JPH0529608B2 - - Google Patents
Info
- Publication number
- JPH0529608B2 JPH0529608B2 JP22534288A JP22534288A JPH0529608B2 JP H0529608 B2 JPH0529608 B2 JP H0529608B2 JP 22534288 A JP22534288 A JP 22534288A JP 22534288 A JP22534288 A JP 22534288A JP H0529608 B2 JPH0529608 B2 JP H0529608B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- fibers
- carbonate
- metal
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000835 fiber Substances 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- -1 Titanium alkoxide Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 238000009987 spinning Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 102000005717 Myeloma Proteins Human genes 0.000 description 2
- 108010045503 Myeloma Proteins Proteins 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007716 flux method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
- Inorganic Fibers (AREA)
- Compounds Of Iron (AREA)
Description
産業上の利用分野
本発明はホーランダイト型構造を有するチタン
酸塩の繊維または膜状物の製造法に関する。これ
らは耐熱性、断熱性に優れ、耐熱、断熱材料とし
て有用であり、またプラスチツク、金属、セメン
ト等の補強材料としても用いられる。
従来の技術
従来アルミナ繊維、ジルコニア繊維などの無機
繊維の製造法として、前駆ポリマー法、スラリー
法、無機塩法、ゾル法などが知られている。これ
らの方法の代表例を挙げると次の通りである。
前駆ポリマー法は−Al−Ｏからなる主鎖を有
する無機重合体のポリアルミノキサンを含む粘稠
溶液にけい酸エステルを混合して乾式紡糸して焼
成する。
スラリー法はAl2O3微粉及び少量のMgCl2・
6H2Ｏにバインダー成分としてAl2（OH）3Clを加
えて粘稠なスラリーとし、これを乾式紡糸して焼
成する。
無機塩法はアルミニウム塩の水溶液にポリエチ
レノキサイドやPVAなどの水溶性有機高分子を
加え、更に水溶性ポリシロキサンを混合して粘稠
液となし、ノズルより吹き出し、これを焼成す
る。
ゾル法はHCOO、CH3COOなどのイオンを含
むアルミナゾルにシリカゾル、ほう酸を加えて粘
稠液とし、これを紡糸して焼成する。
これらの方法では本発明のホーランダイト型構
造を有するチタン酸塩の繊維または膜状物を製造
し得ない。
ホーランダイト型構造を有するチタン酸塩の繊
維を製造する方法としては、本出願人が開発した
フラツクス法（特願昭58−116459号）が知られて
いる。その方法はその製造原料にモリブデン酸金
属塩を加えて溶融し、その溶融体から結晶育成す
る方法である。
この方法ではその製造に長時間を必要とするた
め、生産能率が悪く、また10mm以下の短繊維しか
得られず利用分野も限定される問題点があつた。
発明の目的
本発明は前記方法の問題点をなくすべくなされ
たもので、その目的はその組成原料を含有する粘
稠性の紡糸液を作り、これをノズルより押し出し
て成形した後、焼成することにより、連続的に製
造し得られる一般式
AxMyTi8-yO16
（ただし、ＡはＫ，Rb，CsまたはBa、Ｍは
Mg，Zn，Ni，Al，FeまたはCr，ｘは0.5〜2.0、
ｙはＭが２価のときｘ／２，３価のときはｘの値
を表わす。）
で示されるチタン酸塩の繊維または膜状物を製造
する方法を提供するにある。
発明の構成
本発明者らは前記目的を達成すべく鋭意研究の
結果、
(1) 前記一般式で示される組成原料として、チタ
ンはチタンアルコキシド、Ｍ成分はＭ成分の金
属アルコキシドまたは炭酸塩、Ａ成分はその炭
酸塩を使用し、これを
(2) カルボキシル基を１〜３個と水酸基１〜３個
を有機酸またはカルボキシル基２〜３個を有す
る有機酸水溶液と水溶性非イオン有機重合体を
用いて溶解・濃縮すると、紡糸に適する粘稠液
となし得、
(3) これをノズルより押し出し成形した後、焼成
すると、有害ガスの発生もなく、不純物を含有
しない優れたホーランダイト型構造を有するチ
タン酸塩の長繊維または膜状物を容易に製造し
得られることを究明し得た。この知見に基づい
て本発明を完成した。
本発明の要旨は
一般式 AxMyTi8-yO16
（ただし、ＡはＫ，Rb，CsまたはBa、Ｍは
Mg，Zn，Ni，Al，FeまたはCr，ｘは0.5〜2.0、
ｙはＭが２価金属のときｘ／２，３価金属のとき
ｘの値を表わす。）
で示されるホーランダイト型構造を有するチタン
酸塩の製造原料として、チタンアルコキシドとＭ
成分の金属アルコキシドまたは炭酸塩とＡ成分の
炭酸塩を用い、前記一般式の組成割合の各原料
を、
(1) カルボキシル基を１〜３個と水酸基を１〜３
個を有する有機酸、またはカルボキシル基を２〜
３個を有する有機酸水溶液と、(2)水溶性非イオン
有機重合体液を用いて溶解し、これを濃縮して粘
稠液となし、この粘稠液をノズルより押し出し繊
維状または膜状物に形成して1200〜1400℃で焼成
することを特徴とするホーランダイト型構造を有
するチタン酸塩の繊維または膜状物の製造法、に
ある。
本発明における一般式に示される組成物中のＡ
成分はホーランダイト型構造においてトンネル構
造中に配位する金属であり、この原料は炭酸塩で
ある。また、Ｍ成分はトンエルの枠組を作る
TiO6の八面体中のTiの席を置換して占有するこ
とができる金属であり、この原料はアルコキシド
または炭酸塩である。Ti成分の原料もアルコキ
シドである。チタンアルコキシドとしては、チタ
ンテトライソプロポキシド、チタンテトラノルマ
ルブトキシド等が挙げられる。Ｍ成分の金属アル
コキシドとしては、Ｍ成分金属のイソプロポキシ
ド、ノルマルブトキシド、エトキシド等が挙げら
れる。しかし例示のものに限定されるものではな
い。
前記一般式におけるｘの値は0.5〜2.0、好まし
くは1.0〜1.7であることが必要である。またｙの
値はＭが２価金属のときはｘ／２、３価金属のと
きはｘの値であることが必要である。この範囲を
はずれると、ホーランダイト型構造を有するチタ
ン酸塩を得られない。
組成物原料を溶解する有機酸は、カルボキシル
基を１〜３個と水酸基を１〜３個を有する有機酸
あるいはカルボキシル基を２〜３個を有する有機
酸であることが必要である。
これらの有機酸としては、
酒石酸
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing titanate fibers or membranes having a hollandite structure. These materials have excellent heat resistance and heat insulation properties, and are useful as heat resistance and heat insulation materials, and are also used as reinforcing materials for plastics, metals, cement, and the like. BACKGROUND ART Conventionally, known methods for producing inorganic fibers such as alumina fibers and zirconia fibers include a precursor polymer method, a slurry method, an inorganic salt method, and a sol method. Representative examples of these methods are as follows. In the precursor polymer method, a silicate ester is mixed into a viscous solution containing polyaluminoxane, an inorganic polymer having a main chain consisting of -Al-O, and the mixture is dry-spun and fired. The slurry method uses Al2O3 fine powder and a small amount of MgCl2 .
Al 2 (OH) 3 Cl is added as a binder component to 6H 2 O to form a viscous slurry, which is dry spun and fired. In the inorganic salt method, a water-soluble organic polymer such as polyethylene oxide or PVA is added to an aqueous solution of aluminum salt, and water-soluble polysiloxane is further mixed to form a viscous liquid, which is then blown out from a nozzle and fired. In the sol method, silica sol and boric acid are added to alumina sol containing ions such as HCOO and CH 3 COO to form a viscous liquid, which is then spun and fired. These methods cannot produce the titanate fibers or membranes having the hollandite structure of the present invention. As a method for producing titanate fibers having a hollandite structure, the flux method developed by the present applicant (Japanese Patent Application No. 116459/1982) is known. The method is to add molybdate metal salt to the raw material, melt it, and grow crystals from the melt. This method requires a long time to produce, resulting in poor production efficiency and problems in that only short fibers of 10 mm or less can be obtained, limiting the field of application. Purpose of the Invention The present invention was made to eliminate the problems of the above-mentioned method, and its purpose is to prepare a viscous spinning solution containing the composition raw materials, extrude it through a nozzle, shape it, and then sinter it. General formula A x M y Ti 8-y O 16 (A is K, Rb, Cs or Ba, M is
Mg, Zn, Ni, Al, Fe or Cr, x is 0.5 to 2.0,
y represents the value of x/2 when M is divalent, and represents the value of x when M is trivalent. ) Provides a method for producing a titanate fiber or film-like material shown in the following. Structure of the Invention As a result of intensive research to achieve the above object, the present inventors have found that (1) titanium is a titanium alkoxide, the M component is a metal alkoxide or carbonate of the M component, and A The carbonate is used as a component, and this is mixed with (2) an organic acid having 1 to 3 carboxyl groups and 1 to 3 hydroxyl groups, or an aqueous solution of an organic acid having 2 to 3 carboxyl groups, and a water-soluble nonionic organic polymer. (3) When this is extruded through a nozzle and then fired, it produces an excellent hollandite-type structure that does not generate any harmful gases and does not contain any impurities. It has been found that long fibers or films of titanate having the following properties can be easily produced and obtained. The present invention was completed based on this knowledge. The gist of the present invention is the general formula A x M y Ti 8-y O 16 (where A is K, Rb, Cs or Ba, and M is
Mg, Zn, Ni, Al, Fe or Cr, x is 0.5 to 2.0,
y represents the value of x/2 when M is a divalent metal, and represents the value of x when M is a trivalent metal. ) Titanium alkoxide and M
Using the metal alkoxide or carbonate as the component and the carbonate as the component A, each raw material having the composition ratio of the above general formula, (1) 1 to 3 carboxyl groups and 1 to 3 hydroxyl groups
or an organic acid having 2 to 2 carboxyl groups.
(2) A water-soluble nonionic organic polymer solution is dissolved in an aqueous solution of an organic acid having 3 polymers, concentrated to form a viscous liquid, and this viscous liquid is extruded through a nozzle to form a fibrous or film-like material. A method for producing a titanate fiber or film having a hollandite structure, which comprises forming the fiber or film at 1200 to 1400°C. A in the composition represented by the general formula in the present invention
The component is a metal that coordinates in the tunnel structure in a hollandite-type structure, and the raw material is a carbonate. Also, the M component creates the framework of the tunnel
TiO is a metal that can replace and occupy the Ti seat in the octahedron of 6 , and this raw material is an alkoxide or carbonate. The raw material for the Ti component is also an alkoxide. Examples of the titanium alkoxide include titanium tetraisopropoxide, titanium tetra-normal butoxide, and the like. Examples of the metal alkoxide of the M component include isopropoxide, normal butoxide, and ethoxide of the M component metal. However, the invention is not limited to the examples. The value of x in the general formula needs to be 0.5 to 2.0, preferably 1.0 to 1.7. Further, the value of y needs to be x/2 when M is a divalent metal, and the value of x when M is a trivalent metal. Outside this range, titanate having a hollandite structure cannot be obtained. The organic acid that dissolves the composition raw material needs to be an organic acid having 1 to 3 carboxyl groups and 1 to 3 hydroxyl groups, or an organic acid having 2 to 3 carboxyl groups. These organic acids include tartaric acid
【式】 リンゴ酸【formula】 malic acid
【式】 クエン酸【formula】 citric acid
【式】 シユウ酸【formula】 Oxalic acid
【式】 マロン酸【formula】 malonic acid
【式】
等が挙げられる。
好ましいものはシユウ酸、クエン酸である。こ
れらの有機酸の水溶液は金属アルコキシド１モル
に対し、20〜50倍モルの水を用いることが好まし
い。また、水溶性非イオン有機重合体としては、
例えばポリビニールアルコール、ポリエチレンオ
キサイドが挙げられる。これらの分子量は１×
104〜１×106の範囲のものが好ましい。その濃度
は原料組成金属を酸化物とみて、その酸化物に対
し２〜15重量％、好ましくは５〜10重量％の範囲
のものが好ましい。
組成原料を前記有機酸水溶液と水溶性非イオン
有機重合体の液に溶解する。その時の温度は室温
〜50℃で行う。これにより、Ti、Ｍ成分のアル
コキシドは有機酸の水溶液で加水分解され、錯イ
オンを形成し、透明な均一溶液となる。また、Ａ
成分の炭酸塩は添加によりCo2を放出して溶解す
る。
このような錯イオンは錯イオンを形成している
極性基が水溶性非イオン有機重合体の有する水酸
基やエーテル基と水分子を介して相互作用により
粘稠性となる。得られた水溶液を常圧あるいは減
圧下で溶液粘度が１〜1000ポイズ、好ましくは50
〜500ポイズになるまで濃縮する。
この粘稠液を例えば70〜80℃に加熱してノズル
あるいはスリツトから室温乾燥大気中あるいは冷
却乾燥大気中に押し出すと、連続した繊維あるい
は膜状物が得られる。また、太目の口径ノズルよ
り押し出し、火炎で焼成吹き飛ばすと極細の短繊
維が得られる。
得られた繊維、膜状物を水分を除去し、700〜
1000℃で空気中で加熱して有機物を分解除去した
後、1200〜1400℃で焼成すると、ホーランダイト
型構造を有するチタン酸塩の繊維または膜状物が
得られる。1200℃未満では焼結が完結せず、1400
℃を超えると溶融し始める。
実施例 １
シユウ酸・２水和物3.1ｇ（モル数でチタンテ
トライソプロポキシドとアルミニウムイソプロポ
キシドの合計をモル数の２倍モル数量）を蒸留水
20mlに溶解した溶液にチタンテトラプロポキシド
2.84ｇを滴下し、完全に溶解するまで攪拌した。
この溶液に炭酸カリウム0.16ｇを徐々に加え、炭
酸ガスの泡が消失し透明な液になるまで攪拌し
た。これに混合されたチタン、Ａ、Ｍ成分を酸化
物として換算した重量の５％に当たるポリビニー
ルアルコール（平均重合度1500）0.05ｇを加えて
完全に溶解するまで攪拌した。以上の操作はすべ
て室温で行つた。
得られた溶液を100℃に加熱して粘度が300ポイ
ズになるまで濃縮して紡糸液とした。この液は放
冷すると固化する。流動性を保つた状態でノズル
より室温乾燥大気雰囲気下に押し出し、直径５〜
100μmの長繊維を得た。
得られた繊維を100℃で１晩乾燥し、次いで900
℃で２時間処理して有機物を分解除去した後、
1350℃で３時間焼成した。得られた繊維はK1.5
Al1.5Ti6.5O16組成のホーランダイト型構造を有す
るチタン酸塩の繊維であつた。
実施例 ２
シユウ酸・２水和物2.52ｇを蒸留水20mlに溶解
した液にチタンテトライソプロポキシド2.84ｇを
滴下し完全に溶解するまで攪拌した。これに炭酸
カリウム0.154ｇを加えて炭酸ガスの泡が消失す
るまで攪拌し、次いで炭酸マグネシウム0.094ｇ
を徐々に加え、炭酸ガスの泡が消失するまで攪拌
して透明液を得た。これにポリビニルアルコール
（平均重合度1500）0.05ｇを加えて攪拌し完全に
溶解させた。得られた液を100℃に加熱して粘度
が300ポイズになるまで濃縮して紡糸液とした。
以下実施例１と同様（ただし、焼結温度1350℃）
にして繊維を得た。得られた繊維はK1.6Al0.8Ti7.2
O16組成のホーランダイト型構造を有するチタン
酸塩の繊維であつた。
実施例 ３
クエン酸2.04ｇ、シユウ酸・２水和物2.24ｇを
蒸留水20mlに溶解させた液にチタンテトライソプ
ロポキシド2.84ｇを滴下し溶解させ、次いでアル
ミニウムイソプロポキシド0.92ｇを加えて溶解さ
せた。これに更に炭酸バリウム0.41ｇを徐々に加
え炭酸ガスの泡が消失するまで攪拌して均一透明
液を得た。この透明液にポリビニールアルコール
（平均重合度1500）0.07ｇを加え、100℃で加熱し
て粘度が300ポイズになるまで濃縮して紡糸液と
した。
以下実施例２と同様にして繊維を得た。得られ
た繊維はBa1.18Al2.36Ti5.64O16組成のホーランダ
イト型構造を有するチタン酸塩の繊維であつた。
以上、Ａ成分、Ｍ成分の代表例、また有機酸も
代表例のもので示したが、それぞれ、前記に示し
た他の成分に変え、また有機酸を変えるのみで、
それに該当する組成のホーランダイト型構造を有
するチタン酸塩繊維が得られる。
また、紡糸ノズルに代えてスリツトを用いると
膜状物が得られ、また、太目の口径ノズルより押
し出し、火災で焼成吹き飛ばすと極細の短繊維が
得られる。
発明の効果
本発明は従来の紡糸による無機繊維の製造法で
は得られないホーランダイト型構造を有するチタ
ン酸塩の繊維を紡糸法による製造を可能にし、ま
た、従来のフラツクス法では得られなかつた長繊
維または膜状物を製造し得られると共に組成原料
がアルコキシドまたは炭酸塩であり、紡糸形成液
も有機酸及び水溶性非イオン有機重合体であるた
め、製造に際し有害ガスの発生がなく、得られる
繊維または膜状物には不純物の混入がなく高純度
に得られる優れた効果を有する。[Formula] etc. Preferred are oxalic acid and citric acid. For the aqueous solution of these organic acids, it is preferable to use water in an amount of 20 to 50 times the mole of metal alkoxide. In addition, water-soluble nonionic organic polymers include:
Examples include polyvinyl alcohol and polyethylene oxide. These molecular weights are 1×
It is preferably in the range of 10 4 to 1×10 6 . The concentration is preferably in the range of 2 to 15% by weight, preferably 5 to 10% by weight, based on the oxide of the raw material metal. The composition raw materials are dissolved in the organic acid aqueous solution and the water-soluble nonionic organic polymer liquid. The temperature at that time is room temperature to 50°C. As a result, the alkoxides of the Ti and M components are hydrolyzed with the organic acid aqueous solution to form complex ions, resulting in a transparent homogeneous solution. Also, A
The component carbonate releases Co2 and dissolves upon addition. Such a complex ion becomes viscous when the polar group forming the complex ion interacts with the hydroxyl group or ether group of the water-soluble nonionic organic polymer via water molecules. The obtained aqueous solution has a solution viscosity of 1 to 1000 poise under normal pressure or reduced pressure, preferably 50 poise.
Concentrate to ~500 poise. When this viscous liquid is heated to, for example, 70 to 80°C and extruded through a nozzle or slit into a room temperature dry atmosphere or a cooled dry atmosphere, a continuous fiber or film is obtained. In addition, ultra-fine short fibers can be obtained by extruding through a thick diameter nozzle and burning and blowing away with flame. The resulting fibers and membranes were dehydrated and heated to 700~
After heating in the air at 1000°C to decompose and remove organic substances, firing at 1200-1400°C yields titanate fibers or membranes having a hollandite structure. Sintering will not be completed below 1200℃,
When the temperature exceeds ℃, it begins to melt. Example 1 3.1 g of oxalic acid dihydrate (twice the total number of moles of titanium tetraisopropoxide and aluminum isopropoxide in moles) was added to distilled water.
Titanium tetrapropoxide in solution dissolved in 20ml
2.84 g was added dropwise and stirred until completely dissolved.
0.16 g of potassium carbonate was gradually added to this solution, and the mixture was stirred until the carbon dioxide bubbles disappeared and the mixture became a clear liquid. To this was added 0.05 g of polyvinyl alcohol (average degree of polymerization 1500) corresponding to 5% of the weight of the mixed titanium, A, and M components as oxides, and the mixture was stirred until completely dissolved. All the above operations were performed at room temperature. The obtained solution was heated to 100° C. and concentrated until the viscosity reached 300 poise to obtain a spinning solution. This liquid solidifies when left to cool. While maintaining fluidity, extrude through a nozzle into a dry air atmosphere at room temperature to form a diameter of 5~
A long fiber of 100 μm was obtained. The resulting fibers were dried at 100°C overnight and then heated at 900°C.
After treating at ℃ for 2 hours to decompose and remove organic matter,
It was baked at 1350°C for 3 hours. The fiber obtained has a K 1.5
The fibers were titanate fibers with a hollandite structure of Al 1.5 Ti 6.5 O 16 composition. Example 2 2.84 g of titanium tetraisopropoxide was added dropwise to a solution of 2.52 g of oxalic acid dihydrate dissolved in 20 ml of distilled water, and the mixture was stirred until completely dissolved. Add 0.154g of potassium carbonate to this and stir until the carbon dioxide bubbles disappear, then 0.094g of magnesium carbonate.
was gradually added and stirred until the carbon dioxide bubbles disappeared to obtain a clear liquid. To this was added 0.05 g of polyvinyl alcohol (average degree of polymerization 1500) and stirred to completely dissolve. The resulting solution was heated to 100° C. and concentrated until the viscosity reached 300 poise to obtain a spinning solution.
Same as Example 1 (but sintering temperature 1350℃)
and obtained fiber. The obtained fiber is K 1.6 Al 0.8 Ti 7.2
It was a titanate fiber with a hollandite type structure of O 16 composition. Example 3 2.84 g of titanium tetraisopropoxide was added dropwise to a solution of 2.04 g of citric acid and 2.24 g of oxalic acid dihydrate dissolved in 20 ml of distilled water, and then 0.92 g of aluminum isopropoxide was added. Dissolved. Further, 0.41 g of barium carbonate was gradually added to the mixture and stirred until the carbon dioxide bubbles disappeared to obtain a homogeneous transparent liquid. 0.07 g of polyvinyl alcohol (average degree of polymerization 1500) was added to this transparent liquid, heated at 100° C., and concentrated until the viscosity reached 300 poise to obtain a spinning solution. Thereafter, fibers were obtained in the same manner as in Example 2. The obtained fibers were titanate fibers having a hollandite-type structure with a Ba 1.18 Al 2.36 Ti 5.64 O 16 composition. Above, we have shown typical examples of the A component and M component, as well as typical examples of the organic acid, but by simply changing the components to the other components shown above or changing the organic acid,
Titanate fibers having a hollandite-type structure with a corresponding composition are obtained. Also, if a slit is used instead of a spinning nozzle, a film-like product can be obtained, and if the material is extruded through a thick diameter nozzle and burned and blown away with a fire, ultrafine short fibers can be obtained. Effects of the Invention The present invention enables the production of titanate fibers with a hollandite structure, which cannot be obtained by the conventional spinning method, and also makes it possible to produce titanate fibers having a hollandite structure, which cannot be obtained by the conventional flux method. In addition to producing long fibers or membranes, the composition raw materials are alkoxides or carbonates, and the spinning solution is also an organic acid and a water-soluble nonionic organic polymer, so no harmful gases are generated during production, and the product is obtained. The resulting fibers or membranes are free of impurities and have an excellent effect of being highly pure.
Claims (1)
Mg，Zn，Ni，Al，FeまたはCr，ｘは0.5〜2.0、
ｙはＭが２価金属のときｘ／２，３価金属のとき
ｘの値を表わす。） で示されるホーランダイト型構造を有するチタン
酸塩の製造原料として、チタンアルコキシドとＭ
成分の金属アルコキシドまたは炭酸塩とＡ成分の
炭酸塩を用い、前記一般式の組成割合の各原料
を、 (1) カルボキシル基を１〜３個と水酸基を１〜３
個有する有機酸、またはカルボキシル基を２〜３
個を有する有機酸水溶液と、(2)水溶性非イオン有
機重合体液を用いて溶解し、これを濃縮して粘稠
液となし、この粘稠液をノズルより押し出し繊維
状または膜状物に形成して1200〜1400℃で焼成す
ることを特徴とするホーランダイト型構造を有す
るチタン酸塩の繊維または膜状物の製造法。[Claims] 1 General formula A x M y Ti 8-y O 16 (However, A is K, Rb, Cs or Ba, M is
Mg, Zn, Ni, Al, Fe or Cr, x is 0.5 to 2.0,
y represents the value of x/2 when M is a divalent metal, and represents the value of x when M is a trivalent metal. ) Titanium alkoxide and M
Using the metal alkoxide or carbonate as the component and the carbonate as the component A, each raw material having the composition ratio of the above general formula, (1) 1 to 3 carboxyl groups and 1 to 3 hydroxyl groups
2 to 3 organic acids or carboxyl groups
(2) A water-soluble nonionic organic polymer solution is used to dissolve the organic acid aqueous solution, which is concentrated to form a viscous liquid, and this viscous liquid is extruded through a nozzle to form a fibrous or film-like material. A method for producing a titanate fiber or film having a hollandite structure, which comprises forming and firing at 1200 to 1400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22534288A JPH0274526A (en) | 1988-09-08 | 1988-09-08 | Production of fibrous or filmy substance of titanate having hollandite type structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22534288A JPH0274526A (en) | 1988-09-08 | 1988-09-08 | Production of fibrous or filmy substance of titanate having hollandite type structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0274526A JPH0274526A (en) | 1990-03-14 |
| JPH0529608B2 true JPH0529608B2 (en) | 1993-05-06 |
Family
ID=16827842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22534288A Granted JPH0274526A (en) | 1988-09-08 | 1988-09-08 | Production of fibrous or filmy substance of titanate having hollandite type structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0274526A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997000340A1 (en) * | 1995-06-14 | 1997-01-03 | Otsuka Kagaku Kabushiki Kaisha | Titanate whisker and process for the production thereof |
| US6551533B1 (en) * | 2000-11-28 | 2003-04-22 | Chemat Technology, Inc. | Method of forming fibrous materials and articles therefrom |
| FR2833257B1 (en) * | 2001-12-11 | 2004-01-30 | Commissariat Energie Atomique | HOLLANDITE STRUCTURE CERAMIC INCORPORATING CESIUM FOR USE IN POSSIBLE CONDITIONING OF RADIOACTIVE CESIUM AND PROCESSES FOR SYNTHESIS |
| JP4995489B2 (en) * | 2006-05-31 | 2012-08-08 | 帝人株式会社 | Metal oxide fiber and method for producing the same |
-
1988
- 1988-09-08 JP JP22534288A patent/JPH0274526A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0274526A (en) | 1990-03-14 |
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