JPS63282131A - Production of whisker-reinforced glass - Google Patents
Production of whisker-reinforced glassInfo
- Publication number
- JPS63282131A JPS63282131A JP11375887A JP11375887A JPS63282131A JP S63282131 A JPS63282131 A JP S63282131A JP 11375887 A JP11375887 A JP 11375887A JP 11375887 A JP11375887 A JP 11375887A JP S63282131 A JPS63282131 A JP S63282131A
- Authority
- JP
- Japan
- Prior art keywords
- whiskers
- whisker
- glass
- sol
- glass powder
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000843 powder Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000000499 gel Substances 0.000 claims abstract description 23
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000011240 wet gel Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 16
- 239000006058 strengthened glass Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000005341 toughened glass Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910003465 moissanite Inorganic materials 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- 239000008119 colloidal silica Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000005354 aluminosilicate glass Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000012905 Brassica oleracea var viridis Nutrition 0.000 description 1
- -1 NaCAT Chemical compound 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000008258 liquid foam Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011226 reinforced ceramic Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/06—Whiskers ss
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/32—Nature of the non-vitreous component comprising a sol-gel process
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、ウィスカー強化ガラスの製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing whisker tempered glass.
ガラスをウィスカーで強化した複合材料は、ガラスのみ
からなる材料に比較して弾性率９強度。Composite materials made of glass reinforced with whiskers have an elastic modulus of 9 and strength compared to materials made only of glass.
破壊靭性などの機械的特性や熱膨張率、熱伝導率などの
熱的特性が改善されるためにいろいろな分野で注目され
ている。It is attracting attention in various fields because it improves mechanical properties such as fracture toughness and thermal properties such as coefficient of thermal expansion and thermal conductivity.
そのような複合材料を製造する方法としては。As a method of manufacturing such composite materials.
ライス男−とガラス粉末を混合した後にホットプレスす
る方法が通常用いられている。例えば、刊行物（Ｆｒａ
ｎｋ Ｄ 、ＧＢｃら、Ｐｅｒｆｏｒｍａｎｃｅ ｏｆ
Ｃｏｍｍｅｒｃｉａｌ ａｎｄ Ｒｅａｅ４ｒｃｈ Ｇ
ｒａｄｅ ＳｉＯＷｈｉｓｋｅｒｓｉｎ ａ Ｂｏｒｏ
ｓｉｌｉｃａｔｅ Ｇｌａｓｓ Ｍａｔｒｉｘ ”Ｃｅ
ｒａｍｉｃ Ｅｎｇｉｎｅｅｒｉｎｇ ａｎｄ ５ｃｉ
ｅｎｃｅ ＰｒｏｃｅｅｄｉｎｇｓＶｏ７？ 、７．Ｃ
７−８〕、（１９８６）、ＰＰ９７８〜９８２）にはウ
ィスカーとガラス粉末とをボールミル法で混合し、ホッ
トプレスすることによシ９１Ｇウィスカー強化ガラスを
製造する方法が記載されている。しかしながら、かかる
従来の方法には、以下に述べるような欠点がある。A commonly used method is to mix rice powder and glass powder and then hot press the mixture. For example, publications (Fra
nk D, GBc et al. Performance of
Commercial and Reae4rch G
rade SiOWhiskersin a Boro
silicate Glass Matrix “Ce”
ramic engineering and 5ci
ence ProceedingsVo7? ,7. C
7-8], (1986), PP978-982) describes a method for producing 91G whisker-reinforced glass by mixing whiskers and glass powder using a ball mill method and hot pressing the mixture. However, such conventional methods have drawbacks as described below.
すなわち、上記従来の方法では、ウィスカーとガラス粉
末を混合するための工程でウィスカーの損傷を生じやす
（そのために複合化後に、マトリックス中でウィスカー
の持つ本来の特性を発揮できないという欠点がある。That is, in the conventional method described above, the whiskers tend to be damaged in the process of mixing the whiskers and the glass powder (therefore, the whiskers have the disadvantage that the original characteristics of the whiskers cannot be exhibited in the matrix after compositing.
このような製造過程中に生じる強化態勢、すなわちウィ
スカーの損傷を防止するために、最近。Recently, in order to prevent damage to the reinforcement, i.e. whiskers, which occurs during the manufacturing process.
ゾルΦゲル法を用いてウィスカー強化セラミックスを製
造することも試みられている。例えば、刊行物（Ｊ 、
Ｊ 、 Ｌ５１ｎｎｕｔｔｉとＤ 、Ｒ，０１ａｒｋ
の報告” Ｓｏｌ −Ｇｅｍ Ｄｅｒｉｒｅｄ Ｃｏａ
ｔｉｎｇｓ Ｏｎ ５ｉＣａｎｄ ５ｉｌｉｃａｔｅ
Ｆｉｂｅｒｓ″、 Ｃｅｒａｍｉｃ Ｅｎｇｉｎｅｅｒ
ｉｎｇａｎｄ ＳｃｉｅｎｃｅＰｒｏｃｅｅｄｉｎｇｓ
、 Ｖｏｌｌ 、 ５ 、 ［７−８〕。Attempts have also been made to produce whisker-reinforced ceramics using the sol Φ-gel method. For example, publications (J,
J, L51nnutti and D, R,01ark
Report on “Sol-Gem Deired Coa”
tings On 5iCand 5ilicate
Ceramic Engineer
ingand ScienceProceedings
, Voll, 5, [7-8].
１（１９８６）、ＰＰ５７４〜５８２）にはＳｉＣウィ
スカーとＡｌ２Ｏ２をフリージング（Ｆｒｅｅｚｉｎｇ
）法により複合化することが報告されており、ゾルの原
料としてｈｚ２ｏ５ のかわりに５ｌｏ２を用いれば
ウィスカー強化ガラスを容易に製造することが出来る可
能性を持っている。1 (1986), PP574-582), SiC whiskers and Al2O2 were
) method, and it is possible to easily produce whisker-reinforced glass by using 5lo2 instead of hz2o5 as the raw material for the sol.
上記ゾル・ゲル法を用いた方法では、ウィスカーを含む
ゾル液がウェットゲル複合体を経てドライゲル化する過
程でゾルの収縮が大きく、たとえば、ゾルの出発原料と
してケイ酸エチル（Ｓｉ（Ｃ！２Ｈ５０）４）を用いた
場合には数１０％の体積収縮を生じ、収縮のないウィス
カーとの間に大きな引張応力を生じ、ガラスストリンク
スにクランクを生じてしまうという欠点かメジ、大きな
バルク状の複合材料が得られないという致命的な欠点を
持っていた。In the method using the above-mentioned sol-gel method, the sol shrinks significantly during the process in which the sol solution containing whiskers passes through the wet gel complex and becomes a dry gel. ) When using 4), the volume shrinks by several tens of percent, creating a large tensile stress between the non-shrinking whiskers and creating a crank in the glass strings. It had the fatal drawback of not being able to produce composite materials.
この発明は、かかる問題点を解決するためになされたも
ので、ウィスカーの損傷を最小限とし。This invention was made to solve this problem, and minimizes damage to the whiskers.
強化効果が高（、大きなバルク状の成形物も容易に得ら
れるウィスカー強化ガラスの製造方法を得ることを目的
とする。The purpose of the present invention is to provide a method for manufacturing whisker-strengthened glass that has a high strengthening effect (and can easily produce large bulk molded products).
この発明のウィスカー強化ガラスの製造方法は。 A method for manufacturing whisker tempered glass according to the present invention.
シリカゾル液の粘度を０．０５〜２．０ポアズにする粘
度調整工程、粘度調整されたシリカゾル液に。A viscosity adjustment step to adjust the viscosity of the silica sol to 0.05 to 2.0 poise, resulting in a viscosity-adjusted silica sol.
ウィスカーおよびガラス粉末を混合する混合工程。Mixing process to mix whiskers and glass powder.
混合液をウェットゲル化するウェットゲル化工程。Wet gelling process that turns the mixed liquid into a wet gel.
ウェットゲルを昇温し、ドライゲル複合体を得るドライ
ゲル化工程、およびドライゲル複合体を不活性雰囲気中
で焼結する焼結工程を施すものである。A dry gelling process in which the wet gel is heated to obtain a dry gel composite, and a sintering process in which the dry gel composite is sintered in an inert atmosphere are performed.
この発明において、低粘度のゾル状態にあるシリカゾル
液中に強化素材のウィスカーとマトリックスの一部とな
るガラス粉末を同時に添加して。In this invention, whiskers, which are reinforcing materials, and glass powder, which will become part of the matrix, are simultaneously added to a silica sol liquid in a low viscosity sol state.
混合攪拌しウィスカーを分散させるために、ウィスカー
の損傷を最小限にできる。ま念ガラス粉末を添加したた
めにウィスカーとガラス粉末を含むシリカゾル液をウェ
ットグルからドライグルへ乾燥させる過程での収縮率を
小さくすることが可能となり、また、添加したガラス粉
末は、乾燥収縮時に、添加されたウィスカーとともにド
ライゲル自体を強化する作用をも持つのでクランクを含
まないドライゲル複合体を得ることができ、大きな複合
体も亀裂が生じに（い。さらに、このような効果は、ド
ライゲル複合体を最終焼結する過程まで持続する効果が
るシ、優れた機械的特性を持つウィスカー強化ガラスの
大きなパルグ状成形体をも容易に製造することができる
。Mixing and stirring to disperse the whiskers can minimize whisker damage. By adding the glass powder, it is possible to reduce the shrinkage rate during the process of drying the silica sol solution containing whiskers and glass powder from wet glue to dry glue. Together with the added whiskers, they also have the effect of strengthening the dry gel itself, making it possible to obtain a dry gel composite that does not contain cranks, and also to prevent cracks from forming in large composites. It has an effect that lasts until the final sintering process, and it is also possible to easily produce large pulg-shaped molded bodies of whisker-reinforced glass with excellent mechanical properties.
第１図はこの発明の実施例のウィスカー強化ガラスの製
造方法の工程を示す工程図である。FIG. 1 is a process diagram showing the steps of a method for manufacturing whisker-strengthened glass according to an embodiment of the present invention.
この発明に係わるシリカゾル液は、シリカ成分を２０重
量％以上含むものを用いるのが望ましい。The silica sol liquid according to the present invention preferably contains 20% by weight or more of a silica component.
このシリカゾルは、オルトケイ酸（Ｈ２Ｓ１０ａ）を水
やエタノール、イソプロパツール、エチルセロソルブお
よびこれらのアルコール類の混合物で加水分解し、溶液
中に８１０２ をコロイド状としたものを含むものが
用いられる。また、前記オルトケイ酸を部分加水分解し
て水溶液中のシリカ成分を４０重量％とじたものを上記
の方法で加水分解し水溶液中に８１０２ のコロイド
粒子を含むようにしたものを用いてもよい。さらに、コ
ロイダルシリカを水溶液中に含む形で調整されたコロイ
ダルシリカ水溶液を用いても良い。このようなコロイダ
ルシリカを含む水溶液はたとえば米国デュポン社からＬ
ｕｃＬｏｘ■ という商品名で市販されているものが用
いられても良い。The silica sol used is one in which orthosilicic acid (H2S10a) is hydrolyzed with water, ethanol, isopropanol, ethyl cellosolve, or a mixture of these alcohols, and the solution contains 8102 in colloidal form. Alternatively, a product obtained by partially hydrolyzing the orthosilicic acid to remove 40% by weight of the silica component in the aqueous solution and hydrolyzing it by the above method so that the aqueous solution contains colloidal particles of 8102 may be used. Furthermore, a colloidal silica aqueous solution prepared in such a manner that the aqueous solution contains colloidal silica may be used. An aqueous solution containing such colloidal silica is available from DuPont in the United States, for example.
A product commercially available under the trade name ucLox■ may be used.
ウィスカーとガラス粉末を混合するためのコロイダルシ
リカ水溶液は、前記の加水分解されたコロイダルシリカ
を含むシリカゾル溶液やデュポン社などから販売されて
いるコロイダルシリカ水溶液をそのまま用いても良いが
、ウィスカーとガラス粉末を混合し、均一な分散を得る
ためや、ゲル化速度を調整するためには、前記コロイダ
ルシリカを含む水溶液にＨＣＩ 、 Ｈ２ＳＯ４などの
酸性水溶液やＮａＣＡＴ のような塩酸又はその水溶
液がさらに加えられＰＨ調整される。このときの酸、塩
の水溶液の濃度やコロイダルシリカを含む水溶液への添
加量は、製造時の温度やゲル化の時間を考慮して適当に
決定される。As the colloidal silica aqueous solution for mixing the whiskers and the glass powder, the silica sol solution containing the hydrolyzed colloidal silica mentioned above or the colloidal silica aqueous solution sold by DuPont and others may be used as is, but the whiskers and the glass powder In order to obtain a uniform dispersion or to adjust the gelation rate, an acidic aqueous solution such as HCI or H2SO4, hydrochloric acid such as NaCAT, or an aqueous solution thereof is further added to the aqueous solution containing colloidal silica. be adjusted. At this time, the concentration of the aqueous solution of acid and salt and the amount added to the aqueous solution containing colloidal silica are appropriately determined in consideration of the temperature during production and gelation time.
コロイダルシリカのゾル水溶液の粘度が０．０５〜２．
０ポアズ望ましくｄ、０．１〜１．０ポアズの範囲にな
った時点でウィスカーとガラス粉末がコロイダルシリカ
のゾル液中に添加され混合攪拌される。The viscosity of the aqueous sol solution of colloidal silica is 0.05 to 2.
When the poise is preferably in the range of 0.1 to 1.0 poise, whiskers and glass powder are added to the colloidal silica sol solution and mixed and stirred.
このとき、ライスカーとコロイダルシリカのゾル液との
ぬれ性を改善するために、ゾル液中にウィスカーとガラ
ス粉末を添加する前あるいは添加時に界面活性材として
アニオン系あるいはノニオン系の界面活性材が添加され
ても良い。また、界面活性材の添加によシリカゾル液が
発泡する場合には消泡剤を同時に用いても良い。なお、
ウィスカーとガラス粉末のコロイダルシリカのゾル液中
への添加は、ゾル粘度が０．０５〜２．０ポアズの範囲
であれば、ウィスカーとガラス粉末を別々に加えても良
（、この場合にはウィスカー、ガラス粉末のいずれか先
に添加されても良い。また、ウィスカーとガラス粉末が
同時に加えられても良い。At this time, in order to improve the wettability between rice car and colloidal silica sol, an anionic or nonionic surfactant is added as a surfactant before or during the addition of whiskers and glass powder to the sol. It's okay to be. Further, when the silica sol liquid foams due to the addition of a surfactant, an antifoaming agent may be used at the same time. In addition,
When adding whiskers and glass powder to the colloidal silica sol solution, whiskers and glass powder may be added separately as long as the sol viscosity is in the range of 0.05 to 2.0 poise (in this case, Either the whiskers or the glass powder may be added first.The whiskers and the glass powder may also be added at the same time.
コロイダルシリカのゾル液の粘度が０．０５ポアズ以下
の場合にはウィスカーとガラス粉末を添加後にゾルをゲ
ル化するまでに長時間を要し、ウィスカーとガラス粉末
がゾル液中で、沈殿を生じ易（なる。さらに沈殿を防止
するために攪拌し続けるとウィスカーに損傷を生じやす
い欠点がある。またゾルの粘度が２．０ポアズ以上とな
るとウィスカーとガラス粉末の混合攪拌時にウィスカー
に大きな力が働き、ウィスカーの破損が生じやす（なる
。If the viscosity of the colloidal silica sol is 0.05 poise or less, it will take a long time to gel the sol after whiskers and glass powder are added, and the whiskers and glass powder will precipitate in the sol. Furthermore, if you continue to stir to prevent precipitation, the whiskers are likely to be damaged.Also, if the viscosity of the sol is 2.0 poise or more, a large force will be applied to the whiskers when mixing and stirring the whiskers and glass powder. This may cause the whiskers to break.
したがって、ウィスカーとガラス粉末をゾルに混合する
時点でのゾル水溶液の粘度ｉｏ、０５〜２．０ポアズ特
に０．１〜１，０ポアズの範囲の低粘度が好ましい。Therefore, the viscosity of the sol aqueous solution at the time of mixing the whiskers and the glass powder into the sol is preferably a low viscosity io of 0.5 to 2.0 poise, particularly a range of 0.1 to 1.0 poise.
この発明に係わる強化用に用いられるウィスカーｉ Ｓ
ｉＣ、５ｉ３Ｎ４ 、 Ａｚ２ｏ３ 、炭素などの無機
質系のものならばいずれのものが用いられても良（。Whisker iS used for reinforcement related to this invention
Any inorganic material such as iC, 5i3N4, Az2o3, carbon, etc. may be used (.
これらの無機質系のウィスカーを２種類以上組み合せて
も良い。ウィスカーのガラスマトリックス中での総体積
率は、最終焼結後のウィスカー強化ガラス中の体積％に
して５〜４５％の間に設定されるのが望ましい。ウィス
カーの総体積率が５％よりも小さいとウィスカー添加に
よる複合効果が得難い。またウィスカーの総体積率が４
５％を越エルトガラスマトリックス中でウィスカー同志
の接触が生じゃすくなシ最終的な複合体中でガラスマト
リックスとの十分な複合化が困難で微少な空孔を生じた
りする。また、ウィスカーの総体積が大きな場合にはゾ
ル液中にウィスカーとガラス粉末を添加したものの混合
攪拌に大きな力が必要でウィスカーが均一に分散しに（
（なるとともにウィスカーの損傷も大きくなる。したが
ってウィスカーのガラスマトリックス中での総体積率は
５％から４５％の間に設定するのが望ましい。Two or more types of these inorganic whiskers may be combined. The total volume fraction of the whiskers in the glass matrix is desirably set between 5 and 45% by volume in the whisker-strengthened glass after final sintering. If the total volume fraction of whiskers is less than 5%, it is difficult to obtain a composite effect by adding whiskers. Also, the total volume ratio of whiskers is 4
If the whiskers exceed 5% in the glass matrix, contact between the whiskers will not occur, and it will be difficult to sufficiently combine the whiskers with the glass matrix in the final composite, resulting in the formation of minute pores. In addition, when the total volume of whiskers is large, a large amount of force is required to mix and stir the whiskers and glass powder added to the sol solution, making it difficult for the whiskers to be uniformly dispersed (
(The more the damage to the whiskers increases, the more the damage to the whiskers increases. Therefore, it is desirable that the total volume fraction of the whiskers in the glass matrix is set between 5% and 45%.
この発明に係わるガラス粉末としては、平均粒度が３μ
ｍ〜２００μｍのものが用いられるのが望ましい。ガラ
ス粉末の平均粒度が２００μｍ以上の場合には、ウィス
カーに比較して寸法が大きいためにウィスカーとガラス
粉末を混合する場合に均一な分散を得ることが困難であ
り、ウィスカーに対して損傷を与えやす（なる。ガラス
粒子の平均粒度が３μｍ以下では、ウィスカーとゾル液
中で混合した場合に均一な分散が得られるが、単位体積
あたシのゾルの体積に換算した場合、ガラス粒子の総表
面積が著しく大きくなシ、この発明で対象にしているよ
うなゾル会ゲルの反応過程に太き（影響し、ウィスカー
とガラス粉末を混合するのに適したゾル液の状態を安定
に保つことが難しくなり、工業化も困難でるる。The glass powder according to this invention has an average particle size of 3 μm.
It is desirable to use a material with a diameter of m to 200 μm. When the average particle size of the glass powder is 200 μm or more, it is difficult to obtain uniform dispersion when mixing the whiskers and the glass powder because the size is large compared to the whiskers, and it may cause damage to the whiskers. When the average particle size of glass particles is 3 μm or less, uniform dispersion can be obtained when whiskers and sol are mixed together, but when converted to the volume of sol per unit volume, the total glass particle size is The extremely large surface area has a large effect on the reaction process of the sol-gel, which is the target of this invention, and makes it difficult to maintain a stable state of the sol solution suitable for mixing whiskers and glass powder. It will become more difficult and difficult to industrialize.
又、ガラス粉末としては、非晶質および結晶質のものが
用いられて良（、また、その化学組成は望ましくはＳｉ
Ｏ２ を４５重量％以上含むものが用いられる。たと
えば粉末ガラスとしては１石英ガラス、はうけい酸ガラ
ス、アルミノ珪酸ガラスやβ−ユークリプタイトやβ−
スポジュメンなどのりチウムアルミノ珪酸ガラス、コー
ジライト（マグネシウムアルミノ珪酸ガラス）粉末が用
いられる。In addition, as the glass powder, amorphous and crystalline ones may be used (and the chemical composition is preferably Si).
A material containing 45% by weight or more of O2 is used. For example, powdered glasses include quartz glass, silicate glass, aluminosilicate glass, β-eucryptite, β-
Glue aluminosilicate glass such as spodumene, and cordierite (magnesium aluminosilicate glass) powder are used.
ガラス粉末のコロイダルシリカのゾル液に添加される量
は、最終的に得られるウィスカー強化ガラス中のガラス
マトリックスに占める添加ガラス粉末の体積率で規定さ
れる。したがってウィスカーの体積率によらず前記添加
ガラス粉末体積率は５％から７０％が望ましい。ガラス
粉末の体積率が５％以下では、ウェットケール複合体を
乾燥しドライゲルを得る段階でガラス粉末添加の効果が
明白でｒｒｙｘ＜、ウィスカーの体積率によらずドライ
ゲル複合体中にクランクを生じることが多（なる。ガラ
ス粉末の体積率が７０％を越えるとウィスカーとガラス
粉末を含むコロイダルシリカのゾルを攪拌することが難
しく、ウィスカーの均一な分散が得難（、ウィスカーの
損傷の防止が困難となる。The amount of glass powder added to the colloidal silica sol solution is defined by the volume percentage of the added glass powder in the glass matrix in the whisker-reinforced glass finally obtained. Therefore, the volume fraction of the added glass powder is preferably 5% to 70%, regardless of the whisker volume fraction. When the volume ratio of glass powder is 5% or less, the effect of adding glass powder is obvious at the stage of drying the wet kale composite to obtain a dry gel. When the volume percentage of glass powder exceeds 70%, it is difficult to stir the colloidal silica sol containing whiskers and glass powder, and it is difficult to obtain uniform dispersion of whiskers (and it is difficult to prevent whisker damage). becomes.
上記の方法にて得られたこの発明に係わるドライゲル化
した複合体は１例えば通常のガラス粉末が焼結される温
度又はそれ以下の温度で焼結し。The dry gelled composite according to the present invention obtained by the above method is sintered at a temperature at or below the temperature at which, for example, ordinary glass powder is sintered.
緻密化される。焼結に際したとえばホントプレス。It is elaborated. For example, when sintering, use a real press.
熱間静水圧加圧装置にて加圧し、高温高圧？で焼結して
もよ（この場合さらに緻密化が促進される。Pressurized with a hot isostatic pressurization device, high temperature and high pressure? (In this case, densification is further promoted.)
以下、この発明を実施例により説明する。This invention will be explained below with reference to Examples.
強化用材料としてタテホ化学（株ン製の５ｉｓＮ４ウイ
スカーおよびＳｉＣウィスカーを用いた。径ｕｏ、ｏｓ
〜５μｍ、アスペクト比は５〜１００である。ゾルとし
てはＳｉＯ２を４０重量％含むコロイダルシリカ（Ｄｕ
ｐｏｎ’ｔ ＬｕａｏＦ Ｉ’ｌ Ｓ −４Ｃ１）を用
いた。このコロイダルシリカは１５６℃において１．２
９ｇ／ｃ！Ｉの密度のものでるる。ガラス粉末としては
９６重量％の珪酸ガラス（コーニング社。5isN4 whiskers and SiC whiskers manufactured by Tateho Chemical Co., Ltd. were used as reinforcing materials.
~5 μm, aspect ratio is 5-100. The sol is colloidal silica (Du
pon't LuaoFI'lS-4C1) was used. This colloidal silica has a temperature of 1.2 at 156°C.
9g/c! It has a density of I. The glass powder is 96% by weight silicate glass (Corning Company).
コード番号７９１３）を３２５メツシユ以下の粒度とし
たものを用いた。Code number 7913) with a particle size of 325 mesh or less was used.
コロイダルシリカ（Ｌｕｄｏｘ” 、 ＨＳ −４０）
にｏ、ｏ １Ｎ。Colloidal silica (Ludox”, HS-40)
ni o, o 1N.
ＨＣｌ水溶液を２０°Ｃにて加え、コロイダルシリカに
ＨＯＡ’を加えた水溶液の粘度が０．２ポアズ以上とな
った時点で、ウィスカーとガラス粉末とを混合水溶液中
に入れ十分に攪拌した。このとき、最終的に得られるウ
ィスカー強化ガラス複合態勢のガラスマトリックス中で
ウィスカーの体積率が０．０５． ０．１． ０．１５
． ０．２． ０．２５． ０．３となるように添加す
るウィスカーの重量％を調整するとともに、マトリック
スのガラス総体積に占める添加ガラス粉末の体積％がゼ
ロ（０）から０．７となるように添加するガラス粉末の
重量を調整した。An aqueous HCl solution was added at 20°C, and when the viscosity of the aqueous solution of colloidal silica and HOA' reached 0.2 poise or more, whiskers and glass powder were added to the mixed aqueous solution and stirred thoroughly. At this time, the volume fraction of whiskers in the glass matrix of the whisker-reinforced glass composite structure finally obtained is 0.05. 0.1. 0.15
．． 0.2. 0.25. Adjust the weight percent of the whisker to be added so that it is 0.3, and the weight of the glass powder to be added so that the volume percent of the added glass powder to the total glass volume of the matrix is from zero (0) to 0.7. adjusted.
ウィスカーとガラス粉末を含むコロイダルシリ力混合水
溶液をゲル化させてウィスカーを含むウェットゲルを得
るために、上記混合溶液を５０℃のウォーターバス中で
ウィスカーの損傷が生じないように細心の注意を払いな
がら静かに攪拌し。In order to obtain a wet gel containing whiskers by gelling a colloidal silica mixed aqueous solution containing whiskers and glass powder, the above mixed solution was placed in a water bath at 50°C with great care so as not to damage the whiskers. While stirring gently.
混合溶液の粘度が１．０ポアズとなるまでコロイダルシ
リカ溶液のゲル化反応゛を進行させた。The gelation reaction of the colloidal silica solution was allowed to proceed until the viscosity of the mixed solution reached 1.0 poise.
その後、混合溶液の攪拌を中止し、混合溶液を１．２５
℃／時間の昇温速度で５０°Ｃから１８０°Ｃまで徐々
に昇温し、ウィスカーを含むドライゲル複合体を得た。After that, stirring of the mixed solution was stopped, and the mixed solution was
The temperature was gradually raised from 50°C to 180°C at a temperature increase rate of °C/hour to obtain a dry gel composite containing whiskers.
徐々に昇温したのはクランクの発生を抑制する目的であ
り、１０〜ｂ
とが好ましい。The temperature was gradually raised to suppress the occurrence of cranking, and a temperature of 10 to b is preferable.
ついて、ウィスカーを含むドライゲル複合体をＮ２ 雰
囲気中で１５５０°Ｃの温度にて１時間焼結し、最終的
なウィスカー強化ガラスを得た。また。The dry gel composite containing the whiskers was then sintered at a temperature of 1550° C. for 1 hour in an N2 atmosphere to obtain the final whisker-reinforced glass. Also.
ドライゲル複合体の一部は、１５５０℃の湿度にて１に
９／−の加圧力下でホットプレスして最終的なウィスカ
ー強化ガラスを得た。A portion of the dry gel composite was hot pressed under a pressure of 1 to 9/- at a humidity of 1550°C to obtain the final whisker-strengthened glass.
第２図はこの発明の実施例に係わる焼結前のウィスカー
を含むガラスのドライグル複合体の部分的外観図である
。第２図は、 Ｓｉ３Ｎ４ウィスカーを複合体中に体
積％にして２０％含み、全ガラスマトリックス体積に対
するガラス粉末の添加体積％が２０％の場合である。FIG. 2 is a partial external view of a glass dreigle composite including whiskers before sintering according to an embodiment of the present invention. FIG. 2 shows a case where the composite contains 20% by volume of Si3N4 whiskers and the added volume% of glass powder is 20% with respect to the total glass matrix volume.
ウィスカーを含むドライゲル中にはクランクの発生もな
い複合体が得られているっ
第３図は、第２図に示したＳｉＣウィスカーを含むドラ
イゲル複合体をＮ２ 雰囲気中、ｔｓｓ。A composite was obtained in which no cranking occurred in the dry gel containing whiskers. Figure 3 shows the dry gel composite containing SiC whiskers shown in Figure 2 in a N2 atmosphere using TSS.
℃の温度で１時間焼結したものから曲げ試験片を切り出
し１曲げ破壊した後の破面の組織状態を示す走査型電子
顕微鏡写真である。It is a scanning electron micrograph showing the structure of the fracture surface after a bending test piece was cut out from a piece sintered at a temperature of 1 hour at a temperature of 0.degree. C. and fractured by one bend.
ＳＩＣウィスカーがガラスマトリックス中で三次元的に
ランダムにかつほぼ均一な間隔で分散している。The SIC whiskers are randomly and approximately uniformly distributed in three dimensions within the glass matrix.
第４図は第２図に示した８１５Ｎ４ウイスカーを含むド
ライゲル複合体をＮ２ 雰囲気中、ｔｓｓｏ℃で１ｋ
ｇ／ｌ１１１の加圧力下でホットプレスしたものの断面
の組織状態を示す光学顕微鏡写真であるっホントプレス
の加圧方向に垂直な面ではＳｉ３Ｎ４ウィスカーが二次
元ランダムに配列している。Figure 4 shows the dry gel composite containing the 815N4 whiskers shown in Figure 2 at 1k at tsso℃ in N2 atmosphere.
This is an optical micrograph showing the microstructure of a cross section of a product hot-pressed under a pressure of 111 g/l. Si3N4 whiskers are two-dimensionally randomly arranged in a plane perpendicular to the pressing direction of the hot press.
このように、最終焼結をホットプレス法にて行った５１
ＳＮ４ウイス力−強化ガラスについて代表的な機械的特
性である強度と破壊靭性を調べた。第５図および第６図
は、これらの測定結果を示したものでるる。なお、第５
図および第６図は各々この発明の実施例によるウィスカ
ー強化ガラスのウィスカ一体積率による曲げ強度変化を
示す特性図およびウィスカ一体積率による臨界応力拡大
係数変化を示す特性図であるう各図中、 （ＡＩ）〜
（Ａ６）。In this way, the final sintering was performed using the hot press method51
Typical mechanical properties of SN4 Wiss-strengthened glass, such as strength and fracture toughness, were investigated. Figures 5 and 6 show the results of these measurements. In addition, the fifth
6 and 6 are a characteristic diagram showing the bending strength change depending on the whisker volume ratio and a characteristic diagram showing the change in the critical stress intensity factor depending on the whisker volume ratio of the whisker-strengthened glass according to the embodiment of the present invention, respectively. , (AI)~
(A6).
（Ｂす〜（Ｂ６）はこの発明の実施例によるウィスカー
強化ガラスの各１５本の試験片の上記特性の測定結果の
平均値を示したものである。又、 （Ｘ）、 （Ｙ）は
比較のために、この発明におけるウィスカーを含まない
他はこの発明の実施例と同様にして得たガラスマトリッ
クス単体の上記と同様の測定結果を示す、これらの図か
ら明らかなように、この発明の実施例によるウィスカー
強化ガラスにウィスカー未強化のガラスに比較してはる
かに優れた機械的性質を示している。(B~(B6) shows the average value of the measurement results of the above characteristics of each of 15 test pieces of whisker-reinforced glass according to the example of this invention. Also, (X) and (Y) For comparison, the same measurement results as above are shown for a single glass matrix obtained in the same manner as in the examples of the present invention except that the whiskers of the present invention are not included. The whisker-strengthened glass according to the example shows far superior mechanical properties compared to glass without whisker reinforcement.
以上、実施例をもって説明したがこの発明の実施例によ
れば、Ｗに、最終的な複合材料中でのウィスカーが総体
積％が５％から４５％の範囲にあシ、また。最終的な複
合体側斜中のガラスマトリックス総体積に対する添加ガ
ラス粉末の体積率が５％から７０％の範囲であれば、良
好な状態のウィスカーを含む亀裂の生じに（い、バルク
のドライゲル複合体が得られ易（、またこのようにして
得られたウィスカーを含むドライゲル複合体は。As explained above with reference to Examples, according to the Examples of the present invention, the total volume % of whiskers in the final composite material is in the range of 5% to 45% in W. If the volume fraction of the added glass powder to the total volume of the glass matrix in the final composite side is in the range of 5% to 70%, the formation of cracks containing whiskers in good condition (in the bulk dry gel composite) (and the whisker-containing dry gel composite thus obtained.
焼結後にも劉れを生じることもないことが確かめらねた
。It was not confirmed that no cracking would occur even after sintering.
以上説明したとおり、この発明はシリカゾル液の粘度を
０．０５〜２．０ポアズにする粘度調整工程。As explained above, the present invention is a viscosity adjustment process in which the viscosity of a silica sol liquid is adjusted to 0.05 to 2.0 poise.
粘度調整されたシリカゾル液にウィスカーおよびガラス
粉末を混合する混合工程、混合液をウェットゲル化する
ウェットゲル化工程、ウェットゲルを昇温し、ドライゲ
ル複合体を得るドライゲル化工程、およびドライゲル複
合体を不活性雰囲気中で焼結する焼結工程を施すことに
より、ウイスカ−の損傷を最小限とし９強化効果が高く
、大きなバルク状の成形物も容易に得られるウィスカー
強化ガラスの製造方法を得ることができる。A mixing step of mixing whiskers and glass powder into a viscosity-adjusted silica sol solution, a wet gelling step of turning the mixed solution into a wet gel, a dry gelling step of raising the temperature of the wet gel to obtain a dry gel composite, and a dry gelling step of forming a dry gel composite. To obtain a method for manufacturing whisker-strengthened glass that minimizes damage to whiskers, has a high strengthening effect, and can easily produce large bulk molded products by performing a sintering process in which the glass is sintered in an inert atmosphere. Can be done.
Claims (9)
する粘度調整工程、粘度調整されたシリカゾル液に、ウ
ィスカーおよびガラス粉末を混合する混合工程、混合液
をウェットゲル化するウェットゲル化工程、ウェットゲ
ルを昇温し、ドライゲル複合体を得るドライゲル化工程
、およびドライゲル複合体を不活性雰囲気中で焼結する
焼結工程を施すウィスカー強化ガラスの製造方法。(1) A viscosity adjustment step to adjust the viscosity of the silica sol solution to 0.05 to 2.0 poise, a mixing step of mixing whiskers and glass powder into the viscosity-adjusted silica sol solution, and a wet gelling step of turning the mixed solution into a wet gel. A method for producing whisker-strengthened glass, which comprises: a dry gelling step of heating a wet gel to obtain a dry gel composite; and a sintering step of sintering the dry gel composite in an inert atmosphere.
特許請求の範囲第１項記載のウィスカー強化ガラスの製
造方法。(2) The method for producing whisker-strengthened glass according to claim 1, wherein the silica sol contains 20% by weight or more of a silica component.
積率が５〜４５％の範囲である特許請求の範囲第１項又
は第２項記載のウィスカー強化ガラスの製造方法。(3) The method for producing whisker-strengthened glass according to claim 1 or 2, wherein the total volume ratio of whiskers to the whisker-strengthened glass is in the range of 5 to 45%.
Ｏ＿３および炭素の内の少なくとも１種である特許請求
の範囲第１項ないし第３項の何れかに記載のウィスカー
強化ガラスの製造方法。(4) Whiskers are SiC, Si_3N_4, Al_2
The method for producing whisker tempered glass according to any one of claims 1 to 3, wherein the whisker tempered glass is at least one of O_3 and carbon.
ある特許請求の範囲第１項ないし第４項の何れかに記載
の強化ガラスの製造方法。(5) The method for producing tempered glass according to any one of claims 1 to 4, wherein the glass powder has an average particle size in the range of 3 to 200 μm.
におけるガラスマトリックスに対する割合として、５％
から７０％である特許請求の範囲第１項ないし第５項の
何れかに記載のウィスカー強化ガラスの製造方法。(6) The volume fraction of glass powder is 5% as a proportion to the glass matrix in the whisker-strengthened glass.
70% of the whisker tempered glass according to any one of claims 1 to 5.
む組成のガラスを用いる特許請求の範囲第１項ないし第
６項の何れかに記載のウィスカー強化ガラスの製造方法
。(7) A method for producing whisker-strengthened glass according to any one of claims 1 to 6, using glass having a composition containing 45% by weight or more of SiO_2 as glass powder.
合で徐々に昇温しながらドライゲル化させる特許請求の
範囲第１項ないし第７項の何れかに記載のウィスカー強
化ガラスの製造方法。(8) The method for producing whisker-strengthened glass according to any one of claims 1 to 7, in which the mixed silica sol liquid is dry-gelled while gradually heating the mixed silica sol solution at a rate of 10 to 100°C/day.
特許請求の範囲第１項ないし第８項の何れかに記載のウ
ィスカー強化ガラスの製造方法。(9) A method for producing whisker-strengthened glass according to any one of claims 1 to 8, which comprises sintering the dry gelled composite at high temperature and high pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11375887A JPS63282131A (en) | 1987-05-11 | 1987-05-11 | Production of whisker-reinforced glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11375887A JPS63282131A (en) | 1987-05-11 | 1987-05-11 | Production of whisker-reinforced glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63282131A true JPS63282131A (en) | 1988-11-18 |
Family
ID=14620394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11375887A Pending JPS63282131A (en) | 1987-05-11 | 1987-05-11 | Production of whisker-reinforced glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63282131A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391213A (en) * | 1991-12-03 | 1995-02-21 | Deutsche Forschungsanstalt Fur Luft- Und Raumfahrt E.V. | Method for manufacturing fibre-reinforced structures with a glass matrix |
| US5512351A (en) * | 1993-12-28 | 1996-04-30 | Nikkiso Company Limited | Prepreg, process for preparation of prepreg, and products derived therefrom |
| CN105621896A (en) * | 2015-12-30 | 2016-06-01 | 常州聚和新材料股份有限公司 | Glass powder for back electrode slurry of solar battery and preparation method of glass powder |
-
1987
- 1987-05-11 JP JP11375887A patent/JPS63282131A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391213A (en) * | 1991-12-03 | 1995-02-21 | Deutsche Forschungsanstalt Fur Luft- Und Raumfahrt E.V. | Method for manufacturing fibre-reinforced structures with a glass matrix |
| US5512351A (en) * | 1993-12-28 | 1996-04-30 | Nikkiso Company Limited | Prepreg, process for preparation of prepreg, and products derived therefrom |
| CN105621896A (en) * | 2015-12-30 | 2016-06-01 | 常州聚和新材料股份有限公司 | Glass powder for back electrode slurry of solar battery and preparation method of glass powder |
| CN105621896B (en) * | 2015-12-30 | 2017-10-31 | 常州聚和新材料股份有限公司 | Glass dust for rear surface of solar cell electrode slurry and preparation method thereof |
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