JPH07302678A - Heating element and its manufacture - Google Patents
Heating element and its manufactureInfo
- Publication number
- JPH07302678A JPH07302678A JP6096301A JP9630194A JPH07302678A JP H07302678 A JPH07302678 A JP H07302678A JP 6096301 A JP6096301 A JP 6096301A JP 9630194 A JP9630194 A JP 9630194A JP H07302678 A JPH07302678 A JP H07302678A
- Authority
- JP
- Japan
- Prior art keywords
- heating element
- weight
- crystallized glass
- catalyst layer
- catalyst
- 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
- 238000010438 heat treatment Methods 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011521 glass Substances 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010457 zeolite Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 abstract description 4
- 238000004332 deodorization Methods 0.000 abstract description 3
- 230000020169 heat generation Effects 0.000 abstract 3
- 238000001962 electrophoresis Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- 239000000523 sample Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 5
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 5
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010292 electrical insulation Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 235000019645 odor Nutrition 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 238000005485 electric heating Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気エネルギーを熱源
として、触媒を効率的に作用させて、各種暖房器、給湯
器、乾燥器、調理器、冷蔵庫、空調用機器などの排ガス
浄化や脱臭に用いられる発熱体およびその製造方法に関
するものである。BACKGROUND OF THE INVENTION The present invention relates to exhaust gas purification and deodorization of various heaters, water heaters, dryers, cookers, refrigerators, air conditioners, etc. by efficiently operating a catalyst using electric energy as a heat source. The present invention relates to a heating element used in the above and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】従来、脱臭を目的とした触媒体として、
（１）コージライト、アルミナなどの材料でハニカム状
に成型したバルクタイプ、（２）基材に触媒スラリーを
塗布し、焼成したコーティングタイプがある。そして、
それらの触媒を効率的に作用させるためには、触媒体を
３００℃以上の温度に加熱する必要がある。（１）のタ
イプは、触媒の加熱源として、触媒体に直接ヒータを装
着して加熱する方法、または機器からの排熱を利用して
触媒体を加熱する方法が用いられている。また、最近で
は、図３に示すように、石英管５にコイル状発熱体４を
内蔵させた石英管ヒータの表面に、触媒層６をコーティ
ングする（２）のタイプが提案されている。2. Description of the Related Art Conventionally, as a catalyst body for deodorization,
There are (1) a bulk type in which a material such as cordierite and alumina is molded into a honeycomb shape, and (2) a coating type in which a catalyst slurry is applied to a base material and fired. And
In order for these catalysts to act efficiently, it is necessary to heat the catalyst body to a temperature of 300 ° C. or higher. The type (1) uses a method in which a heater is directly attached to the catalyst body to heat the catalyst body as a heat source for the catalyst, or a method in which the catalyst body is heated by utilizing exhaust heat from the device. Further, recently, as shown in FIG. 3, there has been proposed a type (2) in which the surface of a quartz tube heater in which a coil-shaped heating element 4 is built in a quartz tube 5 is coated with a catalyst layer 6.
【０００３】[0003]
【発明が解決しようとする課題】上記（１）のタイプの
触媒体は、触媒体の熱容量が大きいため、触媒体が効果
的に作用する温度に到達するのに時間がかかり、機器立
ち上がり時には、有害ガス、悪臭などの除去が困難であ
った。また、（２）のタイプの触媒体は、（１）のバル
クタイプに比べ、速熱性に優れるため、機器の立ち上が
り時における有害ガス、悪臭などの除去に効果的であ
る。しかしながら、このタイプはヒータの電気絶縁性の
観点から、限られた形状のものしかなく、触媒素子を搭
載した機器の軽薄短小化に対して限界があった。本発明
は、上記従来技術の課題を解決し、触媒を効率的に作用
させるために速熱性があり、しかも機器のコンパクト化
を達成させる発熱体およびその製造方法を提供すること
を目的とする。In the catalyst body of the above type (1), since the heat capacity of the catalyst body is large, it takes time to reach the temperature at which the catalyst body effectively works, and when the equipment starts up, It was difficult to remove harmful gases and odors. Further, the type (2) type catalyst body is superior in rapid heating property to the type (1) bulk type catalyst body, and is therefore effective in removing harmful gases and odors when the equipment is started up. However, this type has only a limited shape from the viewpoint of the electric insulation of the heater, and there is a limit to the reduction of the weight, thinness and shortness of the device in which the catalyst element is mounted. SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art, and to provide a heating element which has fast heating property for allowing the catalyst to act efficiently, and which achieves downsizing of the device, and a manufacturing method thereof.
【０００４】[0004]
【課題を解決するための手段】本発明の発熱体は、電気
抵抗発熱体表面に結晶化ガラス層を形成し、この結晶化
ガラス層の上に触媒層を形成したものである。ここで、
前記結晶化ガラスは、ＭｇＯが１６−５０重量％、Ｓｉ
Ｏ2が７−３０重量％、Ｂ2Ｏ3が５−３４重量％、Ｂａ
Ｏが０−５０重量％、Ｌａ2Ｏ3が０−４０重量％、Ｃａ
Ｏが０−２０重量％、Ｐ2Ｏ5が０−５重量％、ＭＯ2が
０−５重量％（ただし、ＭはＺｒ、ＴｉおよびＳｎより
なる群から選択される少なくとも一種の元素）の組成で
あることが好ましい。また、前記触媒層は、ゼオライ
ト、無機バインダー、および貴金属を担持したアルミナ
からなるものが好ましい。本発明の発熱体の製造方法
は、電気抵抗発熱体表面に電気泳動電着法により結晶化
ガラス粒子を被着し、焼成して結晶化ガラス層を形成す
る工程と、前記結晶化ガラス層上に触媒層を形成する工
程を有する。The heating element of the present invention comprises a crystallized glass layer formed on the surface of an electric resistance heating element, and a catalyst layer formed on the crystallized glass layer. here,
The crystallized glass contains MgO in an amount of 16-50 wt%, Si
7-30% by weight of O 2, 5-34% by weight of B 2 O 3 , Ba
O is 0-50% by weight, La 2 O 3 is 0-40% by weight, Ca
O is 0-20% by weight, P 2 O 5 is 0-5% by weight, MO 2 is 0-5% by weight (where M is at least one element selected from the group consisting of Zr, Ti and Sn). It is preferably a composition. Further, the catalyst layer is preferably composed of zeolite, an inorganic binder, and alumina carrying a noble metal. The method for producing a heating element according to the present invention comprises a step of depositing crystallized glass particles on the surface of an electric resistance heating element by an electrophoretic electrodeposition method and firing to form a crystallized glass layer; And a step of forming a catalyst layer.
【０００５】[0005]
【作用】結晶化ガラスは、電気絶縁性および密着性に優
れているところから、発熱体自体を小型に構成すること
ができるとともに、結晶化ガラス層に接して触媒層が設
けられているので、触媒層は電気抵抗発熱体により短時
間に触媒の活性化温度まで加熱される。こうして触媒が
その活性化温度に加熱された発熱体に接触する空気中の
臭気成分、例えばアンモニアや脂肪酸は、触媒作用によ
り容易に酸化、浄化される。また、触媒層がゼオライト
を含むときには、その吸着特性により、発熱体に通電し
ないとき臭気物質を吸着することができる。そして、発
熱体への通電により、吸着した臭気物質を脱着し、元の
状態へ再生できる。結晶化ガラスが、上記組成に示した
ように、アルカリ成分（Ｌｉ2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏ）を
全く含まない無アルカリ結晶化ガラスであるときは、電
気絶縁性が飛躍的に向上する。また、このガラスは焼き
付けるときに無数の微結晶が析出するので、セラミック
スに近く、９００℃程度の耐熱性を有する。さらに、析
出した針状結晶によって、この上に形成される触媒層と
の密着性が大幅に向上し、熱サイクル寿命特性に優れた
発熱体を提供することができる。Since the crystallized glass is excellent in electrical insulation and adhesion, the heating element itself can be made compact, and the catalyst layer is provided in contact with the crystallized glass layer. The catalyst layer is heated to the activation temperature of the catalyst in a short time by the electric resistance heating element. Thus, the odorous components in the air, such as ammonia and fatty acids, which come into contact with the heating element heated by the catalyst to its activation temperature are easily oxidized and purified by the catalytic action. In addition, when the catalyst layer contains zeolite, the odor substance can be adsorbed when the heating element is not energized due to its adsorption property. Then, by energizing the heating element, the adsorbed odorous substance can be desorbed and regenerated to the original state. As shown in the above composition, when the crystallized glass is an alkali-free crystallized glass that does not contain any alkali component (Li 2 O, Na 2 O, K 2 O), the electrical insulating property is remarkably improved. To do. In addition, since this glass deposits innumerable fine crystals during baking, it has a heat resistance of about 900 ° C., which is close to that of ceramics. Furthermore, the deposited needle-like crystals significantly improve the adhesion to the catalyst layer formed thereon, and can provide a heating element having excellent thermal cycle life characteristics.
【０００６】[0006]
【実施例】以下、本発明の好ましい発熱体およびその製
造方法について説明する。 （１）電気抵抗発熱体 電気抵抗発熱体は、基本的には薄帯状、ラス網状、コイ
ル状のＦｅ−Ｎｉ合金、Ｆｅ−Ｎｉ−Ｃｒ合金、ステン
レス鋼などの各種電気抵抗発熱材が好ましい。The preferred heating element of the present invention and its manufacturing method will be described below. (1) Electric resistance heating element As the electric resistance heating element, various electric resistance heating materials such as a ribbon-shaped, lath mesh-shaped, coil-shaped Fe-Ni alloy, Fe-Ni-Cr alloy, and stainless steel are basically preferable.
【０００７】（２）結晶化ガラス層 結晶化ガラス層は、電気絶縁性、耐熱性の観点から、焼
成によって、たとえばＭｇＯ系の結晶相を析出する無ア
ルカリ結晶化ガラスで構成されるのが好ましい。そのガ
ラス組成は、特に、ＭｇＯが１６−５０重量％、ＳｉＯ
2が７−３０重量％、Ｂ2Ｏ3が５−３４重量％、ＢａＯ
が０−５０重量％、Ｌａ2Ｏ3が０−４０重量％、ＣａＯ
が０−２０重量％、Ｐ2Ｏ5が０−５重量％、ＭＯ2が０
−５重量％（ただし、ＭはＺｒ、ＴｉおよびＳｎよりな
る群から選択される少なくとも一種の元素）であること
がより好ましい。このように結晶化ガラス材料が選択さ
れる理由の１つは、ガラス層の耐熱温度が高くなるため
である。すなわち、触媒層をガラス層を介して電気抵抗
発熱体により加熱するため、電気抵抗発熱体を被覆する
ガラス層は、少なくとも９００℃程度の高温度に耐える
必要がある。(2) Crystallized Glass Layer From the viewpoint of electrical insulation and heat resistance, the crystallized glass layer is preferably made of alkali-free crystallized glass that precipitates, for example, a MgO-based crystal phase by firing. . The glass composition is, in particular, 16-50 wt% MgO, SiO 2.
2 is 7-30% by weight, B 2 O 3 is 5-34% by weight, BaO
Is 0-50% by weight, La 2 O 3 is 0-40% by weight, CaO
Is 0-20% by weight, P 2 O 5 is 0-5% by weight, and MO 2 is 0.
More preferably, it is -5% by weight (where M is at least one element selected from the group consisting of Zr, Ti and Sn). One of the reasons why the crystallized glass material is selected is that the glass layer has a high heat resistant temperature. That is, since the catalyst layer is heated by the electric resistance heating element via the glass layer, the glass layer covering the electric resistance heating element must withstand a high temperature of at least about 900 ° C.
【０００８】本発明に用いるガラス材料は、結晶化させ
ることにより耐熱温度が９００℃以上になる。９００℃
でもガラスが流動しないので、電気発熱体に通電加熱し
ても、ガラス層内の泡が大きく成長しない。その結果、
絶縁耐力は劣化しない。それに対して、一般の非晶質ガ
ラスは、再加熱しても結晶化しないので、耐熱性は工場
しない。非晶質ガラスは、約６００℃以上でガラスが流
動するので、８００℃以上で焼成すると、ガラス層内の
泡が大きく成長して絶縁耐力の低下を招く。結晶化ガラ
ス材料が選択されるもう１つの理由は、電気抵抗発熱体
とガラス層との密着性を強固にするためである。特に、
上記の組成のガラスは、非常に強固な密着性が得られ
る。The glass material used in the present invention has a heat resistant temperature of 900 ° C. or higher when crystallized. 900 ° C
However, since the glass does not flow, the bubbles in the glass layer do not grow large even when the electric heating element is electrically heated. as a result,
Dielectric strength does not deteriorate. On the other hand, general amorphous glass does not crystallize even if it is reheated, and therefore has no heat resistance. Since amorphous glass flows at a temperature of about 600 ° C. or higher, when it is fired at 800 ° C. or higher, bubbles in the glass layer grow large and the dielectric strength is reduced. Another reason for selecting the crystallized glass material is to strengthen the adhesion between the electric resistance heating element and the glass layer. In particular,
The glass having the above composition provides very strong adhesion.
【０００９】（３）結晶化ガラス層の形成法 結晶化ガラス層を電気抵抗発熱体上に被覆する方法とし
て、通常のスプレー法、粉末静電塗装法、電気泳動電着
法等がある。このなかで、被膜の緻密性、電気絶縁性等
の観点から、電気泳動電着法が最も好ましい。この方法
に用いられるスラリーは、ガラスとアルコールおよび少
量の水をボールミル中で約２０時間粉砕、混合して調製
される。こうして得られるスラリー中のガラスの平均粒
径は１〜５μｍ程度である。得られたスラリーを電解槽
に入れて液を循環する。そして、電気抵抗発熱体をスラ
リー中に浸漬し、１００〜４００Ｖで陰分極させること
により、電気抵抗発熱体表面にガラス粒子を析出させ
る。これを乾燥後、８５０〜９００℃で１０分〜１時間
焼成する。これによって、ガラスの微粒子が溶融すると
ともに、ガラス成分と金属材料が相互拡散するため、結
晶化ガラス層と電気抵抗発熱体との強固な密着が得られ
る。なお、焼成は常温から徐々に昇温して上記温度に到
達させる方法をとると、微細針状結晶が無数に析出し、
耐熱性および触媒被覆層との密着性がより向上するので
好ましい。(3) Method for forming crystallized glass layer As a method for coating the crystallized glass layer on the electric resistance heating element, there are a usual spray method, a powder electrostatic coating method, an electrophoretic electrodeposition method and the like. Among them, the electrophoretic electrodeposition method is the most preferable from the viewpoint of the denseness of the coating film, the electric insulation property, and the like. The slurry used in this method is prepared by grinding and mixing glass, alcohol and a small amount of water in a ball mill for about 20 hours. The average particle size of the glass in the slurry thus obtained is about 1 to 5 μm. The obtained slurry is put in an electrolytic cell and the liquid is circulated. Then, the electric resistance heating element is dipped in the slurry and negatively polarized at 100 to 400 V to deposit glass particles on the surface of the electric resistance heating element. After this is dried, it is baked at 850 to 900 ° C. for 10 minutes to 1 hour. As a result, the glass fine particles are melted and the glass component and the metal material are mutually diffused, so that the crystallized glass layer and the electric resistance heating element can be firmly adhered to each other. Incidentally, when firing is performed by gradually increasing the temperature from room temperature to reach the above temperature, innumerable fine needle-like crystals are precipitated,
It is preferable because the heat resistance and the adhesion to the catalyst coating layer are further improved.
【００１０】（４）触媒層 触媒層は、ゼオライト、無機バインダー、および表面に
貴金属を担持したアルミナから構成されのが好ましい。
触媒層に、吸着特性に優れるゼオライトを含有させるこ
とにより、発熱体に通電しないときには、臭気物質を吸
着することが可能である。この場合、ゼオライトの吸着
能力が飽和に達した時点で、電気抵抗発熱体に通電する
ことにより、吸着された臭気成分の触媒による酸化分解
とゼオライトの再生を行うことができる。触媒層中に含
有するアルミナは、βー、γー、δー、θー、ρー、χ
ー、ηーアルミナなどの準安定アルミナである。なお、
アルミナ表面に希土類酸化物などの助触媒を担持させる
ことにより、さらに活性の向上が期待できる。アルミナ
の触媒層における含有量は、２０〜６０重量％が好まし
い。アルミナ含有量が２０重量％未満の場合、触媒貴金
属が分散しにくくなるため充分な触媒活性が得られな
い。また、６０重量％を越えると触媒の臭気吸着能力が
減少し好ましくない。(4) Catalyst Layer The catalyst layer is preferably composed of zeolite, an inorganic binder, and alumina having a noble metal supported on the surface thereof.
By containing zeolite having excellent adsorption properties in the catalyst layer, it is possible to adsorb odorous substances when the heating element is not energized. In this case, when the adsorption capacity of the zeolite reaches saturation, the oxidative decomposition of the adsorbed odorous component and the regeneration of the zeolite can be performed by energizing the electric resistance heating element. Alumina contained in the catalyst layer is β-, γ-, δ-, θ-, ρ-, χ
And metastable alumina such as η-alumina. In addition,
Further improvement in activity can be expected by supporting a promoter such as a rare earth oxide on the surface of alumina. The content of alumina in the catalyst layer is preferably 20 to 60% by weight. If the alumina content is less than 20% by weight, the catalytic noble metal becomes difficult to disperse, and sufficient catalytic activity cannot be obtained. On the other hand, if it exceeds 60% by weight, the odor adsorbing ability of the catalyst decreases, which is not preferable.
【００１１】さらに、無機バインダーとしては、シリカ
が最も優れており、触媒特性を低下させることなく、ガ
ラス層との優れた高密着性が得られる。シリカの含有量
は１０〜４０重量％が好ましい。４０重量％を越える
と、触媒層中に亀裂が入りやすくなる。また、１０重量
％未満では十分な密着性が得られない。貴金属として
は、白金またはパラジウムを用いるのが望ましく、白金
とパラジウムの両方を用いた場合さらに好ましい。触媒
層中に酸化セリウムを含有することが好ましい。酸化セ
リウムは炭化水素化合物に対する触媒酸化分解活性を向
上することができる。その含有量は２〜１５重量％が好
ましい。含有量が１５重量％を越えると酸化分解特性が
低下する。また、２重量％未満では、添加効果が得られ
ない。触媒層の形成方法は、スプレー、ディップ、静電
塗装、電着、ロールコート、スクリーン印刷法などがあ
る。次に、具体的な実施例について説明する。Further, silica is the most excellent inorganic binder, and excellent adhesion to the glass layer can be obtained without deteriorating the catalytic properties. The content of silica is preferably 10 to 40% by weight. If it exceeds 40% by weight, cracks are likely to occur in the catalyst layer. If it is less than 10% by weight, sufficient adhesion cannot be obtained. It is desirable to use platinum or palladium as the noble metal, and it is more preferable to use both platinum and palladium. It is preferable to contain cerium oxide in the catalyst layer. Cerium oxide can improve the catalytic oxidative decomposition activity for hydrocarbon compounds. The content is preferably 2 to 15% by weight. If the content exceeds 15% by weight, the oxidative decomposition characteristics deteriorate. If it is less than 2% by weight, the effect of addition cannot be obtained. Examples of the method for forming the catalyst layer include spraying, dipping, electrostatic coating, electrodeposition, roll coating and screen printing. Next, specific examples will be described.
【００１２】［実施例１］表２のＮｏ．７に示す組成の
結晶化ガラスにアルコールおよび少量の水を加え、ボー
ルミル中で約２０時間粉砕、混合し、電着用スラリーを
調製した。このスラリー中に、図１に示した形状のステ
ンレス鋼ＳＵＳ４３０製電気抵抗発熱体１を浸漬し、そ
の表面を１５０Ｖ／ｃｍの電圧勾配で陰分極する電気泳
動電着法により、表面にガラス粒子を厚さ１００μｍ被
着し、さらに８８０℃で１０分間焼成して、結晶化ガラ
ス層２を形成して発熱素子サンプルとした。一方、Ｐｔ
を担持したアルミナ１６０ｇ、無水珪酸を２０重量％相
当含む無水珪酸コロイド溶液４００ｇ、水２００ｇ、お
よび銅イオン交換Ａ型ゼオライト１６０ｇを、ボールミ
ルを用いて十分に混合して平均粒径４．５μｍの触媒用
スラリーを調製した。このスラリーを上記発熱素子サン
プル表面にスプレーで塗装した後、１００℃で２時間乾
燥し、次に５００℃で１時間焼成して触媒層３を形成し
た。[Example 1] No. 1 in Table 2 Alcohol and a small amount of water were added to the crystallized glass having the composition shown in 7, and the mixture was ground in a ball mill for about 20 hours and mixed to prepare a slurry for electrodeposition. An electric resistance heating element 1 made of stainless steel SUS430 having the shape shown in FIG. 1 was immersed in this slurry, and glass particles were formed on the surface by an electrophoretic electrodeposition method in which the surface was negatively polarized with a voltage gradient of 150 V / cm. A 100 μm-thick coating was applied and further baked at 880 ° C. for 10 minutes to form a crystallized glass layer 2 to obtain a heating element sample. On the other hand, Pt
160 g of alumina supporting silica, 400 g of a silicic acid colloidal solution containing 20% by weight of silicic acid anhydride, 200 g of water, and 160 g of copper ion-exchanged A-type zeolite were thoroughly mixed using a ball mill to obtain a catalyst having an average particle size of 4.5 μm. A slurry was prepared. The slurry was applied on the surface of the heating element sample by spraying, dried at 100 ° C. for 2 hours, and then baked at 500 ° C. for 1 hour to form a catalyst layer 3.
【００１３】［比較例１］Ｎｏ．７の組成のガラス１０
０重量部に粘土４重量部、亜硝酸ソーダ０．１重量部お
よび水３５重量部を添加し、１時間ボールミル粉砕し、
ホーロスリップとした。これを電気抵抗発熱体表面にス
プレーガンで約１００μｍ形成し、８８０℃で１０分間
焼成しガラス層を形成して発熱素子サンプルとした。次
いで、この発熱素子サンプルに実施例１と同様にして触
媒層を形成した。Comparative Example 1 No. Glass 10 of composition 7
4 parts by weight of clay, 0.1 parts by weight of sodium nitrite and 35 parts by weight of water were added to 0 parts by weight, and ball-milled for 1 hour,
It was a horo slip. This was formed on the surface of the electric resistance heating element with a spray gun to a thickness of about 100 μm and baked at 880 ° C. for 10 minutes to form a glass layer, which was used as a heating element sample. Then, a catalyst layer was formed on this heating element sample in the same manner as in Example 1.
【００１４】［比較例２］比較例１で作製したホーロス
リップ中に電気抵抗発熱体を浸漬した後、８８０℃で１
０分間焼成してガラス層を形成して発熱素子サンプルと
した。次いで、この発熱素子サンプルに実施例１と同様
にして触媒層を形成した。[Comparative Example 2] An electric resistance heating element was dipped in the holo-slip prepared in Comparative Example 1 and then subjected to 1 at 880 ° C.
A glass layer was formed by firing for 0 minutes to obtain a heating element sample. Then, a catalyst layer was formed on this heating element sample in the same manner as in Example 1.
【００１５】以上の各発熱素子サンプルについて絶縁性
を評価した結果を説明する。絶縁評価は、発熱素子サン
プルおよび対極を水中に浸漬し、対極と発熱素子間の絶
縁抵抗と絶縁耐力を測定した。なお、絶縁抵抗は、サン
プルと対極間に５００Ｖの電圧を印加した時の抵抗を測
定した。絶縁耐力は、国洋電機（株）製耐圧絶縁自動試
験器を用い、遮断電流を１０ｍＡに設定し、サンプルと
対極間に１０００Ｖの電圧を１分間印加した時のリーク
の有無を×、○で表した。評価結果を表１に示す。表１
から明らかなように、電着法でガラス層を形成した発熱
素子は、電気絶縁性に著しく優れている。スプレー法、
ディップ法は、ホーロを均一に被膜化することは難しい
ため、ホーロ欠陥部が電気絶縁性不良部となる。それに
対し、電着法は、電気化学的にガラス層を均一に形成す
ることができるため、ホーロ欠陥部がなく、電気絶縁性
に優れている。The results of evaluating the insulation of each of the above heating element samples will be described. In the insulation evaluation, the heating element sample and the counter electrode were immersed in water, and the insulation resistance and the dielectric strength between the counter electrode and the heating element were measured. The insulation resistance was measured when a voltage of 500 V was applied between the sample and the counter electrode. With respect to the dielectric strength, a voltage withstanding automatic tester manufactured by Kuniyo Denki Co., Ltd. was used, the breaking current was set to 10 mA, and the presence or absence of leakage when a voltage of 1000 V was applied between the sample and the counter electrode for 1 minute was marked with × and ○ expressed. The evaluation results are shown in Table 1. Table 1
As is clear from the above, the heating element having the glass layer formed by the electrodeposition method is remarkably excellent in electrical insulation. Spray method,
In the dipping method, it is difficult to coat the holo uniformly, so that the holo defect part becomes a poor electrical insulation part. On the other hand, the electrodeposition method is capable of electrochemically forming a uniform glass layer, and therefore has no hollow defects and is excellent in electrical insulation.
【００１６】[0016]
【表１】 [Table 1]
【００１７】［実施例２］図１に示した形状のステンレ
ス鋼ＳＵＳ４３０製電気抵抗発熱体の表面に、電気泳動
電着法により各種組成の結晶化ガラスを１００μｍの厚
さに被着し、８８０℃で１０分間焼成して結晶化ガラス
層を形成した。これらのサンプルについて、結晶化ガラ
ス層の表面粗度、うねり性、耐熱性等の諸特性を調べ
た。その結果をガラスの組成とともに表２〜表７に示し
ている。[Embodiment 2] Crystallized glass of various compositions is deposited to a thickness of 100 μm on the surface of an electric resistance heating element made of stainless steel SUS430 having the shape shown in FIG. The glass was fired at 10 ° C. for 10 minutes to form a crystallized glass layer. With respect to these samples, various properties such as surface roughness, waviness and heat resistance of the crystallized glass layer were examined. The results are shown in Tables 2 to 7 together with the glass compositions.
【００１８】表面粗度は、タリサーフ表面粗さ計で測定
し、表面中心線平均粗さＲａで示し、絶縁耐圧は実施例
１の絶縁耐力評価と同じ方法で行った。また、耐熱性
は、サンプルを８５０℃の電気炉中に１０分間入れ、次
に炉から取り出して３０分間自然放冷する操作を繰り返
すスポーリングテストを行って、サンプルのクラックや
剥離の状態を調べた。なお、クラックの有無は、サンプ
ルを赤インク中に浸漬した後、表面を拭き取った際、目
視観察による残存インクの有無で判定した。そして、上
記の操作を１０サイクル以上行ってもクラックが認めら
れないものを○印、５〜９サイクルでクラックが発生し
たものを△印、４サイクル以下でクラックが発生したも
のを×印で表した。密着性は、サンプルの曲げ試験を行
い、ガラス層が電気抵抗発熱体から剥離して金属部が露
出したものを×印、金属部が一部だけ露出したものを△
印、金属部が露出していないものを○印で表した。The surface roughness was measured with a Talysurf surface roughness meter and indicated by the surface center line average roughness Ra, and the withstand voltage was measured by the same method as the dielectric strength evaluation of Example 1. For heat resistance, the sample was placed in an electric furnace at 850 ° C for 10 minutes, then taken out of the furnace and allowed to cool naturally for 30 minutes. A spalling test was repeated to examine the state of cracks and peeling of the sample. It was The presence / absence of cracks was judged by the presence / absence of residual ink by visual observation when the surface was wiped after the sample was immersed in red ink. And, the cracks are not recognized even after 10 cycles or more of the above-mentioned operations, the cracks are shown in 5 to 9 cycles, and the cracks are shown in 4 cycles or less. did. The adhesion was evaluated by conducting a bending test on the sample, and the glass layer was peeled from the electric resistance heating element to expose the metal part, and the metal part was exposed.
The mark and the part where the metal part is not exposed are indicated by a circle.
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【表４】 [Table 4]
【００２２】[0022]
【表５】 [Table 5]
【００２３】[0023]
【表６】 [Table 6]
【００２４】[0024]
【表７】 [Table 7]
【００２５】以上の評価にもとずき総合評価を行い、そ
の結果を優（○）、良（△）、可（×）で示した。Ｎ
ｏ．１〜８は他の成分を一定として、ＳｉＯ2とＢ2Ｏ3
を変化させたもの、Ｎｏ．９〜１５は、ＳｉＯ2／Ｂ2Ｏ
3をほぼ一定にし、ＭｇＯ量を変化させたもの、Ｎｏ．
１６〜１９は同じくＣａＯ量を変化させたもの。Ｎｏ．
２０〜２４は、同じくＢａＯ量を変化させたもの、Ｎ
ｏ．２５〜２９は、同じくＬａ2Ｏ3量を変化させたも
の、Ｎｏ．３０〜４２はそれぞれ、ＺｒＯ2、ＴｉＯ2、
ＳｎＯ2、Ｐ2Ｏ5、ＺｎＯの影響を示す。表から明らか
なように、いずれの組成でも電着法で形成すれば、絶縁
耐圧は問題なかったが、その他の特性は組成によって変
化した。ＳｉＯ2を増加させれば、耐熱性は向上する
が、表面性および密着性が悪くなる。逆に、Ｂ2Ｏ3量を
増加させれば、表面性、密着性は向上するが、耐熱性は
低下する。したがって、ＳｉＯ2７〜３０重量％、Ｂ2Ｏ
3５〜３４重量％の範囲内が好ましい。Based on the above evaluations, a comprehensive evaluation was performed, and the results are shown as excellent (◯), good (Δ), and acceptable (x). N
o. 1 to 8 are SiO 2 and B 2 O 3 with other components being constant.
No. 9 to 15 are SiO 2 / B 2 O
No. 3 in which the MgO amount was changed while keeping 3 almost constant.
16 to 19 are the ones with the same CaO content. No.
Nos. 20 to 24 have the same amount of BaO, N
o. Nos. 25 to 29 have the same La 2 O 3 content, No. 30 to 42 are ZrO 2 , TiO 2 , and
The influence of SnO 2 , P 2 O 5 , and ZnO is shown. As is clear from the table, when any composition was formed by the electrodeposition method, there was no problem with the dielectric strength, but other characteristics varied depending on the composition. If the amount of SiO 2 is increased, the heat resistance is improved, but the surface property and the adhesion are deteriorated. On the contrary, when the amount of B 2 O 3 is increased, the surface property and the adhesion are improved, but the heat resistance is decreased. Therefore, SiO 2 7 to 30 wt%, B 2 O
It is preferably within the range of 35 to 34% by weight.
【００２６】ＭｇＯ量は結晶性と相関があり、１６重量
％未満では結晶析出が不十分で、耐熱性に劣る。また、
５０重量％を越えると、結晶が析出しやすく、ガラス溶
融時に簡単に結晶化し、均質なガラスを得ることが難し
く、また表面粗度が大きくなる。ＣａＯ量は、２０重量
％を越えると、表面性が悪くなり好ましくない。ＢａＯ
量は、５０重量％を越えると、耐熱性および密着性が劣
化し好ましくない。Ｌａ2Ｏ3は、４０重量％を越える
と、耐熱性が劣化し好ましくない。その他の添加可能な
成分はＺｒＯ2、ＴｉＯ2、ＳｎＯ2、Ｐ2Ｏ5、ＺｎＯな
どが挙げられるが、５重量％ｍａでなら添加可能であ
る。The amount of MgO has a correlation with the crystallinity, and if it is less than 16% by weight, the precipitation of crystals is insufficient and the heat resistance is poor. Also,
If it exceeds 50% by weight, crystals tend to precipitate, it is difficult to crystallize when the glass melts, it is difficult to obtain a homogeneous glass, and the surface roughness increases. When the amount of CaO exceeds 20% by weight, the surface property is deteriorated, which is not preferable. BaO
If the amount exceeds 50% by weight, heat resistance and adhesion are deteriorated, which is not preferable. When La 2 O 3 exceeds 40% by weight, the heat resistance deteriorates, which is not preferable. Other additives can be component of ZrO 2, TiO 2, SnO 2 , P 2 O 5, but including ZnO and the like, can be added if a 5 wt% ma.
【００２７】［実施例３］実施例１の発熱体および図３
に示した従来例の発熱体を用いて、イソ吉草酸浄化試験
および耐熱衝撃試験を行った。イソ吉草酸浄化試験は、
２５０リットルの立方体のフッ素樹脂製容器の中に上記
発熱体を置き、濃度が４０ｐｐｍになるようにイソ吉草
酸を容器内に注入し、所定時間発熱体に通電後、イソ吉
草酸の濃度を調べた。表８に、発熱体への通電時間とイ
ソ吉草酸の残存率の関係を示した。[Embodiment 3] The heating element of Embodiment 1 and FIG.
An isovaleric acid purification test and a thermal shock test were conducted using the heating element of the conventional example shown in FIG. Isovaleric acid purification test
The above heating element is placed in a 250 liter cubic container made of fluororesin, and isovaleric acid is injected into the container so that the concentration becomes 40 ppm. After the heating element is energized for a predetermined time, the concentration of isovaleric acid is examined. It was Table 8 shows the relationship between the energization time to the heating element and the residual ratio of isovaleric acid.
【００２８】[0028]
【表８】 [Table 8]
【００２９】表８から明らかなように、本発明による発
熱体では、触媒による浄化作用が効果的に行われる活性
温度に到達するのが早く、浄化性能に優れる。熱衝撃試
験は、発熱体への印加電圧を変化させて、触媒層温度を
２５℃きざみに変化させて、その温度で１０分間保持し
た後、水中に投下し、触媒層の剥離の有無を調べ、剥離
を起こさない最高温度を耐熱衝撃温度とした。表９に発
熱体の熱衝撃試験結果を示す。表９から明らかなよう
に、本発明の発熱体は、従来例より耐熱衝撃性に優れて
いる。As is clear from Table 8, the heating element according to the present invention quickly reaches the activation temperature at which the catalytic purifying action is effectively performed, and the purifying performance is excellent. In the thermal shock test, the applied voltage to the heating element is changed to change the temperature of the catalyst layer in steps of 25 ° C., the temperature is held for 10 minutes, and then the temperature is dropped into water to check whether the catalyst layer is peeled. The maximum temperature at which peeling did not occur was defined as the thermal shock resistance temperature. Table 9 shows the thermal shock test results of the heating element. As is clear from Table 9, the heating element of the present invention is superior in thermal shock resistance to the conventional example.
【００３０】[0030]
【表９】 [Table 9]
【００３１】[0031]
【発明の効果】以上のように本発明によれば、触媒を効
率的に作用させるための速熱性を有し、機器のコンパク
ト化を可能にする発熱体を得ることができる。As described above, according to the present invention, it is possible to obtain a heating element which has a rapid heating property for allowing the catalyst to act efficiently, and which enables the equipment to be made compact.
【図１】本発明の実施例に用いた電気抵抗発熱体を示す
平面図である。FIG. 1 is a plan view showing an electric resistance heating element used in an example of the present invention.
【図２】本発明の実施例における発熱体の要部の拡大断
面図である。FIG. 2 is an enlarged cross-sectional view of a main part of the heating element according to the embodiment of the present invention.
【図３】従来の発熱体の断面図である。FIG. 3 is a cross-sectional view of a conventional heating element.
１ 電気抵抗発熱体 ２ 結晶化ガラス層 ３ 触媒層 1 Electric resistance heating element 2 Crystallized glass layer 3 Catalyst layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０３Ｃ 3/064 10/00 Ｈ０５Ｂ 3/10 Ｚ 7512−3Ｋ (72)発明者 吉田 昭彦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C03C 3/064 10/00 H05B 3/10 Z 7512-3K (72) Inventor Akihiko Yoshida Kadoma Osaka Prefecture 1006 Kadoma, Oita-shi Matsushita Electric Industrial Co., Ltd.
Claims (4)
形成するとともに前記結晶化ガラス層の上に触媒層を形
成したことを特徴とする発熱体。1. A heating element comprising a crystallized glass layer formed on the surface of an electric resistance heating element and a catalyst layer formed on the crystallized glass layer.
６−５０重量％、ＳｉＯ2が７−３０重量％、Ｂ2Ｏ3が
５−３４重量％、ＢａＯが０−５０重量％、Ｌａ2Ｏ3が
０−４０重量％、ＣａＯが０−２０重量％、Ｐ2Ｏ5が０
−５重量％、ＭＯ2が０−５重量％（ただし、ＭはＺ
ｒ、ＴｉおよびＳｎよりなる群から選択される少なくと
も一種の元素）である請求項１記載の発熱体。2. The composition of the crystallized glass is such that MgO is 1
6-50% by weight, SiO 2 7-30% by weight, B 2 O 3 5-34% by weight, BaO 0-50% by weight, La 2 O 3 0-40% by weight, CaO 0-20. % By weight, P 2 O 5 is 0
-5 wt%, MO 2 0-5 wt% (where M is Z
The heating element according to claim 1, which is at least one element selected from the group consisting of r, Ti, and Sn.
ダー、および貴金属を担持したアルミナからなる請求項
１または２記載の発熱体。3. The heating element according to claim 1, wherein the catalyst layer is made of zeolite, an inorganic binder, and alumina carrying a noble metal.
より結晶化ガラス粒子を被着し、焼成して結晶化ガラス
層を形成する工程と、前記結晶化ガラス層上に触媒層を
形成する工程を有する発熱体の製造方法。4. A step of depositing crystallized glass particles on the surface of an electric resistance heating element by an electrophoretic electrodeposition method and firing to form a crystallized glass layer, and forming a catalyst layer on the crystallized glass layer. The manufacturing method of the heat generating body which has the process to do.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6096301A JPH07302678A (en) | 1994-05-10 | 1994-05-10 | Heating element and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6096301A JPH07302678A (en) | 1994-05-10 | 1994-05-10 | Heating element and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07302678A true JPH07302678A (en) | 1995-11-14 |
Family
ID=14161216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6096301A Pending JPH07302678A (en) | 1994-05-10 | 1994-05-10 | Heating element and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07302678A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005132643A (en) * | 2003-10-28 | 2005-05-26 | Denso Corp | Hydrogen storage feed system |
| JP2011168480A (en) * | 2010-02-15 | 2011-09-01 | Schott Ag | High-temperature glass solder and its use |
| US9296644B2 (en) | 2010-02-15 | 2016-03-29 | Schott Ag | High-temperature glass solder and its uses |
-
1994
- 1994-05-10 JP JP6096301A patent/JPH07302678A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005132643A (en) * | 2003-10-28 | 2005-05-26 | Denso Corp | Hydrogen storage feed system |
| JP2011168480A (en) * | 2010-02-15 | 2011-09-01 | Schott Ag | High-temperature glass solder and its use |
| US9296644B2 (en) | 2010-02-15 | 2016-03-29 | Schott Ag | High-temperature glass solder and its uses |
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