JP6669205B2 - High alumina composition inorganic fiber, inorganic fiber aggregate and inorganic fiber molded body - Google Patents
High alumina composition inorganic fiber, inorganic fiber aggregate and inorganic fiber molded body Download PDFInfo
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- 239000012784 inorganic fiber Substances 0.000 title claims description 129
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 title description 6
- 239000000835 fiber Substances 0.000 claims description 81
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000009987 spinning Methods 0.000 description 33
- 239000000460 chlorine Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 18
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000010304 firing Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 150000003377 silicon compounds Chemical class 0.000 description 12
- 239000012701 inorganic fiber precursor Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229920000620 organic polymer Polymers 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000012779 reinforcing material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- -1 alkoxysilanes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
Description
本発明は、高アルミナ組成の無機繊維、無機繊維集合体及び無機繊維成型体に係り、特に加熱炉や溶鉱炉、還元雰囲気炉、アルミ溶解炉等における炉壁や天井の断熱部材や繊維強化金属部材の補強材として用いるのに好適な無機繊維、無機繊維集合体及び無機繊維成型体に関する。 The present invention relates to an inorganic fiber having a high alumina composition, an inorganic fiber aggregate, and an inorganic fiber molded body, and particularly relates to a heat insulating member or a fiber reinforced metal member for a furnace wall or a ceiling in a heating furnace, a blast furnace, a reducing atmosphere furnace, an aluminum melting furnace, and the like. The present invention relates to an inorganic fiber, an inorganic fiber aggregate, and an inorganic fiber molded body suitable for use as a reinforcing material of the invention.
従来の高アルミナ組成の無機繊維、無機繊維集合体及び無機繊維成型体は、その優れた耐熱性、耐還元性、低ＳｉＯ２及び高硬度等の優れた特性を活かし、加熱炉、溶鉱炉、還元雰囲気炉及びアルミ溶解炉等に断熱部材や繊維強化金属部材の補強材として用いられている。 Conventional inorganic fibers, inorganic fiber aggregates, and inorganic fiber molded products having a high alumina composition utilize their excellent properties such as excellent heat resistance, reduction resistance, low SiO 2, and high hardness to form a heating furnace, a blast furnace, and a reduction furnace. It is used as a reinforcing material for heat insulation members and fiber reinforced metal members in atmosphere furnaces, aluminum melting furnaces, and the like.
特許文献１には、金属化合物と有機珪素化合物を含有する液状組成物から、無機繊維を紡糸し、アルミナ相をより低温化で生成する方法が記載されている。 Patent Document 1 describes a method in which inorganic fibers are spun from a liquid composition containing a metal compound and an organosilicon compound to generate an alumina phase at a lower temperature.
特許文献２には、無機繊維集合体の引張強さを改良するため、無機繊維の配向方法をそろえ捕集する方法が記載されている。 Patent Literature 2 discloses a method of collecting inorganic fibers by aligning inorganic fibers in order to improve the tensile strength of the inorganic fiber aggregates.
特許文献１、２に記載の方法で製造した無機繊維は、燃焼後、繊維に黄色みがつくという問題点があった。これは無機繊維の製造過程で繊維内部に塩素が残渣として存在しているためである。 The inorganic fibers produced by the methods described in Patent Documents 1 and 2 have a problem that the fibers become yellowish after burning. This is because chlorine is present as a residue in the fiber during the production process of the inorganic fiber.
このことは、断熱材として加熱炉内で使用した場合、輻射率が下がり、断熱効率が悪くなる。その結果、操業上のランニングコストの増加や、炉壁の温度が上がるためといった操業上の問題点がある。 This means that when used as a heat insulating material in a heating furnace, the emissivity is reduced and the heat insulating efficiency is reduced. As a result, there are operational problems such as an increase in operational running costs and an increase in furnace wall temperature.
特に水溶性珪素化合物を原料にした場合は、従来原料として使用されているシリカゾル等に比べて、繊維中の構成粒子がより細かく均一になる。このため、粒子の表面面積がシリカゾル等を使用した系と比べて大きくなるため、結晶開始温度が低くなる。より低い温度で結晶化が始まるということは、より低い温度でゲル中の気孔が閉じることを意味する。このため、燃焼時に不純物等が粒子内の気孔に閉じ込められ、残渣として残りやすい問題がある。特に水溶性シリコーンオイル等は、溶解の容易さと分散性の点から用いられることが多いが、水溶性シリコーンオイル中には燃焼物質である炭化水素や水溶性官能基含有有機物質を含んでいるため、該物質の残渣が残りやすいという問題点がある。また、ポリ塩化アルミニウム等の塩素系材料を併用した場合は、水溶性珪素化合物と塩素が強く結びつく傾向があるために、比較的低い温度では塩素等が抜けにくく、焼成後の繊維内部の塩素量が増えるという問題点がある。 In particular, when a water-soluble silicon compound is used as a raw material, the constituent particles in the fiber are finer and more uniform than in a silica sol or the like conventionally used as a raw material. For this reason, since the surface area of the particles is larger than that of a system using silica sol or the like, the crystallization starting temperature is lowered. The onset of crystallization at lower temperatures means that pores in the gel close at lower temperatures. Therefore, there is a problem that impurities and the like are trapped in the pores in the particles at the time of combustion, and are likely to remain as residues. In particular, water-soluble silicone oils are often used from the viewpoint of ease of dissolution and dispersibility, but since water-soluble silicone oils contain hydrocarbons as combustion substances and organic substances containing water-soluble functional groups. However, there is a problem that residues of the substance tend to remain. In addition, when a chlorine-based material such as polyaluminum chloride is used in combination, chlorine tends to be strongly bound to the water-soluble silicon compound. There is a problem that increases.
アルミ製造関係の断熱材や繊維強化金属の強化材に使用した場合は、繊維中に残留塩素が存在することは、コンタミの観点から問題となる。特に繊維強化金属の強化材として使用した場合、金属と塩素が反応し、繊維と金属の界面から腐食が発生する。このことにより、繊維強化金属の寿命を縮めるといった問題点がある。 When used as a heat insulating material related to aluminum production or a reinforcing material of fiber reinforced metal, the presence of residual chlorine in the fiber poses a problem from the viewpoint of contamination. In particular, when used as a reinforcing material for a fiber-reinforced metal, the metal reacts with chlorine, and corrosion occurs from the interface between the fiber and the metal. As a result, there is a problem that the life of the fiber reinforced metal is shortened.
また繊維内部に残渣塩素が存在すると、加熱炉内で長期間使用した際に徐々に塩素が抜け出てくる可能性がある。このことは、加熱炉内部の金属を腐食させ、設備の寿命を縮めるだけでなく、大気中へ塩素を放出するという問題がある。 If residual chlorine is present inside the fiber, chlorine may gradually come out when used in a heating furnace for a long time. This not only corrodes the metal inside the heating furnace and shortens the life of the equipment, but also releases chlorine into the atmosphere.
また、塩素が抜けださない場合も、断熱材の取替え工事等で、廃棄する場合も塩素が含まれていることは、環境上の問題がある。 In addition, there is an environmental problem that chlorine is contained even when chlorine is not discharged, and when it is discarded due to replacement of heat insulating material.
本発明は、繊維をより白色にすることを目的とする。詳しくは、繊維中の残留塩素濃度を下げることで上記の目的を達成するものである。 The present invention aims to make the fibers whiter. Specifically, the above object is achieved by reducing the residual chlorine concentration in the fiber.
本発明者等は上記実情に鑑み、繊維をより白色にするために鋭意検討した結果、無機繊維中の塩素含有量を０．２５重量％以下にすることにより、本発明の目的が達成されることを見出し、本発明を完成させた。 In view of the above circumstances, the present inventors have conducted intensive studies to make the fiber whiter, and as a result, the object of the present invention is achieved by reducing the chlorine content in the inorganic fiber to 0.25% by weight or less. That is, the present invention has been completed.
即ち、本発明の要旨は、以下に存する。
［１］Ａｌ２Ｏ３が９１〜９９重量及びＳｉＯ２が１〜９重量％であり、かつＣｌが２５００ｐｐｍ以下であることを特徴とする無機繊維。
［２］塩基性塩化アルミニウム及び珪素化合物を含有する紡糸液を紡糸して無機繊維前駆体を得た後に、該無機繊維前駆体を焼成することにより得られる無機繊維であって、該珪素化合物が水溶性珪素化合物である、［１］に記載の無機繊維。
［３］前記水溶性珪素化合物が水溶性シリコーンオイルである、［２］に記載の無機繊維。
［４］［１］〜［３］のいずれか一項に記載の無機繊維を有する無機繊維集合体。
［５］［４］に記載の無機繊維集合体を含有する無機繊維成形体。
That is, the gist of the present invention resides in the following.
[1] Al 2 O 3 is 91 to 99 weight and SiO 2 is 1 to 9 wt%, and inorganic fibers, wherein the Cl is less than 2500 ppm.
[2] An inorganic fiber obtained by spinning a spinning solution containing basic aluminum chloride and a silicon compound to obtain an inorganic fiber precursor, and then firing the inorganic fiber precursor, wherein the silicon compound is The inorganic fiber according to [1], which is a water-soluble silicon compound.
[3] The inorganic fiber according to [2], wherein the water-soluble silicon compound is a water-soluble silicone oil.
[4] An inorganic fiber aggregate having the inorganic fiber according to any one of [1] to [3].
[5] An inorganic fiber molded article containing the inorganic fiber aggregate according to [4].
本発明によって、繊維中の残留塩素が少なくなることで、黄色みが抑えられているため、輻射率の低下を防ぐことができる。また繊維強化金属の強化材として、好適な無機繊維を提供することができる。 According to the present invention, since the residual chlorine in the fiber is reduced, yellowing is suppressed, so that a decrease in emissivity can be prevented. In addition, a suitable inorganic fiber can be provided as a reinforcing material of the fiber-reinforced metal.
＜無機繊維＞
本発明の無機繊維の組成は、Ａｌ２０３が９１〜９９重量％及びＳｉＯ２が１〜９重量％である。ＳｉＯ２の量が上記よりも少ない場合は、無機繊維を構成するアルミナがα‐アルミナになりやすく、しかもアルミナ粒子の粗大化により、繊維強度が著しく低くなり、無機繊維集合体としての形状を保持することが困難になるおそれがある。ＳｉＯ２が上記よりも多い場合は、還元雰囲気炉等での使用が難しいおそれがある。また、アルミナ比率が下がることによって硬度が低くなるため、繊維強化金属の強化材として使用することが難しいおそれがある。
<Inorganic fiber>
Composition of the inorganic fiber of the present invention, Al 2 0 3 is 91 to 99 wt% and SiO 2 is 1 to 9 wt%. When the amount of SiO 2 is smaller than the above, the alumina constituting the inorganic fibers tends to be α-alumina, and the coarseness of the alumina particles causes the fiber strength to be extremely low, thereby maintaining the shape of the inorganic fiber aggregate. May be difficult to do. If the amount of SiO 2 is larger than the above, use in a reducing atmosphere furnace or the like may be difficult. Further, since the hardness is lowered by lowering the alumina ratio, it may be difficult to use as a reinforcing material of the fiber reinforced metal.
本発明の無機繊維中のＣｌが２５００ｐｐｍ以下であり、好ましくは、１０〜２０００ｐｐｍである。無機繊維中のＣｌが２５００ｐｐｍより高いと、上述した課題が問題となり、逆に無機繊維中のＣｌが１０ｐｐｍよりも低くする場合は、過度に繊維に熱を加え繊維の結晶を粗大化するか、過度に粉砕する等しないと達成困難となる。そのため繊維として集合体や成型体を形成することが難しくなる。 Cl in the inorganic fiber of the present invention is 2500 ppm or less, preferably 10 to 2000 ppm. When Cl in the inorganic fiber is higher than 2500 ppm, the above-described problem becomes a problem. Conversely, when Cl in the inorganic fiber is lower than 10 ppm, excessively applying heat to the fiber to coarsen the crystal of the fiber, It is difficult to achieve this without excessive grinding. Therefore, it is difficult to form an aggregate or a molded body as a fiber.
無機繊維中の塩素濃度の測定方法は、無機繊維を酸素気流下で完全に燃焼することで、塩素を含むガスを生成し、水溶液中で塩素原子を含むガスを回収し、該水溶液をイオンクロマトグラフにより測定することで残留塩素濃度を測定する。 The method of measuring the chlorine concentration in the inorganic fiber is such that a gas containing chlorine is generated by completely burning the inorganic fiber under an oxygen stream, a gas containing chlorine atoms is recovered in an aqueous solution, and the aqueous solution is subjected to ion chromatography. The residual chlorine concentration is measured by measuring with a graph.
具体的には、無機繊維１０ｍｇに、酸素気流条件下で燃焼を行う。その際に、公知の装置（例えば、三菱化学株式会社製 ＡＱＦ−２１００Ｎ）を用いることができる。なお、燃焼時に、必要に応じて、助燃剤を含めてもよい。 Specifically, 10 mg of the inorganic fibers are burned under an oxygen gas flow condition. At that time, a known device (for example, AQF-2100N manufactured by Mitsubishi Chemical Corporation) can be used. At the time of combustion, an auxiliary agent may be included as necessary.
上記燃焼により生成した、塩素原子を含むガス全量を、２．７ｍＭ Ｎａ２ＣＯ３ − ０．３ｍＭ ＮａＨＣＯ３水溶液に吸収させる。該水溶液を公知のイオンクロマトグラフにより測定することで、無機繊維中に含まれる塩素元素の濃度を測定する。その際に、公知の装置（例えば、サーモフィッシャーサイエンティフィック株式会社製 ＤＸ−５００）を使用することができる。 The total amount of gas containing chlorine atoms generated by the above combustion is absorbed in a 2.7 mM Na 2 CO 3 -0.3 mM NaHCO 3 aqueous solution. The concentration of the chlorine element contained in the inorganic fibers is measured by measuring the aqueous solution by a known ion chromatograph. At that time, a known device (for example, DX-500 manufactured by Thermo Fisher Scientific Inc.) can be used.
本発明の無機繊維の引張強度は、特段の制限はないが、通常２００Ｎ／ｍｍ２以上であり、好ましくは５００Ｎ／ｍｍ２以上、特に好ましくは７５０Ｎ／ｍｍ２以上である。無機繊維の引張強度が２００Ｎ／ｍｍ２以上であることにより、無機繊維として、集合体や成型体にすることが容易になるため好ましい。上限には特段の制限はないが、２０００Ｎ／ｍｍ２以下であることが好ましい。 Tensile strength of the inorganic fibers of the present invention is not particular limitation, is generally 200 N / mm 2 or more, preferably 500 N / mm 2 or more, particularly preferably 750 N / mm 2 or more. It is preferable that the tensile strength of the inorganic fiber be 200 N / mm 2 or more, since it becomes easy to form an aggregate or a molded body as the inorganic fiber. The upper limit is not particularly limited, but is preferably 2000 N / mm 2 or less.
本発明の無機繊維の比表面積は、特段の制限はないが、通常１００．０ｍ２／ｇ以下であり、好ましくは１．０ｍ２／ｇ以上、特に好ましくは０．３ｍ２／ｇ以上である。無機繊維の比表面積が１０ｍ２／ｇ以下となることで、繊維に空隙が少なくなり、繊維が脆くなりにくくなる点で好ましい。また、繊維に空孔を持たせ、触媒等を担持させる場合は、３０ｍ２／ｇ以上ある方が良い。下限には特段の制限はないが、０．１ｍ２／ｇ以上であることが好ましい。 The specific surface area of the inorganic fiber of the present invention is not particularly limited, but is usually 100.0 m 2 / g or less, preferably 1.0 m 2 / g or more, particularly preferably 0.3 m 2 / g or more. . It is preferable that the specific surface area of the inorganic fiber be 10 m 2 / g or less, since voids are reduced in the fiber and the fiber is less likely to be brittle. Further, in the case where the fibers are provided with holes and a catalyst or the like is supported, it is preferable that the fibers have 30 m 2 / g or more. The lower limit is not particularly limited, but is preferably 0.1 m 2 / g or more.
本発明の無機繊維は、繊維径３μｍ以下の繊維を実質的に含まないことが好ましい。ここで繊維径３μｍ以下の繊維を実質的に含まないとは、繊維径３μｍ以下の繊維が全繊維重量の０．１質量％以下であることをさす。 It is preferable that the inorganic fiber of the present invention does not substantially contain a fiber having a fiber diameter of 3 μm or less. Here, the expression that the fiber having a fiber diameter of 3 μm or less is not substantially contained means that the fiber having a fiber diameter of 3 μm or less accounts for 0.1% by mass or less of the total fiber weight.
無機繊維の平均繊維径は５〜７μｍであることが好ましい。平均繊維径が５μｍ以上であれば、空気中に浮遊する発塵量が少なくなり、また３μｍ以下の繊維が含まれる確率が実質低くなる。平均繊維径を７μｍ以下にすることで、繊維の反発力、靭性が向上するため、繊維の強度が上がり好ましい。 The average fiber diameter of the inorganic fibers is preferably 5 to 7 μm. When the average fiber diameter is 5 μm or more, the amount of dust floating in the air is reduced, and the probability that fibers having a size of 3 μm or less are contained is substantially reduced. By setting the average fiber diameter to 7 μm or less, the resilience and toughness of the fiber are improved, so that the fiber strength is preferably increased.
上述の好適な平均繊維径を有し、かつ、繊維径３μｍ以下の繊維を実質的に含まない無機繊維集合体は、ゾルーゲル法による無機繊維集合体の製造において、紡糸液粘度の制御、紡糸ノズルに用いる空気流の制御、延伸糸の乾燥の制御により得ることができる。 The inorganic fiber aggregate having the above-mentioned preferred average fiber diameter and substantially containing no fiber having a fiber diameter of 3 μm or less is used in the production of the inorganic fiber aggregate by the sol-gel method, by controlling the viscosity of the spinning solution and by controlling the spinning nozzle. By controlling the air flow used for drying and controlling the drying of the drawn yarn.
本発明の無機繊維のＹＩ値は、特段の制限はないが、５．０以下が好ましく、２．０以下がより好ましく、特に好ましくは１．２以下である。本発明の無機繊維のＹＩ値が５．０以下であることで、繊維中の残留塩素が少ないことを意味し、結果として繊維強化金属の強化材として、好適な無機繊維を提供することができる点で好ましい。
＜無機繊維集合体＞
本発明の無機繊維集合体は、特に制限はないが、本発明の無機繊維を紙漉やニードリング処理工程によって得ることができる。特にニードリング処理をすることで、無機繊維集合体の嵩密度、面密度、厚さを容易に調整でき、また反発力をもった無機繊維集合体を得ることができる。
The YI value of the inorganic fiber of the present invention is not particularly limited, but is preferably 5.0 or less, more preferably 2.0 or less, and particularly preferably 1.2 or less. When the YI value of the inorganic fiber of the present invention is 5.0 or less, it means that the residual chlorine in the fiber is small, and as a result, a suitable inorganic fiber can be provided as a reinforcing material of the fiber-reinforced metal. It is preferred in that respect.
<Inorganic fiber aggregate>
The inorganic fiber aggregate of the present invention is not particularly limited, but the inorganic fiber of the present invention can be obtained by a paper filter or needling process. In particular, by performing the needling treatment, the bulk density, area density, and thickness of the inorganic fiber aggregate can be easily adjusted, and the inorganic fiber aggregate having a repulsive force can be obtained.
このニードルリングを施した無機繊維集合体は、ゾル−ゲル法により無機繊維前駆体の集合体を得る工程と、得られた無機繊維前駆体の集合体に、ニードリング処理を施す工程と、ニードリング処理された無機繊維前駆体の集合体を焼成して無機繊維の集合体とする焼成工程とを経て製造される。 The inorganic fiber aggregate subjected to the needle ring is obtained by a step of obtaining an aggregate of inorganic fiber precursors by a sol-gel method, a step of performing a needling process on the aggregate of the obtained inorganic fiber precursors, And baking an aggregate of the ring-processed inorganic fiber precursor into an aggregate of inorganic fibers.
本発明の無機繊維集合体の嵩密度は、０．０５〜０．５ｇ／ｃｍ３であることが好ましく、０．０６〜０．４ｇ／ｃｍ３であることがより好ましく、より好ましくは０．０８〜０．２０ｇ／ｃｍ３である。嵩密度が低すぎると脆弱な無機繊維成形体しか得られず、また、嵩密度が高すぎると無機繊維成形体の嵩密度が増大するとともに反発力が失われ、靭性の低い成形体となる。 The bulk density of the inorganic fiber aggregate of the present invention is preferably from 0.05 to 0.5 g / cm 3, more preferably 0.06~0.4g / cm 3, more preferably 0. is a 08~0.20g / cm 3. If the bulk density is too low, only a fragile inorganic fiber molded article is obtained, and if the bulk density is too high, the bulk density of the inorganic fiber molded article increases and repulsion is lost, resulting in a molded article having low toughness.
本発明の無機繊維集合体の面密度は、４００〜５０００ｇ／ｍ２、特に６００〜４０００ｇ／ｍ２、とりわけ８００〜３５００ｇ／ｍ２であることが好ましい。この無機繊維集合体の面密度が小さ過ぎると、繊維量が少なく、極薄い成形体しか得られず、断熱用無機繊維成形体としての有用性が低くなり、面密度が大き過ぎると繊維量が多すぎることにより、ニードリング処理による厚み制御が困難となる。 The areal density of the inorganic fiber aggregate of the present invention is preferably 400 to 5000 g / m 2 , more preferably 600 to 4000 g / m 2 , and particularly preferably 800 to 3500 g / m 2 . If the areal density of this inorganic fiber aggregate is too small, the amount of fibers is small, only an extremely thin molded body is obtained, and the usefulness as an inorganic fiber molded body for heat insulation is reduced. If the amount is too large, it becomes difficult to control the thickness by needling.
本発明の無機繊維集合体の厚さは、好ましくは２〜３５ｍｍ程度である。 The thickness of the inorganic fiber aggregate of the present invention is preferably about 2 to 35 mm.
本発明の無機繊維集合体の引張強度は、特段の制限はないが、２５ｍｍ幅のサンプルの引張強度を測定した場合、通常５ｋｇｆ以上であり、好ましくは７ｋｇｆ以上、特に好ましくは１０ｋｇｆ以上である。無機繊維の引張強度が５ｋｇｆ以上であることにより、無機繊維集合体としての、使用する際のハンドリング強度がある点で好ましい。上限には特段の制限はないが、２５ｋｇｆ以下であることが好ましい。
本発明の無機繊維集合体の嵩密度０．４ｇ／ｃｍ３での面圧は、特段の制限はないが、通常２５０ｋＰａ以上であり、好ましくは４００ｋＰａ以上、特に好ましくは５００ｋＰａ以上である。無機繊維の引張強度が２５０ｋＰａ以上であることにより、無機繊維集合体の反発力を利用した施工に適する点で好ましい。上限には特段の制限はないが、１０００ｋＰａ以下であることが好ましい。
＜無機繊維成形体＞
本発明の無機繊維成形体には、特に制限はないが、本発明の無機繊維集合体を折りたたんだり、重ねたりし無機繊維成型体としてもよい。この場合には、ＰＰバンドや金具等、所定の方法で結束させることができる。このことにより断熱材としての施工がしやすくなる点で好ましい。
Although the tensile strength of the inorganic fiber aggregate of the present invention is not particularly limited, it is usually 5 kgf or more, preferably 7 kgf or more, particularly preferably 10 kgf or more when measuring the tensile strength of a sample having a width of 25 mm. When the tensile strength of the inorganic fiber is 5 kgf or more, it is preferable because the inorganic fiber aggregate has handling strength when used. There is no particular upper limit, but it is preferably 25 kgf or less.
Surface pressure at a bulk density of 0.4 g / cm 3 of the inorganic fiber aggregate of the present invention is not particular limitation, is generally 250 k Pa or more, preferably 400 k Pa or more, particularly preferably 500 k Pa That is all. By the tensile strength of the inorganic fibers is not less than 250 k Pa, preferably in that the suitable construction utilizing the repulsive force of the inorganic fiber aggregate. Although there is no particular limitation on the upper limit is preferably not more than 1000 k Pa.
<Inorganic fiber molded body>
The inorganic fiber molded body of the present invention is not particularly limited, but the inorganic fiber aggregate of the present invention may be folded or overlapped to form an inorganic fiber molded body. In this case, it can be bound by a predetermined method such as a PP band or a metal fitting. This is preferable because it facilitates construction as a heat insulating material.
また、本発明の無機繊維や本発明の無機繊維集合体に有機バインダーや、無機バインダーを添加して、無機繊維成型体としてもよい。この場合には、無機繊維を解繊させて、バインダーや溶媒を混ぜてスラリー状にしても良く、また無機繊維集合体に直接バインダーを含浸させてもよい。これらの方法により、無機繊維成型に所定の固さ、可撓性、形状を持たせることができる。
＜製造方法＞
次に、本発明に関する無機繊維の製造方法について説明する。
［紡糸工程］
ゾル−ゲル法によりアルミナ／シリカ系繊維のマット状集合体を製造するには、まず、塩基性塩化アルミニウム、珪素化合物、増粘剤としての有機重合体及び水を含有する紡糸液をブローイング法で紡糸してアルミナ／シリカ繊維前駆体の集合体を得る。
［紡糸液の調整］
塩基性塩化アルミニウム；Ａｌ（ＯＨ）３−ｘＣｌｘは、例えば、塩酸又は塩化アルミニウム水溶液に金属アルミニウムを溶解させることにより調製することができる。上記の化学式におけるｘの値は、通常０．４５〜０．５４、好ましくは０．５〜０．５３である珪素化合物としては、シリカゾル、水ガラス、シリコーン化合物、アルコキシシラン類、シロキサン類、ケイ酸塩類等を適宜しようすることができるが、その中でも、水溶性珪素化合物であることが好ましく、水溶性シリコーンオイルが、焼成後の珪素を均一に分散させるため特に好ましい。
Further, an inorganic fiber molded body may be obtained by adding an organic binder or an inorganic binder to the inorganic fiber of the present invention or the inorganic fiber aggregate of the present invention. In this case, the inorganic fibers may be defibrated and mixed with a binder or a solvent to form a slurry, or the inorganic fiber aggregate may be directly impregnated with the binder. By these methods, the inorganic fiber molding can be given a predetermined hardness, flexibility and shape.
<Production method>
Next, a method for producing an inorganic fiber according to the present invention will be described.
[Spinning process]
In order to produce a mat-like aggregate of alumina / silica fibers by a sol-gel method, first, a spinning solution containing basic aluminum chloride, a silicon compound, an organic polymer as a thickener, and water is blown. Spin to obtain an aggregate of alumina / silica fiber precursor.
[Adjustment of spinning solution]
Basic aluminum chloride; Al (OH) 3-x Cl x can be prepared, for example, by dissolving metallic aluminum in hydrochloric acid or an aqueous solution of aluminum chloride. The value of x in the above chemical formula is usually 0.45 to 0.54, preferably 0.5 to 0.53. Examples of the silicon compound include silica sol, water glass, silicone compound, alkoxysilanes, siloxanes and silica. Acid salts and the like can be appropriately used, and among them, a water-soluble silicon compound is preferable, and a water-soluble silicone oil is particularly preferable because silicon after firing is uniformly dispersed.
増粘剤としては、ポリビニルアルコール、ポリエチレンオキシド−ポロプロピレンオキシド共重合体、ポリアクリルアミド、ポリビニルピロリドン、糖類、セルロース化合物等が挙げられる。ポリビニルアルコール、ポリエチレングリコール等の水溶性高分子化合物が好適に用いられる。 Examples of the thickener include polyvinyl alcohol, polyethylene oxide-polypropylene oxide copolymer, polyacrylamide, polyvinylpyrrolidone, saccharides, and cellulose compounds. Water-soluble polymer compounds such as polyvinyl alcohol and polyethylene glycol are preferably used.
紡糸液には、水の他、アルコール等の有機溶媒を含有していてもよい。有機溶媒としては、水溶性の有機溶媒が好ましく、具体的には、アルコール類、ケトン類、エーテル類、アミド化合物等が挙げられる。 The spinning solution may contain an organic solvent such as alcohol in addition to water. As the organic solvent, a water-soluble organic solvent is preferable, and specific examples thereof include alcohols, ketones, ethers, and amide compounds.
紡糸液中のアルミニウムの濃度が１６０ｇ／Ｌ未満の場合又は有機重合体の濃度が２０ｇ／Ｌ未満の場合は、何れも、紡糸液の適当な粘度が得られずに得られる無機繊維の繊維径が細くなる。すなわち、紡糸液中の遊離水が多すぎる結果、ブローイング法による紡糸の際の乾燥速度が遅く、延伸が過度に進み、紡糸された前駆体繊維の繊維径が変化し、所定の平均繊維径で且つ繊維径分布がシャープな短繊維が得られない。しかも、アルミニウムの濃度が１６０ｇ／Ｌ未満の場合は、生産性が低下する。有機重合体とは、一般的に増粘材のことを、表し、シリコーン化合物類や、アルコキシシラン類等の珪素化合物は含まない。 When the concentration of aluminum in the spinning solution is less than 160 g / L or when the concentration of the organic polymer is less than 20 g / L, the fiber diameter of the inorganic fiber obtained without obtaining an appropriate viscosity of the spinning solution is obtained. Becomes thinner. That is, as a result of too much free water in the spinning solution, the drying speed at the time of spinning by the blowing method is slow, drawing proceeds excessively, the fiber diameter of the spun precursor fiber changes, and at a predetermined average fiber diameter. Also, short fibers having a sharp fiber diameter distribution cannot be obtained. In addition, when the aluminum concentration is less than 160 g / L, the productivity is reduced. The organic polymer generally means a thickener, and does not include silicone compounds or silicon compounds such as alkoxysilanes.
一方、アルミニウムの濃度が２１０ｇ／Ｌを超える場合又は有機重合体の濃度が５０ｇ／Ｌを超える場合は、何れも、粘度が高すぎて紡糸液にはならない。紡糸液中のアルミニウムの好ましい濃度は１７０〜２００ｇ／Ｌであり、有機重合体の好ましい濃度は２０〜４０ｇ／Ｌである。 On the other hand, when the concentration of aluminum exceeds 210 g / L or when the concentration of the organic polymer exceeds 50 g / L, the viscosity is too high to form a spinning solution. The preferred concentration of aluminum in the spinning solution is 170-200 g / L, and the preferred concentration of the organic polymer is 20-40 g / L.
上記の紡糸液は、塩基性塩化アルミニウム水溶液に上記Ａｌ２Ｏ３：ＳｉＯ２比となる量の硅素化合物と有機重合体を添加し、アルミニウム及び有機重合体の濃度が上記の範囲となるように濃縮することによって調製される。
［紡糸］
紡糸（紡糸液の繊維化）は、通常、高速の紡糸気流中に紡糸液を供給するブローイング法によって行われ、これにより、無機繊維前駆体が得られる。上記の紡糸の際に使用する紡糸ノズルの構造は、特に制限はないが、例えば、エアーノズルより吹き出される空気流と紡糸液供給ノズルより押し出される紡糸液流とは並行流となり、しかも、空気の並行流は充分に整流されて紡糸液と接触する構造のものが好ましい。具体的には、特許第２６０２４６０号公報に記載されている構造が挙げられる。
The above spinning solution is prepared by adding a silicon compound and an organic polymer in an amount of the Al 2 O 3 : SiO 2 ratio to a basic aluminum chloride aqueous solution so that the concentration of aluminum and the organic polymer is in the above range. It is prepared by concentration.
[spinning]
The spinning (fibrillation of the spinning solution) is usually performed by a blowing method in which the spinning solution is supplied into a high-speed spinning air stream, whereby an inorganic fiber precursor is obtained. The structure of the spinning nozzle used in the spinning is not particularly limited.For example, the air flow blown out from the air nozzle and the spinning solution flow pushed out from the spinning solution supply nozzle are parallel flows, and the air Is preferably of such a structure that the flow is sufficiently rectified and comes into contact with the spinning solution. Specifically, the structure described in Japanese Patent No. 2602460 is cited.
また、紡糸に際しては、先ず、水分の蒸発や紡糸液の分解が抑制された条件下において、紡糸液から充分に延伸された繊維が形成され、次いで、この繊維が速やかに乾燥されることが好ましい。そのためには、紡糸液から繊維が形成されて繊維捕集器に到達するまでの過程において、雰囲気を水分の蒸発を抑制する状態から水分の蒸発を促進する状態に変化させることが好ましい。 In the spinning, first, it is preferable that a sufficiently drawn fiber is formed from the spinning solution under a condition in which evaporation of water and decomposition of the spinning solution are suppressed, and then the fiber is dried quickly. . For this purpose, it is preferable to change the atmosphere from a state in which evaporation of moisture is suppressed to a state in which evaporation of moisture is promoted in a process from when fibers are formed from the spinning solution to reach the fiber collector.
無機繊維前駆体の集合体は、紡糸気流に対して略直角となるように金網製の無端ベルトを設置し、無端ベルトを回転させつつ、これに無機系繊維前駆体を含む紡糸気流を衝突させる構造の集積装置により連続シート（薄層シート）として回収することができる。この薄層シートを積み重ねて、無機繊維前駆体の集合体を得ることができる。
［ニードリング処理工程］
紡糸により得られた無機系繊維前駆体の集合体は、次いでニードリング処理を施してもよい。ニードリング処理により、得られる無機繊維集合体を構成する無機繊維同士が絡んだ、強固な無機繊維集合体となるだけでなく、無機繊維集合体の厚みを調整することも可能となる。ニードル密度は適宜選択して決定すればよいが、中でも２〜２００打／ｃｍ２、更には２〜１５０打／ｃｍ２、とりわけ２〜１００打／ｃｍ２、特に２〜５０打／ｃｍ２であることが好ましい。このニードル密度が低過ぎると、無機繊維成形体としての厚み均一性や耐熱衝撃性が低下する等の問題が生ずる恐れがある。逆に高過ぎても、繊維を傷め、焼成後に収縮し易くなる恐れや繊維が飛散しやすくなる恐れがある。
［焼成工程］
無機繊維前駆体の焼成は、必要に応じて乾燥処理を施した後、焼成される。焼成温度は、通常５００℃以上、好ましくは７００℃〜１４００℃の温度で行う。５００℃よりも低い場合は、結晶化や有機重合体の焼成除去が不十分なため、強度が低い脆弱な繊維しか得ることができない。焼成温度が１４００℃を超えると、繊維中の結晶の粒子成長が進行して、強度の低い繊維しか得ることができない。
The aggregate of the inorganic fiber precursor is provided with an endless belt made of wire mesh so as to be substantially perpendicular to the spinning airflow, and the spinning airflow containing the inorganic fiber precursor is collided with the endless belt while rotating the endless belt. It can be collected as a continuous sheet (thin layer sheet) by the integrated device having the structure. By stacking the thin sheets, an aggregate of the inorganic fiber precursor can be obtained.
[Needling process]
The aggregate of the inorganic fiber precursor obtained by spinning may then be subjected to needling treatment. By the needling treatment, not only a strong inorganic fiber aggregate in which the inorganic fibers constituting the obtained inorganic fiber aggregate are entangled, but also the thickness of the inorganic fiber aggregate can be adjusted. Needle density may be appropriately selected and determined, but is preferably 2 to 200 hits / cm 2 , more preferably 2 to 150 hits / cm 2 , especially 2 to 100 hits / cm 2 , particularly 2 to 50 hits / cm 2 . Preferably, there is. If the needle density is too low, there is a possibility that problems such as a decrease in thickness uniformity and thermal shock resistance of the inorganic fiber molded body may occur. Conversely, if it is too high, the fibers may be damaged and shrink easily after firing, or the fibers may be easily scattered.
[Firing step]
The inorganic fiber precursor is fired after performing a drying treatment as necessary. The firing temperature is usually 500 ° C. or higher, preferably 700 ° C. to 1400 ° C. If the temperature is lower than 500 ° C., crystallization or removal of the organic polymer by firing is insufficient, so that only fragile fibers having low strength can be obtained. When the firing temperature exceeds 1400 ° C., the crystal grains in the fibers grow, and only fibers having low strength can be obtained.
また、焼成中の雰囲気は、水蒸気を多く含んだ雰囲気にするほうが良い。水蒸気を焼成雰囲気に含ませることで、前駆体溶液中の塩化物を塩化水素として、効率良く除去することができる。また水蒸気を含んだ雰囲気にする好ましい温度は限定的であり、８００℃以上が好ましく、８００℃〜８５０℃が最も好ましい。８００℃以下では、前駆体中でＡｌ、Ｓｉ原子等と強固に結合したＣｌを除去することができず、８５０℃以上では、無機繊維中の細孔が閉気孔となるため、水蒸気を添加する効果が限定的になり、繊維内部の塩素原子を除去しにくくなる。 The atmosphere during firing is preferably an atmosphere containing a large amount of water vapor. By including steam in the firing atmosphere, chlorides in the precursor solution can be efficiently removed as hydrogen chloride. A preferable temperature for forming the atmosphere containing water vapor is limited, is preferably 800 ° C. or higher, and most preferably 800 ° C. to 850 ° C. At 800 ° C. or lower, Cl firmly bonded to Al, Si atoms and the like in the precursor cannot be removed, and at 850 ° C. or higher, water vapor is added because the pores in the inorganic fiber become closed pores. The effect is limited, and it becomes difficult to remove chlorine atoms in the fiber.
たとえば、無機繊維もしくは、無機繊維集合体に酸化物前駆体含有液を含浸させた後に、乾燥及び／又は焼成させることで、無機繊維成型体としてもよい。この場合は、焼成後の酸化物添着量が含浸部無機繊維１００質量部に対して２〜５０質量部となるように調整することが望ましい。添着量が少ない場合は、所望の物性が得られない場合がある。逆に多すぎると、熱収縮率の悪化や耐熱衝撃性、耐機械衝撃性の低下が見られる場合がある。 For example, the inorganic fiber or the inorganic fiber aggregate may be impregnated with the oxide precursor-containing liquid, and then dried and / or fired to form an inorganic fiber molded body. In this case, it is desirable to adjust the amount of the oxide impregnated after firing to be 2 to 50 parts by mass with respect to 100 parts by mass of the inorganic fiber in the impregnated portion. If the amount of attachment is small, desired physical properties may not be obtained. Conversely, if it is too large, the heat shrinkage may deteriorate, and the thermal shock resistance and mechanical shock resistance may decrease.
この酸化物前駆体含有液の酸化物前駆体としては、焼成によりアルミナ、スピネル、ジルコニア、チタニア、カルシア及びマグネシアを生成する群から選ばれる１種又は２種以上を含むものが好ましく用いられる。またこれらは、水酸化物、塩化物、酢酸化物、乳酸化物、硝酸化物、ゾルを含む。 As the oxide precursor of the oxide precursor-containing liquid, one containing one or more members selected from the group of producing alumina, spinel, zirconia, titania, calcia and magnesia by firing is preferably used. These also include hydroxides, chlorides, acetates, lactates, nitrates and sols.
特にカルシアやマグネシアの酸化物前駆体溶液を使用した場合は、無機繊維成形体の耐スケール性が向上し、チタニアの酸化物前駆体溶液を使用した場合は、無機繊維成形体の輻射率が向上する点で好ましい。 In particular, when an oxide precursor solution of calcia or magnesia is used, the scale resistance of the inorganic fiber molded body is improved, and when the oxide precursor solution of titania is used, the emissivity of the inorganic fiber molded body is improved. Is preferred.
無機繊維もしくは、無機繊維集合体を解繊し、そこへ溶媒や各種バインダー等を添加してスラリー状にしてもよい。これらをスラリー状で使用しても良いし、脱水成形を施して、セラミックファーバーモジュールとしてもよい。 The inorganic fiber or the inorganic fiber aggregate may be defibrated, and a solvent or various binders may be added thereto to form a slurry. These may be used in the form of a slurry, or may be subjected to dehydration molding to form a ceramic fiber module.
無機繊維もしくは、無機繊維集合体に有機バインダーを含浸、もしくは添着させてもよい。また有機バインダーを用いることで、繊維の飛散を防ぐことができる。添着厚みや添着量を調整することで、厚み、可撓性、反発量等を調整することができる。 The inorganic fiber or the inorganic fiber aggregate may be impregnated or impregnated with an organic binder. In addition, by using an organic binder, scattering of fibers can be prevented. The thickness, flexibility, amount of rebound, and the like can be adjusted by adjusting the attached thickness and the attached amount.
以下に実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples at all without departing from the gist thereof.
なお、以下の実施例等において得られた無機繊維成形体の各種物性や特性の測定、評価方法は、以下の通りである。
［Ｃｌ濃度測定］
試料（無機繊維）１０ｍｇに燃焼装置（三菱化学株式会社製 ＡＱＦ−２１００Ｎ）を使用し酸素気流中で完全に燃焼し、発生したガスを２．７ｍＭ Ｎａ２ＣＯ３ − ０．３ｍＭ ＮａＨＣＯ３水溶液に吸収させ、分析装置（サーモフィッシャーサイエンティフィック株式会社製 ＤＸ−５００）によりイオンクロマトグラフ分析を実施し、無機繊維中のＣｌ残渣を測定した。
［単繊維 引張強度］
アルミナ／シリカ系繊維を、１ｍｍ各のダイヤモンド基板上に載せて、島津製作所製微小圧縮試験機 ＭＣＴＭ−５００にて、直径５０μｍの平面圧子を用いて、破壊荷重を測定した。破壊荷重より引張強度を求め、５点の引張強度の平均値を算出して、繊維の引張強度とした。
［引張強度］＝２×［破壊強度］／（［円周率］×［繊維径］×［繊維長］）
［ＹＩ値］
得られた無機繊維を以下の条件でＹＩ値を測定した。ＹＩ値が２以下を合格とし、２より高い場合を不可とした。ＹＩ値は、得られた繊維を、すり鉢にて細かく粉砕した後、分光色分計（製品名：ＣＭ−７００ｄ コニカミノルタ製）にて、試験品の裏側に白色板を置き、ＪＩＳ Ｚ ８７２２に基づき試験品の、分光反射率および三刺激値 ＸＹＺｘｙを測定した。その後ＪＩＳ Ｋ ７３７３に基づき試験品の黄色度 ＹＩ値を求めた。測定条件は、Ｃ光源、ＳＣＥ（ｄｅ：８°）、視野角２°とした。白色版単体の三刺激値は、Ｘ＝８３．２６、Ｙ＝８５．５０、Ｚ＝９７．８７であった。
［繊維集合体 引張強度］
得られた無機繊維集合体を、２５ｍｍ幅に切り取り、万能試験機にて、無機繊維集合体の両端を固定し、１００ｍｍ／ｍｉｎのスピードで、破壊されるまで引っ張り、最大荷重を求め、３点の平均値を算出して、集合体の引張強度とした。
［繊維集合体 面圧］
得られた無機繊維集合体を、５０ｍｍ角に切り取り、万能試験機にて１ｍｍ／ｍｉｎのスピードで所定の嵩密度になるまで圧縮した。嵩密度 ０．２、０．３、０．４ｇ／ｃｍ３の部分の荷重を求め、試験片面積で割り、それぞれの嵩密度での面圧値とした。３点測定し、平均値を、集合体の面圧値とした。
［実施例１］
塩基性塩化アルミニウム（アルミニウム含有量７０ｇ／Ｌ、Ａｌ／Ｃｌ＝１．８（原子比））水溶液に、水溶性シリコーンオイルを、最終的に得られるアルミナ繊維の組成がＡｌ ２ Ｏ ３ ：ＳｉＯ ２ ＝９５：５（質量比）となるように加え、更に、ポリビニルアルコールを加えた後、濃縮して、粘度４０ポイズ、アルミナ・シリカ含量約３０質量％の紡糸液を調製し、該紡糸液を用いてブローイング法で紡糸した。
これを集綿積層し、このマット状繊維集合体にニードル密度３打／ｃｍ ２ 以上にてニードルパンチを実施しアルミナ／シリカ系繊維前駆体のマット状繊維集合体を得た。表１で示すように、電気炉にて、大気条件化で８００℃まで６０分かけて昇温し、その後、電気炉内へ流入する空気を水中に通過させることで、水蒸気を多く含んだ空気に切り替え、８００℃で６０分間保持し、アルミナ／シリカ系の繊維集合体を得た。
得られたアルミナ／シリカ系繊維中のＡｌ２Ｏ３とＳｉＯ２の含有量は、表２で示すように、それぞれ９５重量％と５重量％であった。得られた繊維集合体において、上記の測定項目の結果を表２に示す。
The methods for measuring and evaluating various physical properties and properties of the inorganic fiber molded article obtained in the following Examples and the like are as follows.
[Cl concentration measurement]
10 mg of the sample (inorganic fiber) was completely burned in an oxygen stream using a combustion apparatus (AQF-2100N manufactured by Mitsubishi Chemical Corporation), and the generated gas was converted to a 2.7 mM Na 2 CO 3 -0.3 mM NaHCO 3 aqueous solution. Absorption was performed, and ion chromatography was performed using an analyzer (DX-500 manufactured by Thermo Fisher Scientific KK) to measure Cl residue in the inorganic fibers.
[Tensile strength of single fiber]
The alumina / silica fiber was placed on each 1 mm diamond substrate, and the breaking load was measured with a micro compression tester MCTM-500 manufactured by Shimadzu Corporation using a plane indenter having a diameter of 50 μm. The tensile strength was determined from the breaking load, the average value of the tensile strength at five points was calculated, and the result was defined as the tensile strength of the fiber.
[Tensile strength] = 2 x [breaking strength] / ([pi] x [fiber diameter] x [fiber length])
[YI value]
The YI value of the obtained inorganic fiber was measured under the following conditions. When the YI value was 2 or less, it was judged as acceptable, and when it was higher than 2, it was unacceptable. The YI value was obtained by finely crushing the obtained fiber in a mortar, placing a white plate on the back side of the test product with a spectral colorimeter (product name: CM-700d, manufactured by Konica Minolta), and applying JIS Z 8722 Based on this, the spectral reflectance and tristimulus value XYZxy of the test article were measured. Thereafter, the yellowness YI value of the test article was determined based on JIS K 7373. The measurement conditions were a C light source, SCE (de: 8 °), and a viewing angle of 2 °. The tristimulus values of the white plate alone were X = 83.26, Y = 85.50, Z = 97.87.
[Fiber aggregate tensile strength]
The obtained inorganic fiber aggregate was cut into a width of 25 mm, and both ends of the inorganic fiber aggregate were fixed with a universal testing machine, pulled at a speed of 100 mm / min until breaking, and the maximum load was determined. Was calculated as the tensile strength of the aggregate.
[Fiber assembly surface pressure]
The obtained inorganic fiber aggregate was cut into a square of 50 mm, and compressed by a universal testing machine at a speed of 1 mm / min to a predetermined bulk density. Bulk densities Loads at 0.2, 0.3, and 0.4 g / cm 3 were determined, divided by the test piece area, and determined as the surface pressure value at each bulk density. Three points were measured, and the average value was taken as the surface pressure value of the aggregate.
[Example 1]
A water-soluble silicone oil is added to an aqueous solution of basic aluminum chloride (aluminum content: 70 g / L, Al / Cl = 1.8 (atomic ratio)), and the final alumina fiber composition is Al 2 O 3 : SiO 2 = 95: 5 (mass ratio), and further, after adding polyvinyl alcohol, concentrating to prepare a spinning solution having a viscosity of 40 poise and an alumina-silica content of about 30% by mass. And spun by a blowing method.
This was collected and laminated, and this mat-like fiber aggregate was needle-punched at a needle density of 3 punches / cm 2 or more to obtain a mat-like fiber aggregate of an alumina / silica-based fiber precursor. As shown in Table 1, in an electric furnace, the temperature was raised to 800 ° C. over 60 minutes under atmospheric conditions, and then the air flowing into the electric furnace was passed through water, so that air containing a large amount of water vapor was obtained. And kept at 800 ° C. for 60 minutes to obtain an alumina / silica-based fiber aggregate.
As shown in Table 2, the contents of Al 2 O 3 and SiO 2 in the obtained alumina / silica fiber were 95% by weight and 5% by weight, respectively. Table 2 shows the results of the above measurement items in the obtained fiber assembly.
［実施例２及び比較例１−６］
実施例１と同様に得られた、アルミナ／シリカ系繊維前駆体のマット状繊維集合体を、表１で示す焼成条件で焼成し、アルミナ／シリカ系の無機繊維集合体を得た。得られた繊維集合体において、上記の測定項目の結果を表２に示す。
[Example 2 and Comparative Examples 1-6]
The mat-like fiber aggregate of the alumina / silica-based fiber precursor obtained in the same manner as in Example 1 was fired under the firing conditions shown in Table 1 to obtain an alumina / silica-based inorganic fiber aggregate. Table 2 shows the results of the above measurement items in the obtained fiber assembly.
なお、比較例２〜４は昇温条件３の後は保持せずに室温に戻した。 In Comparative Examples 2 to 4, the temperature was returned to room temperature without holding after the temperature rising condition 3.
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Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
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| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |