JPS624338B2 - - Google Patents
Info
- Publication number
- JPS624338B2 JPS624338B2 JP56137765A JP13776581A JPS624338B2 JP S624338 B2 JPS624338 B2 JP S624338B2 JP 56137765 A JP56137765 A JP 56137765A JP 13776581 A JP13776581 A JP 13776581A JP S624338 B2 JPS624338 B2 JP S624338B2
- Authority
- JP
- Japan
- Prior art keywords
- sealing
- cao
- oxide
- oxides
- sodium
- 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
Links
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 3CaO Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Glass Compositions (AREA)
Description
この発明はセラミツク相互間又はセラミツクと
金属との封着に適用できる封着用酸化物に関し、
特に高圧ナトリウムランプ等の封着に使用するこ
とのできる封着用の酸化物に関するものである。
従来、封着用酸化物としては、CaO―Al2O3―
MgO系、CaO―Al2O3―BaO系、CaO―Al2O3―
SiO2が用いられてきた。最近になつて、CaO―
Al2O3―SrO系が用いられるようになつてきた。
しかし、これらの封着用酸化物はランプの点滅に
より封着溶融体中に微細クラツクが発生し、長時
間のランプ点灯にてナトリウムが封着溶融体中に
拡散し、気密不良の原因となつていた。また、こ
れらの封着用酸化物は封着温度（良好な溶融温
度）が1400℃以上と高く、低温での封着が望まれ
ていた。
このため、従来は、封着時に12CaO・7Al2O3
の存在を無くす為に高温（1400℃以上）で封着用
酸化物を溶融させていた。
12CaO・7Al2O3は微細クラツクの発生やナト
リウムの拡散の原因となる結晶で、封着時の存在
及びランプ点滅中の析出は望ましくない。
この発明は、高圧ナトリウムランプなどの封着
を極めて低温で行なうことができ、高温ナトリウ
ム蒸気下で長時間（15000時間以上）使用しても
封着部からの気密不良が生じないような封着用酸
化物を提供することを目的とするものである。
以下、本発明の実施例を説明する。
封着用酸化物の原料として、酸化物に換算して
重量パーセントでAl2O330〜50％、CaO30〜50
％、SrO5〜20％、にY2O30.3〜５％、La2O30.3〜
５％、ZrO20.3〜５％のうち少なくとも２つを添
加して、調合する。アセトンのような溶剤を用い
て、ボールミルで長時間粉砕混合し、乾燥する。
出発原料が炭酸塩の場合は仮焼を行なつて酸化
物とした後、酢酸ビニルポリマー等の結合剤を加
えて、乾燥し、顆粒状に原料を調製する。この調
製された原料粉を所望の形に成形し、その後、結
合剤を飛散させ、さらに成形品の形状を保つため
に、1100℃〜1200℃で焼成を行なう。
焼成された封着用酸化物を高圧ナトリウムラン
プの封着部にはめ込み、真空又は不活性雰囲気中
で1350〜1400℃で加熱することにより封着用酸化
物を溶融させ、冷却固化して、封着を行なう。
Al2O3―CaO―SrO系封着用酸化物による高圧
ナトリウムランプの封着における各成分の効用を
記せば、それぞれAl2O3はアルミナセラミツクと
の結合、CaOはニオビウムとの結合を増すもので
あり、SrOは耐ナトリウム性に優れるCaO・
Al2O3、3CaO・Al2O3の結晶化をはかるととも
に、耐ナトリウム性に劣る12CaO・7Al2O3の析
出を抑制するのに有効なものである。
さらに封着用酸化物が溶融され冷却固化された
時に高圧ナトリウムランプのアセンブリに使用さ
れるアルミナセラミツクおよびニオビウムの熱膨
脹係数が一致していることがクラツク発生を防ぐ
点から肝要である。たとえば重量パーセントで
Al2O330〜50％、CaO30〜50％、SrO5〜20％の範
囲で、アルミナセラミツクとニオビウムとの熱膨
脹係数をほぼ一致させることができる。
本発明における封着用酸化物はAl2O3―CaO―
SrO系にY2O3、La2O3、ZrO2のうち少なくとも２
つを添加したものであるが、これらを添加するこ
とによつて低温での封着が可能になつた。すなわ
ち、Y2O3、La2O3、ZrO2のうち少なくとも２つ
を添加することによつてAl2O3―CaO―SrO系の
融点を下げることができるのである。低温での封
着で耐ナトリウム性に劣る12CaO・7Al2O3の析
出が無く、不活性ガス中や真空中で長時間高温に
さらされても結晶の変化は極めて少なく、安定し
ている。
実験例を述べれば、封着用酸化物を真空中1360
℃で溶融し、冷却固化して、試料を得る。試料を
Ｘ線解析後、850℃アルゴンガス中で2000時間熱
処理（H.T.）を行ない、再びＸ線解析を行な
い、結晶の変化を調べた。代表的な調合例につい
て実験結果を表１に示す。
The present invention relates to a sealing oxide that can be applied to sealing between ceramics or between ceramics and metals,
In particular, it relates to a sealing oxide that can be used for sealing high-pressure sodium lamps and the like. Conventionally, the sealing oxide is CaO―Al 2 O 3 ―
MgO series, CaO―Al 2 O 3 ― BaO series, CaO― Al 2 O 3 ―
SiO 2 has been used. Recently, CaO―
The Al 2 O 3 -SrO system has come into use.
However, with these sealing oxides, minute cracks occur in the molten seal when the lamp flashes, and sodium diffuses into the molten seal when the lamp is on for a long time, causing poor airtightness. Ta. In addition, these sealing oxides have a high sealing temperature (favorable melting temperature) of 1400° C. or higher, so sealing at low temperatures has been desired. For this reason, conventionally, 12CaO・7Al 2 O 3 was used during sealing.
In order to eliminate the presence of oxides, the sealing oxide was melted at high temperatures (1400°C or higher). 12CaO.7Al 2 O 3 is a crystal that causes minute cracks and sodium diffusion, and its presence during sealing and precipitation during lamp flashing is undesirable. This invention is capable of sealing high-pressure sodium lamps, etc. at extremely low temperatures, and is a sealing method that does not cause airtightness from the sealed part even when used for a long time (15,000 hours or more) under high-temperature sodium vapor. The purpose is to provide oxides. Examples of the present invention will be described below. As raw materials for sealing oxides, Al 2 O 3 30-50%, CaO 30-50 in weight percent in terms of oxides.
%, SrO5~20%, Y2O3 0.3 ~5%, La2O3 0.3 ~
5%, and at least two of ZrO2 0.3-5%. Grind and mix in a ball mill for a long time using a solvent such as acetone and dry. When the starting material is a carbonate, it is calcined to form an oxide, and then a binder such as vinyl acetate polymer is added and dried to prepare the material in the form of granules. This prepared raw material powder is molded into a desired shape, and then the binder is dispersed, and further, in order to maintain the shape of the molded product, baking is performed at 1100°C to 1200°C. The fired sealing oxide is fitted into the sealing part of a high-pressure sodium lamp, and the sealing oxide is melted by heating at 1350 to 1400°C in a vacuum or inert atmosphere, and then cooled and solidified to complete the sealing. Let's do it. If we describe the effectiveness of each component in sealing high-pressure sodium lamps using Al 2 O 3 - CaO - SrO based sealing oxides, Al 2 O 3 increases the bond with alumina ceramic, and CaO increases the bond with niobium. SrO is CaO, which has excellent sodium resistance.
It is effective for crystallizing Al 2 O 3 and 3CaO.Al 2 O 3 and suppressing the precipitation of 12CaO.7Al 2 O 3 , which has poor sodium resistance. Furthermore, it is important to prevent cracks from occurring that the thermal expansion coefficients of the alumina ceramic and niobium used in the assembly of the high-pressure sodium lamp match when the sealing oxide is melted, cooled, and solidified. For example, weight percentage
The thermal expansion coefficients of alumina ceramic and niobium can be almost matched within the ranges of Al 2 O 3 30 to 50%, CaO 30 to 50%, and SrO 5 to 20%. The sealing oxide in the present invention is Al 2 O 3 -CaO-
At least 2 of Y 2 O 3 , La 2 O 3 , and ZrO 2 in SrO system
The addition of these materials made it possible to seal at low temperatures. That is, by adding at least two of Y 2 O 3 , La 2 O 3 , and ZrO 2 , the melting point of the Al 2 O 3 —CaO—SrO system can be lowered. Sealing at low temperatures eliminates the precipitation of 12CaO and 7Al 2 O 3 , which have poor sodium resistance, and the crystals remain stable with very little change even when exposed to high temperatures for long periods in inert gas or vacuum. To give an example of an experiment, sealing oxide was heated at 1360℃ in vacuum.
A sample is obtained by melting at ℃ and solidifying by cooling. After X-ray analysis of the sample, heat treatment (HT) was performed for 2000 hours at 850°C in argon gas, and X-ray analysis was performed again to examine changes in the crystals. Table 1 shows experimental results for typical formulation examples.
【表】
さらに、これらの封着用酸化物を使用して高圧
ナトリウムランプを製作した。
1360℃の封着で試料No.１の配合のものは溶融体
の流れが悪く、封着が困難であり、試料No.２、
３、４の配合のものは溶融体の流れは良好で封着
は容易であつた。
また、そのようにして製作された高圧ナトリウ
ムランプをフイールド試験にかけたところ、試料
No.１について封着酸化物溶融体に微細クラツクの
発生が見られ、7000時間で気密不良になつた。試
料No.２、３、４については、15000時間でも気密
不良が発生せず、Y2O3、La2O3、ZrO2のうち少
なくとも２つを添加したものについては耐ナトリ
ウム性に有効であつた。これは封着溶融体に
12CaO・7Al2O3の存在が極めて少なく、長時間
高温にさらされても、12CaO・7Al2O3の析出が
ほとんど見られず、CaO、Al2O3や3CaO、Al2O3
の結晶が極めて安定している為と考えられる。[Table] Furthermore, high-pressure sodium lamps were manufactured using these sealing oxides. When sealing at 1360°C, sample No. 1 had poor flow of the melt and was difficult to seal, while sample No. 2 and
In the case of compositions 3 and 4, the melt flow was good and sealing was easy. In addition, when the high-pressure sodium lamp manufactured in this way was subjected to field tests, the sample
Regarding No. 1, the occurrence of fine cracks in the sealing oxide melt was observed, and the airtightness became poor after 7000 hours. Regarding sample Nos. 2, 3, and 4, no airtight failure occurred even after 15,000 hours, and samples containing at least two of Y 2 O 3 , La 2 O 3 , and ZrO 2 were effective for sodium resistance. It was hot. This is the sealing melt.
The presence of 12CaO・7Al 2 O 3 is extremely small, and even if exposed to high temperatures for a long time, almost no precipitation of 12CaO・7Al 2 O 3 is observed, and CaO, Al 2 O 3 , 3CaO, Al 2 O 3
This is thought to be because the crystals are extremely stable.
Claims (1)
50％、SrO5〜20％にY2O30.3〜５％、La2O30.3〜
５％、ZrO20.3〜５％のうち少なくとも２つを含
む組成を有することを特徴とする封着用の酸化
物。1 Al 2 O 3 30-50%, CaO30-50% by weight
50%, SrO5~20%, Y2O3 0.3 ~5%, La2O3 0.3 ~
5% and ZrO 2 0.3 to 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56137765A JPS5841766A (en) | 1981-09-03 | 1981-09-03 | Sealing oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56137765A JPS5841766A (en) | 1981-09-03 | 1981-09-03 | Sealing oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5841766A JPS5841766A (en) | 1983-03-11 |
| JPS624338B2 true JPS624338B2 (en) | 1987-01-29 |
Family
ID=15206299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56137765A Granted JPS5841766A (en) | 1981-09-03 | 1981-09-03 | Sealing oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5841766A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215986A (en) * | 1988-02-24 | 1989-08-29 | Hitachi Ltd | Dry etching method |
| HU202011B (en) * | 1988-09-07 | 1991-01-28 | Tungsram Reszvenytarsasag | Soldering enamel for end-sealing of the ceramic discharge-bulb of discharge lamps |
| JP3399103B2 (en) * | 1994-07-25 | 2003-04-21 | 日本電池株式会社 | Unsaturated vapor pressure type high pressure sodium lamp |
-
1981
- 1981-09-03 JP JP56137765A patent/JPS5841766A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5841766A (en) | 1983-03-11 |
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