JPH05279075A - Sealing glass for glass capsule hip of silicon nitride molding - Google Patents
Sealing glass for glass capsule hip of silicon nitride moldingInfo
- Publication number
- JPH05279075A JPH05279075A JP4105431A JP10543192A JPH05279075A JP H05279075 A JPH05279075 A JP H05279075A JP 4105431 A JP4105431 A JP 4105431A JP 10543192 A JP10543192 A JP 10543192A JP H05279075 A JPH05279075 A JP H05279075A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- silicon nitride
- sealing
- earth metal
- alkaline earth
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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 Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、窒化珪素成形体をガラ
スでシールし、熱間静水圧プレス法によって高緻密質の
窒化珪素焼結体を生成する方法（以下、ガラスカプセル
ＨＩＰ処理という）に用いる前記シール用のガラスに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of sealing a silicon nitride compact with glass and producing a highly dense silicon nitride sintered body by hot isostatic pressing (hereinafter referred to as glass capsule HIP treatment). The present invention relates to the above-mentioned glass for sealing.
【０００２】[0002]
【従来の技術】シール用のガラス（以下、シールガラス
という）として硼珪酸ガラスの１つである安価なパイレ
ックスガラスが使用されることが一般的であるが、パイ
レックスガラスに含有される約5 ％のNa2O等のアルカリ
成分によって窒化珪素焼結体の表面が浸蝕されるため、
浸蝕部分を研削しなければならないことに鑑み、その浸
蝕部分を薄くするためガラスカプセルＨＩＰ処理する前
に窒化珪素成形体（以下、成形体という）の表面に窒化
硼素粉末を付着させる方法がある（特開昭55-89405
号）。一方、アルカリ成分を含まないシールガラスを用
いる方法も研究されている（特開昭62-107768 号）。2. Description of the Related Art It is common to use an inexpensive Pyrex glass, which is one of borosilicate glasses, as a glass for sealing (hereinafter referred to as a seal glass), but about 5% contained in Pyrex glass. Since the surface of the silicon nitride sintered body is eroded by the alkaline component such as Na 2 O,
In view of the fact that the eroded portion must be ground, there is a method of attaching boron nitride powder to the surface of a silicon nitride compact (hereinafter referred to as compact) before the glass capsule HIP treatment in order to thin the eroded portion ( JP-A-55-89405
issue). On the other hand, a method of using a seal glass containing no alkali component has also been studied (Japanese Patent Laid-Open No. 62-107768).
【０００３】[0003]
【発明が解決しようとする課題】前者の方法は、高価な
窒化硼素粉末を成形体表面に均一に付着させるには、技
術を要する工程が増えるため、製造コストが高くなる。
一方、後者の方法は、非常に高い温度で調合しないとガ
ラス生成ができないため、製造コストがかかり、工業的
でない。而も、軟化点温度が高く、ガラスカプセルＨＩ
Ｐ処理時のガラス粘性が高いために、成形体とのシール
性が悪く、緻密質の焼結体が得られない。In the former method, since the number of steps that require a technique is increased to uniformly attach the expensive boron nitride powder to the surface of the compact, the manufacturing cost becomes high.
On the other hand, the latter method is not industrial since it cannot produce glass unless it is blended at a very high temperature, resulting in high manufacturing costs. Moreover, the glass capsule HI has a high softening point temperature.
Since the glass viscosity at the time of P treatment is high, the sealing property with the compact is poor and a dense sintered body cannot be obtained.
【０００４】[0004]
【課題を解決するための手段】本発明は、研究を重ねた
結果、窒化珪素材の焼結助剤となるアルカリ土類金属酸
化物を適量添加し、Al2O3 の含有量を限定することで、
ガラス製造コストがかからず、且つシール性に優れ、焼
結体表面が浸蝕されないシールガラスの開発に成功した
ものである。即ち、その構成とは、主成分がSiO2及びB2
O3から成り、アルカリ土類金属酸化物の総含有量が1.0
〜10.0％であり、且つAl2O3 の含有量が0.5 〜5.0 ％で
あることにある。また、1000°Ｃにおける粘度が1 ×10
6 Ｐ以下であることにある。さらに、前記アルカリ土類
金属酸化物が、SrO 及びMgO 及びBeO の内、何れか１種
類以上を含有することにある。As a result of repeated studies, the present invention limits the content of Al 2 O 3 by adding an appropriate amount of an alkaline earth metal oxide that serves as a sintering aid for a silicon nitride material. By that,
We have succeeded in developing a seal glass that does not cost the glass manufacturing cost, has excellent sealing properties, and does not corrode the surface of the sintered body. That is, the composition means that the main components are SiO 2 and B 2
Consists of O 3 with a total alkaline earth metal oxide content of 1.0
˜10.0%, and the content of Al 2 O 3 is 0.5 to 5.0%. Also, the viscosity at 1000 ° C is 1 × 10
6 P or less. Further, the alkaline earth metal oxide contains at least one of SrO 2, MgO 2 and BeO 2.
【０００５】[0005]
【作用】ガラスの組成をSiO2及びB2O3を主成分とし、ア
ルカリ土類金属酸化物の総含有量を1.0 〜10.0％、且つ
Al2O3 の含有量を0.5 〜5.0 ％とすることによって、成
形体をガラスシールＨＩＰ処理する場合に、シール性が
損なわれることなく、焼結体表面が浸蝕されることが少
ない。また、1000°Ｃにおけるガラスの粘度が1 ×106
Ｐ以下となるようにガラスを組成するか、アルカリ土類
金属酸化物をSrO 及びMgO 及びBeO の内、何れかとして
も同様の効果を奏することができる。[Function] The composition of the glass is SiO 2 and B 2 O 3 as main components, the total content of alkaline earth metal oxides is 1.0 to 10.0%, and
By setting the content of Al 2 O 3 to 0.5 to 5.0%, when the molded body is subjected to the glass seal HIP treatment, the surface of the sintered body is less likely to be corroded without impairing the sealing property. The viscosity of the glass at 1000 ° C is 1 × 10 6
The same effect can be obtained even if the glass is composed so as to be P or less or the alkaline earth metal oxide is any one of SrO 2, MgO 2 and BeO 2.
【０００６】[0006]
【実施例】以下、本発明のシールガラスを用いたガラス
カプセルＨＩＰ処理によって成形体を焼結した実験につ
いて説明する。先ず、平均粒径0.5 μのSi3N4 94％及び
焼結助剤Y2N43 ％及びMgO 3 ％をポットミルにて6hr 湿
式粉砕して得られたスラリーに乾式プレス用成形助剤を
添加した後、スプレードライヤーで粉末にし、その粉末
を成形圧1.5ton/cm2で金型プレス成形すると、φ60×50
×6mm の成形体が得られた。そして、大気雰囲気中500
°Ｃ×3hr で熱処理を行ない、成形助剤を除去した。EXAMPLE An experiment in which a molded body is sintered by the HIP treatment of a glass capsule using the seal glass of the present invention will be described below. First, 94% of Si 3 N 4 having an average particle diameter of 0.5 μ, Y 2 N 4 3% of sintering aid, and MgO 3% of sintering aid were wet-milled for 6 hours with a pot mill, and a slurry was obtained. After adding, make powder with a spray dryer and press-mold the powder with a molding pressure of 1.5 ton / cm 2 to obtain φ60 × 50
A molded product of × 6 mm was obtained. And in the atmosphere 500
A heat treatment was performed at ° C x 3 hr to remove the molding aid.
【０００７】図１中の１は、ガラスカプセルＨＩＰ処理
に用いるグラファイトルツボである。２は黒鉛ホイル、
３は本発明のシールガラスで、SiO2及びB2O3を主成分と
し、少量のAl2O3 とアルカリ土類金属酸化物の一例であ
るMgO を少量含有したものである（SiO2 80.0 ％、 B2O3
13.0 ％、 Al2O3 3.0％、 MgO 4.0％ )。前記成形体は
図の４に示すようにシールガラス３内に埋没されてい
る。次に、その状態において1700°Ｃ×1hr、1000atm で
ガラスカプセルＨＩＰ処理を行なった結果、表面がガラ
スで覆われた焼結体が得られた。そして、その焼結体を
サンドブラストによって表面のガラスを除去すると共
に、所定の形状に加工し、焼結体の密度の測定とJIS R1
601 に基づいた4 点曲げ強度の測定をすると、表１に示
すように、それぞれ3.21g/cc、95kg/mm2であり、高緻密
質で高強度を有することが解った。また、焼結体表面の
浸蝕程度を知るために、板状体の断面を鏡面仕上げし、
EPMAでアルカリ土類金属元素とアルミニュウム元素の分
布を測定すると、表１に示すように浸蝕距離0.07/0.03m
m であり、浸蝕は殆どされていないことが解った。尚、
1000°Ｃにおけるシールガラスの粘度は1 ×106 Ｐであ
った。以下、シールガラスの組成を変更し、上記同様の
実験を行なった結果、表１に示す測定データを得ること
ができた（実施例２〜４）。以上より、ガラスの組成を
主成分がSiO2及びB2O3、アルカリ土類金属酸化物の総含
有量が1.0 〜10.0％、Al2O3 の含有量が0.5 〜5.0 ％と
なるようにすることで、従来の諸課題を解決できること
が明らかとなった。また、シールガラスの粘度を1000°
Ｃにおいて1 ×106 Ｐ以下となるように組成するか、ア
ルカリ土類金属酸化物を、SrO 及びMgO 及びBeO の内、
何れかとしても、同様に解決できることが解った。Reference numeral 1 in FIG. 1 denotes a graphite crucible used for the glass capsule HIP treatment. 2 is graphite foil,
3 is a seal glass of the present invention, which is composed mainly of SiO 2 and B 2 O 3, and contains a small amount of Al 2 O 3 and a small amount of MgO which is an example of an alkaline earth metal oxide (SiO 2 80.0 %, B 2 O 3
13.0%, Al 2 O 3 3.0%, MgO 4.0%). The molded body is embedded in the seal glass 3 as shown in FIG. Then, in that state, glass capsule HIP treatment was performed at 1700 ° C. × 1 hr at 1000 atm, and as a result, a sintered body having a surface covered with glass was obtained. Then, while removing the glass on the surface of the sintered body by sandblasting, it was processed into a predetermined shape, and the density of the sintered body was measured and JIS R1
When four-point bending strength was measured based on 601, as shown in Table 1, they were 3.21 g / cc and 95 kg / mm 2 , respectively, and it was found that they have high density and high strength. Also, in order to know the degree of erosion of the surface of the sintered body, the cross section of the plate-shaped body is mirror-finished,
When the distribution of alkaline earth metal elements and aluminum elements is measured by EPMA, the erosion distance is 0.07 / 0.03m as shown in Table 1.
It was m, and it was found that erosion was hardly performed. still,
The viscosity of the seal glass at 1000 ° C. was 1 × 10 6 P. Hereinafter, the composition of the seal glass was changed and the same experiment as above was carried out. As a result, the measurement data shown in Table 1 could be obtained (Examples 2 to 4). From the above, the composition of the glass is such that the main components are SiO 2 and B 2 O 3 , the total content of alkaline earth metal oxides is 1.0 to 10.0%, and the content of Al 2 O 3 is 0.5 to 5.0%. By doing so, it became clear that various conventional problems can be solved. In addition, the viscosity of the seal glass is 1000 °
The composition of C should be 1 × 10 6 P or less, or the alkaline earth metal oxide should be one of SrO, MgO, and BeO.
It was found that either of them can be solved in the same manner.
【０００８】尚、シールガラスを上記のように組成しな
ければ、従来の諸課題を解決できないことは、表１の比
較例１〜３に示す測定結果から明らかである。即ち、比
較例１のようにAl2O3 を8.0 ％にすると、粘度が1 ×10
7 Ｐと、高くなるため、成形体に対するガラスのシール
性が悪く、ＨＩＰ処理による効果が小さいために、高緻
密度な成形体を得ることができなかった。また、比較例
２のようにMgO を20.0％にすると、焼結体の浸蝕距離が
0.70/0.03mm と、深くなるため、浸蝕部分を除去するの
に手間がかかると共に、目的の形状が損なわれやすい。
さらに、比較例３のようにAl2O3 を0.3 ％、SrO を1.0
％にすると、ガラスを生成することができなかった。It is clear from the measurement results shown in Comparative Examples 1 to 3 in Table 1 that the conventional problems cannot be solved unless the sealing glass is composed as described above. That is, when Al 2 O 3 is set to 8.0% as in Comparative Example 1, the viscosity becomes 1 × 10 5.
Since it was 7 P, the sealing property of the glass with respect to the molded product was poor, and the effect of the HIP treatment was small, so that a highly dense molded product could not be obtained. When MgO is set to 20.0% as in Comparative Example 2, the erosion distance of the sintered body is
Since the depth is 0.70 / 0.03mm, it takes a lot of time to remove the eroded portion, and the target shape is easily damaged.
Further, as in Comparative Example 3, Al 2 O 3 is 0.3% and SrO is 1.0%.
%, Glass could not be produced.
【０００９】[0009]
【発明の効果】本発明のシールガラスは、シール性に優
れているため、強度に富んだ緻密質の焼結体を生成する
ことができる。また、焼結体の表面が殆ど浸蝕されない
ので、仕上げが容易になる。而も、軟化点が低いため、
生成コストの低減を図ることができる。Since the seal glass of the present invention is excellent in sealing property, it is possible to form a dense sintered body having a high strength. Moreover, since the surface of the sintered body is hardly corroded, the finish is easy. Moreover, since the softening point is low,
It is possible to reduce the generation cost.
【図１】窒化珪素成形体をガラスを充填したグラファイ
トルツボに埋没させ、ガラスシールＨＩＰ処理する状態
を示す説明図である。FIG. 1 is an explanatory diagram showing a state in which a silicon nitride molded body is embedded in a graphite crucible filled with glass and a glass seal HIP process is performed.
１・・グラファイトルツボ、２・・黒鉛ホイル、３・・
ガラス、４・・成形体。1 ... Graphite crucible, 2 ... Graphite foil, 3 ...
Glass, 4 ...
【表１】 [Table 1]
Claims (3)
シールガラスであって、主成分がSiO2及びB2O3から成
り、アルカリ土類金属酸化物の総含有量が1.0 〜10.0％
であり、且つAl2O3 の含有量が0.5 〜5.0 ％であること
を特徴とする窒化珪素成形体のガラスカプセルＨＩＰ用
シールガラス。1. A sealing glass for a glass capsule HIP of a silicon nitride molded body, the main components of which are SiO 2 and B 2 O 3 , and the total content of alkaline earth metal oxides is 1.0 to 10.0%.
And a content of Al 2 O 3 of 0.5 to 5.0%, a glass capsule of a silicon nitride molded body, a sealing glass for HIP.
あることを特徴とする請求項１記載の窒化珪素成形体の
ガラスカプセルＨＩＰ用シールガラス。2. The seal glass for glass capsule HIP of a silicon nitride molded body according to claim 1, which has a viscosity at 1000 ° C. of 1 × 10 6 P or less.
MgO 及びBeO の内、何れか１種類以上を含有することを
特徴とする請求項１又は請求項２記載の窒化珪素成形体
のガラスカプセルＨＩＰ用シールガラス。3. The alkaline earth metal oxide is SrO 2 and
The seal glass for glass capsule HIP of the silicon nitride molded body according to claim 1 or 2, which contains at least one of MgO and BeO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04105431A JP3111191B2 (en) | 1992-03-30 | 1992-03-30 | Silicon nitride molded glass seal glass for HIP seal glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04105431A JP3111191B2 (en) | 1992-03-30 | 1992-03-30 | Silicon nitride molded glass seal glass for HIP seal glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05279075A true JPH05279075A (en) | 1993-10-26 |
| JP3111191B2 JP3111191B2 (en) | 2000-11-20 |
Family
ID=14407412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04105431A Expired - Fee Related JP3111191B2 (en) | 1992-03-30 | 1992-03-30 | Silicon nitride molded glass seal glass for HIP seal glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3111191B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0721926A3 (en) * | 1995-01-11 | 1996-11-13 | Saint Gobain Norton Ind Cerami | Hipped silicon nitride having a reduced reaction layer |
-
1992
- 1992-03-30 JP JP04105431A patent/JP3111191B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0721926A3 (en) * | 1995-01-11 | 1996-11-13 | Saint Gobain Norton Ind Cerami | Hipped silicon nitride having a reduced reaction layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3111191B2 (en) | 2000-11-20 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |