018-08-28 | 中国科学院宁波材料技术与工程研究所 | A kind of hollow silicon carbide ceramic fiber and preparation method thereof |
| CN108456949B (en) * | 2018-01-23 | 2020-11-10 | 中国科学院宁波材料技术与工程研究所 | Hollow silicon carbide ceramic fiber and preparation method thereof |
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