CN103113026B - Glass powder for electronic paste and preparation method thereof - Google Patents
Glass powder for electronic paste and preparation method thereof Download PDFInfo
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- CN103113026B CN103113026B CN201310071613.XA CN201310071613A CN103113026B CN 103113026 B CN103113026 B CN 103113026B CN 201310071613 A CN201310071613 A CN 201310071613A CN 103113026 B CN103113026 B CN 103113026B
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- 239000000843 powder Substances 0.000 title claims abstract description 90
- 239000011521 glass Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 54
- 229910052726 zirconium Inorganic materials 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000009288 screen filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 abstract description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000036541 health Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000005476 soldering Methods 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003985 ceramic capacitor Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000007650 screen-printing Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 24
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000003801 milling Methods 0.000 description 9
- 239000006060 molten glass Substances 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241001300078 Vitrea Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000005331 crown glasses (windows) Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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Abstract
The invention relates to the technical field of lead-free glass powder and a preparation method thereof and in particular relates to glass powder for electronic paste and the preparation method thereof. The glass powder for the electronic paste comprises the following components in percentage by weight: 76-82% of Bi2O3, 3-8% of ZnO, 11-18% of B2O3, 1-4% of SiO2, 0.1-0.4% of Al2O3 and 0.1-0.4% of MgO. According to the glass powder for electronic paste, the Bi2O3 is adopted to replace PbO, the glass powder does not contain matters such as lead and cadmium which are harmful for human health and environments and has very strong adaptability for high-temperature lead-free soldering; the chemical stability and wetting property are improved, the expansion factor is increased, and meanwhile, the thermal sealing temperature and the softening temperature are lowered; and the glass powder can be taken as a bonding phase of the electronic paste, and the production cost is greatly lowered. After the produced lead-free glass powder is ground and uniformly mixed with metal powder, additives and organic vehicles and is printed on a substrate of a ceramic capacitor by utilizing silk-screen printing to form a conduction electrode, the lead-free glass powder has excellent adhesive force, weldability and electrical conductivity with the substrate. The preparation method for the glass powder provided by the invention has the advantages of simple preparation process, convenience in operation and low cost.
Description
Technical field
The present invention relates to lead-free glass powder and preparation method thereof technical field, more specifically, relate to a kind of electric slurry glass powder and preparation method thereof.
Background technology
Traditional glass powder for silver electronic paste, the objectionable impurities such as how leaded, cadmium, and its welding temperature is at about 230 DEG C.On July 1st, 2006; European Union's " about being limited in electronic and electrical equipment the instruction using some objectionable constituent " (Restriction of Hazardous Substances) starts formally to implement; this standard is mainly used in the material and progress standard of specification electronic and electrical equipment, makes it advantageously in HUMAN HEALTH and environment protection.The object of this standard is to eliminate the objectionable impurities such as lead, cadmium in motor electronic product.So far, reduce the consumption of the objectionable impuritiess such as lead, cadmium in silver electronic paste and auxiliary material thereof, or develop the silver electronic paste of not leaded, cadmium and so on objectionable impurities and auxiliary material thereof and become the direction that development & production mechanism of various countries puts forth effort to move ahead.After this standard is implemented, in ceramic condenser welding lead process, a large amount of welding compound used changes Pb-free solder into by leaded scolding tin, and welding temperature also brings up to more than 250 ~ 260 DEG C from 230 DEG C, this just proposes the glass powder used as caking agent and removes plumbous, cadmium and the requirement of high temperature resistant welding.
So far, the surrogate finding the objectionable impuritiess such as other are not leaded, cadmium is just very urgent.Roughly there are following three aspects in the direction of setting about researching and developing.One, Bi
2o
3introduce PbO-ZnO-B
2o
3system; Replace the PbO wherein originally contained, but there is Bi
2o
3consumption is large, and sticking temperature is higher, the problem that the coefficient of expansion is excessive, have impact on the application in practice of this system; Chinese patent 200810200747.6,200910102521.7,2010557210.2,2011102036.4 and 201210184927.6 all reported for work this system glass powder preparation.Especially 200810200747.6 preparations of glass powder of having reported for work a kind of this system typical.Its two, develop with V
2o
5be main V
2o
5-ZnO-B
2o
3system, Chinese patent CN200410015104.6 reports V
2o
5-ZnO-B
2o
3the practical application of sealing glass powder on silver electronic paste of system; Its three, develop the SnO-ZnO-P based on SnO
2o
5system.
The performance major part of above-mentioned crown glass powder has reached or close to the level of the traditional glass powder in various matrix or purposes, but yet there is a series of problem, as chemical stability and wettability decline, melting temperature sealing and softening temperature raise, and expansion coefficient mismatch etc., the more important thing is that the melt temperature of glass powder is high, many more than 1200 DEG C, and component is many, technique is often consuming time, and this all increases cost.
Summary of the invention
The present invention is intended to solve the problems of the technologies described above at least to a certain extent.
Primary and foremost purpose of the present invention is to provide a kind of electric slurry glass powder of excellent property, not leaded, cadmium etc. is harmful to the material of HUMAN HEALTH and environment, to the welding of high temperature lead-free solder, there is very strong adaptability, its fusing point be low, stable chemical performance, significantly reduce production cost.
A further object of the present invention is to provide a kind of preparation method of electric slurry glass powder.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of electric slurry glass powder is provided, comprises each component of following weight percent: 76 ~ 82%Bi
2o
3, 3 ~ 8%ZnO, 11 ~ 18%B
2o
3, 1 ~ 4%SiO
2, 0.1 ~ 0.4%Al
2o
3, 0.1 ~ 0.4%MgO.Adopt the glass powder stable chemical performance that technical solution of the present invention obtains, its glass melting temperature is low to moderate 980 ~ 1100 DEG C, not leaded, cadmium etc. is harmful to the material of HUMAN HEALTH and environment, have very strong adaptability, and production cost is low to the welding of high temperature lead-free solder.
The present invention adopts Bi
2o
3after substituting PbO, cause the change of chemical stability and thermostability, the coefficient of expansion is increased, simultaneously by adding the 5SiO of suitable proportion
22Al
2o
32MgO, to turn down the coefficient of expansion of glass, improves the performance of glass powder.When lead-free glass powder of the present invention is used as the binding agent in electric slurry, by with metal powder, additive and organic carrier grind be mixed even, be screen-printed to after ceramic condenser substrate forms conductor electrode, there is between itself and substrate excellent sticking power, weldability and electroconductibility.
Preferably, described ZnO and B
2o
3total amount and Bi
2o
3the ratio of weight be 20:80, described Al
2o
3with total amount and the SiO of MgO
2the ratio of weight be 20:80.Bi of the present invention
2o
3consumption be greater than 70%, SiO
2consumption be less than 5%, this is all the taboo of traditional fusion cast glass, Bi
2o
3consumption large, affect the chemical stability of glass and the increase of thermal expansivity, and SiO
2consumption be littlely then unfavorable for Vitrea formation.The present invention is by control ZnO and B
2o
3total amount and Bi
2o
3the ratio of weight be 20:80, Al
2o
3with total amount and the SiO of MgO
2the ratio of weight be 20:80.Simultaneously by controlling the 5SiO added
22Al
2o
32MgO is the structure of similar cyanines green stone, with the formation of favourable glass, turns down the coefficient of expansion of glass, improves the performance of glass powder.The present invention, by determining the ratio framework of two 20:80, in increasing bismuth oxide consumption situation, reduces glass melting temperature, improves chemical stability and the thermostability of glass powder further; Improve the performance of glass powder, especially the coefficient of expansion of glass powder, SiO
2, Al
2o
3, the suitable proportioning of MgO plays crucial effect especially.
Present invention also offers a kind of preparation method as above-mentioned arbitrary electric slurry glass powder, comprise the following steps:
S1. SiO is taken respectively
2, Al
2o
3, MgO, grinding, mixing;
S2. Bi is taken respectively
2o
3, ZnO, B
2o
3, mix with step S1 gained material;
S3. step S2 gained material is placed in melting at 980 ~ 1100 DEG C of temperature, pours in normal temperature pure water after taking-up, collect product and also dry;
S4. step S3 gained material is rolled into particle, then ball milling;
S5. step S4 gained material is sieved, dries, electric slurry glass powder.
In such scheme:
In step s3, the fusion time is 10 ~ 30min, and the product of collection dries 5 ~ 8h at 90 DEG C of temperature;
In step s 4 which, particle ball milling 30 ~ 60min under the rotating speed of 600r/min;
In step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1;
In step s 5, material 300 ~ 400 order screen filtration.
In addition, the coefficient of expansion of electric slurry glass powder is 56 ~ 70 × 10
-7/ DEG C, sticking power is 19 ~ 23N.
Compared with prior art, the invention has the beneficial effects as follows:
Electric slurry glass powder of the present invention adopts Bi
2o
3substitute PbO, not leaded, cadmium etc. is harmful to the material of HUMAN HEALTH and environment, to the welding of high temperature lead-free solder, there is very strong adaptability, chemical stability and wettability improve, the coefficient of expansion increases, melting temperature sealing and softening temperature reduce simultaneously, can be applicable to electric slurry and make bonding phase, significantly reduce production cost.By even with metal powder, additive and organic carrier ground and mixed after this lead-free glass powder is obtained, is screen-printed to after ceramic condenser substrate forms conductor electrode, there is between itself and substrate excellent sticking power, weldability and electroconductibility.
The temperature of its fusion cast glass powder of preparation method of electric slurry glass powder of the present invention is reduced to 980 ~ 1100 DEG C, preparation technology is simple, easy to operate and cost is low, the fusing point of the lead-free glass powder using this preparation method to obtain is low, stable chemical performance, prepares simple and convenient.This invention greatly reduces glass smelting temperature, lower than the temperature limitation of 1200 DEG C, greatly reduce cost, save the energy.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
embodiment 1
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 7.2g SiO is taken respectively with electronic platform scale
2, 0.9g Al
2o
3, 0.9g MgO, put into ceramic mortar grinding, mixing;
S2. 231g Bi is taken respectively
2o
3, 9g ZnO, 48g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 10min at 1050 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 5h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 30min;
S5. by the 300 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 2
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 7.2g SiO is taken respectively with electronic platform scale
2, 0.9g Al
2o
3, 0.9g MgO, put into ceramic mortar grinding, mixing;
S2. 231g Bi is taken respectively
2o
3, 15g ZnO, 42g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 10min at 1040 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 5h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 30min;
S5. by the 300 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 3
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 7.2g SiO is taken respectively with electronic platform scale
2, 0.9g Al
2o
3, 0.9g MgO, put into ceramic mortar grinding, mixing;
S2. 231g Bi is taken respectively
2o
3, 21g ZnO, 39g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 18min at 1030 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 5h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 30min;
S5. by the 300 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 4
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 9.6g SiO is taken respectively with electronic platform scale
2, 1.2g Al
2o
3, 1.2g MgO, put into ceramic mortar grinding, mixing;
S2. 228g Bi is taken respectively
2o
3, 9g ZnO, 54g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 18min at 1020 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 6h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 40min;
S5. by the 300 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 5
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 9.6g SiO is taken respectively with electronic platform scale
2, 1.2g Al
2o
3, 1.2g MgO, put into ceramic mortar grinding, mixing;
S2. 228g Bi is taken respectively
2o
3, 15g ZnO, 48g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 22min at 1040 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 6h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 40min;
S5. by the 300 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 6
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 9.6g SiO is taken respectively with electronic platform scale
2, 1.2g Al
2o
3, 1.2g MgO, put into ceramic mortar grinding, mixing;
S2. 228g Bi is taken respectively
2o
3, 21g ZnO, 42g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 22min at 1030 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 7h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 45min;
S5. by the 400 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 7
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 4.8g SiO is taken respectively with electronic platform scale
2, 0.6g Al
2o
3, 0.6g MgO, put into ceramic mortar grinding, mixing;
S2. 240g Bi is taken respectively
2o
3, 9g ZnO, 45g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 26min at 1020 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 7h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 50min;
S5. by the 400 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 8
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 4.8g SiO is taken respectively with electronic platform scale
2, 0.6g Al
2o
3, 0.6g MgO, put into ceramic mortar grinding, mixing;
S2. 240g Bi is taken respectively
2o
3, 15g ZnO, 39g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 26min at 1000 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 8h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 55min;
S5. by the 400 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
embodiment 9
The preparation method of the present embodiment electric slurry glass powder is as follows:
S1. 4.8g SiO is taken respectively with electronic platform scale
2, 0.6g Al
2o
3, 0.6g MgO, put into ceramic mortar grinding, mixing;
S2. 240g Bi is taken respectively
2o
3, 21g ZnO, 33g B
2o
3, together load in the Stainless steel basin of capacity 5L with the mixture powder of step S1 gained and mix;
S3. the mixing starting material of step S2 gained is moved in the ceramic crucible of capacity 200ml, put in retort furnace, melting 30min at 980 DEG C of temperature, pour in normal temperature (about 25 DEG C) pure water after molten glass liquid being taken out again and carry out shrend, the product collected after shrend dries 8h at 90 DEG C of temperature in baking oven;
S4. the two rod mill milling of step S3 gained material is become particle, then under the rotating speed of 600r/min ball milling 60min;
S5. by the 400 order stainless steel sift net filtrations of gained material after step S4 ball milling, oven dry, electric slurry glass powder.
Wherein, in step s 4 which, use the zirconium ball with two kinds of diameters and pure water to be medium during ball milling, in conjunction with zirconium ball ball grinding stirring, production time more than 24h can be saved, and then significantly reduce production cost; The diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
As shown in table 1 is the softening temperature test result of the obtained electric slurry glass powder of above-described embodiment 1 ~ 9.
The softening temperature test result of table 1 electric slurry glass powder
As shown in Table 1, the softening point temperature of electric slurry glass powder of the present invention is between 550 ~ 630 DEG C.
Due to Bi
2o
3after substituting PbO, the change of chemical stability and thermostability can be caused, especially the coefficient of expansion increases, therefore, the embodiment of the present invention is by determining the ratio framework of two 20:80, in increasing bismuth oxide consumption situation, reduce glass melting temperature, improve chemical stability and the thermostability of glass powder; Improve the performance of glass powder, especially the coefficient of expansion of glass powder, SiO
2, Al
2o
3, the suitable proportioning of MgO plays crucial effect especially.The foundation of the modulation glass powder coefficient of expansion is: a=P
1a
1+ P
na
n, reach the performance improving glass powder; Wherein, P is the weight percentage of component, and a is the coefficient of expansion of component.
With embodiment of the present invention glass powder as binder making silver electronic paste, be printed onto on ceramic substrate, 250 ~ 280 DEG C of oven dry, 800 DEG C of sintering, then soldering lead-in wire, test sticking power with puller system, the results are shown in Table 2.For silver electronic paste, its sticking power on a ceramic substrate should be not less than the 15N required by Technical specifications.
The technological standard of table 2 electric slurry glass powder
As seen from the results in Table 2, embodiment of the present invention glass powder is as the silver electronic paste of binder making after being sintered on ceramic substrate, and its sticking power reaches more than 19N, and weldability is excellent.
According to inventive concept and method, invention has been a large amount of experiments, all obtain and stablize and the experimental result of Be very effective.Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (8)
1. an electric slurry glass powder, is characterized in that, described electric slurry glass powder is made up of following component by weight percentage: 76 ~ 82%Bi
2o
3, 3 ~ 8%ZnO, 11 ~ 18%B
2o
3, 1 ~ 4%SiO
2, 0.1 ~ 0.4%Al
2o
3, 0.1 ~ 0.4%MgO;
Wherein, described ZnO and B
2o
3total amount and Bi
2o
3the ratio of weight be 20:80, described Al
2o
3with total amount and the SiO of MgO
2the ratio of weight be 20:80.
2. a preparation method for electric slurry glass powder as claimed in claim 1, is characterized in that, comprise the following steps:
S1. SiO is taken respectively
2, Al
2o
3, MgO, grinding, mixing;
S2. Bi is taken respectively
2o
3, ZnO, B
2o
3, mix with step S1 gained material;
S3. step S2 gained material is placed in melting at 980 ~ 1100 DEG C of temperature, pours in normal temperature pure water after taking-up, collect product and also dry;
S4. step S3 gained material is rolled into particle, then ball milling;
S5. step S4 gained material is sieved, dries, electric slurry glass powder.
3. the preparation method of electric slurry glass powder according to claim 2, is characterized in that, in step s3, the fusion time is 10 ~ 30min.
4. the preparation method of electric slurry glass powder according to claim 2, is characterized in that, in step s3, the product of collection dries 5 ~ 8h at 90 DEG C of temperature.
5. the preparation method of electric slurry glass powder according to claim 2, is characterized in that, in step s 4 which, particle is ball milling 30 ~ 60min under the rotating speed of 600r/min.
6. the preparation method of electric slurry glass powder according to claim 2, is characterized in that, in step s 4 which, uses the zirconium ball with two kinds of diameters and pure water to be medium during ball milling.
7. the preparation method of electric slurry glass powder according to claim 6, is characterized in that, the diameter of two kinds of zirconium balls is respectively 3mm and 5mm, and amount ratio is 3mm zirconium ball: 5mm zirconium ball=2: 1.
8. the preparation method of electric slurry glass powder according to claim 2, is characterized in that, in step s 5, and material 300 ~ 400 order screen filtration.
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| CN105347688A (en) * | 2015-12-14 | 2016-02-24 | 周妙思 | Preparation method of glass powder for electronic paste |
| CN105502952A (en) * | 2015-12-14 | 2016-04-20 | 周妙思 | Glass powder |
| CN105417954A (en) * | 2015-12-14 | 2016-03-23 | 周妙思 | Unleaded glass powder |
| CN106825978B (en) * | 2017-02-24 | 2019-08-27 | 哈尔滨工业大学深圳研究生院 | A kind of brazing material and welding method for ceramics and metal welding |
| CN114078613A (en) * | 2020-08-20 | 2022-02-22 | 赖秋郎 | A kind of preparation method of fine copper conductive paste of ceramic filter for 5G |
| CN113698104B (en) * | 2021-10-19 | 2022-05-24 | 西北大学 | A kind of lead-free glass powder decorated with bismuth trioxide nanolayer and preparation method thereof |
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