JPH0688879B2 - Method for manufacturing aluminum borate whiskers - Google Patents
Method for manufacturing aluminum borate whiskersInfo
- Publication number
- JPH0688879B2 JPH0688879B2 JP12856690A JP12856690A JPH0688879B2 JP H0688879 B2 JPH0688879 B2 JP H0688879B2 JP 12856690 A JP12856690 A JP 12856690A JP 12856690 A JP12856690 A JP 12856690A JP H0688879 B2 JPH0688879 B2 JP H0688879B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- component
- whiskers
- range
- borate whiskers
- 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 - Fee Related
Links
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- -1 alkali metal aluminates Chemical class 0.000 claims description 7
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 5
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
- 235000010339 sodium tetraborate Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はホウ酸アルミニウムウィスカーの製造方法に関
するものである。TECHNICAL FIELD The present invention relates to a method for manufacturing aluminum borate whiskers.
本発明方法によって得られるホウ酸アルミニウムウィス
カーは機械的強度、耐熱性、断熱性、耐薬品性、電気絶
縁性及び中性子線吸収能に優れており、熱可塑性樹脂、
熱硬化性樹脂、セメント、ガラス及び金属等の補強材と
して有用である。Aluminum borate whiskers obtained by the method of the present invention are excellent in mechanical strength, heat resistance, heat insulation, chemical resistance, electrical insulation and neutron absorption, and are thermoplastic resins,
It is useful as a reinforcing material for thermosetting resins, cement, glass and metals.
従来の技術 機械的強度、耐薬品性等に優れているホウ酸アルミニウ
ムウィスカーの合成について種々の方法が試みられてお
り、その方法は気相法と溶融剤を用いる液相法とに大別
できる。BACKGROUND ART Various methods have been attempted for the synthesis of aluminum borate whiskers which are excellent in mechanical strength, chemical resistance, etc., and the methods can be roughly classified into a gas phase method and a liquid phase method using a melting agent. .
気相法に関しては、1000〜1400℃にて気体状態のフッ化
アルミニウムと酸化ホウ素中に水蒸気を通すことによ
り、4Al2O3・B2O3の組成をもつウィスカーが得られるこ
とが米国特許第3350166号明細書に記載されている。Regarding the vapor phase method, it is possible to obtain whiskers having a composition of 4Al 2 O 3 · B 2 O 3 by passing water vapor through gaseous aluminum fluoride and boron oxide at 1000 to 1400 ° C. No. 3,350,166.
一方液相法に関しては、水酸化アルミニウムと酸化ホウ
素の混合物を1400℃に加熱することにより3Al2O3・B2O3
及び9Al2O3・B2O3の組成をもつウィスカーが得られるこ
とが米国特許第3080242号明細書に記載されている。こ
の場合には、過剰の酸化ホウ素が溶融剤成分としての役
割を果たしている。また米国内務省鉱山局の報告によれ
ば、酸化アルミニウム、四ホウ酸ナトリウム及び塩化リ
チウムの混合物を1200℃に加熱することにより2.5Al2O3
・B2O3の組成をもつウィスカーが得られ、また酸化アル
ミニウム、四ホウ酸ナトリウム及び酸化ホウ素の混合物
を1400℃に加熱することにより4.8Al2O3・B2O3の組成を
もつウィスカーが得られることが知られている。〔ビュ
ーロー オブマインズ レポート オブ インベスティ
ゲーション“Bureau of Mines Report of Investigatio
ns 6575"（1965）〕この場合においても、過剰の四ホウ
酸ナトリウム及び塩化リチウムの混合物あるいは過剰の
四ホウ酸ナトリウム及び酸化ホウ素の混合物が溶融剤成
分としての役割を果たしており、通常当量の３倍以上の
ホウ酸成分が混合され、過剰分の成分が溶融剤として作
用する、内部溶融剤法と呼ばれているものである。この
方法は大きいウイスカーを得ることが可能だが、溶解力
の強い無水ホウ酸成分が化学量論量よりもかなり過剰で
あるため、生成したウイスカーを溶解してしまい収率が
大幅に低下すること及び反応後系がガラス状になるため
ウイスカーの分離が困難であるという、工業的製法とし
ては大きな欠点がある。On the other hand, regarding the liquid phase method, a mixture of aluminum hydroxide and boron oxide was heated to 1400 ° C. to produce 3Al 2 O 3 · B 2 O 3
And 9Al 2 O 3 · B 2 that whiskers having the composition O 3 is obtained is described in U.S. Patent No. 3,080,242. In this case, excess boron oxide serves as a melting agent component. According to a report from the US Department of the Interior Mining Bureau, a mixture of aluminum oxide, sodium tetraborate and lithium chloride was heated to 1200 ° C. to produce 2.5 Al 2 O 3
A whisker having a composition of B 2 O 3 is obtained, and a whisker having a composition of 4.8 Al 2 O 3 · B 2 O 3 is obtained by heating a mixture of aluminum oxide, sodium tetraborate and boron oxide to 1400 ° C. Is known to be obtained. [Bureau of Mines Report of Investigatio
In this case, too, a mixture of excess sodium tetraborate and lithium chloride or a mixture of excess sodium tetraborate and boron oxide plays a role as a melting agent component, and is usually equivalent to 3 parts. This is called an internal melting agent method in which more than twice the amount of boric acid component is mixed and the excess component acts as a melting agent.This method can obtain large whiskers, but has a strong dissolving power. Since the content of boric anhydride is much more than the stoichiometric amount, the generated whiskers are dissolved and the yield is greatly reduced, and the reaction system becomes glassy, making it difficult to separate the whiskers. That is, there is a big drawback as an industrial manufacturing method.
本発明者等は、特開昭63-319298号公報及び同63-319299
号公報において、ホウ酸アルミニウムの生成反応に直接
関与しない溶融剤を用いる製法により、これらの問題が
解決しうることを提案した。The inventors of the present invention have disclosed in JP-A-63-319298 and 63-319299.
In the gazette, it was proposed that these problems could be solved by a manufacturing method using a melting agent that does not directly participate in the aluminum borate formation reaction.
発明が解決しようとする課題 本発明の目的とするところは、さらに収率が高く且つ工
業的な規模における製造に適したホウ酸アルミニウムウ
イスカーの製造方法を提供するにある。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a method for producing aluminum borate whiskers which has a higher yield and is suitable for production on an industrial scale.
また、この種のウイスカーをFRP、FRM、FRCの強化材と
して用いる場合、そこで要求されれるウイスカーの繊維
径はまちまちであり、例えばFRPで0.5〜1.0μｍ、FRMで
は1.0〜5.0、FRCでは0.1〜0.5μｍである。When using this type of whisker as a reinforcing material for FRP, FRM, and FRC, the fiber diameter of the whisker required there is various, for example, 0.5 to 1.0 μm for FRP, 1.0 to 5.0 for FRM, and 0.1 to 5.0 for FRC. It is 0.5 μm.
本発明者等が明らかにした前述の特許出願によれば、こ
れらの範囲のホウ酸アルミニウムウイスカーを製造する
ことは可能であるが、この場合目的とする大きさに応じ
てアルミニウム供給成分、無水ホウ酸供給成分及び溶融
剤成分を選定しなければならない。また大きいウイスカ
ーを得るためには内部溶融剤の力を借りる必要があり、
収率が低下してしまうという難点があった。According to the above-mentioned patent application clarified by the present inventors, it is possible to produce aluminum borate whiskers in these ranges, but in this case, according to the intended size, the aluminum supply component, anhydrous boron The acid feed component and the melt component must be selected. Also, in order to obtain a large whisker, it is necessary to borrow the power of the internal melting agent,
There is a drawback that the yield is reduced.
課題を解決するための手段 本発明者等は、このような事情に鑑み鋭意試験研究を重
ねた結果、アルカリ金属のアルミン酸塩及び硫酸を用い
ることにより、所期の目的が達成できることを見出し、
本発明方法を完遂した。Means for Solving the Problems The present inventors, as a result of repeated intensive test research in view of such circumstances, by using an alkali metal aluminate and sulfuric acid, found that the intended purpose can be achieved,
The method of the present invention has been completed.
即ち本発明方法によれば、アルカリ金属のアルミン酸塩
から選ばれた少なくとも一種のアルミニウム供給成分
と、酸化ホウ素、ホウ酸、アルカリ金属ホウ酸塩の中か
ら選ばれた少なくとも一種の無水ホウ酸供給成分と、ア
ルカリ金属の硫酸塩及び塩化物から選ばれた溶融剤成分
で構成される原料系に、硫酸を適量混合したのち900〜1
200℃の温度域で反応することにより、ホウ酸アルミニ
ウムウィスカーの結晶が育成され、そしてアルミニウム
供給成分、無水ホウ酸供給成分、溶融剤成分及び硫酸の
混合比率を所定の範囲に調整することによって、得られ
るホウ酸アルミニウムウイスカーの大きさを高収率で制
御することが可能である。That is, according to the method of the present invention, at least one aluminum supply component selected from alkali metal aluminates, and at least one boric anhydride supply selected from boron oxide, boric acid, and alkali metal borate. 900 to 1 after mixing an appropriate amount of sulfuric acid to the raw material system composed of the components and the melting agent component selected from sulfates and chlorides of alkali metals.
By reacting in a temperature range of 200 ° C., crystals of aluminum borate whiskers are grown, and by adjusting the mixing ratio of the aluminum supply component, the boric anhydride supply component, the melting component and the sulfuric acid within a predetermined range, It is possible to control the size of the obtained aluminum borate whiskers with high yield.
本発明方法の実施に適するアルミニウム供給成分として
はアルミン酸ナトリウム、アルミン酸カリウム等であ
り、これらは２種以上混合してもかまわない。Aluminum supplying components suitable for carrying out the method of the present invention include sodium aluminate, potassium aluminate and the like, and two or more kinds of these may be mixed.
無水ホウ酸供給成分としては、ホウ酸、ピロホウ酸、メ
タホウ酸、四ホウ酸ナトリウム、四ホウ酸カリウム、メ
タホウ酸ナトリウム等及びこれらの塩の水和物並びにB
(OC2H5)3のようなホウ素のアルコキシド化合物が挙げ
ら、これらは２種以上混合してもかまわない。As the boric anhydride supplying component, boric acid, pyroboric acid, metaboric acid, sodium tetraborate, potassium tetraborate, sodium metaborate, etc. and hydrates of these salts and B
Examples thereof include boron alkoxide compounds such as (OC 2 H 5 ) 3 , and two or more of them may be mixed.
溶融剤としては、アルカリ金属の硫酸塩及び塩化物であ
り、具体的には硫酸リチウム、硫酸ナトリウム、硫酸カ
リウム、塩化リチウム、塩化ナトリウム、塩化カリウム
及びこれらの水和物であり、２種以上混合してもかまわ
ない。Examples of the melting agent include alkali metal sulfates and chlorides, specifically, lithium sulfate, sodium sulfate, potassium sulfate, lithium chloride, sodium chloride, potassium chloride and hydrates thereof, which are a mixture of two or more kinds. It doesn't matter.
これらの混合割合は、アルミニウムとホウ素のモル比を
6:4〜9:2の範囲、アルミニウムとアルカリ金属のモル比
を1:1〜1:10の範囲、更にアルミニウムと硫酸のモル比
を2:1〜1:5の範囲とすることにより、ホウ酸アルミニウ
ムウイスカーを繊維径0.2〜５μｍ、繊維長２〜200μｍ
に制御することが可能である。The mixing ratio of these is the molar ratio of aluminum and boron.
By setting the molar ratio of aluminum to alkali metal in the range of 6: 4 to 9: 2, the range of 1: 1 to 1:10, and the molar ratio of aluminum to sulfuric acid in the range of 2: 1 to 1: 5, Aluminum borate whiskers with fiber diameter 0.2-5 μm, fiber length 2-200 μm
It is possible to control.
ホウ素に対するアルミニウム量が多いほど、溶融剤成分
が多いほど、大きなウイスカーが得られる。また溶融剤
として、硫酸塩を用いた場合はアルミニウムと硫酸のモ
ル比が2:3に近いほど、そしてアルミニウム２モルに対
しｘモルの塩化物を用いた場合は、アルミニウムと硫酸
のモル比が2:3＋x/2に近いほど大きなウイスカーが得ら
れる。The larger the amount of aluminum with respect to boron and the larger the amount of the melting agent component, the larger the whiskers can be obtained. When a sulfate is used as the melting agent, the molar ratio of aluminum to sulfuric acid is closer to 2: 3, and when x mol of chloride is used to 2 mol of aluminum, the molar ratio of aluminum to sulfuric acid is increased. The closer to 2: 3 + x / 2, the bigger the whisker.
反応温度は900〜1200℃であり、これより高いとアルミ
ナが生成し、低いとウイスカーが十分成長しないため不
適切である。時間は30分〜12時間でよい。The reaction temperature is 900 to 1200 ° C, and if it is higher than this, alumina is formed, and if it is lower than this, whiskers do not grow sufficiently, which is inappropriate. The time may be 30 minutes to 12 hours.
育成されたホウ酸アルミニウムウィスカーを単離するに
は、約1N濃度の熱塩酸、熱硫酸、熱硝酸、熱苛性ソーダ
あるいは熱水等を用いて、溶融材その他水溶性物質を除
去し、十分に水洗をするか、あるいは水不溶の副生成物
がある場合には、残留物からデカンテーション等の処理
でウィスカーを分離したのちに、十分に水洗をすればよ
い。To isolate the grown aluminum borate whiskers, use hot hydrochloric acid, hot sulfuric acid, hot nitric acid, hot caustic soda, or hot water with a concentration of about 1N to remove the molten material and other water-soluble substances, and then wash thoroughly with water. Or if there is a water-insoluble by-product, the whiskers may be separated from the residue by a treatment such as decantation and then washed sufficiently with water.
作用 900〜1200℃の反応温度において、ホウ酸アルミニウム
ウィスカーを構成する物質の一つであるAl2O3は固体で
あるので、ウィスカーを均一に育成させるには、系全体
を液状に近づける必要がある。そのために本発明方法で
はアルミン酸ナトリウム(NaAlO2)、アルミン酸カリウム
(KAlO2)と硫酸を反応させNa3Al(SO4)3またはK3Al(SO4)3
等のトリアルカリアルミニウムトリサルフェートを生成
せしめる。Action At a reaction temperature of 900-1200 ° C, Al 2 O 3, which is one of the substances that make up aluminum borate whiskers, is a solid, so in order to grow whiskers uniformly, it is necessary to bring the entire system closer to a liquid state. is there. Therefore, in the method of the present invention, sodium aluminate (NaAlO 2 ) and potassium aluminate are used.
(KAlO 2 ) with sulfuric acid to react Na 3 Al (SO 4 ) 3 or K 3 Al (SO 4 ) 3
To produce trialkali aluminum trisulfate.
トリアルカリアルミニウムトリサルフェートは通常700
℃付近から溶融が始まり、さらに昇温していくに連れ
て、徐々にAl2O3とアルカリ金属硫酸塩に再分解し、105
0℃付近で反応が完了する。この性質を利用して、700℃
付近で全ての原料を液状均一化させることができる。さ
らに昇温していく過程で再発生してくるアルカリ金属硫
酸塩とトリアルカリアルミニウムトリサルフェートとの
共融混合浴が溶融剤の作用を呈し、同時に発生してくる
Al2O3がB2O3と反応し、ウィスカーとして成長する。こ
のように反応が均一系で進むために、大きくて均一なホ
ウ酸アルミニウムウィスカーが得られる。Trialkali aluminum trisulfate is usually 700
Melting begins at around ℃, and as the temperature further rises, it gradually decomposes into Al 2 O 3 and alkali metal sulfate,
The reaction is completed at around 0 ° C. Utilizing this property, 700 ℃
In the vicinity, all the raw materials can be homogenized in a liquid state. A eutectic mixing bath of alkali metal sulfate and trialkali aluminum trisulfate, which regenerates during the process of further heating, acts as a melting agent and is generated at the same time.
Al 2 O 3 reacts with B 2 O 3 and grows as whiskers. Since the reaction proceeds in a uniform system in this manner, large and uniform aluminum borate whiskers can be obtained.
またアルカリ金属の塩化物も硫酸と反応し容易に硫酸塩
となり、前述と同時にトリアルカリアルミニウムトリサ
ルフェートを生成し、同じ機構でホウ酸アルミニウムウ
イスカーが成長する。Alkali metal chloride also reacts with sulfuric acid to easily form a sulfate, and at the same time, it produces trialkali aluminum trisulfate, and aluminum borate whiskers grow by the same mechanism.
実施例１〜７ 表に示すような各種アルミニウム供給成分、無水ホウ酸
供給成分、溶融剤成分及び硫酸を計量、粉砕、混合した
ものを、内容量50mlのアルミナ坩堝に入れ、電気炉中で
毎分10℃ずつ昇温し、1100℃の温度で４時間反応させ
た。この反応物を冷却し、それに1000mlの1N塩酸を加え
て８時間煮沸し、残留フラックス分を溶解除去したの
ち、水洗、乾燥して9Al2O3・2B2O3を持つホウ酸アルミニ
ウムウイスカーをを得た。このウイスカーの形状及び収
率は次表に示したとおりであり、高収率でウイスカーを
所定の大きさに制御することが可能であった。Examples 1 to 7 Various aluminum supply components, boric anhydride supply components, melting agent components and sulfuric acid as shown in the table were weighed, pulverized and mixed and put into an alumina crucible having an internal volume of 50 ml, and each was placed in an electric furnace. The temperature was raised by 10 ° C per minute, and the reaction was carried out at a temperature of 1100 ° C for 4 hours. This reaction product was cooled, 1000 ml of 1N hydrochloric acid was added to it, and it was boiled for 8 hours to dissolve and remove the residual flux, washed with water and dried to obtain aluminum borate whiskers having 9Al 2 O 3 · 2B 2 O 3. Got The shape and yield of this whisker are shown in the following table, and it was possible to control the whisker to a predetermined size with high yield.
発明の効果 本発明方法によれば、従来の方法と比べて収率が高く、
且つウィスカーの大きさが均一であり、しかもその大き
さの制御が可能であり、工業的製法として好適である。 EFFECTS OF THE INVENTION According to the method of the present invention, the yield is high as compared with the conventional method,
Moreover, the size of the whiskers is uniform, and the size of the whiskers can be controlled, which is suitable as an industrial manufacturing method.
Claims (2)
少なくとも一種のアルミニウム供給成分と、酸化ホウ
素、ホウ酸、アルカリ金属ホウ酸塩の中から選ばれた少
なくとも一種の無水ホウ酸供給成分とアルカリ金属の硫
酸塩及び塩化物から選ばれた溶融剤成分並びに硫酸を均
一に混合したのち、900〜1200℃の温度域で反応させて
育成するホウ酸アルミニウムウィスカーの製造方法。1. At least one aluminum supplying component selected from alkali metal aluminates, and at least one boric anhydride supplying component selected from boron oxide, boric acid and alkali metal borate, and alkali. A method for producing aluminum borate whiskers, wherein a melting agent component selected from metal sulfates and chlorides and sulfuric acid are uniformly mixed and then reacted and grown in a temperature range of 900 to 1200 ° C.
アルミニウムとホウ素のモル比が6:4ないし9:2の範囲と
し、アルミニウム供給成分とフラックス成分をアルミニ
ウムとアルカリ金属のモル比が1:1ないし1:10の範囲と
し、アルミニウムと硫酸のモル比を2:1〜1:5の範囲と
し、繊維径0.2〜５μｍ、繊維長５〜500μｍの所定範囲
にあり、且つ9Al2O3・2B2O3で示される組成をもつ請求項
（１）に記載のホウ酸アルミニウムウィスカーの製造方
法。2. The aluminum supply component and the boric anhydride component have a molar ratio of aluminum and boron in the range of 6: 4 to 9: 2, and the aluminum supply component and the flux component have a molar ratio of aluminum and alkali metal of 1: 1. to the range 1:10, the molar ratio of aluminum to sulfate 2: 1 to 1: in the range of 5, fiber diameter 0.2 to 5 .mu.m, is in the predetermined range of fiber length 5 to 500 [mu] m, and 9Al 2 O 3 · 2B The method for producing aluminum borate whiskers according to claim 1, having a composition represented by 2 O 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12856690A JPH0688879B2 (en) | 1990-05-17 | 1990-05-17 | Method for manufacturing aluminum borate whiskers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12856690A JPH0688879B2 (en) | 1990-05-17 | 1990-05-17 | Method for manufacturing aluminum borate whiskers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0426599A JPH0426599A (en) | 1992-01-29 |
| JPH0688879B2 true JPH0688879B2 (en) | 1994-11-09 |
Family
ID=14987929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12856690A Expired - Fee Related JPH0688879B2 (en) | 1990-05-17 | 1990-05-17 | Method for manufacturing aluminum borate whiskers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688879B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618931A (en) * | 2012-04-06 | 2012-08-01 | 江苏省范群干燥设备厂有限公司 | Method for preparing calcium sulfate whiskers |
-
1990
- 1990-05-17 JP JP12856690A patent/JPH0688879B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618931A (en) * | 2012-04-06 | 2012-08-01 | 江苏省范群干燥设备厂有限公司 | Method for preparing calcium sulfate whiskers |
| CN102618931B (en) * | 2012-04-06 | 2015-04-22 | 江苏省范群干燥设备厂有限公司 | Method for preparing calcium sulfate whiskers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0426599A (en) | 1992-01-29 |
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