JP2006016739A - Calcium aluminate fiber, method for producing the same and its application - Google Patents
Calcium aluminate fiber, method for producing the same and its application Download PDFInfo
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- JP2006016739A JP2006016739A JP2004197899A JP2004197899A JP2006016739A JP 2006016739 A JP2006016739 A JP 2006016739A JP 2004197899 A JP2004197899 A JP 2004197899A JP 2004197899 A JP2004197899 A JP 2004197899A JP 2006016739 A JP2006016739 A JP 2006016739A
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- 239000000835 fiber Substances 0.000 title claims abstract description 102
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- -1 aluminum compound Chemical class 0.000 claims abstract description 10
- 229940043430 calcium compound Drugs 0.000 claims abstract description 9
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
Abstract
Description
本発明は、カルシウムアルミネート繊維、その製造方法及び用途に関する。 The present invention relates to a calcium aluminate fiber, a method for producing the same, and an application thereof.
従来のカルシウムアルミネート繊維は、アルミナ（Ａｌ２Ｏ３）と石灰（ＣａＯ）を含む混合物をペレット化し、その溶融物を圧縮空気でブローイングして製造されたものであって、組成的にはＡｌ２Ｏ３が５０〜８０質量％、ＣａＯが２０〜５０質量％である繊維を少なくとも９０質量％を含み、残部が不純物酸化物であるものが知られている（特許文献１）。このようなブローイング法にあっては、ショットの生成は不可避であり、ショット含有率が３５〜６５質量％程度であることが非特許文献１に記載されている。ショットを多量に含む繊維で構成された成形体は、断熱機能を低下させるだけでなく、強度と耐磨耗性にも悪影響を与える。さらには、このような成形体で構成された炉を用い、例えば高級陶磁器やステンレス薄板等を製造すると、成形体から分離脱落したショットにより製品が傷つく恐れがある。
本発明の目的は、ショット含有率の少ないカルシウムアルミネート繊維、その製造方法及び用途を提供することである。 An object of the present invention is to provide a calcium aluminate fiber having a low shot content, a method for producing the same, and a use thereof.
すなわち、本発明は、ショット含有率が３０質量％未満であることを特徴とするカルシウムアルミネート繊維である。この場合において、（１）ショット含有率が１０質量％未満であること、（２）組成が、ＣａＯが５〜７０質量％、Ａｌ２Ｏ３が９５〜３０質量％であること、（３）平均繊維径が１〜８μｍであること、（４）水中かさ密度が０．０１０〜０．０５０ｇ／ｃｍ３であること、から選ばれた実施態様の１以上であることが好ましい。 That is, the present invention is a calcium aluminate fiber characterized in that the shot content is less than 30% by mass. In this case, (1) the shot content is less than 10% by mass, (2) the composition is 5 to 70% by mass of CaO and 95 to 30 % by mass of Al 2 O 3 , (3) The average fiber diameter is preferably 1 to 8 μm, and (4) the bulk density in water is 0.010 to 0.050 g / cm 3 .
また、本発明は、カルシウム化合物と、アルミニウム化合物と、紡糸助剤とを含む紡糸原液を液糸化した後、焼成することを特徴とするカルシウムアルミネート繊維の製造方法である。この場合において、（５）紡糸原液が、カルシウム化合物とアルミニウム化合物の合計濃度が１５〜４０質量％、紡糸助剤の濃度が３〜１２質量％、粘度が１０００〜１００００ｍＰａ・ｓであること、（６）紡糸原液を、円周面に直径０．１〜０．３ｍｍの孔を複数個設けられてなる中空円盤を周速３０〜８０ｍ／ｓで回転させつつ、一孔あたり８〜２０ｍｌ／ｈｒで供給・吐出させて液糸化し、それを５０〜４００℃で乾燥した後、焼成すること、（７）焼成が、連続炉の前半部において、室温から８００〜１０００℃までの間を１０〜２０℃／ｍｉｎで昇温し、続けて連続炉の後半部において、最高温度１１００〜１５００℃までを２０〜３０℃／ｍｉｎで昇温し、最高温度で１５〜３０分間保持して行われること、から選ばれた実施態様の１以上であることが好ましい。 The present invention is also a method for producing calcium aluminate fibers, characterized in that a spinning stock solution containing a calcium compound, an aluminum compound, and a spinning aid is liquefied and then fired. In this case, (5) the spinning undiluted solution has a total concentration of calcium compound and aluminum compound of 15 to 40% by mass, a concentration of spinning aid of 3 to 12% by mass, and a viscosity of 1000 to 10,000 mPa · s. 6) The spinning dope is rotated at a peripheral speed of 30 to 80 m / s while rotating a hollow disk having a plurality of holes having a diameter of 0.1 to 0.3 mm on the circumferential surface, and 8 to 20 ml / hr per hole. (7) Firing is performed at a temperature between room temperature and 800-1000 ° C. in the first half of the continuous furnace. The temperature is raised at 20 ° C./min, and subsequently, in the latter half of the continuous furnace, the temperature is raised to the maximum temperature of 1100-1500 ° C. at 20-30 ° C./min and held at the maximum temperature for 15-30 minutes. Selected implementation from It is preferable that the one or more like.
さらに、本発明は、上記カルシウムアルミネート繊維で構成されてなることを特徴とする成形体であり、またこの成形体で構成されてなる構造用部材である。 Furthermore, the present invention is a molded body characterized in that it is composed of the calcium aluminate fiber, and is a structural member composed of this molded body.
本発明によれば、ショット含有率の少ない、耐熱性と耐アルカリ性に優れたカルシウムアルミネート繊維が提供される。また、本発明によれば、ショット含有率の少ないカルシウムアルミネート繊維の製造方法が提供される。さらには、本発明によれば、ショット含有率の少ない、耐熱性と耐アルカリ性に優れた成形体、特に構造用材料が提供される。 According to the present invention, a calcium aluminate fiber having a low shot content and excellent heat resistance and alkali resistance is provided. Moreover, according to this invention, the manufacturing method of calcium aluminate fiber with little shot content rate is provided. Furthermore, according to the present invention, a molded article having a low shot content and excellent heat resistance and alkali resistance, particularly a structural material is provided.
本発明のカルシウムアルミネート繊維は、ＣａＯをＣ、Ａｌ２Ｏ３をＡと略記すると、例えばＣ＋Ｃ３Ａ、Ｃ３Ａ、Ｃ３Ａ＋Ｃ１２Ａ７、Ｃ１２Ａ７、Ｃ１２Ａ７＋ＣＡ、ＣＡ、ＣＡ＋ＣＡ２、ＣＡ２、Ｃ３Ａ５、ＣＡ２＋ＣＡ６、ＣＡ６、ＣＡ６＋Ａ等から選ばれた物質の結晶質、又は非結晶質、又は結晶質と非結晶質で構成された繊維である。組成的には、ＣａＯが５〜７０質量％、Ａｌ２Ｏ３が９５〜３０質量％であり、両者の合計が１００質量％であることが最適であるが、最大１質量％までのＦｅ２Ｏ３等の不純物を含有していてもよい。 The calcium aluminate fiber of the present invention, when CaO is abbreviated as C and Al 2 O 3 is abbreviated as A, for example, C + C 3 A, C 3 A, C 3 A + C 12 A 7 , C 12 A 7 , C 12 A 7 + CA, It is composed of a substance selected from CA, CA + CA 2 , CA 2 , C 3 A 5 , CA 2 + CA 6 , CA 6 , CA 6 + A, or the like, or amorphous, or crystalline and amorphous. Fiber. Compositionally, CaO is 5 to 70% by mass, Al 2 O 3 is 95 to 30% by mass, and the total of both is 100% by mass, but Fe 2 up to 1% by mass at maximum. Impurities such as O 3 may be contained.
本発明のカルシウムアルミネート繊維は、ショット含有率が３０質量％未満であり、特に１０質量％未満、更には１質量％未満であることが好ましい。ショットが多く含まれていると、所定厚みの成形体を成形する際のカルシウムアルミネート繊維が多く必要となるほか、成形体の断熱性、強度及び耐磨耗性を悪化させる恐れがある。 The calcium aluminate fiber of the present invention has a shot content of less than 30% by mass, particularly preferably less than 10% by mass, and more preferably less than 1% by mass. When a lot of shots are contained, a large amount of calcium aluminate fiber is required for molding a molded article having a predetermined thickness, and there is a risk of deteriorating the heat insulation, strength and wear resistance of the molded article.
本発明でいう「ショット」とは、非繊維状物質等の固形物であり、次のように測定されたものである。すなわち、繊維５０ｇを直径８０ｍｍ×深さ１５０ｍｍのステンレス製円筒容器に入れ、その上面に板を置いて圧力をかけていき、２０ＭＰａに達したら解放して、圧砕された繊維を、水の流量０．５ｌ／ｍｉｎで水簸分級（沈降分級法の一種）を行い、回収される非繊維状物質等の固形物量のことである。ショット含有率は、試料繊維中の百分率として算出される。 The “shot” in the present invention is a solid such as a non-fibrous substance, and is measured as follows. That is, 50 g of fiber is put in a stainless steel cylindrical container having a diameter of 80 mm and a depth of 150 mm, a plate is placed on the upper surface, pressure is applied, and when the pressure reaches 20 MPa, the crushed fiber is supplied with a water flow rate of 0. It is the amount of solid matter such as non-fibrous material that is recovered by performing elutriation classification (a kind of sedimentation classification method) at .5 l / min. The shot content is calculated as a percentage in the sample fiber.
カルシウムアルミネート繊維の平均繊維径は１〜８μｍであることが好ましい。平均繊維径が１μｍよりも著しく小さいと、粉塵が発生しやすくなる恐れがあり、８μｍよりも著しく大きいと、繊維の脆性的性質が顕著になり、繊維強度が低下する恐れがある。特に好ましい平均繊維径は２〜６μｍである。ここで、平均繊維径は、１０００本以上の繊維のＳＥＭ写真から計測した繊維径の平均値である。 The average fiber diameter of the calcium aluminate fiber is preferably 1 to 8 μm. If the average fiber diameter is remarkably smaller than 1 μm, dust may be easily generated. If the average fiber diameter is remarkably larger than 8 μm, the brittle nature of the fiber becomes remarkable and the fiber strength may be lowered. A particularly preferable average fiber diameter is 2 to 6 μm. Here, the average fiber diameter is an average value of fiber diameters measured from SEM photographs of 1000 or more fibers.
カルシウムアルミネート繊維の水中かさ密度は、０．０１０〜０．０５０ｇ／ｃｍ３、特に０．０１２〜０．０３５ｇ／ｃｍ３であることが好ましい。水中かさ密度は繊維強度の指標である。 The bulk density of the calcium aluminate fibers in water is preferably 0.010 to 0.050 g / cm 3 , and particularly preferably 0.012 to 0.035 g / cm 3 . Underwater bulk density is an indicator of fiber strength.
水中かさ密度の測定は、繊維５ｇを４００ｍｌの水中で、攪拌機を用いて１０００ｒｐｍで１０ｍｉｎ攪拌した後、５００ｍｌのメスシリンダーに移し、水を加えて全容積を５００ｍｌにしてから、３０分間静置し、その沈降容積から求めることができる。 The bulk density in water was measured by stirring 5 g of fiber in 400 ml of water using a stirrer at 1000 rpm for 10 min, transferring to a 500 ml graduated cylinder, adding water to bring the total volume to 500 ml, and allowing to stand for 30 minutes. , And can be determined from the sedimentation volume.
本発明のカルシウムアルミネート繊維の製造方法は、上記した本発明のカルシウムアルミネート繊維を製造するのに適用できるものである。本発明の製造方法は、カルシウム化合物と、アルミニウム化合物と、紡糸助剤とを含む紡糸原液を調製し、それを液糸化した後、焼成する工程を経ることが特徴である。 The manufacturing method of the calcium aluminate fiber of this invention is applicable to manufacturing the above-mentioned calcium aluminate fiber of this invention. The production method of the present invention is characterized in that a spinning stock solution containing a calcium compound, an aluminum compound, and a spinning aid is prepared, liquefied and then fired.
カルシウム化合物としては、例えばカルシウムの塩化物、水酸化物、炭酸塩、硝酸塩等から選ばれた一種又は二種以上が用いられ、アルミニウム化合物としては、例えばアルミニウムの塩基性塩化物、塩基性酢酸塩、塩基性硝酸塩等から選ばれた一種又は二種以上が用いられる。また、紡糸助剤は、カルシウム化合物、アルミニウム化合物を含む溶液に粘性を持たせるために必要な成分であり、これには例えばポリビニルアルコール、でんぷん、ポリエチレンオキサイド、ポリエチレングリコール等が用いられる。 As the calcium compound, for example, one or two or more kinds selected from calcium chloride, hydroxide, carbonate, nitrate and the like are used. As the aluminum compound, for example, basic chloride of aluminum, basic acetate of aluminum One or more selected from basic nitrates and the like are used. The spinning aid is a component necessary for imparting viscosity to a solution containing a calcium compound and an aluminum compound. For example, polyvinyl alcohol, starch, polyethylene oxide, polyethylene glycol or the like is used.
紡糸原液中の、カルシウム化合物と、アルミニウム化合物の合計濃度（固形分濃度）は、１５〜４０質量％であることが好ましい。１５質量％よりも著しく小さいと、液糸の乾燥が不十分になり、集積したときに前駆体繊維同士が接着する恐れがあるほか、平均繊維径が著しく細くなる恐れがある。逆に、４０質量％よりも著しく大きいと、繊維の平均繊維径が著しく太くなるため、脆性的性質が顕著になって、繊維強度が低下する恐れがある。特に好ましい固形分濃度は２０〜３５質量％である。 The total concentration (solid content concentration) of the calcium compound and the aluminum compound in the spinning dope is preferably 15 to 40% by mass. If it is significantly smaller than 15% by mass, drying of the liquid yarn becomes insufficient, and the precursor fibers may adhere to each other when accumulated, and the average fiber diameter may be remarkably reduced. On the other hand, if it is significantly larger than 40% by mass, the average fiber diameter of the fiber is remarkably increased, so that the brittle nature becomes remarkable and the fiber strength may be lowered. A particularly preferred solid content concentration is 20 to 35% by mass.
紡糸原液中の紡糸助剤の濃度は３〜１２質量％であることが好ましい。３質量％よりも著しく小さいと、液糸の延伸が過剰となり、ショット発生の原因となる。逆に、１２質量％よりも著しく大きいと、前駆体繊維を焼成する際、炉内で繊維が発火・燃焼する恐れがある。発火・燃焼した繊維の繊維強度は著しく低下する。特に好ましい紡糸助剤の濃度は５〜１０質量％である。 The concentration of the spinning aid in the spinning dope is preferably 3 to 12% by mass. If it is remarkably smaller than 3% by mass, the drawing of the liquid yarn becomes excessive, causing a shot. On the other hand, if it is significantly larger than 12% by mass, the fiber may ignite and burn in the furnace when firing the precursor fiber. The fiber strength of the ignited / burned fiber is significantly reduced. A particularly preferred concentration of the spinning aid is 5 to 10% by mass.
紡糸原液の粘度は、１０００〜１００００ｍＰａ・ｓであることが好ましい。粘度が１０００ｍＰａ・ｓよりも著しく小さいと紡糸性（液糸性）が劣り、平均繊維径が著しく細くなる恐れがあるか、ショット発生の原因となる恐れがある。逆に、１００００ｍＰａ・ｓよりも著しく大きいと、平均繊維径が著しく太くなるため、脆性的性質が顕著になって、繊維強度が低下する恐れがある。特に好ましい紡糸原液の粘度は１５００〜７０００ｍＰａ・ｓである。 The viscosity of the spinning dope is preferably 1000 to 10000 mPa · s. If the viscosity is remarkably smaller than 1000 mPa · s, the spinnability (liquid yarn property) is inferior, and the average fiber diameter may be remarkably reduced or a shot may be generated. On the other hand, if it is significantly higher than 10000 mPa · s, the average fiber diameter is remarkably increased, so that brittle properties become prominent and the fiber strength may be lowered. The viscosity of a particularly preferred spinning dope is 1500 to 7000 mPa · s.
上記紡糸原液を紡糸（液糸）するには、円周面に直径０．１〜０．３ｍｍの孔を複数個設けられた中空円盤を周速３０〜８０ｍ／ｓｅｃで回転させながら、１孔あたり８〜２０ｍｌ／ｈｒの割合で紡糸原液を吐出させることによって行うことが好ましい。 For spinning (liquid yarn) the spinning dope, a hollow disk having a plurality of holes with a diameter of 0.1 to 0.3 mm on the circumferential surface is rotated at a peripheral speed of 30 to 80 m / sec. It is preferable to discharge the spinning dope at a rate of 8 to 20 ml / hr per unit.
孔の直径が０．１〜０．３ｍｍを著しく逸脱すると、上記平均繊維径の実現が困難となり、また紡糸性が劣ってショット発生の原因となる恐れがある。また、１孔あたりの供給量が８ｍｌ／ｈｒ未満であると、紡糸性が劣ってショット発生の原因となる恐れがあり、供給量が２０ｍｌ／ｈｒよりも著しく多いと、繊維の平均繊維径が著しく太くなり、また繊維の脆性的性質が顕著になって繊維の破壊が起こりやすくなる。特に好ましい１孔あたりの供給量は１０〜１８ｍｌ／ｈｒである。 If the hole diameter deviates significantly from 0.1 to 0.3 mm, it is difficult to realize the above average fiber diameter, and the spinnability is poor, which may cause shots. In addition, if the supply amount per hole is less than 8 ml / hr, the spinnability may be inferior and cause shots. If the supply amount is significantly higher than 20 ml / hr, the average fiber diameter of the fibers may be The fiber becomes extremely thick, and the brittle nature of the fiber becomes remarkable, so that the fiber is easily broken. A particularly preferable supply amount per hole is 10 to 18 ml / hr.
一方、回転円盤の周速が８０ｍ／ｓｅｃよりも著しく大きいと、平均繊維径が著しく細くなると共に、機械的な負荷がかかり、操業上の困難も伴いやすくなり、また３０ｍ／ｓｅｃよりも著しく小さいと液糸化に悪影響を及ぼす恐れがある。特に好ましい回転円盤の周速は４０〜６０ｍ／ｓｅｃである。 On the other hand, if the peripheral speed of the rotating disk is remarkably larger than 80 m / sec, the average fiber diameter is remarkably reduced, a mechanical load is applied, and operational difficulties are easily caused, and it is remarkably smaller than 30 m / sec. And there is a risk of adversely affecting liquid yarn. A particularly preferable peripheral speed of the rotating disk is 40 to 60 m / sec.
その後、液糸は乾燥された後、焼成される。液糸の乾燥は、浮遊状態の液糸に５０〜４００℃の熱風等を供給して行うことが好ましい。焼成は、熱風等によって集綿室まで搬送される間に乾燥された液糸の乾燥物を、集綿室の下方から吸引して集め（以下、この集積物を「前駆体繊維」ともいう。）、それを焼成することが好ましい。 Thereafter, the liquid yarn is dried and then fired. The drying of the liquid yarn is preferably performed by supplying hot air or the like at 50 to 400 ° C. to the floating liquid yarn. In the baking, the dried liquid yarn dried while being conveyed to the cotton collection chamber by hot air or the like is collected by sucking from the bottom of the cotton collection chamber (hereinafter, this accumulation is also referred to as “precursor fiber”). ) And firing it.
液糸の乾燥温度が５０℃よりも著しく低いと、液糸の延伸過多による、平均繊維径の細径化や、前駆体繊維同士の接着が起こる恐れがある。逆に、乾燥温度が４００℃よりも著しく高いと、液糸が十分延伸される前に乾燥されるため、平均繊維径が著しく太くなる恐れがある。特に好ましい乾燥温度は７０〜３５０℃である。 If the drying temperature of the liquid yarn is significantly lower than 50 ° C., the average fiber diameter may be reduced or the precursor fibers may be bonded due to excessive drawing of the liquid yarn. On the other hand, if the drying temperature is significantly higher than 400 ° C., the liquid yarn is dried before it is sufficiently drawn, so that the average fiber diameter may be remarkably increased. A particularly preferable drying temperature is 70 to 350 ° C.
前駆体繊維の焼成は、ローラーハウス炉やウォーキングビーム炉等の連続炉を用い、大気雰囲気下で行うことが好ましい。まず、連続炉の前半部では、室温から８００〜１０００℃までを１０〜２０℃／ｍｉｎで昇温して行い、主として前駆体繊維の水分や紡糸助剤等を除去することが好ましい。連続炉の後半部は、１１００〜１５００℃までを１０〜２０℃／ｍｉｎ昇温するのが好ましく、更にこの最高温度で１５〜３０分間保持することが好ましい。最高温度は、カルシウムアルミネートの組成等によって適宜決定される。 The firing of the precursor fiber is preferably performed in an air atmosphere using a continuous furnace such as a roller house furnace or a walking beam furnace. First, in the first half of the continuous furnace, it is preferable that the temperature is raised from room temperature to 800 to 1000 ° C. at a rate of 10 to 20 ° C./min to mainly remove moisture from the precursor fibers, spinning aids, and the like. In the latter half of the continuous furnace, the temperature is preferably increased from 1100 to 1500 ° C. by 10 to 20 ° C./min, and further preferably maintained at this maximum temperature for 15 to 30 minutes. The maximum temperature is appropriately determined depending on the composition of calcium aluminate.
ここで、連続炉前半部の焼成温度が８００℃未満であると、紡糸助剤中に含まれる有機成分が完全に除去されず、その後の連続炉後半部において最高温度で焼成すると繊維強度が低下する恐れがある。また、前半部の焼成温度が１０００℃を超えると、炉長を必要以上に長くする必要がある。一方、連続炉前半部の昇温速度が１０℃／ｍｉｎ未満であると、所望の温度を達成するには連続炉前半部の炉長を必要以上に長くする必要があり、また昇温速度が２０℃／ｍｉｎを超えると、急激な加熱により前駆体繊維中の紡糸助剤が発火・燃焼し、繊維強度を低下させる恐れがある。 Here, when the firing temperature in the first half of the continuous furnace is less than 800 ° C., the organic components contained in the spinning aid are not completely removed, and the fiber strength decreases when firing at the maximum temperature in the second half of the continuous furnace thereafter. There is a fear. Further, if the firing temperature of the first half exceeds 1000 ° C., it is necessary to make the furnace length longer than necessary. On the other hand, if the heating rate of the first half of the continuous furnace is less than 10 ° C./min, it is necessary to increase the furnace length of the first half of the continuous furnace more than necessary to achieve the desired temperature. If it exceeds 20 ° C./min, the spinning aid in the precursor fiber is ignited and burned by rapid heating, which may reduce the fiber strength.
また、連続炉後半部の温度が１１００℃未満であると、カルシウムアルミネート繊維の緻密化が不十分となる恐れがあり、また１５００℃を超えると、繊維の脆性的性質が顕著になって繊維強度が低下する恐れがある。さらには、連続炉後半部の昇温速度が２０℃／ｍｉｎ未満であると、炉長を必要以上に長くする必要があり、昇温速度が３０℃／ｍｉｎを超えると、急激な加熱により、カルシウムアルミネート繊維に焼きムラができる恐れがある。また、最高温度における保持時間が１５分未満であると、カルシウムアルミネート繊維に焼きムラができる恐れがあり、３０分を超えると、繊維強度が低下する恐れがある。 Further, if the temperature of the latter half of the continuous furnace is less than 1100 ° C., the densification of the calcium aluminate fibers may be insufficient, and if it exceeds 1500 ° C., the brittle nature of the fibers becomes remarkable and the fibers Strength may be reduced. Furthermore, if the rate of temperature rise in the latter half of the continuous furnace is less than 20 ° C./min, it is necessary to make the furnace length longer than necessary, and if the rate of temperature rise exceeds 30 ° C./min, rapid heating causes There is a risk of uneven firing on the calcium aluminate fiber. Further, if the holding time at the maximum temperature is less than 15 minutes, there is a possibility that baking unevenness may be formed on the calcium aluminate fiber, and if it exceeds 30 minutes, the fiber strength may be lowered.
本発明の成形体は、カルシウムアルミネート繊維を、例えば押出成形法、射出成形法、抄造法等の公知方法などで成形されたものである。たとえば、抄造法としては、丸網抄造機、長網抄造機等の連続抄造設備を用いる方式、抄造ボックスにスラリーを流し込むバッチ抄造法式、スラリーから平網で漉き上げる方式等を採用することができる。この際の有機質バインダーの混合は、予め繊維と有機質バインダーを所定量混ぜる方法、繊維のみのスラリーを抄造しケーキとした後、その上方から有機質バインダーを含む溶液をスプレーし下方より吸引する方法、又はその両者を併用して行われる。 The molded body of the present invention is obtained by molding calcium aluminate fibers by a known method such as an extrusion molding method, an injection molding method, or a papermaking method. For example, as a papermaking method, a method using a continuous papermaking machine such as a round net papermaking machine or a long net papermaking machine, a batch papermaking method in which slurry is poured into a papermaking box, a method of rolling up slurry from a flat net, etc. can be adopted. . The mixing of the organic binder at this time is a method of mixing a predetermined amount of fibers and an organic binder in advance, a method in which a slurry containing only fibers is made into a cake, and then a solution containing the organic binder is sprayed from above and sucked from below, or Both are performed in combination.
本発明の構造用材料は、上記成形体の一用途であり、例えば断熱材等として用いられる。その形状としては、ボードやフェルトなどがある。 The structural material of the present invention is an application of the above-mentioned molded body, and is used as a heat insulating material, for example. The shapes include boards and felts.
実施例１
塩化カルシウム水溶液とオキシ塩化アルミニウム水溶液とをＣＡ６組成になるように混合し、更に紡糸助剤としてポリビニルアルコールを混合して紡糸原液を調製した。紡糸原液の固形分濃度は３０質量％、紡糸助剤濃度は８質量％、粘度は４０００ｍＰａ・ｓである。
Example 1
It was mixed so that the aqueous solution of calcium chloride and oxychloride aqueous solution of aluminum CA 6 composition was prepared spinning solution was further mixed with polyvinyl alcohol as a spinning aid. The spinning solution has a solid content concentration of 30% by mass, a spinning aid concentration of 8% by mass, and a viscosity of 4000 mPa · s.
この紡糸原液を、円周面に直径０．２ｍｍの孔を５００個設けた直径１５０ｍｍの中空円盤内に、１孔あたり１５ｍｌ／ｈｒで供給し、この円盤を周速５０ｍ／ｓｅｃで回転させることにより紡糸原液を液糸化し、３００℃の熱風により乾燥させながら集綿室の下部より吸引して集積し、前駆体繊維を製造した。その後、この前駆体繊維を、ローラーハウス炉において、室温から９００℃まで１５℃／ｍｉｎで昇温し、続いて、最高温度１３５０℃まで２５℃／ｍｉｎで昇温した後、最高温度で２０分間保持して焼成を行い、カルシウムアルミネート繊維を製造した。 This spinning dope is supplied at a rate of 15 ml / hr per hole into a hollow disk having a diameter of 150 mm with 500 holes having a diameter of 0.2 mm on the circumferential surface, and the disk is rotated at a peripheral speed of 50 m / sec. Thus, the spinning dope was liquefied and collected by suction from the bottom of the cotton collection chamber while drying with hot air at 300 ° C. to produce precursor fibers. Thereafter, the precursor fiber was heated at a rate of 15 ° C./min from room temperature to 900 ° C. in a roller house furnace, and subsequently heated to a maximum temperature of 1350 ° C. at 25 ° C./min, and then at the maximum temperature for 20 minutes. Holding and firing, calcium aluminate fibers were produced.
実施例２
塩化カルシウム水溶液とオキシ塩化アルミニウム水溶液とをＣ１２Ａ７組成になるように混合したこと以外は、実施例１と同様にしてカルシウムアルミネート繊維を製造した。
Example 2
Calcium aluminate fibers were produced in the same manner as in Example 1 except that an aqueous calcium chloride solution and an aluminum oxychloride aqueous solution were mixed so as to have a C 12 A 7 composition.
比較例１
試薬カルシア粉末と試薬アルミナ粉末とをＣＡ６組成に混合し、ペレット化した後、電気炉内で１６５０℃に溶融し、それをブローイング法によりカルシウムアルミネート繊維を製造した。
Comparative Example 1
Reagent calcia powder and reagent alumina powder were mixed in a CA 6 composition, pelletized, and then melted at 1650 ° C. in an electric furnace to produce calcium aluminate fibers by a blowing method.
比較例２
Ｃ１２Ａ７組成に混合したこと以外は、比較例１と同様にして繊維化をした。
Comparative Example 2
Fiberization was carried out in the same manner as in Comparative Example 1 except that it was mixed with the C 12 A 7 composition.
参考例１
市販のアルミナ質繊維（アルミナ７２質量％、シリカ２８質量％）を用意した。
Reference example 1
A commercially available alumina fiber (alumina 72 mass%, silica 28 mass%) was prepared.
各繊維について、上記に従いショット量、平均繊維径、水中かさ密度を測定した。また、化学分析法により化学組成を測定した。それらの結果を表１に示す。 For each fiber, the shot amount, average fiber diameter, and underwater bulk density were measured in accordance with the above. Further, the chemical composition was measured by a chemical analysis method. The results are shown in Table 1.
つぎに、各繊維４００ｇを水４００００ｇに分散させ、アルミナ濃度２０質量％のアルミナゾル１８０ｇ、カチオン化でんぷん３０ｇを加えてスラリーを調製した。これを抄造成形し、１２０℃で乾燥して、かさ密度０．３ｇ／ｃｍ３、２５０ｍｍ×２５０ｍｍ×厚み２５ｍｍの成形体を製造した。 Next, 400 g of each fiber was dispersed in 40000 g of water, and 180 g of alumina sol having an alumina concentration of 20% by mass and 30 g of cationized starch were added to prepare a slurry. This was paper-molded and dried at 120 ° C. to produce a compact having a bulk density of 0.3 g / cm 3 , 250 mm × 250 mm × thickness 25 mm.
得られた成形体について、以下に従って、耐熱性試験及び耐アルカリ性試験を行った。それらの結果を表２に示す。 About the obtained molded object, the heat resistance test and the alkali resistance test were done according to the following. The results are shown in Table 2.
耐熱性試験：成形体を電気炉にて１０℃／ｍｉｎで１３００℃まで昇温、１３００℃で２４時間保持した後、１０℃／ｍｉｎで降温したときの外観観察と体積変化率を測定した。 Heat resistance test: The molded body was heated to 1300 ° C. at 10 ° C./min in an electric furnace, held at 1300 ° C. for 24 hours, and then observed for appearance and its volume change rate was measured at 10 ° C./min.
耐アルカリ性試験：成形体を５質量％の水酸化ナトリウム水溶液に２４時間浸漬し、乾燥した後、電気炉にて１０℃／ｍｉｎで１３００℃まで昇温、１３００℃で２４時間保持した後、１０℃／ｍｉｎで降温したときの外観観察と体積変化率を測定した。 Alkali resistance test: The molded body was immersed in a 5% by weight aqueous sodium hydroxide solution for 24 hours, dried, then heated to 1300 ° C. at 10 ° C./min in an electric furnace, held at 1300 ° C. for 24 hours, then 10 Appearance observation and volume change rate were measured when the temperature was lowered at ° C./min.
実施例３〜８
紡糸原液の固形分濃度、紡糸助剤濃度、粘度を種々変えたこと以外は、実施例１と同様にしてカルシウムアルミネート繊維（ＣＡ６）を製造した。それらの条件と結果を表３に示す。
Examples 3-8
Calcium aluminate fibers (CA 6 ) were produced in the same manner as in Example 1, except that the solid content concentration, spinning auxiliary agent concentration, and viscosity of the spinning dope were varied. The conditions and results are shown in Table 3.
実施例９〜１６
紡糸条件及び乾燥条件を種々変えたこと以外は、実施例１と同様にしてカルシウムアルミネート繊維（ＣＡ６）を製造した。それらの条件と結果を表４に示す。
Examples 9-16
Calcium aluminate fibers (CA 6 ) were produced in the same manner as in Example 1 except that the spinning conditions and the drying conditions were changed. These conditions and results are shown in Table 4.
実施例１７〜２０
熱処理条件を種々変えたこと以外は、実施例１と同様にしてカルシウムアルミネート繊維（ＣＡ６）を製造した。それらの条件と結果を表５に示す。
Examples 17-20
Calcium aluminate fibers (CA 6 ) were produced in the same manner as in Example 1 except that the heat treatment conditions were variously changed. The conditions and results are shown in Table 5.
表１、２の実施例と比較例の対比から、本発明の製造条件で製造されたカルシウムアルミネート繊維は、比較例及び参考例に比べて、ショット量が少なく、耐熱性と耐アルカリ性に優れていることがわかる。また、表３〜５に示されるように、紡糸原液とその紡糸条件を選ぶことによって、本発明の効果が助長されることがわかる。 From the comparison of Examples and Comparative Examples in Tables 1 and 2, the calcium aluminate fiber produced under the production conditions of the present invention has a smaller shot amount than the Comparative Examples and Reference Examples, and is excellent in heat resistance and alkali resistance. You can see that Moreover, as Tables 3-5 show, the effect of this invention is promoted by selecting a spinning undiluted | stock solution and its spinning conditions.
本発明のカルシウムアルミネート繊維は、構造用材料等の成形体を製造する材料として用いられる。本発明の構造用材料はボードやフェルト等として使用することができる。 The calcium aluminate fiber of the present invention is used as a material for producing a molded body such as a structural material. The structural material of the present invention can be used as a board or felt.
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| JP2011106050A (en) * | 2009-11-17 | 2011-06-02 | Nichias Corp | Method for producing inorganic fiber |
| WO2013114808A1 (en) * | 2012-01-31 | 2013-08-08 | ニチアス株式会社 | Inorganic fiber and process for manufacturing same |
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| JPS6360125A (en) * | 1986-08-29 | 1988-03-16 | Ibiden Co Ltd | Production of inorganic fiber and producing apparatus |
| JPS63190021A (en) * | 1987-01-30 | 1988-08-05 | Ibiden Co Ltd | Ceramic fiber having low shot content |
| JPH06272116A (en) * | 1992-08-26 | 1994-09-27 | Didier Werke Ag | Inorganic fiber |
| WO2004003276A1 (en) * | 2002-06-28 | 2004-01-08 | Denki Kagaku Kogyo Kabushiki Kaisha | Inorganic staple fiber accumulation for holding material, process for producing the same and holding material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011094258A (en) * | 2009-10-29 | 2011-05-12 | Nichias Corp | Inorganic fiber |
| JP2011106050A (en) * | 2009-11-17 | 2011-06-02 | Nichias Corp | Method for producing inorganic fiber |
| WO2013114808A1 (en) * | 2012-01-31 | 2013-08-08 | ニチアス株式会社 | Inorganic fiber and process for manufacturing same |
| JPWO2013114808A1 (en) * | 2012-01-31 | 2015-05-11 | ニチアス株式会社 | Inorganic fiber and method for producing the same |
| US9302947B2 (en) | 2012-01-31 | 2016-04-05 | Nichias Corporation | Inorganic fiber and process for manufacturing same |
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| JP4494887B2 (en) | 2010-06-30 |
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