CN100390905C - Leadless ohmic electrode silver coating for PTC ceramic and its preparation method - Google Patents
Leadless ohmic electrode silver coating for PTC ceramic and its preparation method Download PDFInfo
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- CN100390905C CN100390905C CNB2006100881315A CN200610088131A CN100390905C CN 100390905 C CN100390905 C CN 100390905C CN B2006100881315 A CNB2006100881315 A CN B2006100881315A CN 200610088131 A CN200610088131 A CN 200610088131A CN 100390905 C CN100390905 C CN 100390905C
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Abstract
The present invention discloses a leadless ohmic electrode silver slurry for PTC ceramics and a preparation method thereof, which is formed by that silver micro powder, zinc powder (or aluminium powder, nickel powder, or a mixture thereof), and an organic carrier are mixed and ground. The present invention discards a traditional preparation method of using glass powder, and when an electrode layer is made by sintering, self-oxidation of the nickel powder, the zinc powder, or the aluminium powder forms oxide bond with a porcelain body, and thereby, the electrode layer is firmly attached to the surface of the porcelain body. The silver slurry of the present invention has the advantages of wide sintering temperature range and strong process adaptability, the slurry is sintered within the temperature range of 480 DEG C to 580 DEG C, and good ohmic contact performance can be formed.
Description
Technical field
The present invention relates to the positive temperature coefficient ceramic leadless ohmic electrode silver coating.
Background technology
Because PTC (semistor) pottery is a kind of semiconductor ceramic material, in manufacture process, must make one deck ohmic electrode layer on its surface, eliminate the surface potential barrier of positive temperature coefficient ceramic, so that form good Ohmic contact between electrode layer and the porcelain body, its various electrical properties just can embody.Making one deck silver electrode layer on ohmic electrode layer again makes it carry out soldering with lead-in wire or pin.
Positive temperature coefficient ohmic electrode silver coating material is formed by raw material formulated such as micro silver powder, zinc powder, glass dust, organic carriers usually.Micro silver powder, zinc powder are the main components of slurry, play conduction and eliminate surface potential barrier in electrode, and glass dust melts in the electrode sintering process, forms bonded layer with the surface of electrode layer attached to ceramic body.Organic carrier plays the dispersion suspension effect, makes slurry can place for a long time and do not precipitate, and organic carrier makes slurry have certain flowability, thixotropy etc. simultaneously, thereby makes slurry have good printing performance.
Usually positive temperature coefficient ohmic electrode silver coating material all adopt the lower borosilicate lead of fusing point be frit as key compound, in the frit of this system, lead is its main composition, and very high ratio is arranged.With lead content in this silver of preparing slurry up to about 2%.Therefore, this slurry can cause bigger pollution to environment in making use.
In order to reduce electronic product pollution to environment in making use, " waste electronic andelectrical equipment decree " (WEEE decree) and " about in electronic electric equipment, banning use of some harmful substance decree (Restriction of Hazardous Substances) " (ROHS decree) have been issued in the Official Journal in European Union on February 13rd, 2003.Two decrees are converted to formal law on August 13rd, 2004, and on August 13rd, 2005 will formally be implemented the WEEE decree, and on July 1st, 2006 will formally be implemented the ROHS decree.Wherein the content of lead, mercury, Cr VI, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers must not surpass 0.1% in the RoHS instruction regulation electronic product, and the content of cadmium must not surpass 0.01%.Except that European Union, global harmful substance control is all in constantly advancing.Japan, the U.S. also have been that legislation is used in the restriction of harmful substance.China Ministry of Information Industry has issued " electronics and IT products pollution control management way " and in execution on July 1 in 2006.Therefore, at present people all in the manufacturing process and the method that strive to find a kind of new leadless ohmic electrode silver coating.
Summary of the invention
The present invention provides a kind of positive temperature coefficient ceramic leadless ohmic electrode silver coating and preparation method thereof, abandon the traditional method that uses glass dust, utilize electrode layer when burning till, form the oxide bonding between the oxidation of one of nickel powder, zinc powder, aluminium powder or its any mixture self and the porcelain body, thereby make the surface of electrode layer firm attachment at ceramic body.
Technical scheme of the present invention is as follows:
The positive temperature coefficient ceramic leadless ohmic electrode silver coating is characterized in that the percentage by weight of its material component is:
Micro silver powder 20-60%
One of nickel powder, zinc powder, aluminium powder or its any mixture 15-60%
Organic carrier 20-40%
Wherein,
Organic carrier the percentage by weight of material component be:
Polymeric adhesive 5-15%
Organic additive 1-10%
Organic solvent 75-94%
Wherein polymeric adhesive is selected one or more in ethyl cellulose, celluloid and the rosin for use; Organic additive adopts one or more in cyclohexanone, lecithin, dibutyl phthalate (DBP) or the castor oil; Organic solvent is selected one or more in terpinol, turpentine oil, the diethylene glycol butyl ether for use.
Described silver slurry is characterized in that the percentage by weight of its material component is:
Micro silver powder 24-60%
One of nickel powder, zinc powder, aluminium powder or its any mixture 15-48%
Organic carrier 20-40%
Wherein,
Organic carrier the percentage by weight of material component be:
Polymeric adhesive 8-10%
Organic additive 1-5%
Organic solvent 85-90%.
Described silver slurry is characterized in that described micro silver powder selects for use granularity less than 1 μ m ball shape silver powder; It is 500-1200 purpose ball-type powder that nickel powder, zinc powder, aluminium powder are selected granularity order number for use.
The described positive temperature coefficient ceramic preparation method of leadless ohmic electrode silver coating is characterized in that:
(1), with each material component of organic carrier, be heated to whole dissolvings, promptly obtain organic carrier;
(2), with micro silver powder, one of nickel powder, zinc powder, aluminium powder or its any mixture, organic carrier mixes and to stir evenly, grind, until granularity less than 15 μ m, promptly.
Select for use lead, cadmium content to be lower than 0.01% nickel powder, zinc powder or aluminium powder, ingenious employing oxide bonding mode replaces the glass bonding, thereby realizes the unleaded of product.
Advantage of the present invention:
Production technology simple, save cost;
2. environmental protection, any harmful substance such as unleaded, cadmium;
3. bonding is reliable, and ageing-resistant performance is superior;
4. firing range broadness, Technological adaptability is strong, and this slurry burns till in 480-580 ℃ of temperature range, can both form the good Ohmic contact performance;
5. the intensive withstanding current capability of metal level is strong.
Embodiment
One, the organic carrier of positive temperature coefficient ceramic in the leadless ohmic electrode silver coating, it is made up of ethyl cellulose, rosin, castor oil, terpinol, and its percentage by weight is
Ethyl cellulose 7%
Rosin 2%
Castor oil 2%
Terpinol 89%
Each component is fully mixed, and heats down at 100 ℃ ethyl cellulose and rosin are fully dissolved.
Two, positive temperature coefficient ceramic leadless ohmic electrode silver coating, it is by micro silver powder, nickel powder or zinc powder or aluminium powder or its any mixture, organic carrier is formed, and its percentage by weight is
Micro silver powder 42%
Nickel powder (or zinc powder or aluminium powder or zinc powder, nickel powder, aluminium powder any mixture) 28%
Organic carrier 30%
Micro silver powder selects for use granularity less than 1 μ m ball shape silver powder; It is the 500-1200 order that nickel powder (or aluminium powder or zinc powder) is selected granularity order number for use, and plumbous, cadmium content is lower than 0.01% spherical powder.Micro silver powder, nickel powder (or any mixture of zinc powder or aluminium powder or zinc powder, nickel powder, aluminium powder), organic carrier are mixed, grind rolling granularity through three-roll grinder and obtain the ohmic electrode silver coating finished product for behind＜15 μ m until slurry.
Size performance:
Granularity:＜15um
Firing temperature: 480-580 ℃
Ohmic contact characteristic: be better than indium and transfer electrode
Adhesive force:＞10N/mm
2
Ageing properties: poach 24 hours, resistance varying-ratio＜5%
Lead content:＜0.01%
Cadmium content:＜0.005%
Mercury content does not have
Content of 6-valence Cr ions does not have
Polybrominated biphenyl content does not have
The Polybrominated biphenyl ether content does not have
Claims (3)
1. positive temperature coefficient ceramic leadless ohmic electrode silver coating is characterized in that the percentage by weight of its material component is:
Micro silver powder 20-60%
One of nickel powder, zinc powder, aluminium powder or its any mixture 15-60%
Organic carrier 20-40%
Described micro silver powder selects for use granularity less than 1 μ m ball shape silver powder; It is 500-1200 purpose ball-type powder that nickel powder, zinc powder, aluminium powder are selected granularity order number for use; Plumbous in nickel powder, aluminium powder or the zinc powder, cadmium content is lower than 0.01%
Wherein,
The percentage by weight of the material component of organic carrier is:
Polymeric adhesive 5-15%
Organic additive 1-10%
Organic solvent 75-94%
Wherein polymeric adhesive is selected one or more in ethyl cellulose, celluloid and the rosin for use; Organic additive adopts one or more in cyclohexanone, lecithin, dibutyl phthalate (DBP) or the castor oil; Organic solvent is selected one or more in terpinol, turpentine oil, the diethylene glycol butyl ether for use.
2. silver slurry according to claim 1 is characterized in that the percentage by weight of its material component is:
Micro silver powder 24-60%
One of nickel powder, zinc powder, aluminium powder or its any mixture 15-48%
Organic carrier 20-40%
Wherein,
The percentage by weight of the material component of organic carrier is:
Polymeric adhesive 8-10%
Organic additive 1-5%
Organic solvent 85-90%.
3. the positive temperature coefficient ceramic according to claim 1 preparation method of leadless ohmic electrode silver coating is characterized in that:
(1), with each material component of organic carrier, be heated to whole dissolvings, promptly obtain organic carrier;
(2), with micro silver powder, one of nickel powder, zinc powder, aluminium powder or its any mixture, organic carrier mixes and to stir evenly, grind, until granularity less than 15 μ m, promptly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100881315A CN100390905C (en) | 2006-06-28 | 2006-06-28 | Leadless ohmic electrode silver coating for PTC ceramic and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100881315A CN100390905C (en) | 2006-06-28 | 2006-06-28 | Leadless ohmic electrode silver coating for PTC ceramic and its preparation method |
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| Publication Number | Publication Date |
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| CN1870179A CN1870179A (en) | 2006-11-29 |
| CN100390905C true CN100390905C (en) | 2008-05-28 |
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| CNB2006100881315A Expired - Fee Related CN100390905C (en) | 2006-06-28 | 2006-06-28 | Leadless ohmic electrode silver coating for PTC ceramic and its preparation method |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2651625T3 (en) * | 2007-04-25 | 2018-01-29 | Heraeus Precious Metals North America Conshohocken Llc | Formulations for thick film conductors, comprising silver and nickel or silver and nickel alloys and solar cells manufactured therefrom |
| CN101236811B (en) * | 2008-02-27 | 2010-06-02 | 石开轩 | Passive electrode method for heat-sensitive resistor |
| CN101609850B (en) * | 2009-07-14 | 2010-12-08 | 中南大学 | Lead-free silver conductive paste used for positive electrode of solar battery and preparation technique thereof |
| CN101950594B (en) * | 2010-09-20 | 2011-12-07 | 浙江大学 | Lead-free environment-friendly electronic Ag/Al (silver/aluminum) paste and preparation method thereof |
| CN101937736B (en) * | 2010-09-20 | 2012-04-25 | 浙江大学 | Lead-free electronic silver paste and preparation method thereof |
| CN102262919B (en) * | 2011-07-19 | 2012-09-19 | 彩虹集团公司 | Environment-friendly electrode silver paste for piezoresistor and preparation method for paste |
| CN102324266B (en) * | 2011-08-18 | 2012-10-03 | 江苏泓源光电科技有限公司 | Glass-powder-free crystalline silicon solar battery aluminum paste and preparation method thereof |
| CN103137277A (en) * | 2011-12-01 | 2013-06-05 | 上海市电力公司 | Plug-in-class positive temperature coefficient (PTC) resistor production technology |
| CN102496404B (en) * | 2011-12-27 | 2013-10-30 | 华东理工大学 | Electrode silver paste used by high efficiency crystal silicon solar cell |
| TWI538754B (en) * | 2013-06-21 | 2016-06-21 | China Steel Corp | Modification of silver powder and glass - free sintering silver paste manufacturing method |
| CN104637571A (en) * | 2015-02-05 | 2015-05-20 | 合肥圣达电子科技实业公司 | Silver paste for ceramic capacitor and preparation method thereof |
| CN107887051A (en) * | 2017-11-27 | 2018-04-06 | 钦州学院 | A kind of ageing-resistant front electrode silver slurry of crystal silicon solar energy battery and preparation method |
| CN108376586B (en) * | 2018-02-02 | 2019-09-27 | 苏州晶讯科技股份有限公司 | A kind of preparation method for the surface PTC lead-free silver electrode cofiring system slurry |
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| CN1048080A (en) * | 1989-06-16 | 1990-12-26 | 中国科学院上海硅酸盐研究所 | Automobile cold start is with the preparation method of PTC material and element |
| JPH06168621A (en) * | 1992-11-27 | 1994-06-14 | Hokuriku Electric Ind Co Ltd | Conductive paste and electronic parts formed with electrode made of this conductive paste |
| US20030060353A1 (en) * | 2001-09-20 | 2003-03-27 | Takeshi Miki | Conductive paste, method for manufacturing laminated ceraminc electronic component, and laminated ceramic electronic component |
| US20040113127A1 (en) * | 2002-12-17 | 2004-06-17 | Min Gary Yonggang | Resistor compositions having a substantially neutral temperature coefficient of resistance and methods and compositions relating thereto |
| CN1686662A (en) * | 2005-04-29 | 2005-10-26 | 华南理工大学 | Self soldering solder used for brazing connecting PTC ceramic and aluminium alloy |
| US7018864B2 (en) * | 2001-09-20 | 2006-03-28 | Murata Manufacturing Co., Ltd. | Conductive paste for terminal electrodes of monolithic ceramic electronic component, method for making monolithic ceramic electronic component, and monolithic ceramic electronic component |
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2006
- 2006-06-28 CN CNB2006100881315A patent/CN100390905C/en not_active Expired - Fee Related
Patent Citations (7)
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| CN87102932A (en) * | 1987-04-19 | 1988-11-02 | 中国科学技术大学 | Positive temperature coefficient (PTC) material manufacturing method and equipment thereof |
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| JPH06168621A (en) * | 1992-11-27 | 1994-06-14 | Hokuriku Electric Ind Co Ltd | Conductive paste and electronic parts formed with electrode made of this conductive paste |
| US20030060353A1 (en) * | 2001-09-20 | 2003-03-27 | Takeshi Miki | Conductive paste, method for manufacturing laminated ceraminc electronic component, and laminated ceramic electronic component |
| US7018864B2 (en) * | 2001-09-20 | 2006-03-28 | Murata Manufacturing Co., Ltd. | Conductive paste for terminal electrodes of monolithic ceramic electronic component, method for making monolithic ceramic electronic component, and monolithic ceramic electronic component |
| US20040113127A1 (en) * | 2002-12-17 | 2004-06-17 | Min Gary Yonggang | Resistor compositions having a substantially neutral temperature coefficient of resistance and methods and compositions relating thereto |
| CN1686662A (en) * | 2005-04-29 | 2005-10-26 | 华南理工大学 | Self soldering solder used for brazing connecting PTC ceramic and aluminium alloy |
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| CN1870179A (en) | 2006-11-29 |
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Owner name: HEFEI SHENGDA ELECTRONICS INDUSTRY CO., LTD. Free format text: FORMER NAME: HEFEI SHENGDA INDUSTRIAL CORP, HUADONG MICROELECTRONIC TECHNOLOGY INST. |
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Address after: 230022 No. 260, Jixi Road, Hefei, Anhui Patentee after: HEFEI SHENGDA ELECTRONIC TECHNOLOGY INDUSTRIAL CO., LTD. Address before: 230022 No. 260, Jixi Road, Hefei, Anhui Patentee before: East China Microelectronic Technology Research Institute, Hefei Shengda Electronics Industry Co.,Ltd. |
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Granted publication date: 20080528 Termination date: 20170628 |