JPH0244774B2 - - Google Patents
Info
- Publication number
- JPH0244774B2 JPH0244774B2 JP58209215A JP20921583A JPH0244774B2 JP H0244774 B2 JPH0244774 B2 JP H0244774B2 JP 58209215 A JP58209215 A JP 58209215A JP 20921583 A JP20921583 A JP 20921583A JP H0244774 B2 JPH0244774 B2 JP H0244774B2
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- potassium
- slurry
- potassium titanate
- titanium oxide
- 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 80
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 29
- 229910052700 potassium Inorganic materials 0.000 claims description 29
- 239000011591 potassium Substances 0.000 claims description 29
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 description 6
- 235000011151 potassium sulphates Nutrition 0.000 description 6
- 238000007716 flux method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Inorganic Fibers (AREA)
Description
【発明の詳細な説明】
本発明は断熱性、耐熱性、耐化学薬品性に優れ
ているために断熱材、耐熱材、プラスチツクス及
びガラスの強化材、摩擦材、耐熱吸音材等幅広い
用途が期待されている六チタン酸カリウム繊維の
製造方法に関するものである。[Detailed description of the invention] The present invention has excellent heat insulating properties, heat resistance, and chemical resistance, so it can be used in a wide range of applications such as heat insulating materials, heat resistant materials, reinforcing materials for plastics and glass, friction materials, and heat resistant sound absorbing materials. The present invention relates to a method for producing potassium hexatitanate fibers, which is expected to be produced.
従来チタン酸カリウム繊維の製造法にはフラツ
クス法、水熱法及び焼成法等があるが、工業的観
点から比較するとフラツクス法及び焼成法が大規
模化連続化の点で有利であるとされている。しか
しながら、フラツクス法には製造装置に高価な耐
食性の材質を用いる必要があるために製造コスト
が高くなるという欠点があり、焼成法にはフラツ
クス法よりも安価に製造し得るとの利点があるも
のの合成されるチタン酸カリウム繊維の長さはフ
ラツクス法で合成されるチタン酸カリウム繊維の
長さよりも短かいという欠点がある。 Conventional methods for producing potassium titanate fibers include the flux method, hydrothermal method, and calcination method, but from an industrial perspective, the flux method and calcination method are considered to be advantageous in terms of large-scale and continuous production. There is. However, the flux method has the disadvantage of increasing manufacturing costs because it requires the use of expensive corrosion-resistant materials in the manufacturing equipment, while the sintering method has the advantage of being cheaper to manufacture than the flux method. The disadvantage is that the length of the potassium titanate fibers synthesized is shorter than that of the potassium titanate fibers synthesized by the flux method.
そこで本発明者らは、従来の焼成法で得られる
チタン酸カリウム繊維よりも長いチタン酸カリウ
ム繊維を大量安価に製造することを目的にして鋭
意研究を重ねた結果、TiO2源にSO3として１〜
10％の硫酸を含む含水酸化チタンを用いこれに炭
酸カリウムを一般式K2O・nTiO2（ただしｎ＝２
〜４）で示される割合で配合混練した後、900〜
1200℃で焼成することにより平均繊維長が100〜
150μｍ程度の四チタン酸カリウム繊維あるいは
四チタン酸カリウムと六チタン酸カリウムとの混
合相繊維が合成されること、更にはこれらの繊維
を水又は温水にて単繊維に解繊した後、該スラリ
ーに酸を添加して、スラリーのPHを9.0〜10.0に
調整することにより、チタン酸カリウム繊維の組
成がK2O・6TiO2・nH2Oに変化し、次いでこの
繊維を600℃以上に加熱すると六チタン酸カリウ
ム繊維が生成すること等を発見し、本発明を完成
したものである。 Therefore, the present inventors conducted intensive research with the aim of manufacturing potassium titanate fibers in large quantities and at low cost, which are longer than potassium titanate fibers obtained by conventional firing methods . 1~
Hydrous titanium oxide containing 10% sulfuric acid is used, and potassium carbonate is added to it using the general formula K 2 O・nTiO 2 (where n=2
After mixing and kneading at the ratio shown in ~4), 900 ~
By firing at 1200℃, the average fiber length can be increased to 100~
Potassium tetratitanate fibers of about 150 μm or mixed phase fibers of potassium tetratitanate and potassium hexatitanate are synthesized, and furthermore, after these fibers are defibrated into single fibers in water or hot water, the slurry is prepared. By adding acid to adjust the pH of the slurry to 9.0 to 10.0, the composition of the potassium titanate fiber changes to K2O・6TiO2・nH2O , and then the fiber is heated to over 600℃. This led to the discovery that potassium hexatitanate fibers were produced, and the present invention was completed.
次に本発明の構成について説明する。 Next, the configuration of the present invention will be explained.
本発明は、SO3として１〜10％の硫酸を含有す
る含水酸化チタンと炭酸カリウムとを一般式
K2O・nTiO2（ただしｎ＝２〜４）で示される割
合で配合混練した後、900〜1200℃で焼成して、
塊状のチタン酸カリウム繊維を生成せしめ、次い
で該塊状生成物を水又は温水中に浸漬して単繊維
に解繊した後、該スラリーに酸を添加してスラリ
ーのPHを9.0〜10.0に調整することにより、チタ
ン酸カリウム繊維の組成がK2O・6nTiO2・nH2O
の組成となるように処理し、更に600℃以上に加
熱することを特徴とする六チタン酸カリウム繊維
の製造方法である。 The present invention combines hydrous titanium oxide containing 1 to 10% sulfuric acid as SO 3 and potassium carbonate using the general formula
After mixing and kneading in the ratio shown by K 2 O・nTiO 2 (however, n = 2 to 4), it is fired at 900 to 1200 °C,
After generating bulk potassium titanate fibers, then defibrating the bulk product into single fibers by immersing it in water or hot water, add acid to the slurry to adjust the pH of the slurry to 9.0 to 10.0. As a result, the composition of potassium titanate fiber is K 2 O・6nTiO 2・nH 2 O
This is a method for producing potassium hexatitanate fibers, which is characterized by treating the fibers so that the fibers have a composition of
本発明において含水酸化チタンに含まれる硫酸
は、SO3として１〜10％が適切である。即ち硫酸
含有率が10％以上の場合には、10μｍ以下の短繊
維の割合が非常に多くなり繊維長のバラツキが大
きいなど品質の均質性の点で問題がある。又硫酸
含有率が１％以下の場合、得られる繊維の長さが
短く、TiO2源として酸化チタンを使用した場合
とほぼ同等の長さの繊維（平均繊維長20μｍ程
度）しか得られない。 In the present invention, the sulfuric acid contained in the hydrous titanium oxide is suitably 1 to 10% as SO 3 . That is, when the sulfuric acid content is 10% or more, the proportion of short fibers of 10 μm or less becomes very large, causing problems in terms of uniformity of quality, such as large variations in fiber length. Further, when the sulfuric acid content is 1% or less, the length of the fibers obtained is short, and only fibers of approximately the same length (average fiber length of about 20 μm) can be obtained as when titanium oxide is used as the TiO 2 source.
硫酸を含有する含水酸化チタンをTiO2源とし
て使用すると、TiO2源として酸化チタンを使用
した場合に比べ長いチタン酸カリウム繊維が生成
する理由については次の様に考えられる。 The reason why longer potassium titanate fibers are produced when hydrous titanium oxide containing sulfuric acid is used as a TiO 2 source than when titanium oxide is used as a TiO 2 source is thought to be as follows.
即ち、硫酸を含有する含水酸化チタンと炭酸カ
リウムとの混合物を900℃以上に加熱した場合、
含水酸化チタンに含まれる硫酸は分解して亜硫酸
ガスとして揮散するが、この時に大半の亜硫酸ガ
スは炭酸カリウムと反応して硫酸カリウムとな
り、この反応がチタン酸カリウム繊維の成長反応
に大きく関与しているものと推察される。尚亜硫
酸ガスと炭酸カリウムとの反応により生成した硫
酸カリウムが融剤として作用したために、得られ
るチタン酸カリウム繊維の長さが長くなるのでは
ないかとも考えられるが、酸化チタンをTiO2
源としてチタン酸カリウム繊維を合成する際に硫
酸カリウムを添加しても硫酸を含む含水酸化チタ
ンをTiO2源として使用した程には長いチタン酸
カリウム繊維を合成できないこと、含水酸化チ
タン中の硫酸含有量が10％以上になると長さ10μ
ｍ以下の短繊維が非常に多くなること等から、単
に硫酸カリウムが融剤として作用したために合成
されるチタン酸カリウム繊維の長さが長くなつた
のではなく、硫酸カリウムの生成反応自体がチタ
ン酸カリウム繊維の生長反応に大きく影響を及ぼ
しているものと判断される。 That is, when a mixture of hydrous titanium oxide containing sulfuric acid and potassium carbonate is heated to 900°C or higher,
The sulfuric acid contained in hydrous titanium oxide decomposes and evaporates as sulfur dioxide gas, but at this time, most of the sulfur dioxide gas reacts with potassium carbonate to become potassium sulfate, and this reaction is greatly involved in the growth reaction of potassium titanate fibers. It is presumed that there are. It is possible that the potassium titanate fibers obtained become longer because the potassium sulfate produced by the reaction between sulfur dioxide gas and potassium carbonate acts as a fluxing agent.
Even if potassium sulfate is added when synthesizing potassium titanate fibers as a source, it is not possible to synthesize potassium titanate fibers as long as when hydrous titanium oxide containing sulfuric acid is used as a TiO 2 source. When the content is 10% or more, the length is 10μ
Since the number of short fibers of less than m is very large, the length of the synthesized potassium titanate fibers is not simply due to the action of potassium sulfate as a fluxing agent, but rather the production reaction of potassium sulfate itself is responsible for the increase in the length of titanate fibers. It is judged that potassium acid has a large influence on the growth reaction of fibers.
含水酸化チタンと炭酸カリウムとの配合割合に
ついては、一般式K2O・nTiO2で表わしてｎ＝２
〜４が好適である。即ちｎが２よりも小さい場
合、10μｍ以下の長さの短繊維の中に少量の長繊
維が混在した状態の品質の均質性が低い繊維しか
合成されず、ｎが４以上では得られるチタン酸カ
リウム繊維の長さは短い。 The blending ratio of hydrous titanium oxide and potassium carbonate is expressed by the general formula K 2 O・nTiO 2 and n = 2.
-4 is suitable. In other words, when n is smaller than 2, only fibers with low homogeneity of quality are synthesized, with short fibers with a length of 10 μm or less mixed with a small amount of long fibers, and when n is 4 or more, the titanic acid obtained Potassium fibers are short in length.
焼成温度は900〜1200℃の範囲が好ましい。即
ち焼成温度が900℃より低いと反応が遅く、得ら
れるチタン酸カリウム繊維の長さは短い。又焼成
温度が1200℃より高いと装置の侵食が激しくなり
実用的でない。尚焼成時間は１〜10時間、好まし
くは３〜５時間が適切である。 The firing temperature is preferably in the range of 900 to 1200°C. That is, when the firing temperature is lower than 900°C, the reaction is slow and the length of the obtained potassium titanate fibers is short. Furthermore, if the firing temperature is higher than 1200°C, the equipment will be severely eroded, making it impractical. The appropriate firing time is 1 to 10 hours, preferably 3 to 5 hours.
塊状焼成物の解繊操作は、焼成物を適量の水又
は温水中に投入して１〜10時間浸漬後撹拌するこ
とによりなされる。この浸漬時間はチタン酸カリ
ウム繊維合成時の焼成温度が高くなる程長時間を
要する。 The defibration operation of the fired mass is carried out by placing the fired product in an appropriate amount of water or warm water, immersing it for 1 to 10 hours, and then stirring. The longer the immersion time becomes, the higher the firing temperature during potassium titanate fiber synthesis.
解繊終了時のスラリーのPHはスラリー濃度によ
り異なるが通常12〜13程度であり、チタン酸カリ
ウム繊維は四チタン酸カリウム水和物繊維単一相
あるいは四チタン酸カリウム水和物繊維と六チタ
ン酸カリウム繊維との混合相の状態にある。従つ
て、この状態で過、洗浄、乾燥、焼成の操作を
行なつても六チタン酸カリウム繊維の単独相は得
られずに四チタン酸カリウム繊維と六チタン酸カ
リウム繊維の混合相となる。そこで四チタン酸カ
リウム水和物繊維の組成をK2O・4TiO2・nH2O
からK2O・6TiO2・nH2Oに変化させることを目
的として、解繊終了後のスラリーに酸を添加して
スラリーのPHを9.0〜10.0に調整する。この時の
PHが10.0より高い場合には四チタン酸カリウム水
和物の組成を完全にK2O・6TiO2・nH2Oまで変
化させることができないため、最終製品に四チタ
ン酸カリウムが混在する。又PHが9.0より低い場
合には、四チタン酸カリウム水和物からカリウム
イオンの抽出が進みすぎて最終製品に酸化チタン
が混在する。 The pH of the slurry at the end of fibrillation varies depending on the slurry concentration, but is usually around 12 to 13. Potassium titanate fibers consist of a single phase of potassium tetratitanate hydrate fibers, or a combination of potassium tetratitanate hydrate fibers and hexatitanium. It is in a mixed phase state with acid potassium fiber. Therefore, even if filtering, washing, drying, and firing operations are performed in this state, a single phase of potassium hexatitanate fibers will not be obtained, but a mixed phase of potassium tetratitanate fibers and potassium hexatitanate fibers will be obtained. Therefore, the composition of potassium tetratitanate hydrate fiber is K 2 O・4TiO 2・nH 2 O
For the purpose of changing from K 2 O.6TiO 2.nH 2 O to K 2 O.6TiO 2.nH 2 O, acid is added to the slurry after fibrillation to adjust the pH of the slurry to 9.0 to 10.0. at this time
When the pH is higher than 10.0, the composition of potassium tetratitanate hydrate cannot be completely changed to K 2 O.6TiO 2.nH 2 O, so potassium tetratitanate is mixed in the final product. If the pH is lower than 9.0, the extraction of potassium ions from potassium tetratitanate hydrate will proceed too much and titanium oxide will be mixed in the final product.
スラリーのPHを調整するために添加する酸の種
類としては、硫酸、塩酸、硝酸、リン酸、酢酸等
が使用できるが、工業的には硫酸あるいは塩酸が
好ましい。 As the type of acid added to adjust the pH of the slurry, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, etc. can be used, but sulfuric acid or hydrochloric acid is preferred industrially.
従来、六チタン酸アルカリよりもアルカリを多
く含有する繊維の組成を六チタン酸アルカリの組
成に変換する方法としてアルカリを多く含む繊維
を水又は酸で処理する方法が開示されている（特
公昭55−32647号公報参照）。しかしながら、この
変換方法には「抽出を急激に行うと表面部分のみ
のアルカリ金属成分を抽出することとなり、芯部
のアルカリ金属成分が充分に除去できず、又長時
間の抽出処理は、抽出が進みすぎてTiO2（アナタ
ーゼ又はルテル）成分を混在させる欠点がある」
（特公昭55−32647号公報参照）とされていること
から、この方法を工業的に実施する場合に均一な
組成を有する六チタン酸カリウム繊維を得ること
は困難である。そこで工業的に簡単に均質な六チ
タン酸カリウウが得られる変換方法を鋭意検討し
たところ、チタン酸カリウム繊維を分散したスラ
リーのPHを9.0〜10.0に調整するという極く簡単
な操作により、繊維の表面だけではなく芯部まで
均一な組成の六チタン酸カリウム繊維を容易に得
ることができることを発見し、本発明を完成した
ものである。 Conventionally, a method has been disclosed in which fibers containing a large amount of alkali are treated with water or acid as a method for converting the composition of fibers containing more alkali than alkali hexatitanate into the composition of alkali hexatitanate (Japanese Patent Publication No. 1983 -Refer to Publication No. 32647). However, this conversion method requires that ``If extraction is performed rapidly, only the alkali metal components on the surface will be extracted, and the alkali metal components in the core will not be sufficiently removed. It has the disadvantage of being too advanced and mixing TiO 2 (anatase or lutel) components.
(See Japanese Patent Publication No. 55-32647). Therefore, when this method is carried out industrially, it is difficult to obtain potassium hexatitanate fibers having a uniform composition. Therefore, we intensively investigated a conversion method that could industrially easily obtain homogeneous potassium hexatitanate.We found that by an extremely simple operation of adjusting the pH of a slurry in which potassium titanate fibers were dispersed to between 9.0 and 10.0, fibers could be easily converted into potassium titanate. The present invention was completed by discovering that potassium hexatitanate fibers having a uniform composition not only on the surface but also in the core can be easily obtained.
又組成変換を行なつた後の加熱脱水処理温度は
600℃以上溶融点以下ならば特に問題はないが、
工業的な実施を考慮すると700〜900℃の範囲が好
適である。 Also, the heating dehydration treatment temperature after the composition conversion is
There is no particular problem if the temperature is above 600℃ and below the melting point, but
Considering industrial implementation, a range of 700 to 900°C is suitable.
本発明を更に充分に示すために以下に実施例を
記載する。 Examples are included below to more fully illustrate the invention.
実施例 １
SO3として6.5％の硫酸を含有する含水酸化チ
タン700ｇ及び炭酸カリウム360ｇを秤量し、160
mlの水を添加後、ニーダーで20分間混練した。こ
の混練物をアルミナ製ルツボに入れ、電気炉中で
昇温速度250℃／時、保持温度1000℃、保持時間
４時間の条件で焼成した後、200℃／時の速度で
降温した。Example 1 Weighed 700 g of hydrous titanium oxide containing 6.5% sulfuric acid as SO 3 and 360 g of potassium carbonate,
After adding ml of water, the mixture was kneaded in a kneader for 20 minutes. This kneaded product was placed in an alumina crucible and fired in an electric furnace at a temperature increase rate of 250°C/hour, a holding temperature of 1000°C, and a holding time of 4 hours, and then the temperature was lowered at a rate of 200°C/hour.
焼成物をステンレス容器中の６の温水に投入
して７時間浸漬した後、500rpmで30分間撹拌し、
5N−塩酸を滴下してスラリーのPHを9.5に調整し
た。過、洗浄後700℃で２時間焼成してチタン
酸カリウム繊維を得た。 The baked product was placed in warm water in step 6 in a stainless steel container and soaked for 7 hours, then stirred at 500 rpm for 30 minutes.
5N-hydrochloric acid was added dropwise to adjust the pH of the slurry to 9.5. After filtering and washing, the fibers were fired at 700°C for 2 hours to obtain potassium titanate fibers.
この繊維をＸ線回折により同定したところ、六
チタン酸カリウムの単一相であつた。又光学顕微
鏡により繊維を観察したところ、平均的な繊維長
は150μｍ程度であつた。 This fiber was identified by X-ray diffraction and was found to be a single phase of potassium hexatitanate. When the fibers were observed using an optical microscope, the average fiber length was about 150 μm.
実施例 ２
SO3として2.9％の硫酸を含有する含水酸化チ
タン700ｇ及び炭酸カリウム300ｇを秤りとり、
150mlの水を添加後、ニーダーで20分間混練した。
この混練物をアルミナ製ルツボに入れ、電気炉中
で昇温速度250℃／時、保持温度1100℃保持時間
２時間の条件で焼成した後、200℃／時の速度で
降温した。Example 2 Weighed 700 g of hydrous titanium oxide containing 2.9% sulfuric acid as SO 3 and 300 g of potassium carbonate,
After adding 150 ml of water, the mixture was kneaded in a kneader for 20 minutes.
This kneaded material was placed in an alumina crucible and fired in an electric furnace at a heating rate of 250°C/hour and a holding temperature of 1100°C for a holding time of 2 hours, followed by cooling at a rate of 200°C/hour.
以後、実施例１と同様な条件で解繊及び組成変
換を行なつて得た含水チタン酸カリウム繊維を
900℃で30分間加熱してチタン酸カリウムの無水
和物とした。この繊維をＸ線回折により同定した
ところ六チタン酸カリウムの単一相であつた。
又、光学顕微鏡により繊維を観察したところ、平
均的な繊維長は120μｍ程度であつた。 Thereafter, hydrated potassium titanate fibers obtained by defibrating and changing the composition under the same conditions as in Example 1 were used.
The mixture was heated at 900°C for 30 minutes to form potassium titanate anhydrate. This fiber was identified by X-ray diffraction and was found to be a single phase of potassium hexatitanate.
Further, when the fibers were observed using an optical microscope, the average fiber length was about 120 μm.
実施例 ３
SO3として8.0％の硫酸を含有する含水酸化チ
タン700ｇ及び炭酸カリウム320ｇを秤りとり、
150mlの水を添加後、ニーダーで20分間混練した。
この混練物をアルミナ製ルツボに入れ、電気炉中
で昇温速度250℃／時、保持温度950℃、保持時間
５時間の条件で焼成した後、150℃／時の速度で
降温した。Example 3 Weighed 700 g of hydrous titanium oxide containing 8.0% sulfuric acid as SO 3 and 320 g of potassium carbonate,
After adding 150 ml of water, the mixture was kneaded in a kneader for 20 minutes.
This kneaded material was placed in an alumina crucible and fired in an electric furnace at a heating rate of 250°C/hour, a holding temperature of 950°C, and a holding time of 5 hours, and then the temperature was lowered at a rate of 150°C/hour.
焼成物をステンレス製容器中の５の温水に投
入して２時間浸漬した後、500rpmで30分間撹拌
し、3N−塩酸を滴下してスラリーのPHを9.3に調
整した。過、洗浄後800℃で１時間焼成してチ
タン酸カリウム繊維を得た。 The baked product was placed in warm water in a stainless steel container and immersed for 2 hours, stirred at 500 rpm for 30 minutes, and 3N hydrochloric acid was added dropwise to adjust the pH of the slurry to 9.3. After filtering and washing, the fibers were fired at 800°C for 1 hour to obtain potassium titanate fibers.
この繊維をＸ線回折により同定したところ六チ
タン酸カリウムの単一相であつた。又光学顕微鏡
により繊維を観察したところ、平均的な繊維長は
100μｍ程度であつた。 This fiber was identified by X-ray diffraction and was found to be a single phase of potassium hexatitanate. Furthermore, when the fibers were observed using an optical microscope, the average fiber length was
It was about 100 μm.
実施例 ４
実施例３で得られた含水チタン酸カリウム繊維
を1100℃で30分間加熱して無水和物とした。この
繊維をＸ線回折により同定したところ六チタン酸
カリウムの単一相であつた。又光学顕微鏡下で観
察したところ繊維の形状及び長さともに、実施例
３で得られた六チタン酸カリウム繊維と比較して
特に差は認められなかつた。Example 4 The hydrous potassium titanate fiber obtained in Example 3 was heated at 1100° C. for 30 minutes to make it anhydrous. This fiber was identified by X-ray diffraction and was found to be a single phase of potassium hexatitanate. Further, when observed under an optical microscope, no particular difference was observed in both the shape and length of the fibers compared to the potassium hexatitanate fibers obtained in Example 3.
比較例 １
TiO2源として酸化チタンを使用した実験を実
施例２と同様な条件で行なつたところ、六チタン
酸カリウムの単一相は合成されたものの、平均繊
維長は20μｍであつた。Comparative Example 1 An experiment using titanium oxide as a TiO 2 source was conducted under the same conditions as in Example 2. Although a single phase of potassium hexatitanate was synthesized, the average fiber length was 20 μm.
比較例 ２
TiO2源として酸化チタンを使用し、TiO2に対
して５％の硫酸カリウムを添加した実験を実施例
２と同様な条件で行なつたところ、六チタン酸カ
リウムの単一相は合成されたものの、平均繊維長
は50μｍであつた。Comparative Example 2 An experiment using titanium oxide as a TiO 2 source and adding 5% potassium sulfate to TiO 2 under the same conditions as Example 2 revealed that the single phase of potassium hexatitanate was Although synthesized, the average fiber length was 50 μm.
Claims (1)
化チタンと炭酸カリウムとを一般式K2O・nTiO2
（ただしｎ＝２〜４）で示される割合で配合混練
した後、900〜1200℃で焼成して、塊状のチタン
酸カリウム繊維を生成せしめ、次いで該塊状生成
物を水又は温水中に浸漬して単繊維に解繊した
後、該スラリーに酸を添加してPHを9.0〜10.0に
調整することにより、チタン酸カリウム繊維の組
成がK2O・6TiO2・nH2Oの組成となるように処
理し、更に600℃以上に加熱することを特徴とす
る六チタン酸カリウム繊維の製造方法。1 Hydrous titanium oxide containing 1 to 10% sulfuric acid as SO 3 and potassium carbonate are combined with the general formula K 2 O・nTiO 2
(However, n = 2 to 4) After mixing and kneading in the ratio shown, calcining at 900 to 1200 ° C. to produce lumpy potassium titanate fibers, and then immersing the lumped product in water or hot water. After the slurry is defibrated into single fibers, an acid is added to the slurry to adjust the pH to 9.0 to 10.0, so that the composition of the potassium titanate fibers becomes K 2 O・6TiO 2・nH 2 O. A method for producing potassium hexatitanate fibers, which comprises treating the fibers with water and heating the fibers to 600°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20921583A JPS60104522A (en) | 1983-11-09 | 1983-11-09 | Preparation of fiber of potassium hexatitanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20921583A JPS60104522A (en) | 1983-11-09 | 1983-11-09 | Preparation of fiber of potassium hexatitanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60104522A JPS60104522A (en) | 1985-06-08 |
| JPH0244774B2 true JPH0244774B2 (en) | 1990-10-05 |
Family
ID=16569251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20921583A Granted JPS60104522A (en) | 1983-11-09 | 1983-11-09 | Preparation of fiber of potassium hexatitanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60104522A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01301516A (en) * | 1987-12-25 | 1989-12-05 | Titan Kogyo Kk | Tunnel-structured potassium hexatitanate fiber, its production and composite material containing same |
| JPH0457922A (en) * | 1990-06-26 | 1992-02-25 | Kubota Corp | Production of polycrystalline fiber of potassium hexatitanate |
| JP2816908B2 (en) * | 1991-10-18 | 1998-10-27 | 株式会社クボタ | Method for producing potassium hexatitanate fiber |
| JP2019206634A (en) * | 2018-05-29 | 2019-12-05 | 西川ゴム工業株式会社 | Coating composition, and automobile sealant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4856600A (en) * | 1971-09-29 | 1973-08-08 | ||
| JPS5250000A (en) * | 1975-10-20 | 1977-04-21 | Matsushita Electric Ind Co Ltd | Method for producing fibrous alkali tianate |
| JPS54106624A (en) * | 1978-02-06 | 1979-08-21 | Kagaku Gijutsucho Mukizai | Production of alkali metal titanate fiber |
| JPS5532647A (en) * | 1978-08-30 | 1980-03-07 | Kobe Steel Ltd | Method for extrusion molding of oil-containing high molecular material |
-
1983
- 1983-11-09 JP JP20921583A patent/JPS60104522A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4856600A (en) * | 1971-09-29 | 1973-08-08 | ||
| JPS5250000A (en) * | 1975-10-20 | 1977-04-21 | Matsushita Electric Ind Co Ltd | Method for producing fibrous alkali tianate |
| JPS54106624A (en) * | 1978-02-06 | 1979-08-21 | Kagaku Gijutsucho Mukizai | Production of alkali metal titanate fiber |
| JPS5532647A (en) * | 1978-08-30 | 1980-03-07 | Kobe Steel Ltd | Method for extrusion molding of oil-containing high molecular material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60104522A (en) | 1985-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0244774B2 (en) | ||
| US4064224A (en) | Method of making fibrous alkali titanates | |
| JPH10310428A (en) | Lithium titanate hydrate and production of lithium titanate | |
| JP2747916B2 (en) | Potassium titanate long fiber and method for producing titania fiber using the same | |
| JPS63319298A (en) | Aluminum borate whisker and production thereof | |
| JP2704351B2 (en) | Monoclinic titanium dioxide fiber and method for producing the same | |
| JPH02107600A (en) | Production of aluminum borate whisker | |
| JP2021075439A (en) | Method for producing tobermorite-containing housing material, tobermorite, and tobermorite-containing housing material | |
| JPS6330400A (en) | Production of potassium titanate fiber | |
| US4390513A (en) | Process for manufacturing fibrous potassium titanate | |
| JPS5930724A (en) | Manufacture of fibrous potassium titanate | |
| JP2791460B2 (en) | Potassium aluminate titanate whisker and method for producing the same | |
| JPH0788278B2 (en) | Method for producing potassium hexatitanate fiber | |
| JP3028398B2 (en) | Method for producing sodium titanate fiber | |
| JPS60259627A (en) | Production of potassium hexatitanate fiber or its composite fiber | |
| JPH05105447A (en) | Production of potassium hexatitanate fiber | |
| JPH10212625A (en) | Production of potassium titanate fiber | |
| JP2627955B2 (en) | Method for producing fibrous alkaline earth metal titanate | |
| JPH0338239B2 (en) | ||
| JPS62226896A (en) | Production of long fibrous alkali metal salt of titanic acid | |
| JPS60210528A (en) | Production of fibrous alkali metal titanate | |
| RU2366609C1 (en) | Method for preparation of crystalline potassium titanate | |
| JPH07242420A (en) | Production of polycrystalline fiber of alkaline earth metal titanate | |
| KR0173767B1 (en) | Process for the preparation of titanate derivatives | |
| JPH0543236A (en) | Production of combined barium hexatitanate fiber |