JPS624337B2 - - Google Patents
Info
- Publication number
- JPS624337B2 JPS624337B2 JP56137764A JP13776481A JPS624337B2 JP S624337 B2 JPS624337 B2 JP S624337B2 JP 56137764 A JP56137764 A JP 56137764A JP 13776481 A JP13776481 A JP 13776481A JP S624337 B2 JPS624337 B2 JP S624337B2
- Authority
- JP
- Japan
- Prior art keywords
- sealing
- oxide
- cao
- sodium
- lamp
- 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 9
- 238000007789 sealing Methods 0.000 description 22
- 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 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 239000013078 crystal Substances 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
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 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
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
金属との接着に使うことのできる封着用酸化物に
関するもので、特に高圧ナトリウムランプ等の封
着に適した封着用酸化物に関するものである。
従来、封着用酸化物として、CaO―Al2O3―
MgO系、CaO―Al2O3―BaO系、CaO―Al2O3―
SiO2系がよく用いられていた。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。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好ましくないのであ
る。
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（約700
℃）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
％、BaO5〜20％、MgO0.5〜10％にLa2O30.3・10
％、ZrO20.3〜10％のうち少なくとも１つを添加
し、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い、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、顆粒状に原料粉を調製する。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。焼成後の封着用
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1380〜1420℃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。
CaO―Al2O3―BaO―MgO系酸化物は高圧ナト
リウムランプの封着剤として用いられてきた。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。重量パーセントAl2O330〜50％、
CaO30〜50％、BaO5〜20％、MgO0.5〜10％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。
この発明における封着用酸化物はAl2O3―CaO
―BaO―MgO系にLa2O3、ZrO2のうち少なくとも
１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。更
に、低温の封着にもかかわらず、耐ナトリウム性
に劣る12CaO・7Al2O3の析出が極めて少なく、
不活性ガス中や真空中で長時間高温にさらされて
も結晶変化は極めて少なく、安定している。
さらに実験例を述べれば、封着用酸化物を真空
中1380℃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 used to bond ceramics together or to bond ceramics and metals, and particularly relates to a sealing oxide suitable for sealing high-pressure sodium lamps and the like. Conventionally, CaO―Al 2 O 3 ― has been used as a sealing oxide.
MgO series, CaO―Al 2 O 3 ― BaO series, CaO― Al 2 O 3 ―
SiO 2 system was often used. 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. For this reason, conventionally, the sealing oxide was melted at a high temperature (1400° C. or higher) in order to eliminate the presence of 12CaO.7Al 2 O 3 during sealing. 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 makes it possible to seal high-pressure sodium lamps, etc. at extremely low temperatures, and at high temperatures (approx.
The object of the present invention is to provide a sealing oxide that does not cause airtightness from the sealed part even when used for a long time (15,000 hours or more) under sodium vapor. 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.
%, BaO5~20%, MgO0.5~10% with La 2 O 3 0.3・10
%, ZrO 2 0.3-10% and blend. Using a solvent like acetone,
Grind and mix in a ball mill for a long time and dry. If the starting material is carbonate, it is calcined to form an oxide, and then a binder such as vinyl acetate polymer is added.
Dry and prepare raw material powder into granules. This prepared raw material powder is molded into a desired shape, then a binder is scattered, and further, in order to maintain the shape of the molded product,
Firing is performed at 1100°C to 1200°C. After firing, the sealing oxide is fitted into the sealing part of a high-pressure sodium lamp, and the sealing oxide is melted by heating at 1380 to 1420°C in a vacuum or inert atmosphere, and then cooled and solidified to complete the sealing. Let's do it. CaO-Al 2 O 3 -BaO-MgO-based oxides have been used as sealants for high-pressure sodium lamps. It is important to prevent cracks from occurring when the sealing oxide is melted, cooled, and solidified so that the coefficients of thermal expansion of the alumina ceramic and niobium used in the assembly of the high-pressure sodium lamp match. Weight percent Al2O3 30-50 %,
Thermal expansion coefficients of alumina ceramic and niobium can be almost matched within the ranges of CaO30 to 50%, BaO5 to 20%, and MgO0.5 to 10%. The sealing oxide in this invention is Al 2 O 3 -CaO
-BaO-MgO system to which at least one of La 2 O 3 and ZrO 2 is added, and the addition of these makes it possible to seal at low temperatures. Furthermore, despite low-temperature sealing, there is extremely little precipitation of 12CaO・7Al 2 O 3 , which has poor sodium resistance.
Even when exposed to high temperatures for long periods of time in an inert gas or vacuum, there is very little crystal change and it remains stable. To describe a further experimental example, a sample is obtained by melting the sealing oxide at 1380° C. in a vacuum and solidifying it by cooling.
After X-ray analysis of the sample, it was heated to 850℃ in argon gas for 2000℃.
Time heat treatment (HT) was performed, 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（封着温度1380℃）、
フイールド試験を行つたところ、試料No.１につい
ては封着部のナトリウム蒸気による浸蝕が速く、
8000時間で気密不良が見られた。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、La2O3、ZrO2の添加が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（約700℃）
にさらされても、12CaO・7Al2O3の析出がほと
んど見られず、耐ナトリウム性に優れるCaO―
Al2O3、3CaO―Al2O3の結晶が極めて安定してい
るためと考えられる。[Table] Furthermore, a high-pressure sodium lamp was manufactured using these sealing oxides (sealing temperature 1380℃),
When conducting field tests, it was found that sample No. 1 was rapidly eroded by sodium vapor at the sealing part.
Poor airtightness was observed after 8000 hours. Sample No. 2, 3,
Regarding No. 4, no airtight failure occurred even after 15,000 hours, and the addition of La 2 O 3 and ZrO 2 was effective for sodium resistance. This is 12CaO・7Al 2 O 3 in the sealing melt.
There is very little presence of
Even when exposed to
This is thought to be because the crystals of Al 2 O 3 and 3CaO—Al 2 O 3 are extremely stable.
Claims (1)
〜50％、BaO5〜20％、MgO0.5〜10％にLa2O30.3
〜10％、ZrO20.3〜10％のうち少なくとも１つを
含む組成を有することを特徴とする封着用酸化
物。1 In weight percent, Al 2 O 3 30-50%, CaO30
La2O30.3 to ~50%, BaO5~20%, MgO0.5 ~10%
10% of ZrO 2 and 0.3 to 10% of ZrO 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56137764A JPS5841765A (en) | 1981-09-03 | 1981-09-03 | Sealing oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56137764A JPS5841765A (en) | 1981-09-03 | 1981-09-03 | Sealing oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5841765A JPS5841765A (en) | 1983-03-11 |
| JPS624337B2 true JPS624337B2 (en) | 1987-01-29 |
Family
ID=15206276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56137764A Granted JPS5841765A (en) | 1981-09-03 | 1981-09-03 | Sealing oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5841765A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6065304A (en) * | 1983-09-20 | 1985-04-15 | Toyota Motor Corp | Teaching point correcting method of robot |
-
1981
- 1981-09-03 JP JP56137764A patent/JPS5841765A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5841765A (en) | 1983-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2911721B2 (en) | Alumina-calcia-yttria sealant composition | |
| WO2003045864A1 (en) | Sealing composition and sealing material | |
| US3441421A (en) | Calcia-magnesia-alumina seal compositions | |
| JPS586715B2 (en) | Sealing compositions comprising aluminum oxide, calcium oxide, barium oxide, and strontium oxide and products thereof | |
| JPS624338B2 (en) | ||
| KR20070057181A (en) | AS product with reduced leachability | |
| JPS624337B2 (en) | ||
| US2962136A (en) | Composite metal-forsterite ceramic bodies | |
| JP2879255B2 (en) | Molten yttrium oxide molded body | |
| JP5926369B2 (en) | Glass-ceramic composite fired material | |
| JPH10236844A (en) | Sealing composition | |
| EP0001710B1 (en) | A heat resistant sealing composition, a method of making this composition, a method of making a ceramic-cermet seal in electric discharge devices and the device thus obtained | |
| US4330629A (en) | Heat-resistant sealing materials | |
| JPS596277B2 (en) | Sealing composition | |
| US2409844A (en) | Basic cast refractory | |
| CA1123020A (en) | Alumina, calcia, baria sealing composition and article of manufacture | |
| JP2762495B2 (en) | Zirconia sintered body with excellent corrosion resistance and hot water resistance | |
| JPH07315867A (en) | Composition for sealing | |
| JPS6350375A (en) | Ceramic porous formed body | |
| JP2005035845A (en) | Heat-resistant adhesive composition | |
| SU1472953A1 (en) | Electro insulating composition | |
| US3035929A (en) | Process of preparation of refractory products containing zirconia, alumina and silica | |
| JPH04349146A (en) | High expansion seal bonding material having low melting point | |
| JPS6252168A (en) | Zircon refractories | |
| JPH05117019A (en) | Basic refractory brick |