[go: up one dir, main page]

WO2008014677A1 - Rare earth electrode slurry for rare earth thick-film circuit based on metal substrate and producing process thereof - Google Patents

Rare earth electrode slurry for rare earth thick-film circuit based on metal substrate and producing process thereof Download PDF

Info

Publication number
WO2008014677A1
WO2008014677A1 PCT/CN2007/002223 CN2007002223W WO2008014677A1 WO 2008014677 A1 WO2008014677 A1 WO 2008014677A1 CN 2007002223 W CN2007002223 W CN 2007002223W WO 2008014677 A1 WO2008014677 A1 WO 2008014677A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
rare earth
glass
palladium
silver
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.)
Ceased
Application number
PCT/CN2007/002223
Other languages
French (fr)
Chinese (zh)
Inventor
Kezheng Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of WO2008014677A1 publication Critical patent/WO2008014677A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H01C17/06546—Oxides of zinc or cadmium
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013—Heaters using resistive films or coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters

Definitions

  • the invention relates to a rare earth electrode slurry for a rare earth thick film circuit based on a metal substrate, in particular to a ferritic stainless steel series substrate, for example, a rare earth electrode paste for a high power rare earth thick film circuit such as a national standard brand lCrl5, lCrl7, 00Crl2 and the like Its preparation process technology.
  • the new heating element requires small volume, high power, small thermal inertia, large surface thermal load, low power consumption, high thermal efficiency, fast hot start, stable power, uniform temperature field, and process. Good sex, self-controlled temperature, safe and reliable operation, long life, adapt to the scope of the wide. At present, there is no heating element that can meet the above requirements, so the research of a new type of electric heating element such as a rare earth thick film electric heating element is imperative.
  • the object of the present invention is to provide a rare earth thick based on a metal substrate which has good electrical conductivity, strong adhesion, excellent printing characteristics, sintering characteristics, environmental performance, and excellent wettability with metal substrates, resistor blades, and dielectric pastes.
  • Membrane circuit rare earth electrode paste is to provide a rare earth thick based on a metal substrate which has good electrical conductivity, strong adhesion, excellent printing characteristics, sintering characteristics, environmental performance, and excellent wettability with metal substrates, resistor blades, and dielectric pastes.
  • Another object of the present invention is to provide a rare earth thick film circuit based on the above metal substrate. Preparation process of soil electrode slurry.
  • the rare earth electrode slurry of the rare earth thick film circuit based on the metal substrate is composed of a solid phase component and an organic solvent carrier, and the weight ratio thereof is: (70 to 90): (30 to 10).
  • the solid phase component comprises: a silver-palladium-ruthenium composite powder and a glass-ceramic powder, the weight ratio of which is: (99.4 ⁇ 94): (0.6 ⁇ 6), the palladium powder, the silver powder and the tantalum powder in the silver-palladium-ruthenium composite powder The particle size is less than 2 ⁇ ⁇ .
  • the weight ratio of palladium powder, silver powder and strontium powder is: (0.6 ⁇ 10) : (99 ⁇ 82) : (0.4 ⁇ 8).
  • the glass ceramic is a SiO 2 -Al 2 0 3 -CaO-B 2 0 3 -Bi 2 0 3 -La 2 0 3 -based glass ceramic, and the weight ratio of each oxide component is: Si0 2 ( 20 ⁇ 60%), A1 2 0 3 (5 ⁇ 35%), CaO (10 ⁇ 35%), B 2 0 3 (1 ⁇ 15%), La 2 0 3 (0 ⁇ 3 ⁇ 15%), Bi 2 0 3 (10 ⁇ 30%), Ti0 2 (Bu 10%), Zr0 2 (1 ⁇ 10%).
  • the group distribution ratio (by weight) of the organic solvent carrier is: terpineol (60 to 98%), tributyl citrate (10 to 30%), ethyl cellulose (2 to 10%), and nitrocellulose. (1 ⁇ 5%), hydrogenated castor oil (0.1 ⁇ 5%), lecithin (0.1 ⁇ 5%).
  • the preparation process of the invention is as follows: (1) Preparation of rare earth glass-ceramic powder-2 Preparation of silver-palladium-composite powder-3 Preparation of organic solvent carrier-four-dimensional three-dimensional mixing three-rolling rolling one 5 rare earth electrode paddle preparation one 6 bottled for use .
  • the expansion coefficient is matched with the metal substrate and the dielectric slurry, and the combination is firm, and the electrical conductivity, the breakdown strength and the insulation performance are effectively improved.
  • the electrode paste and the metal substrate are enhanced in oxidation resistance and ductility, and the bonding strength is improved.
  • Rare earth lanthanum (La) doping greatly changes the sintering properties, microstructure, density, phase composition and physical and mechanical properties of the glass-ceramic material phase. Thereby, the dielectric strength, electrical performance, process performance of the rare earth thick film circuit electric heating element and the wettability, compatibility and molecular bonding strength of the electronic paddle are improved. Improve the process and significantly improve the product's excellent rate.
  • the rare earth electrode paddle of the rare earth thick film circuit of the invention has excellent printing performance and sintering performance. It has excellent wettability and compatibility with rare earth resist paste and medium paste.
  • an excellent solvent such as hydrogenated castor oil is used as a thixotropic agent to form a good colloidal structure, so that the slurry has good thixotropy and anti-settling effect.
  • the rare earth functional electrode paste of the present invention can be prepared not only on a metal substrate but also on a glass ceramic, ceramic and other metal non-metal substrate. It can be prepared not only on a flat surface but also on a curved surface.
  • the rare earth electrode slurry of the invention has good electrical conductivity, good enthalpy performance, good contact performance, good solder joint integrity and firm connection; the material of the invention does not need to rely on import, 100% localization, reduce precious metal dosage, low cost, material consumption Less, energy-saving; in line with the new industrialization road of circular economy advocated by China (high scientific and technological content, good economic efficiency, low resource consumption, low environmental pollution), and has a strong prospect of foreign exchange earning.
  • the rare earth electrode slurry for rare earth thick film circuit of the invention and the preparation technique thereof are applicable to a ferritic series stainless steel substrate.
  • a ferritic series stainless steel substrate For example: national brand number lCrl5, lCrl7, 00Crl2, etc., foreign brand number 429#, 430#, 410L# and so on.
  • the electrode paddle is compatible with a variety of metal substrate dielectric materials and resistor pastes.
  • metal substrate dielectric materials and resistor pastes For example, an alumina substrate (A1 2 0 3 ), an aluminum nitride (AIN) substrate, a glass-ceramic substrate, a metal alloy aluminum, a titanium alloy substrate, or the like.
  • the heating element adopting the invention is the only one that meets the requirements of small volume, high power, small thermal inertia, large surface heat load, low power consumption, high thermal efficiency, fast heat start, stable power, uniform temperature field, good processability, and self-property. Electric heating element with temperature control, safe and reliable operation, long service life and wide range of requirements. detailed description .
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • This embodiment is a rare earth electrode paste for a rare earth thick film circuit used for a 1CT15 (429#) series stainless steel substrate.
  • the electrode slurry is composed of a solid phase component and an organic solvent carrier, and the solid phase component comprises a silver palladium ruthenium composite powder and a glass ceramic powder.
  • the specific formulation and process are as follows -
  • Glass-ceramic formula The weight ratio of each oxide component is: Si0 2 (28%), Al 2 0 3 (l, 6 D /.), Ca0 (14%), B 2 0 3 (7% ), La 2 0 3 (5%), Bi 2 0 3 ' (22%), Ti0 2 (5%), Zr0 2 (2%):
  • Glass-ceramic smelting process The smelting temperature is: 1350 ⁇ After 120 minutes of heat preservation, it is quickly quenched by water to obtain glass micro slag. The glass slag was placed in a two-stage ball mill to prepare a glass-ceramic powder having a particle diameter of less than 3 ⁇ m.
  • the particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 ⁇ m.
  • the weight ratio of palladium powder, silver powder and strontium powder is: 2: 97: 1.
  • Organic solvent carrier formulation and dissolution process The distribution ratio (weight) of each group of organic solvent carrier is: terpineol (78%), tributyl citrate (18%), ethyl cellulose (4%), nitrate Cellulose (2), hydrogenated castor oil (0.6%), lecithin (0.8%).
  • the above mixed organic solvent is mixed and dissolved in 85 ⁇ water temperature for several hours to adjust the content of ethyl cellulose and nitrocellulose to make organic
  • the solvent carrier viscosity was controlled in the range of 245 mPas.
  • the slurry consists of a solid phase component and an organic solvent carrier.
  • the weight ratio is: 78: 22.
  • the weight ratio of the silver-palladium-ruthenium composite powder to the glass-ceramic powder is 98. 5: 1. 5.
  • the particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 ⁇ m.
  • the above-mentioned proportioning raw materials were placed in a three-dimensional mixer and stirred and dispersed, and then placed in a three-roll mill to obtain a rare earth electrode slurry.
  • the viscosity of the test slurry was 186 PaS/RPM.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the present embodiment is a rare earth electrode pad for a rare earth thick film circuit for a lCrl7 (430#) series stainless steel substrate, the electrode slurry is composed of a solid phase component and an organic solvent carrier, and the solid phase component comprises a silver palladium ruthenium composite powder and a micro Crystal glass powder, its specific process and formula are as follows -
  • Glass-ceramic formula The weight ratio of each oxide component is: Si0 2 (30%), Al 2 0 3 (16%), Ca0 (13%). B 2 0 3 (8%), La 2 0 3 (6%), Bi 2 0 3 (26%), Ti0 2 (6%), Zr0 2 (3%):
  • Glass-ceramic smelting process The smelting temperature is: 135CTC After 120 minutes of heat preservation, it is quickly quenched by water to obtain glass micro slag. The glass slag was placed in a two-stage ball mill to prepare a glass-ceramic powder having a particle diameter of less than 3 ⁇ m.
  • Modulation of silver-palladium-ruthenium composite powder The particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 ⁇ m.
  • the weight ratio of palladium powder, silver powder and tantalum powder is 1: 98: 1.
  • Organic solvent carrier formulation and dissolution process The distribution ratio of each group of organic solvent carrier is (by weight): terpineol (76%), tributyl citrate (17 ° /.), ethyl cellulose (3%) ), nitrocellulose (3), hydrogenated castor oil (0.7%), lecithin (0.3%).
  • the above mixed organic solvent was mixed and dissolved in 85 Torr of water for several hours to adjust the content of ethyl cellulose and nitrocellulose to control the viscosity of the organic solvent carrier to be in the range of 250 mPas.
  • the slurry consists of a solid phase component and an organic solvent carrier.
  • the weight ratio is: 77: 23.
  • the weight ratio of the silver-palladium-ruthenium composite powder to the glass-ceramic powder in the solid phase component is 98:2.
  • the particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 ⁇ m.
  • the above-mentioned proportioning raw materials were placed in a three-dimensional mixer and stirred and dispersed, and then placed in a three-roll mill to obtain a rare earth electrode slurry.
  • the viscosity of the test slurry was 190 PaS/RPM.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Glass Compositions (AREA)
  • Conductive Materials (AREA)

Abstract

A rare earth electrode slurry for a rare earth thick-film circuit based on a metal substrate and producing process thereof, the slurry is composed of a solid phase component and an organic solvent carrier in wt ratio of (70-90):(30-10). The solid phase component includes an Ag-Pd-Y compound powder and a microcrystal glass powder in wt ratio of (99.4-94):(0.6-6). The wt ratio of Pd powder, Ag powder and Y powder in the Ag-Pd-Y compound powder is (0.6-10):(99-82):(0.4-8). The microcrystal glass powder is SiO2-Al2O3-CaO-B2O3-Bi2O3-La2O3-based microcrystal glass. Its producing process includes following steps: (1) preparing the microcrystal glass powder;(2) preparing the Ag-Pd-Y compound powder;(3) preparing the organic solvent carrier;(4) roller trio mixing and roller trio rolling;(5) preparing the rare earth electrode slurry;(6) bottling for use.

Description

基于金属基板的稀土厚膜电路用稀土电极桨料及其制备工艺 技术领域  Rare earth electrode paddle for rare earth thick film circuit based on metal substrate and preparation process thereof

本发明涉及一种基于金属基板的稀土厚膜电路稀土电极浆料，特别涉 及基于铁素体不锈钢系列基板， 例如： 国标牌号 lCrl5、 lCrl7、 00Crl2 等大功率稀土厚膜电路用稀土电极浆料及其制备工艺技术。  The invention relates to a rare earth electrode slurry for a rare earth thick film circuit based on a metal substrate, in particular to a ferritic stainless steel series substrate, for example, a rare earth electrode paste for a high power rare earth thick film circuit such as a national standard brand lCrl5, lCrl7, 00Crl2 and the like Its preparation process technology.

背景技术 Background technique

环境保护和提高能量利用率、改善能量结构是我国的可持续发展战略 的一部份。 在电加热领域中， 新型的加热元件要求体积要小、 功率要大、 热惰性要小、 表面热负荷要大、 耗电低、 热效率要高、 热启动快、 功率稳 定、 温度场均匀、 工艺性好、 本体自控温、 运行安全可靠， 寿命长，适应 范'围广。 目前， 还没有能满足上述要求的加热元件， 因此采用的新型电热 元件如稀土厚膜电路电热元件的研究势在必行。  Environmental protection and improved energy efficiency and improved energy structure are part of our sustainable development strategy. In the field of electric heating, the new heating element requires small volume, high power, small thermal inertia, large surface thermal load, low power consumption, high thermal efficiency, fast hot start, stable power, uniform temperature field, and process. Good sex, self-controlled temperature, safe and reliable operation, long life, adapt to the scope of the wide. At present, there is no heating element that can meet the above requirements, so the research of a new type of electric heating element such as a rare earth thick film electric heating element is imperative.

二十一世纪初，美国杜邦公司将其用于咖啡壶的不锈钢发热盘推向中 国布场， 国内科研院校 '2003年也陆续推出用于不锈钢基板的厚膜电路电 子浆料， 但都使用同一种基板， 同一类电子浆料， 包括介质浆料、 贵金属 电阻浆料 （银钯）、 导电浆料。 其技术成本、 质量成本、 产品质量、 应用 范围都受到限制， 尤其是介质浆料制备效率低、 电器性能、 湿润性差， 电 阻浆料稳定性欠佳、 成本高居不下， 还存在电极浆料易氧化、 高温下银离 子易迁移、 附着力不牢等缺陷， 致使该技术推广应用发展缓慢。  At the beginning of the 21st century, DuPont of the United States pushed its stainless steel heating plate for coffee pots to the Chinese cloth field. Domestic research institutes also launched thick film electronic pastes for stainless steel substrates in 2003, but they all used The same type of substrate, the same type of electronic paste, including dielectric paste, noble metal resistance paste (silver palladium), conductive paste. Its technical cost, quality cost, product quality and application range are limited, especially the low efficiency of dielectric slurry preparation, poor electrical performance and wettability, poor stability of resistive paste, high cost, and electrode paste oxidation. The silver ions are easy to migrate at high temperature, and the adhesion is not strong enough, which makes the development and application of this technology develop slowly.

发明内容 Summary of the invention

本发明的目的在于提供一种导电性能好、 附着力强、 印刷特性、 烧结 特性、 环保性能优良且与金属基板、 电阻桨料、 介质浆料湿润性相容性优 良的基于金属基板的稀土厚膜电路稀土电极浆料。  The object of the present invention is to provide a rare earth thick based on a metal substrate which has good electrical conductivity, strong adhesion, excellent printing characteristics, sintering characteristics, environmental performance, and excellent wettability with metal substrates, resistor blades, and dielectric pastes. Membrane circuit rare earth electrode paste.

本发明的另一目的在于提供一种上述基于金属基板的稀土厚膜电路稀 土电极浆料的制备工艺。 Another object of the present invention is to provide a rare earth thick film circuit based on the above metal substrate. Preparation process of soil electrode slurry.

本发明是通过如下技术方案来实现上述目的：  The present invention achieves the above objects by the following technical solutions:

本发明基于金属基板的稀土厚膜电路稀土电极浆料， 是由固相成分与 有机溶剂载体组成， 其重量比为： （70〜90 ) ： ( 30〜10)。 所述固相成分 包括：银钯钇复合粉与微晶玻璃粉，其重量比为：（99.4〜94 ) ： ( 0.6〜6)， 该银钯钇复合粉中钯粉、 银粉与钇粉的粒径小于 2 μ ιη。 钯粉、 银粉与钇 粉的重量比为： （0.6〜10 ) ： ( 99〜82 ) ： ( 0.4〜8)。  The rare earth electrode slurry of the rare earth thick film circuit based on the metal substrate is composed of a solid phase component and an organic solvent carrier, and the weight ratio thereof is: (70 to 90): (30 to 10). The solid phase component comprises: a silver-palladium-ruthenium composite powder and a glass-ceramic powder, the weight ratio of which is: (99.4~94): (0.6~6), the palladium powder, the silver powder and the tantalum powder in the silver-palladium-ruthenium composite powder The particle size is less than 2 μ ιη. The weight ratio of palladium powder, silver powder and strontium powder is: (0.6~10) : (99~82) : (0.4~8).

所述微晶玻璃为 Si02-Al203-CaO-B203-Bi203-La203系微晶玻璃， 各氧 化物的成分重量配比为： Si02 ( 20〜60%)、 A1203 ( 5〜35%)、 CaO(10〜 35%)、 B203 ( 1〜15%)、 La203 ( 0·3〜15%)、 Bi203 ( 10〜30%)、 Ti02 (卜 10%)、 Zr02 ( 1〜10%)。 The glass ceramic is a SiO 2 -Al 2 0 3 -CaO-B 2 0 3 -Bi 2 0 3 -La 2 0 3 -based glass ceramic, and the weight ratio of each oxide component is: Si0 2 ( 20~ 60%), A1 2 0 3 (5~35%), CaO (10~35%), B 2 0 3 (1~15%), La 2 0 3 (0· 3 ~15%), Bi 2 0 3 (10~30%), Ti0 2 (Bu 10%), Zr0 2 (1~10%).

所述有机溶剂载体的组分配比 （重量） 为： 松油醇 （60〜98%)、 柠檬 酸三丁酯 （10〜30%)、 乙基纤维素 （2〜10%)、 硝基纤维素 （1〜5%)、 氢化篦麻油 （0.1〜5%)、 卵磷脂 （0.1〜5%)。  The group distribution ratio (by weight) of the organic solvent carrier is: terpineol (60 to 98%), tributyl citrate (10 to 30%), ethyl cellulose (2 to 10%), and nitrocellulose. (1~5%), hydrogenated castor oil (0.1~5%), lecithin (0.1~5%).

本发明的制备工艺为： ①制备稀土微晶玻璃粉一②制备银钯^复合粉 —③配制有机溶剂载体一④三维混料三棍轧制一⑤稀土电极桨料调制一 ⑥装瓶待用。  The preparation process of the invention is as follows: (1) Preparation of rare earth glass-ceramic powder-2 Preparation of silver-palladium-composite powder-3 Preparation of organic solvent carrier-four-dimensional three-dimensional mixing three-rolling rolling one 5 rare earth electrode paddle preparation one 6 bottled for use .

采用上述配方组份的基于金属基板的稀土厚膜电路稀土电极浆料及其 制备工艺优点在于，  The metal substrate-based rare earth thick film circuit rare earth electrode slurry using the above-mentioned formula component and its preparation process have the advantages that

1 . 通过对国内外厚膜电路用电子浆料物理、 化学性能及工艺性能研究 分析， 决定在电子桨料中参杂稀土镧 (La)和钇（Y)， 实验证明电极浆料 中由于稀土的加入， 浆料的电性能、 湿润性、 相溶性、 分子间键结合强 ά 及工艺性都有很大提高。通过对 Si02— Α1203— CaO— Β203— La203系微晶 玻璃膨涨系数、 玻璃化温度、 玻璃软化温度及形核长大的动力学分析， 确 定稀土电极桨料微晶玻璃配方及制备工艺。使之膨胀系数和金属基板、 介 质浆料匹配， 结合牢靠， 有效提高导电性能、 击穿强度和绝缘性能。 2. 采用稀土氧化钇 （Y203 )， 降低烧结温度， 促进烧结， 改进工艺， 提高效率， 节省能源。 增强电极浆料、 金属基板的抗氧化性和延展性， 提 高结合强度。 1. Through the analysis of the physical, chemical properties and process properties of electronic paste for thick film circuits at home and abroad, it is decided to dope rare earth lanthanum (La) and yttrium (Y) in the electronic paddle. The experiment proves that the electrode slurry is due to rare earth. With the addition, the electrical properties, wettability, compatibility, intermolecular bond strength and processability of the slurry are greatly improved. Determination of rare earth electrode paddles by kinetic analysis of Si0 2 - Α1 2 0 3 - CaO- Β 2 0 3 - La 2 0 3 system glass-ceramic expansion coefficient, glass transition temperature, glass softening temperature and nucleation growth Glass crystallizing formula and preparation process. The expansion coefficient is matched with the metal substrate and the dielectric slurry, and the combination is firm, and the electrical conductivity, the breakdown strength and the insulation performance are effectively improved. 2. Use rare earth yttrium oxide (Y 2 0 3 ) to reduce the sintering temperature, promote sintering, improve the process, improve efficiency and save energy. The electrode paste and the metal substrate are enhanced in oxidation resistance and ductility, and the bonding strength is improved.

3. 稀土镧（La)掺杂极大地改变微晶玻璃材料相的烧结性能、 微观结 构、 致密度、 相组成及物理和机械性能。 从而提高稀土厚膜电路电热元 件的介质强度、 电器性能、 工艺性能及电子桨料的湿润性、 兼容性和分子 健结合强度。 改善工艺， 显著提高产品优良率。  3. Rare earth lanthanum (La) doping greatly changes the sintering properties, microstructure, density, phase composition and physical and mechanical properties of the glass-ceramic material phase. Thereby, the dielectric strength, electrical performance, process performance of the rare earth thick film circuit electric heating element and the wettability, compatibility and molecular bonding strength of the electronic paddle are improved. Improve the process and significantly improve the product's excellent rate.

4. 本发明稀土厚膜电路稀土电极桨料印刷性能、 烧结性能优良。 与稀 土电阻浆料、 介质浆料有优良的湿润性和相溶性。  4. The rare earth electrode paddle of the rare earth thick film circuit of the invention has excellent printing performance and sintering performance. It has excellent wettability and compatibility with rare earth resist paste and medium paste.

5. 基于对稀土电子浆料中各有机溶剂机理的深刻认识， 将不同沸点及 挥发速度的主溶剂按比例合理配制使浆料在印刷、 烘干、烧结等过程中均 匀挥发并排出， 避免溶剂集中挥发形成开裂、 针孔等缺陷， 可有效提高成 品合格率。  5. Based on the deep understanding of the mechanism of various organic solvents in rare earth electronic pastes, the main solvents with different boiling points and volatilization speeds are proportioned reasonably, so that the slurry is uniformly volatilized and discharged during printing, drying, sintering, etc., avoiding solvents. Concentrate volatilization to form defects such as cracks and pinholes, which can effectively improve the yield of finished products.

6.在有机溶剂配方中选用氢化篦麻油等优良溶剂作触变剂以形成良好 的胶体结构， 使浆料具有良好的触变性和防沉效果。  6. In the organic solvent formulation, an excellent solvent such as hydrogenated castor oil is used as a thixotropic agent to form a good colloidal structure, so that the slurry has good thixotropy and anti-settling effect.

7.用途范围相当广泛； 本发明所配稀土功能电极浆料不仅能制备在金 属基板上， 还能制备在微晶玻璃、 陶瓷及其它金属非金属基板上。 不仅能 制备在平面上， 还能制备在曲面上。  7. The scope of application is quite extensive; the rare earth functional electrode paste of the present invention can be prepared not only on a metal substrate but also on a glass ceramic, ceramic and other metal non-metal substrate. It can be prepared not only on a flat surface but also on a curved surface.

本发明稀土电极浆料的导电性能、 可悍性能、 接触性能良好， 焊点完 整性好、 连接牢靠； 本发明的材料不需依赖进口， 100%国产化， 减少贵金 属用量， 成本低廉， 材料消耗少， 节能； 符合我国倡导的循环经济的新型 工业化道路（科技含量高、 经济效益好、 资源消耗低、 环境污染少） 的要 求， 而且有很强的出口创汇前景。  The rare earth electrode slurry of the invention has good electrical conductivity, good enthalpy performance, good contact performance, good solder joint integrity and firm connection; the material of the invention does not need to rely on import, 100% localization, reduce precious metal dosage, low cost, material consumption Less, energy-saving; in line with the new industrialization road of circular economy advocated by China (high scientific and technological content, good economic efficiency, low resource consumption, low environmental pollution), and has a strong prospect of foreign exchange earning.

本发明稀土厚膜电路用稀土电极浆料及其制备技术适用于铁素体系列 不锈钢基板。 例如： 国标牌号 lCrl5、 lCrl7、 00Crl2等， 国外牌号 429#、 430#、 410L#等。 The rare earth electrode slurry for rare earth thick film circuit of the invention and the preparation technique thereof are applicable to a ferritic series stainless steel substrate. For example: national brand number lCrl5, lCrl7, 00Crl2, etc., foreign brand number 429#, 430#, 410L# and so on.

本发朋通过调整固相成分、 含量及烧结工艺， 该电极桨料可和多种金 属基板介质 料、电阻浆料相容。例如：氧化铝基板（A1203)、氮化铝（AIN) 基板、 微晶玻璃基板、 金属合金铝、 钛合金基板等。 By adjusting the solid phase composition, content and sintering process, the electrode paddle is compatible with a variety of metal substrate dielectric materials and resistor pastes. For example, an alumina substrate (A1 2 0 3 ), an aluminum nitride (AIN) substrate, a glass-ceramic substrate, a metal alloy aluminum, a titanium alloy substrate, or the like.

采用了本发明的加热元件是目前唯一符合体积小、 功率大、 热惰性小、 表面热负荷大、 耗电低、 热效率高、 热启动快、 功率稳定、 温度场均匀、 工艺性好、本体自控温、运行安全可靠， 寿命长，适应范围广的要求的电加 热元件。 具体实施方式 .  The heating element adopting the invention is the only one that meets the requirements of small volume, high power, small thermal inertia, large surface heat load, low power consumption, high thermal efficiency, fast heat start, stable power, uniform temperature field, good processability, and self-property. Electric heating element with temperature control, safe and reliable operation, long service life and wide range of requirements. detailed description .

实施例一： Embodiment 1:

本实施例是用于 1CT15 (429#)系列不锈钢基板的稀土厚膜电路用稀土 电极浆料。该电极浆料由固相成分与有机溶剂载体组成， 固相成分包括银 钯钇复合粉与微晶玻璃粉， 其具体配方及工艺如下- This embodiment is a rare earth electrode paste for a rare earth thick film circuit used for a 1CT15 (429#) series stainless steel substrate. The electrode slurry is composed of a solid phase component and an organic solvent carrier, and the solid phase component comprises a silver palladium ruthenium composite powder and a glass ceramic powder. The specific formulation and process are as follows -

1.微晶玻璃配方：各氧化物的成分重量配比为： Si02(28%)、Al203( l,6D/。）、 Ca0 (14%)、 B203 (7%)、 La203 (5%)、 Bi203' (22%)、 Ti02 (5%)、 Zr02 (2%)：1. Glass-ceramic formula: The weight ratio of each oxide component is: Si0 2 (28%), Al 2 0 3 (l, 6 D /.), Ca0 (14%), B 2 0 3 (7% ), La 2 0 3 (5%), Bi 2 0 3 ' (22%), Ti0 2 (5%), Zr0 2 (2%):

2. 微晶玻璃熔炼工艺： 瑢炼温度为： 1350Ό 保温 120分钟后， 迅速 出炉水淬， 得到玻璃微渣。 将玻璃渣置于两级球磨机球磨， 制备出粒径小 于 3微米的微晶玻璃粉。 2. Glass-ceramic smelting process: The smelting temperature is: 1350 Ό After 120 minutes of heat preservation, it is quickly quenched by water to obtain glass micro slag. The glass slag was placed in a two-stage ball mill to prepare a glass-ceramic powder having a particle diameter of less than 3 μm.

3. 调制银钯钇复合粉:  3. Modulation of silver-palladium-ruthenium composite powder:

银钯钇复合粉中钯粉、 银粉与钇粉的粒径小于 2 μ πι。 钯粉、 银粉与钇 粉的重量比为： 2： 97： 1。  The particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 μm. The weight ratio of palladium powder, silver powder and strontium powder is: 2: 97: 1.

4. 有机溶剂载体配方及溶解工艺： 有机溶剂载体各组分配比 （重量） 为： 松油醇 （78%)、 柠檬酸三丁酯 （18%)、 乙基纤维素 （4%)、 硝基纤维 素 （2)、 氢化篦麻油 （0. 6%)、 卵磷脂（0. 8%)。 将上述配比有机溶剂混合 后在 85Ό水温中溶解数小时， 调整乙基纤维素、硝基纤维素含量， 使有机 溶剂载体粘度控制在 245mPas的范围内。 4. Organic solvent carrier formulation and dissolution process: The distribution ratio (weight) of each group of organic solvent carrier is: terpineol (78%), tributyl citrate (18%), ethyl cellulose (4%), nitrate Cellulose (2), hydrogenated castor oil (0.6%), lecithin (0.8%). The above mixed organic solvent is mixed and dissolved in 85 Ό water temperature for several hours to adjust the content of ethyl cellulose and nitrocellulose to make organic The solvent carrier viscosity was controlled in the range of 245 mPas.

5. 稀土电极浆料制备： 该浆料由固相成分与有机溶剂载体组成。 重量 比为： 78 : 22。 所述固相成分中银钯钇复合粉与微晶玻璃粉的重量比为： 98. 5 ： 1. 5。 银钯钇复合粉中钯粉、 银粉与钇粉的粒径小于 2 μ πι。 浆上述 配比原料置于三维混料机中搅拌分散后装入三棍轧机轧制，得到稀土电极 浆料， 测试浆料的粘度为： 186PaS/RPM。  5. Rare Earth Electrode Slurry Preparation: The slurry consists of a solid phase component and an organic solvent carrier. The weight ratio is: 78: 22. The weight ratio of the silver-palladium-ruthenium composite powder to the glass-ceramic powder is 98. 5: 1. 5. The particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 μm. The above-mentioned proportioning raw materials were placed in a three-dimensional mixer and stirred and dispersed, and then placed in a three-roll mill to obtain a rare earth electrode slurry. The viscosity of the test slurry was 186 PaS/RPM.

6. 稀土电极浆料性能：  6. Rare earth electrode slurry performance:

①电性能-  1 electrical performance -

Figure imgf000006_0001
实施例二：
Figure imgf000006_0001
Embodiment 2:

本实施例是用于 lCrl7 (430#)系列不锈钢基板的稀土厚膜电路用稀土 电极桨料， 该电极浆料由固相成分与有机溶剂载体组成， 固相成分包括银 钯钇复合粉与微晶玻璃粉， 其具体工艺及配方如下- The present embodiment is a rare earth electrode pad for a rare earth thick film circuit for a lCrl7 (430#) series stainless steel substrate, the electrode slurry is composed of a solid phase component and an organic solvent carrier, and the solid phase component comprises a silver palladium ruthenium composite powder and a micro Crystal glass powder, its specific process and formula are as follows -

1.微晶玻璃配方：各氧化物的成分重量配比为: Si02 ( 30%)、Al203 ( 16%)、 Ca0 (13%) . B203 (8%)、 La203 (6%)、 Bi203 (26%)、 Ti02 (6%)、 Zr02 (3%)：1. Glass-ceramic formula: The weight ratio of each oxide component is: Si0 2 (30%), Al 2 0 3 (16%), Ca0 (13%). B 2 0 3 (8%), La 2 0 3 (6%), Bi 2 0 3 (26%), Ti0 2 (6%), Zr0 2 (3%):

2. 微晶玻璃熔炼工艺： 熔炼温度为： 135CTC 保温 120分钟后， 迅速 出炉水淬， 得到玻璃微渣。 将玻璃渣置于两级球磨机球磨， 制备出粒径小 于 3微米的微晶玻璃粉。 2. Glass-ceramic smelting process: The smelting temperature is: 135CTC After 120 minutes of heat preservation, it is quickly quenched by water to obtain glass micro slag. The glass slag was placed in a two-stage ball mill to prepare a glass-ceramic powder having a particle diameter of less than 3 μm.

3. 调制银钯钇复合粉： 银钯钇复合粉中钯粉、 银粉与钇粉的粒径小于 2μιη。 钯粉、 银粉与钇 粉的重量比为： 1： 98： 1。 3. Modulation of silver-palladium-ruthenium composite powder: The particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 μm. The weight ratio of palladium powder, silver powder and tantalum powder is 1: 98: 1.

4. 有机溶剂载体配方及溶解工艺： 有机溶剂载体各组分配比.（重量） 为： 松油醇 （76%)、 柠檬酸三丁酯 （17°/。）、 乙基纤维素 （3%)、 硝基纤维 素 （3)、 氢化篦麻油 （0.7%)、 卵磷脂 （0.3%)。 将上述配比有机溶剂混合 后在 85Ό水温中溶解数小时， 调整乙基纤维素、硝基纤维素含量， 使有机 溶剂载体粘度控制在 250mPas的范围内。  4. Organic solvent carrier formulation and dissolution process: The distribution ratio of each group of organic solvent carrier is (by weight): terpineol (76%), tributyl citrate (17 ° /.), ethyl cellulose (3%) ), nitrocellulose (3), hydrogenated castor oil (0.7%), lecithin (0.3%). The above mixed organic solvent was mixed and dissolved in 85 Torr of water for several hours to adjust the content of ethyl cellulose and nitrocellulose to control the viscosity of the organic solvent carrier to be in the range of 250 mPas.

5. 稀土电极浆料制备： 该浆料由固相成分与有机溶剂载体组成。 重量 比为： 77： 23。 所述固相成分中银钯钇复合粉与微晶玻璃粉的重量比为： 98 : 2。 银钯钇复合粉中钯粉、 银粉与钇粉的粒径小于 2μπι。 将上述配比 原料置于三维混料机中搅拌分散后装入三棍轧机轧制， 得到稀土电极浆 料， 测试浆料的粘度为： 190PaS/RPM。  5. Rare Earth Electrode Slurry Preparation: The slurry consists of a solid phase component and an organic solvent carrier. The weight ratio is: 77: 23. The weight ratio of the silver-palladium-ruthenium composite powder to the glass-ceramic powder in the solid phase component is 98:2. The particle size of the palladium powder, the silver powder and the niobium powder in the silver-palladium-ruthenium composite powder is less than 2 μm. The above-mentioned proportioning raw materials were placed in a three-dimensional mixer and stirred and dispersed, and then placed in a three-roll mill to obtain a rare earth electrode slurry. The viscosity of the test slurry was 190 PaS/RPM.

6. 稀土电极浆料性能：  6. Rare earth electrode slurry performance:

①电性能：  1 electrical performance:

方阻 分辨率 抗拉强度 老化强度  Square resistance resolution tensile strength aging strength

<5±2πιΩ/0 0.2mm >15 (N/腿 2) >10(N/mm2) <5±2πιΩ/0 0.2mm >15 (N/leg 2) >10(N/mm2)

②物理性能 2 physical properties

流变特性 ' 电阻层厚度 浆料粘度 单位用量  Rheological properties 'resistive layer thickness slurry viscosity unit dosage

触变 宜网印 12±2μιη 190PaS/RPM。 88cm2/克  Thixotropic screen printing 12±2μιη 190PaS/RPM. 88cm2 / gram

Claims

权利要求 Rights request 1、 一种基于金属基板的稀土厚膜电路稀土电极浆料， 其特征在于， 该 浆料由固相成分与有机溶剂载体组成， 其重量比为： （70〜90) ： (30〜 10)； 其中固相成分包括银钯钇复合粉与微晶玻璃粉， 银钯钇复合粉与微 晶玻璃粉重量比为： （99.4〜94) ： (0.6〜6)。  A rare earth electrode slurry for a rare earth thick film circuit based on a metal substrate, characterized in that the slurry is composed of a solid phase component and an organic solvent carrier, and the weight ratio thereof is: (70 to 90): (30 to 10) The solid phase component comprises a silver-palladium-ruthenium composite powder and a glass-ceramic powder, and the weight ratio of the silver-palladium-iridium composite powder to the glass-ceramic powder is: (99.4~94): (0.6~6). 2、 根据权利要求 1 所述的基于金属基板的稀土厚膜电路稀土电极浆 料， 其特征在于， 该银钯钇复合粉由如下组分 （重量比） 构成， 钯粉、 银 粉与钇粉的重量比为： （0.6〜10) ： (99〜82) ： (0.4〜8)， 其中钯粉、 银粉与钇粉的粒径小于 2 μ m。  The rare earth electrode slurry of a rare earth thick film circuit based on a metal substrate according to claim 1, wherein the silver palladium ruthenium composite powder is composed of the following components (weight ratio), palladium powder, silver powder and strontium powder. The weight ratio is: (0.6~10): (99~82): (0.4~8), wherein the particle size of the palladium powder, the silver powder and the tantalum powder is less than 2 μm. 3、 根据权利要求 1 所述的基于金属基板的稀土厚膜电路稀土电极浆 料， 其特征在于， 所述有机溶剂载体的组分配比（重量）为： 松油醇 60〜 98% 、柠檬酸三丁酯 10〜30% 、乙基纤维素 2〜10% 、硝基纤维素 1〜 5% 、 氢化篦麻油 0.1〜5% 、 卵磷脂 0.1〜5% 。  The rare earth electrode slurry of a rare earth thick film circuit based on a metal substrate according to claim 1, wherein the group distribution ratio (weight) of the organic solvent carrier is: terpineol 60 to 98%, citric acid Tributyl ester 10~30%, ethyl cellulose 2~10%, nitrocellulose 1~5%, hydrogenated castor oil 0.1~5%, lecithin 0.1~5%. 4、 根据权利要求 1 所述的基于金属基板的稀土厚膜电路稀土电极浆 料， 其特征在于， 所述微晶玻璃为 Si02-Al203-CaO-B203- Bi203-La203系微 晶玻璃，由如下氧化物的成分重量配比组成： Si02 20〜60% 、 A1203 5〜 35% 、CaO 10〜35% 、B203 1〜15% 、La203 0.3〜15% 、Bi203 10〜30% 、 Ti02 l〜： 10% 、 ZrO2 l〜10% 。 The rare earth electrode slurry of a rare earth thick film circuit based on a metal substrate according to claim 1, wherein the glass ceramic is Si0 2 -Al 2 0 3 -CaO-B 2 0 3 - Bi 2 0 3 -La 2 0 3 -based glass-ceramics consisting of the following components by weight ratio: Si0 2 20 ~60%, A1 2 0 3 5 ~ 35%, CaO 10~35%, B 2 0 3 1~ 15%, La 2 0 3 0.3~15%, Bi 2 0 3 10~30%, Ti0 2 l~: 10%, ZrO 2 l~10%. 5、一种制备权利要求 1-4任一项的金属基板的厚膜电路稀土电极浆料' 的工艺， 其特征在于： 它包括如下步骤，  A process for preparing a thick film circuit rare earth electrode paste of a metal substrate according to any one of claims 1 to 4, characterized in that it comprises the following steps: ( 1 )制备微晶玻璃粉： 将下列配比的原料（重量％比） SiO220〜60%、 Ai2035〜35%、 CaO 10〜35%、 Bi203 10〜30%、 B203卜 15%、 L O30.3〜 15、 TiO2 l〜10%、 ZrO2 l〜10%、 经混合均匀后高温熔炼， 熔炼温度为： 1100〜1450°C， 保温 1〜3 小时后， 快速将玻璃熔液侵入冷水中水淬， 得 到微渣， 将玻璃微渣经球磨获得粒径小于 3微米的玻璃微粉； (1) Preparation of glass-ceramic powder: The following ratio of raw materials (% by weight) SiO 2 20 to 60%, Ai 2 0 3 5 to 35%, CaO 10 to 35%, Bi 2 0 3 10 to 30% , B 2 0 3 b 15%, LO 3 0.3~ 15, TiO 2 l~10%, ZrO 2 l~10%, after mixing and high temperature melting, the melting temperature is: 1100~1450 ° C, after 1 to 3 hours of heat preservation, the glass melt is quickly intruded into cold water to obtain a micro-slag, and the glass micro-slag is ball-milled to obtain a glass micropowder having a particle diameter of less than 3 μm; (2) 调制银钯钇复合粉；  (2) preparing a silver-palladium-ruthenium composite powder; 银钯钇复合粉中钯粉、 银粉与钇粉的粒径小于 2 μ 1Ώ， 钯粉、 银粉与钇 粉的重量比为： （0.6〜10) ： (99〜82 ) ： (0.4〜8)； The particle size of palladium powder, silver powder and tantalum powder in the silver-palladium- ruthenium composite powder is less than 2 μ 1Ώ , and the weight ratio of palladium powder, silver powder and tantalum powder is: (0.6~10) : (99~82) : (0.4~8) ; (3 ) 有机溶剂载体；  (3) an organic solvent carrier; 有机溶剂载体各组分配比 （重量） 为： 松油醇 60〜98% 、 柠檬酸三 丁酯 10〜30% 、 乙基纤维素 2〜10% 、 硝基纤维素 1〜5% 、 氢化篦麻 油 0.1〜5% 、卵磷脂 0.1〜5% ，将上述配比有机溶剂混合后在 80〜100 °C水温中溶解数小时， 调整乙基纤维素、 硝基纤维素含量， 使有机溶剂载 体粘度控制在 150〜280mPas的范围內； The distribution ratio (weight) of each group of organic solvent carrier is: terpineol 60~98%, tributyl citrate 10~30%, ethyl cellulose 2~10%, nitrocellulose 1~5%, hydrazine hydride Sesame oil 0.1~5%, lecithin 0.1~5%, mixed with the above organic solvent and dissolved in water temperature of 80~100 °C for several hours, adjust the content of ethyl cellulose and nitrocellulose to make the viscosity of organic solvent carrier Control in the range of 150~ 2 80mPas; (4)制备稀土电极浆料： 将上述浆料配比原料置于三维混料机中搅拌 分散后装入三棍轧机轧制，得到稀土电极浆料，测试浆料的粘度为： 150〜
Figure imgf000009_0001
(4) Preparation of rare earth electrode slurry: The above-mentioned slurry proportioning raw material is placed in a three-dimensional mixing machine, stirred and dispersed, and then placed in a three-bar rolling mill to obtain a rare earth electrode slurry. The viscosity of the test slurry is: 150~
Figure imgf000009_0001
 6、根据权利要求 5所述的基于金属基板的厚膜电路稀土电极浆料的制 备工艺， 其特征在于： 所述第 （1 ) 步骤的制备微晶玻璃粉过程中， 微晶 玻璃粉原料是在三维混料机中混合均匀后装入坩埚， 置于高温熔炉熔炼， 得到的微渣装入玛瑙球桶，用星型球磨机球磨获得粒径小于 3微米的玻璃 微粉。  The process for preparing a rare earth electrode slurry for a thick film circuit based on a metal substrate according to claim 5, wherein: in the process of preparing the glass ceramic powder in the step (1), the raw material of the glass ceramic powder is After mixing uniformly in a three-dimensional mixer, the crucible is placed in a high-temperature furnace for melting, and the obtained micro-slag is charged into an agate ball barrel, and ball-milled by a star ball mill to obtain a glass fine powder having a particle diameter of less than 3 μm.
PCT/CN2007/002223 2006-07-28 2007-07-23 Rare earth electrode slurry for rare earth thick-film circuit based on metal substrate and producing process thereof Ceased WO2008014677A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2006100367143A CN100499940C (en) 2006-07-28 2006-07-28 Rare earth electrode slurry of rare earth thick film circuit based on metal plate and its preparation technology
CN200610036714.3 2006-07-28

Publications (1)

Publication Number Publication Date
WO2008014677A1 true WO2008014677A1 (en) 2008-02-07

Family

ID=37700710

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2007/002223 Ceased WO2008014677A1 (en) 2006-07-28 2007-07-23 Rare earth electrode slurry for rare earth thick-film circuit based on metal substrate and producing process thereof

Country Status (2)

Country Link
CN (1) CN100499940C (en)
WO (1) WO2008014677A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2636070A4 (en) * 2010-10-28 2014-04-02 Heraeus Precious Metals North America Conshohocken Llc SOLAR CELL METALLIZATION CONTAINING METAL ADDITIVE
CN114009856A (en) * 2021-09-30 2022-02-08 江苏国瓷泓源光电科技有限公司 Modified electrode slurry of pumping equipment and preparation process

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101106842B (en) * 2007-07-24 2011-12-21 王晨 Thick film circuit heating part based on minicrystal glass base plate and its making technology
CN101436441B (en) * 2008-12-09 2011-06-15 彩虹集团公司 Thick film nanometer gold electrode slurry and preparation method thereof
CN101923911B (en) * 2010-04-27 2011-11-02 电子科技大学 YBCO thick film resistor paste based on stainless steel substrate and preparation method thereof
CN102136308B (en) * 2010-11-23 2012-11-14 湖南威能新材料科技有限公司 Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste
CN102290117B (en) * 2011-04-25 2013-03-06 深圳市唯特偶新材料股份有限公司 Low temperature-sintered nano silver paste and preparation method thereof
CN102568704B (en) * 2012-03-16 2015-01-21 广东羚光新材料股份有限公司 Environment-friendly lead-free semiconductor ceramic capacitive electrode silver paste and preparation method thereof
CN102646459A (en) * 2012-05-23 2012-08-22 湖南利德电子浆料有限公司 Silver paste for front face of mixed silver powder crystalline silicon based solar battery and preparation method thereof
CN102685942B (en) * 2012-05-29 2014-05-07 王克政 Intelligent electric-heating element with PTC (Positive Temperature Coefficient) rare-earth thick film circuit and preparation method thereof
CN104318979A (en) * 2014-09-19 2015-01-28 王晨 Composite-material-based thick-film circuit rare earth electrode slurry and preparation process thereof
CN106205773B (en) * 2016-07-06 2018-04-24 东莞珂洛赫慕电子材料科技有限公司 A kind of rare earth thick film circuit electrode slurry based on stainless steel substrate and preparation method thereof
CN106409380A (en) * 2016-09-27 2017-02-15 东莞珂洛赫慕电子材料科技有限公司 Medium temperature sintering resistance slurry of aluminum alloy substrate thick film circuit and preparation method thereof
CN107068238A (en) * 2016-12-09 2017-08-18 东莞珂洛赫慕电子材料科技有限公司 A kind of aluminium alloy base plate full silver electrode paste of thick film circuit intermediate sintering temperature and preparation method thereof
CN110690010A (en) * 2019-10-18 2020-01-14 泰阳电子(东莞)有限公司 A kind of preparation method of rare earth high temperature carbon paste for glass-ceramic plate
CN113724914B (en) * 2021-11-01 2022-02-25 西安宏星电子浆料科技股份有限公司 Silver-palladium slurry for sulfur-resistant oil level sensor
CN114360762B (en) * 2022-03-14 2022-06-10 西安拓库米电子科技有限公司 Silver migration resistant silver conductor paste for sheet resistor and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0589718A (en) * 1991-01-16 1993-04-09 Sumitomo Metal Mining Co Ltd Conductor paste
US5277844A (en) * 1993-03-29 1994-01-11 Rainey Clifford S Resistor composition
JPH08186006A (en) * 1994-12-28 1996-07-16 Du Pont Kk Thick film resistor composition
JP2002367804A (en) * 2001-06-11 2002-12-20 K-Tech Devices Corp Resistor
CN1424729A (en) * 2002-12-30 2003-06-18 中国人民解放军国防科学技术大学 Medium sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN1424728A (en) * 2002-12-30 2003-06-18 中国人民解放军国防科学技术大学 Conductive sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN1424727A (en) * 2002-12-30 2003-06-18 中国人民解放军国防科学技术大学 Resistance sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN1588573A (en) * 2004-07-28 2005-03-02 王克政 PTC thick film curc uit controllable electric heating element
CN1639806A (en) * 2001-09-06 2005-07-13 诺利塔克股份有限公司 Conductor composition and its manufacturing method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0589718A (en) * 1991-01-16 1993-04-09 Sumitomo Metal Mining Co Ltd Conductor paste
US5277844A (en) * 1993-03-29 1994-01-11 Rainey Clifford S Resistor composition
JPH08186006A (en) * 1994-12-28 1996-07-16 Du Pont Kk Thick film resistor composition
JP2002367804A (en) * 2001-06-11 2002-12-20 K-Tech Devices Corp Resistor
CN1639806A (en) * 2001-09-06 2005-07-13 诺利塔克股份有限公司 Conductor composition and its manufacturing method
CN1424729A (en) * 2002-12-30 2003-06-18 中国人民解放军国防科学技术大学 Medium sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN1424728A (en) * 2002-12-30 2003-06-18 中国人民解放军国防科学技术大学 Conductive sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN1424727A (en) * 2002-12-30 2003-06-18 中国人民解放军国防科学技术大学 Resistance sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN1588573A (en) * 2004-07-28 2005-03-02 王克政 PTC thick film curc uit controllable electric heating element

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2636070A4 (en) * 2010-10-28 2014-04-02 Heraeus Precious Metals North America Conshohocken Llc SOLAR CELL METALLIZATION CONTAINING METAL ADDITIVE
US9466738B2 (en) 2010-10-28 2016-10-11 Heracus Precious Metals North America Conshohocken LLC Solar cell metallizations containing metal additive
CN114009856A (en) * 2021-09-30 2022-02-08 江苏国瓷泓源光电科技有限公司 Modified electrode slurry of pumping equipment and preparation process

Also Published As

Publication number Publication date
CN100499940C (en) 2009-06-10
CN1909748A (en) 2007-02-07

Similar Documents

Publication Publication Date Title
WO2008014677A1 (en) Rare earth electrode slurry for rare earth thick-film circuit based on metal substrate and producing process thereof
WO2008014680A1 (en) Rare earth resistance slurry for rare earth thick-film circuit based on metal substrate and producing process thereof
WO2008014679A1 (en) Rare earth medium slurry for rare earth thick-film circuit based on metal substrate and producing process thereof
CN102685942B (en) Intelligent electric-heating element with PTC (Positive Temperature Coefficient) rare-earth thick film circuit and preparation method thereof
WO2008014678A1 (en) Rare earth base-metal resistance slurry for rare earth thick-film circuit based on metal substrate and producing process thereof
CN102158993B (en) High-temperature aluminum alloy base rare earth thick film circuit electric heating element and preparation technology thereof
CN101106842B (en) Thick film circuit heating part based on minicrystal glass base plate and its making technology
CN1216380C (en) Resistance sizing agent and its producing process for high-power thick-film circuit based on stainless steel substrate
CN105810291A (en) Rare-earth resistance paste of medium- and low-resistance high-power thick film circuit and preparation method of rare-earth resistance paste
CN103183474B (en) A kind of unorganic glass powder and preparation method thereof, a kind of electrocondution slurry and preparation method thereof
CN101847510B (en) conductive paste for multilayer ceramic capacitor and preparation method thereof
CN109994248B (en) A conductive phase composite, thick film resistor paste based on aluminum substrate and preparation method thereof
CN102786294A (en) Insulating layer slurry of chip-type oxygen sensor and insulating layer preparation method
CN105825910A (en) Large-power low-temperature-coefficient thick-film heating element resistor slurry and preparation method thereof
CN110642519A (en) Encapsulation slurry for aluminum nitride substrate and preparation method and application thereof
CN104320866A (en) Composite-material-based thick-film circuit rare earth electrode slurry and preparation process thereof
CN103204632B (en) Conductive glass powder and preparation method thereof, crystal silicon solar energy battery aluminum conductive electric slurry and preparation method
CN111063477B (en) A kind of stainless steel substrate thick film circuit insulating medium slurry and preparation method thereof
CN104992744B (en) A thick film circuit resistance paste for stainless steel substrate and preparation method thereof
CN109461514A (en) A kind of conductive phase compound, thick-film resistor paste and preparation method thereof
CN104318979A (en) Composite-material-based thick-film circuit rare earth electrode slurry and preparation process thereof
CN203632890U (en) Aluminum bronze Cu+ composite backing rear earth thick film circuit intelligent electrothermal chip
CN113066602A (en) Conductive silver paste for automobile sensor and preparation method thereof
CN104318975A (en) Composite-material-based thick-film circuit rare earth electrode slurry and preparation process thereof
CN108665999A (en) A thick film circuit resistor paste and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07785149

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07785149

Country of ref document: EP

Kind code of ref document: A1