CN100454443C - Environment pretection leadless surface silver coating for PTC ceramic and its preparation method - Google Patents
Environment pretection leadless surface silver coating for PTC ceramic and its preparation method Download PDFInfo
- Publication number
- CN100454443C CN100454443C CNB200610088132XA CN200610088132A CN100454443C CN 100454443 C CN100454443 C CN 100454443C CN B200610088132X A CNB200610088132X A CN B200610088132XA CN 200610088132 A CN200610088132 A CN 200610088132A CN 100454443 C CN100454443 C CN 100454443C
- Authority
- CN
- China
- Prior art keywords
- glass powder
- powder
- silver
- lead
- leadless
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
Abstract
The present invention discloses an environment protection leadless silver slurry for PTC ceramics and a preparation method thereof. The present invention is mainly composed of silver micro powder, leadless glass powder and an organic carrier, wherein the leadless glass powder is mainly composed of Bi2O3, B2O3, ZnO, SiO2, Al2O3, CuO, etc. The present invention uses a novel boron bismuth zinc glass system for replacing a commonly used boron lead silicon series glass material, and products are leadless. When glass powder which is prepared by using the boron bismuth zinc glass system of the present invention is used, through adding proper aluminum, copper and silicic oxides, the melting point of the glass material is below 470 DEG C, and simultaneously, the chemical stability, the wettability with PTC ceramic matrices, and the electrical property are superior.
Description
Technical field
The present invention relates to the PTC environment pretection leadless surface silver coating, this slurry by silk screen printing, dry, burn till etc. technology on positive temperature coefficient ceramic element ohmic electrode layer, form can weldering, the surface electrode layer of strong adhesion, superior electrical property.
Background technology
PTC (positive temperature coefficient) pottery is a kind of broad-spectrum semiconductor ceramic material, must use the silver slurry to make one deck silver electrode layer at its Ohmic electrode laminar surface in manufacture process, so that it can carry out soldering with lead-in wire or pin.This silver slurry is commonly referred to the surface silver coating slurry.
Positive temperature coefficient surface silver coating slurry is by micro silver powder, glass dust, and raw material formulated such as organic carrier form.Micro silver powder is the main component of slurry, plays electric action in electrode, and glass dust melts in the electrode sintering process, forms bonded layer with the surface of electrode layer attached to ceramic body, thereby forms the uniform conductive film.Organic carrier plays the dispersion suspension effect, makes slurry become more stable suspended substance, can place for a long time and does not precipitate, and organic carrier makes slurry have certain flowability, thixotropy etc. simultaneously, thereby makes slurry have good printing performance.
Glass dust is important function phase very in the positive temperature coefficient surface silver coating slurry, its performance to positive temperature coefficient has very big influence, the used glass dust of positive temperature coefficient surface silver coating slurry is a kind of B-Pb-Si system frit at present, in the frit of this system, plumbous conduct Main Ingredients and Appearance wherein, its ratio is very high.With the silver slurry of this class frit preparation, its lead content is 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 (Res triction of HazardousSubstances) " (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, people replace the boron lead-silica glass striving to find a kind of new lead-less glasses material, the fusing point of lead-less glasses material is generally higher, this firing temperature that just means slurry will improve, and the characteristic of positive temperature coefficient ceramic self ohmic electrode layer is determining the firing temperature of its electrode generally can not be higher than 600 ℃, therefore it is low to develop fusing point, the lead-less glasses material that the wettability of stable chemical performance and positive temperature coefficient ceramic is good, and then the unleaded electrode silver plasm material of production positive temperature coefficient becomes a global problem.
Summary of the invention
The purpose of this invention is to provide a kind of positive temperature coefficient ceramic environment pretection leadless surface silver coating, the fusing point of frit is lower than 470 ℃, simultaneously its chemical stability, all very superior with the wettability and the electrical property of positive temperature coefficient ceramic matrix.
Technical scheme of the present invention is as follows:
The positive temperature coefficient ceramic environment pretection leadless surface silver coating is characterized in that the silver paste component is respectively by weight percentage:
Micro silver powder 55-80%
Lead-free glass powder 2-8%
Organic carrier 15-40%;
Wherein
The percentage by weight of the material component of organic carrier is:
Polymeric adhesive 4-15%;
Organic additive 1-10%;
Organic solvent 75-95%
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;
The raw material weight percentage of lead-free glass powder is:
Bi
20
3 15-45％
B
2O
3 8-35％
ZnO 1-30％
SiO
2 1-15％
Al
2O
3 0-5％
CuO 0-5％。
Described leadless surface silver coating slurry, its feature is respectively by weight percentage at the silver paste component:
Micro silver powder 62-68%
Lead-free glass powder 4-6%
Organic carrier 28-32%
Wherein
The percentage by weight of the material component of organic carrier is:
Polymeric adhesive 6-10%
Organic additive 2-5%
Organic solvent 85-90%
The raw material weight percentage of lead-free glass powder is:
Bi
2O
3 32-40％
B
2O
3 10-30％
ZnO 20-28％
SiO
2 5-15％
Al
2O
3 0-5％
CuO 1-4％。
The described positive temperature coefficient ceramic preparation method of environment pretection leadless surface silver coating is characterized in that:
(1), micro silver powder selects for use granularity less than 1 μ m ball shape silver powder;
(2), take by weighing each raw material of organic carrier, be heated to whole dissolvings by prescription;
(3), by the prescription with melting after the crown glass powder raw material ground and mixed, again through quenching-in water, add water for ball milling and be crushed to granularity less than 10 μ m, and the oven dry;
(4), take by weighing the material of aforementioned (1), (2), (3) step gained, mixing stirs evenly by prescription, compound is ground, until granularity less than 10 μ m, promptly.
The temperature of described crown glass powder raw material melting is 1050 ℃-1200 ℃, time 20-30min.
Technological progress of the present invention is to adopt newly-designed B-Bi-Zn glass system, replaces used B-Pb-Si system frit usually, has realized the unleaded of product.Use the glass dust of newly-designed B-Bi-Zn glass system preparation, by adding the oxide of suitable aluminium, copper, silicon, make the fusing point of frit be lower than 470 ℃, simultaneously its chemical stability, all very superior with the wettability and the electrical property of positive temperature coefficient ceramic matrix.Thereby the positive temperature coefficient lead-free silver slurry that uses the present invention to produce has following advantage:
1. has good solderability;
2. has very strong adhesive force;
3. has superior ageing resistace;
4. have broad firing range, it can burn till at 480 ℃-600 ℃, and Technological adaptability is good.
Embodiment
One, the organic carrier during positive temperature coefficient ceramic is starched with environmental-friendly lead-free silver, it is made up of ethyl cellulose, rosin, castor oil, terpinol, and its percentage by weight is
Ethyl cellulose 6%
Rosin 2%
Castor oil 2%
Terpinol 90%
Each component is fully mixed, and heats down at 100 ℃ ethyl cellulose and rosin are fully dissolved.
Two, the lead-free glass powder during positive temperature coefficient ceramic is starched with environmental-friendly lead-free silver, it is by Bi
2O
3, B
2O
3, ZnO, SiO2, Al
2O
3, CuO forms, and its percentage by weight is
Bi
2O
3 35.8％
B
2O
3 28％
ZnO 26.9％
SiO
2 6.9％
Al
2O
3 1
CuO 1.4％
Each material ground and mixed is evenly packed in the silica crucible, be placed on 1050 ℃-1200 ℃ electric furnace in melting 20-30min, the frit that will be molten condition is poured quenching-in water rapidly into, then the shrend frit is packed in the ball mill, and add the proper amount of clear water ball mill grinding until granularity less than 10 μ m, drying and dewatering promptly gets the lead-free glass powder that fusion temperature is lower than 470 ℃.
Three, micro silver powder selects for use granularity less than 1 μ m ball shape silver powder.
Four, positive temperature coefficient ceramic is with environmental-friendly lead-free silver slurry, and it is by micro silver powder, lead-free glass powder, and organic carrier is formed, and its percentage by weight is
Micro silver powder 65%
Lead-free glass powder 5%
Organic carrier 30%
With each component batching, mixing, grind rolling granularity through three-roll grinder and obtain finished product for behind＜10 μ m until slurry.
Five, silver paste performance:
Granularity:＜10um
Firing temperature: 480 ℃-600 ℃
Solderability: excellent
Adhesive force:＞10N/mm
2
Side's resistance:＜8m Ω/mouth
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 (4)
1, positive temperature coefficient ceramic is starched with leadless surface silver coating, it is characterized in that the silver paste component is respectively by weight percentage:
Micro silver powder 55-80%
Lead-free glass powder 2-8%
Organic carrier 15-40%;
Wherein
The percentage by weight of the material component of organic carrier is:
Polymeric adhesive 4-15%;
Organic additive 1-10%;
Organic solvent 75-95%
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;
The raw material weight percentage of lead-free glass powder is:
Bi
2O
3 15-45％
B
2O
3 8-35％
ZnO 1-30％
SiO
2 1-15％
Al
2O
3 0-5％
CuO 0-5％。
2, leadless surface silver coating slurry according to claim 1 is characterized in that the silver paste component is respectively by weight percentage:
Micro silver powder 62-68%
Lead-free glass powder 4-6%
Organic carrier 28-32%
Wherein
The percentage by weight of the material component of organic carrier is:
Polymeric adhesive 6-10%
Organic additive 2-5%
Organic solvent 85-90%
The raw material weight percentage of lead-free glass powder is:
Bi
2O
3 32-40％
B
2O
3 10-30％
ZnO 20-28％
SiO
2 5-15％
Al
2O
3 0-5％
CuO 1-4％。
3, positive temperature coefficient ceramic according to claim 1 is characterized in that with the preparation method of leadless surface silver coating slurry:
(1), micro silver powder selects for use granularity less than 1 μ m ball shape silver powder;
(2), take by weighing each raw material of organic carrier, be heated to whole dissolvings by prescription;
(3), by the prescription with melting after the crown glass powder raw material ground and mixed, again through quenching-in water, add water for ball milling and be crushed to granularity less than 10 μ m, and the oven dry;
(4), take by weighing the material of aforementioned (1), (2), (3) step gained, mixing stirs evenly by prescription, compound is ground, until granularity less than 10 μ m, promptly.
4, method according to claim 3, the temperature that it is characterized in that the melting of described crown glass powder raw material are 1050 ℃-1200 ℃, time 20-30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610088132XA CN100454443C (en) | 2006-06-28 | 2006-06-28 | Environment pretection leadless surface silver coating for PTC ceramic and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610088132XA CN100454443C (en) | 2006-06-28 | 2006-06-28 | Environment pretection leadless surface silver coating for PTC ceramic and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1870180A CN1870180A (en) | 2006-11-29 |
| CN100454443C true CN100454443C (en) | 2009-01-21 |
Family
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|---|---|---|---|
| CNB200610088132XA Expired - Fee Related CN100454443C (en) | 2006-06-28 | 2006-06-28 | Environment pretection leadless surface silver coating for PTC ceramic and its preparation method |
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Families Citing this family (17)
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| CN101206957B (en) * | 2007-12-07 | 2010-04-21 | 宁波晶鑫电子材料有限公司 | Preparation of low temperature drying wafer capacitance electrode silver paste |
| CN101217067B (en) * | 2007-12-27 | 2010-04-07 | 广州市儒兴科技开发有限公司 | A lead free aluminum electrode slurry of PTC thermo-sensitive resistor and preparation method |
| CN101271928B (en) * | 2008-05-04 | 2012-02-29 | 常州亿晶光电科技有限公司 | Method for producing high-viscosity solar cell front side silver paste and the same |
| JP5286037B2 (en) * | 2008-11-10 | 2013-09-11 | 太陽誘電株式会社 | Varistor and manufacturing method thereof |
| CN101714607B (en) * | 2009-09-22 | 2011-06-22 | 华南理工大学 | Piezoelectric ceramic element of metal aluminium electrode and preparation method thereof |
| CN101728002A (en) * | 2010-01-15 | 2010-06-09 | 贵阳晶华电子材料有限公司 | End-blocking slurry for flaky component |
| CN101770829B (en) * | 2010-03-16 | 2011-06-01 | 彩虹集团公司 | Special silver electrode paste for touch screen and preparation method thereof |
| CN101964219B (en) * | 2010-08-10 | 2013-02-06 | 上海九晶电子材料股份有限公司 | Silver paste for positive of crystalline silicon solar cell and preparation method thereof |
| CN102432184A (en) * | 2011-09-22 | 2012-05-02 | 上海交通大学 | Low melting point phosphate glass powder for silver paste of solar battery and preparation method thereof |
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| CN104505144B (en) * | 2014-12-16 | 2017-08-29 | 安徽凤阳德诚科技有限公司 | A kind of low-temperature conductive silver paste of heat generating component |
| CN107068237B (en) * | 2016-12-30 | 2019-05-28 | 彩虹集团新能源股份有限公司 | The preparation method of lower Tc PTC heat sensitive electronic component electrode thick liquid without lead and silver |
| 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 |
| CN109859878A (en) * | 2019-02-22 | 2019-06-07 | 肇庆市辰业电子有限公司 | A kind of 5G base of ceramic filter high q-factor electrode silver plasm and preparation method thereof |
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| CN112712911A (en) * | 2020-12-18 | 2021-04-27 | 中国振华集团云科电子有限公司 | Metalized spraying silver paste for surface of dielectric filter and preparation method thereof |
| CN114685102B (en) * | 2020-12-30 | 2023-02-03 | 辽宁省轻工科学研究院有限公司 | Low-temperature glass slurry and preparation method thereof |
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| CN1870180A (en) | 2006-11-29 |
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