JPS5832037A - Preparation of glass containing additive - Google Patents
Preparation of glass containing additiveInfo
- Publication number
- JPS5832037A JPS5832037A JP12597681A JP12597681A JPS5832037A JP S5832037 A JPS5832037 A JP S5832037A JP 12597681 A JP12597681 A JP 12597681A JP 12597681 A JP12597681 A JP 12597681A JP S5832037 A JPS5832037 A JP S5832037A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fine particles
- particles
- sintering
- nitrogen
- 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.)
- Granted
Links
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は高密度で透光性の秀れた添加物含有ガラスの製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing additive-containing glass with high density and excellent light transmission.
一般にガラスの物性２例えば屈折率や透光性などの光学
特性あるいは熱膨張係数などを変えるためガラス成分に
添加物を配合することが行なわれる。ところが微粒子ガ
ラスを焼結することにより熔融ガラス体を造る場合添加
物の種類によっては該添加物をガラス成分中に含有させ
た為に軟化点が上昇し、このためガラス微粒子の焼結が
困難になり熔融した透明ガラス体を得られない場合があ
る。例えば窒素含有石英ガラスについては従前次のよう
なＵＳＰ ４２０３７４４にみられるような製造方法が
知られている。この方法は、先づ第１図に示すように８
１０２の微粒子状の石英ガラス１又は多孔質ガラスを造
り、次にこれをＮＨ，含有雰囲気中で処理した後これを
焼結して窒素をドープした石英ガラス３を得る方法であ
る。ところがこの方法では窒素含有量の多い透光性のあ
るガラス体を得ることができなかった。Generally, additives are added to glass components to change the physical properties of glass, such as optical properties such as refractive index and translucency, or coefficient of thermal expansion. However, when producing a molten glass body by sintering fine glass particles, depending on the type of additive, the softening point may increase due to the inclusion of the additive in the glass component, making it difficult to sinter the glass fine particles. Therefore, it may not be possible to obtain a molten transparent glass body. For example, for nitrogen-containing quartz glass, the following manufacturing method is known, as disclosed in US Pat. No. 4,203,744. In this method, first, as shown in Figure 1, 8
In this method, 102 particles of quartz glass 1 or porous glass are produced, then treated in an atmosphere containing NH, and then sintered to obtain nitrogen-doped silica glass 3. However, with this method, it was not possible to obtain a transparent glass body with a high nitrogen content.
本発明は上記欠点を解消し、比較的窒素含有量の多い、
かつ透光性のあるガラスを提供するものであって、その
構成は、内部よりも低粘性であるガラス微粒子集合体を
形成した後に、該微粒子集合体を焼結することを特徴と
する特
以下に本発明を実施例と共に詳細に説明する。The present invention solves the above-mentioned drawbacks, and the present invention solves the above-mentioned drawbacks.
and a translucent glass, the structure of which is characterized in that after forming a glass particle aggregate having a lower viscosity than the inside, the particle aggregate is sintered. The present invention will be explained in detail together with examples.
本発明はガラス微粒子の内部と外表面層との粘性を変え
、ガラス微粒子内部の粘度を高くし、外表面層の粘度を
低くすることを基本とする。The present invention is based on changing the viscosity between the inside and the outer surface layer of the glass fine particles, increasing the viscosity inside the glass fine particles and lowering the viscosity of the outer surface layer.
添加物を含有させた時に、その粘性が高くなり、このた
め、粘性流動により支配される焼結が進まなくなる場合
、本発明では、添加物を含有した超微粒子を合成し、こ
の微粒子表面層の添加物量を減少させることにより、又
は添加物を含有した超微粒子の表面層上に、添加物の少
ない層を合成することにより微粒子表面を低粘性状態と
し、この物性により焼結を進める。出発材料のガラス微
粒子としては、透過させる光の波長よりも小さ々ガラス
微粒子を用いる。例えば可視光が対象であれば、約０．
５μｍ径以下が望ましい。When additives are added, their viscosity becomes high, which prevents sintering controlled by viscous flow from progressing. In the present invention, ultrafine particles containing additives are synthesized and the surface layer of these particles is By reducing the amount of additives, or by synthesizing a layer with less additives on the surface layer of ultrafine particles containing additives, the surface of the microparticles is brought into a low viscosity state, and sintering proceeds based on this physical property. As the starting material glass particles, glass particles smaller than the wavelength of the light to be transmitted are used. For example, if visible light is the target, approximately 0.
A diameter of 5 μm or less is desirable.
本発明により窒素含有石英ガラスを製造する場合、第２
図に示すように先づ窒化硅素Ｓ ｌ ２Ｎ、の微粒子１
０を造り、該微粒子１０の外表面に二酸化硅素ＳｉＯ□
の外表面層１１を形成し、これを焼結して窒素含有石英
ガラス１２を製造する。When manufacturing nitrogen-containing quartz glass according to the present invention, the second
As shown in the figure, first, silicon nitride S l 2N fine particles 1
silicon dioxide SiO□ on the outer surface of the fine particles 10.
A nitrogen-containing quartz glass 12 is manufactured by forming an outer surface layer 11 and sintering this.
ありかつ分子の小さなガス例えばＨｅガス等を用いると
、これらのガスはガラス中に容易に拡散し、又、ガラス
中に溶解し易いため気泡として残らず、従って残留気泡
の一層少ないものが得られる。When a gas with a small molecular weight, such as He gas, is used, these gases easily diffuse into the glass and are easily dissolved in the glass, so they do not remain as bubbles, and therefore, a product with fewer residual bubbles can be obtained. .
次に内部が高粘性であり、外表面層が低粘性の構成を有
する微粒子を造るには次の２種類の方法がある。第１の
方法は高粘性を有する微粒子を出発材料とし、この微粒
子表面層の組成ないし成分を反応処理して低粘性のもの
に変化させる方法である。例えば出発材料として気相合
成法などで得られる窒化硅素微粒子Ｓｉ、Ｈ，を用い、
この粒子表面を酸化処理して二酸化硅素５Ｉ０２の表面
層を形成する。この場合、急激な酸化処理は好ましくな
い。粒子が小さい場合窒化物の微粒子は酸化され易く不
安定なため急激に酸化すると局所的に粒子全体が酸化物
のシリカＳＩＯ□となり残留窒素が急激に減少するから
である。酸化処理の温度範囲としては７００℃〜１２０
ｃｌが好ましい。この範囲を超えると酸化した微粒子が
焼結し始め均一な酸化を妨げる。上記微粒子を造る第２
の方法は高粘性を有する微粒子表面上に低粘性の膜をコ
ーティングする方法である。Next, there are two methods for producing fine particles having a high viscosity inside and a low viscosity outer surface layer. The first method is to use fine particles having high viscosity as a starting material, and to change the composition or components of the surface layer of the fine particles to a low-viscosity one by subjecting them to a reaction treatment. For example, using silicon nitride fine particles Si, H, obtained by vapor phase synthesis method etc. as a starting material,
The surface of this particle is oxidized to form a surface layer of silicon dioxide 5I02. In this case, rapid oxidation treatment is not preferred. This is because if the particles are small, the nitride fine particles are easily oxidized and unstable, so if they are rapidly oxidized, the entire particle locally becomes an oxide, silica SIO□, and the residual nitrogen is rapidly reduced. The temperature range for oxidation treatment is 700°C to 120°C.
cl is preferred. When this range is exceeded, oxidized fine particles begin to sinter and prevent uniform oxidation. 2nd to make the above fine particles
This method is a method in which a low-viscosity film is coated on the surface of fine particles with high viscosity.
即ち、粘性の高い物質で核を形成し、この核の表面に低
粘性の物質を成長させるように気相反応系の原料１反応
条件を構成する。例えば５ｉＯ２−８２０、系ガラスを
得る場合、原料として５ｔｃｚ、。That is, the reaction conditions for the raw material 1 of the gas phase reaction system are configured so that a nucleus is formed from a highly viscous substance and a low viscosity substance is grown on the surface of this nucleus. For example, when obtaining 5iO2-820 glass, 5tcz is used as the raw material.
ＢＢｒ３ 、０２ を用い、まず最初に約１２００℃以
上の反応温度下で５ＩＣｔ、 、 ０２ を供給し５
ＩＣ４，→５ＩＯ２の均一気相反応を進めてガラス微粒
子の核を生成させ、引き続きＢ Ｂ ｒ−、を供給し、
ＢＢｒ、−＋Ｂ２０．の反応を進めて上記８１０２の表
面に３２０．の膜を形成する。Using BBr3, 02, 5ICt, , 02 was first supplied at a reaction temperature of about 1200°C or higher, and 5
Proceed with the homogeneous gas phase reaction of IC4,→5IO2 to generate nuclei of glass particles, and then supply B B r-,
BBr, -+B20. The reaction proceeds to form 320. on the surface of the above 8102. Forms a film of
次に微粒子を集合して焼結するには次のような方法によ
ればよい。第１の方法は、高粘性の微粒子１０を出発拐
料とし、この微粒子の表面に前述したような表面処理反
応又は低粘性膜のコーティングにより低粘性の表面層１
１を形成し、その後この表面層を有する微粒子を集合さ
せた後に焼結する（第３図（−）参照）。第２の方法は
、第１の方法と同様に表面層を有する微粒子を形成した
後、熱間静圧成形などにより微粒子集合体を成形すると
同時に焼結する（第３図（ｂ） か照）。第３の方法は
予め静圧成形などにより微粒子集合体を形成した後、前
述したような表面処理反応又は低粘性膜のコーティング
により個々の粒子表面に低粘性の表面層を形成し、これ
を焼結する（第３図（ｃ）参照）。Next, the following method may be used to collect and sinter the fine particles. In the first method, high viscosity fine particles 10 are used as a starting material, and a low viscosity surface layer 1 is applied to the surface of the fine particles by a surface treatment reaction or coating with a low viscosity film as described above.
1 is formed, and then the fine particles having this surface layer are aggregated and then sintered (see FIG. 3 (-)). In the second method, like the first method, after forming fine particles with a surface layer, a fine particle aggregate is formed by hot isostatic pressing or the like and simultaneously sintered (see Fig. 3(b)). . The third method is to form a fine particle aggregate in advance by static pressure molding, etc., then form a low-viscosity surface layer on the surface of each particle by the above-mentioned surface treatment reaction or coating with a low-viscosity film, and then bake this. (See Figure 3(c)).
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
実施例１
出発材料として、５ｉＣｔｌｌとＮＨ，とを高周波プラ
ズマ火炎中の高温帯にて反応させた後急冷し、補集して
得た微粒千秋窒化硅素を用意し７た。この粒子はほぼ球
状で約０．５μｍ程度の粒径を有する。この粒子の粉末
をベレット状（１５個φＸ１５＋ｎｍ）に加圧成形し、
この成形体を焼結炉内にセットした。Example 1 As a starting material, fine particles of silicon nitride obtained by reacting 5iCtll and NH in a high-temperature zone in a high-frequency plasma flame, followed by rapid cooling and collection were prepared. The particles are approximately spherical and have a particle size of about 0.5 μm. This particle powder was pressure-molded into a pellet shape (15 pieces φX15+nm),
This compact was placed in a sintering furnace.
炉内温度を５００℃に保ち、Ｈｅ ガス１００ ｃ ｃ
／ｆｊ流した状態で、約１０時間保持した。この後、炉
内温度を９００℃に上昇させ、０２を５０ ｃｃ／分加
え、２時間保持した。引き続き０２ を停止し、Ｈｅ
を流したまま炉温を１６００℃に上昇させ、この状態で
３０分保持した後、約２時間かけて、試料を室温程度に
下げた。得られた試料は殆んど透明であり、窒素の含有
量が約５重量パーセントの窒素含有シリカガラスが得ら
れた。The temperature inside the furnace was maintained at 500°C, and He gas was heated at 100 cc.
/fj was maintained for about 10 hours. Thereafter, the temperature inside the furnace was raised to 900°C, 50 cc/min of 02 was added, and the temperature was maintained for 2 hours. Continue to stop 02 and
The furnace temperature was raised to 1,600° C. while the gas was flowing, and this state was maintained for 30 minutes, and then the sample was cooled to about room temperature over about 2 hours. The resulting sample was almost transparent, yielding a nitrogen-containing silica glass with a nitrogen content of approximately 5 weight percent.
以上、主に窒素含有石英ガラスを例にして本発明を説明
したが、本発明は上記のものに限らず、硅素以外の窒化
物例えばＢＮ 、 ＴＩ 、Ｎ、 、 ＡｔＮなどにつ
いても適用でき、また更に窒化物以外の化合物について
も適用できる。例えば出発材料として酸化物の微粒子を
用い該酸化物微粒子の表面にドーパントを含む低粘性の
表面層を気相反応にて形成し、これを焼結することによ
りドーパント含有量の大きな透光性の秀れたガラスを容
易に製造することができる。また本発明はその他の複合
材料にも適用することができる。The present invention has been explained above mainly using nitrogen-containing quartz glass as an example, but the present invention is not limited to the above, but can also be applied to nitrides other than silicon, such as BN, TI, N, AtN, etc. Furthermore, it can also be applied to compounds other than nitrides. For example, by using oxide fine particles as a starting material, forming a low-viscosity surface layer containing a dopant on the surface of the oxide fine particles through a gas phase reaction, and sintering this, a light-transmitting layer with a large dopant content is formed. Excellent glass can be manufactured easily. The present invention can also be applied to other composite materials.
第１図は従来の製造方法の説明図、第２図は本発明の製
造原理を示す説明図、第３図（ａ）（ｂ）（Ｃ）は本発
明の製造手順の概略を示す説明図である。図面中、１・
・・Ｓ ｒ ０２微粒子、２・・・窒化硅素の表面層、
３・・窒素ドープした石英ガラス、１０・・・微粒子、
１２・・・焼結体である。
特許出願人 日本電信電話公社
住友電気工業株式会社Fig. 1 is an explanatory diagram of the conventional manufacturing method, Fig. 2 is an explanatory diagram showing the manufacturing principle of the present invention, and Fig. 3 (a), (b), and (C) are explanatory diagrams showing the outline of the manufacturing procedure of the present invention. It is. In the drawing, 1.
... S r 02 fine particles, 2 ... silicon nitride surface layer,
3...Nitrogen-doped quartz glass, 10...Fine particles,
12... Sintered body. Patent applicant: Nippon Telegraph and Telephone Public Corporation Sumitomo Electric Industries, Ltd.
Claims (3)
集合体を形成した後に該微粒子の集合体を焼結すること
を特徴とする添加物含有ガラスの製造方法。(1) A method for producing additive-containing glass, which comprises forming an aggregate of glass fine particles in which the outer surface layer has a lower viscosity than the inner layer, and then sintering the aggregate of the fine particles.
面層が二酸化硅素であることを特徴とする特許請求の範
囲第１項記載の添加物含有ガラスの製造方法。(2) The method for producing additive-containing glass according to claim 1, wherein the inside of the glass fine particles is silicon nitride, and the outer surface layer is silicon dioxide.
粒子であることを特徴とする第１項又は第２項記載の添
加物含有ガラスの製造方法。(3) The method for producing additive-containing glass according to item 1 or 2, wherein the glass fine particles are ultrafine particles having a diameter of 0.5 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12597681A JPS5832037A (en) | 1981-08-13 | 1981-08-13 | Preparation of glass containing additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12597681A JPS5832037A (en) | 1981-08-13 | 1981-08-13 | Preparation of glass containing additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5832037A true JPS5832037A (en) | 1983-02-24 |
| JPS6346015B2 JPS6346015B2 (en) | 1988-09-13 |
Family
ID=14923642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12597681A Granted JPS5832037A (en) | 1981-08-13 | 1981-08-13 | Preparation of glass containing additive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5832037A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042244A (en) * | 1983-08-12 | 1985-03-06 | Toshiba Ceramics Co Ltd | Quartz glass having resistance to melting loss |
| JPS6265949A (en) * | 1985-09-13 | 1987-03-25 | Fujikura Ltd | Production of optical glass and optical fiber base material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2525539Y2 (en) * | 1990-03-02 | 1997-02-12 | 三菱鉛筆株式会社 | Liquid applicator |
| JP2525538Y2 (en) * | 1990-03-02 | 1997-02-12 | 三菱鉛筆株式会社 | Liquid applicator |
-
1981
- 1981-08-13 JP JP12597681A patent/JPS5832037A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042244A (en) * | 1983-08-12 | 1985-03-06 | Toshiba Ceramics Co Ltd | Quartz glass having resistance to melting loss |
| JPH0135780B2 (en) * | 1983-08-12 | 1989-07-27 | Toshiba Ceramics Co | |
| JPS6265949A (en) * | 1985-09-13 | 1987-03-25 | Fujikura Ltd | Production of optical glass and optical fiber base material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6346015B2 (en) | 1988-09-13 |
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