CN101817637B - Leadless aluminum dielectric material and preparation method thereof - Google Patents
Leadless aluminum dielectric material and preparation method thereof Download PDFInfo
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- CN101817637B CN101817637B CN2010101607314A CN201010160731A CN101817637B CN 101817637 B CN101817637 B CN 101817637B CN 2010101607314 A CN2010101607314 A CN 2010101607314A CN 201010160731 A CN201010160731 A CN 201010160731A CN 101817637 B CN101817637 B CN 101817637B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention provides a leadless aluminum dielectric material used on pure aluminum or aluminum alloy and a preparation method thereof. The preparation method of the invention comprises the following steps: firstly, mixing SiO2, B2O3, TiO2, Al2O3, ZnO, MgO, K2O, Na2O, Li2O and Bi2O3 in a certain proportion, melting the mixture in a heating furnace at 1000 DEG C, and quenching with water; then carrying out wet milling in a corundum ball milling tank for one hour and drying to obtain the leadless aluminum dielectric material; then mixing the leadless aluminum dielectric material and a certain amount of organic solvent and putting the mixture into the corundum ball milling tank for ball milling to obtain a printing material; printing the printing material onto the pure aluminum or the aluminum alloy; and then drying and sintering. The leadless aluminum dielectric material of the invention has the characteristics of no lead pollution to the environment, acid and alkaline corrosion resistance, high rigidity, good chemical stability, capability of well combining with an aluminum substrate, high insulating property and the like, and is suitable for surface decoration of various colors and insulation voltage resistant protection of the aluminum substrate.
Description
Technical field
The present invention relates to the production technique of a kind of unleaded aluminum or aluminum alloy substrate, particularly relate to a kind of unleaded aluminum or aluminum alloy substrate of on aluminium or aluminium alloy base plate, using with dielectric material and preparation method with dielectric material.
Background technology
At present, in field of electric heating, had stainless steel to be used for heated substrates, still, stainless steel is heavy as substrate quality, and heat-up rate is slow, and is few with the product of the board materials production of unit mass, and the firing temperature height, causes cost higher.The lighter weight of metallic aluminium or duraluminum, fast, the low price of thermal conduction, but melt temperature is lower, probably about 630 ℃, so the sintering temperature of aluminium or aluminium alloy covered material can not be higher than 600 ℃.The coating that at present is used for aluminium or aluminum alloy surface; Low sintering requirement for satisfied 600 ℃; Added a large amount of lead therein; Yet high-load plumbous oxide can cause very big pollution to environment in the production of product and later use, and the heater element major part is to contact with tap water, will work the mischief to human body like this.
Summary of the invention
The objective of the invention is to overcome the weak point of above-mentioned prior art; Also take into account the adaptive unleaded aluminum or aluminum alloy substrate of product when technical problem to be solved provides a kind of enhancing productivity and use the dielectric material preparation method, reach aluminum dielectric material leadless environment-friendly, that meet requirements such as surface characteristic and proof voltage test.
For reaching above-mentioned purpose, leadless aluminum dielectric material of the present invention and preparation method are achieved through following technical proposals:
At first prepare unleaded aluminum or aluminum alloy substrate and use the medium base mateiral, raw material comprises following each component by mass percentage:
Silicon-dioxide SiO
2: 25%~35%
Boron oxide B
2O
3: 11%~18%
Titanium oxide TiO
2: 8%~14%
Aluminium sesquioxide Al
2O
3: 1%~5%
Zinc oxide ZnO:5%~10%
Natural manganese dioxide MgO:0.5%~3%
Potassium oxide K
2O:5%~9%
Sodium oxide Na
2O:15%~22%
Lithium Oxide 98min Li
2O:0.5%~3%
Bismuthous oxide bismuth trioxide Bi
2O
3: 9%~15%;
Each oxide compound by above-mentioned mass percent mixes; Place 1000 ℃ process furnace to melt one hour in this mixture then; Pass through shrend again; According to material after the shrend: ball: the water ratio is 1: (1~1.2): placed corundum ball grinder ball milling one hour after (1~1.2) mixed, cross 200 mesh sieves then, get final product through oven dry; Be placed on according to 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin that ball milling promptly obtains printing slurry in the corundum ball grinder about 2 hours; The surface treatment of aluminium base before the printing: clean zone of oxidation through hot acid earlier, pass through the thermokalite neutralizing treatment again, get final product through clean drying of high temperature washed with de-ionized water then; To print at last slurry use correct printing process with 60 purpose screen printings on aluminium base; Through about 80 ℃ oven dry, 600 ℃ of sintering can be met requirements such as surface characteristic, proof voltage, acid-alkali-corrosive-resisting, adherence after 3~5 minutes the unleaded aluminum or aluminum alloy substrate of finished product is used dielectric material.
Dielectric material provided by the invention belongs to lead-free low-temperature to be fired and forms, and therefore, in products production and the process used afterwards, can not produce environment and human body and pollute and endanger.The present invention utilizes silicon-dioxide SiO
2With boron oxide B
2O
3As basic glass-former, utilize titanium oxide TiO again
2Breast the covering effect that is used for improving dielectric material, simultaneously for promote breast effect, also introduced zinc oxide ZnO, be used for this kind glossiness, improve like turbidity the increase unit elongation.The present invention introduces a certain amount of aluminium oxide Al
2O
3, the high temperature viscosity that is used for adjusting dielectric material prevents crystallization with control surface thickness and quality, improves the chemical resistance of concrete ability of dielectric material, improves resistance to impact shock and hardness.Also introduce an amount of Natural manganese dioxide MgO (less than 8%) simultaneously, enlarge sintering range, increase the coefficient of expansion and regulate firing temperature.In order to increase the coefficient of expansion; Introduce basic metal, but because the present invention uses is the method for silk screen printing, comprehensive viscosity and flow leveling consideration; The introducing amount of potassium oxide generally is no more than 9%; Excessive words will influence the viscosity and the toughness of glass paste, and the introducing amount of sodium oxide is no more than 20%, excessive then easy generation of cracks.The auxiliary material that adds other again reaches the function of needs.Unleaded aluminum or aluminum alloy substrate of the present invention with dielectric material have to environment do not have Lead contamination, acid-resistant chemical stability good, can with characteristics such as aluminium base good binding, high insulation withstand voltage properties, be applicable to versicolor surface decoration and the protection of insulation proof voltage on fine aluminium or the aluminium alloy base plate.
Embodiment
For further understanding characteristic of the present invention, technique means and the specific purposes that reached, function, resolve advantage of the present invention and spirit, by detailed description of the present invention further being understood below in conjunction with embodiment.
Unleaded aluminum or aluminum alloy substrate of the present invention is used dielectric material; Its prescription mainly comprises: silicon-dioxide SiO2, boron oxide B2O3, titanium oxide TiO2, aluminium sesquioxide Al2O3, zinc oxide ZnO, Natural manganese dioxide MgO, potassium oxide K2O, sodium oxide Na2O, Lithium Oxide 98min Li2O, bismuthous oxide bismuth trioxide Bi2O3, and the preparation method is following:
1), each component at unleaded aluminum or aluminum alloy substrate with the mass percent in the medium base mateiral composition system is:
Silicon-dioxide SiO
2: 25%~35%
Boron oxide B
2O
3: 11%~18%
Titanium oxide TiO
2: 8%~14%
Aluminium sesquioxide Al
2O
3: 1%~5%
Zinc oxide ZnO:5%~10%
Natural manganese dioxide MgO:0.5%~3%
Potassium oxide K
2O:5%~9%
Sodium oxide Na
2O:15%~22%
Lithium Oxide 98min Li
2O:0.5%~3%
Bismuthous oxide bismuth trioxide Bi
2O
3: 9%~15%;
2), each oxide compound by above-mentioned mass percent mixes; Then with this mixture as in 1000 ℃ the process furnace fusing one hour; Pass through shrend again; According to material after the shrend: ball: the water ratio is 1: (1~1.2): placed corundum ball grinder ball milling one hour after (1~1.2) mixed, cross 200 mesh sieves then, can obtain dielectric material through oven dry again;
3), be placed on according to 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin that ball milling promptly obtains printing slurry in the corundum ball grinder about 2 hours;
4), the surface treatment of aluminium base before the printing: clean zone of oxidation through hot acid earlier, pass through hot alkali treatment again, get final product through clean drying of high temperature washed with de-ionized water then;
5), respectively organizing mass percent in the above-mentioned organic solvent is:
Terpineol 350: 60~80%, TKK 021: 1~8%
Hydrocerol A tri butyl ester: 10~30% THIXCINs: 0.5~3%
Flow agent: 0.5~1% skimmer: 0~0.5%
Regulating various ratios makes viscosity at 100~200mPas;
6), will print slurry at last uses correct printing process to be printed on the aluminium base with 60 mesh sieves; Through about 80 ℃ oven dry, 600 ℃ of sintering can be met requirements such as surface characteristic, proof voltage, acid-alkali-corrosive-resisting, adherence after 3~5 minutes the unleaded aluminum or aluminum alloy substrate of finished product is used dielectric material.
The present invention is preferable to have following embodiment:
Embodiment one: all kinds of raw materials according to mass ratio are in the unleaded medium base mateiral: 25% SiO
2, 16% B
2O
3, 10% TiO
2, 4.5% Al
2O
3, 7% ZnO, 1.5% MgO, 8% K
2O, 15% Na
2O, 1% Li
2O and 12% Bi
2O
3Mix; Place the process furnace about 1000 ℃ to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is 1: (1~1.2): placed corundum ball grinder ball milling one hour after (1~1.2) mixed, cross 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtains printing slurry in the corundum ball grinder about 2 hours; Use correct printing process to be printed on the surface-treated aluminium base with 60 mesh sieves; Through about 80 ℃ oven dry, 600 ℃ of sintering can be met requirements such as surface characteristic, proof voltage, acid-alkali-corrosive-resisting, adherence after 3~5 minutes the unleaded aluminum or aluminum alloy substrate of finished product is used dielectric material.
Embodiment two: all kinds of raw materials according to mass ratio are in the unleaded aluminum or aluminum alloy substrate use medium base mateiral: 26% SiO
2, 15% B
2O
3, 12% TiO
2, 1.5% Al
2O
3, 8.5% ZnO, 0.5% MgO, 5% K
2O, 17% Na
2O, 0.5% Li
2O and 14% Bi
2O
3Mix; Place the process furnace about 1000 ℃ to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is 1: (1~1.2): placed corundum ball grinder ball milling one hour after (1~1.2) mixed, cross 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtains printing slurry in the corundum ball grinder about 2 hours; Use correct printing process to be printed on the surface-treated aluminium base with 60 mesh sieves; Through about 80 ℃ oven dry, 600 ℃ of sintering can be met requirements such as surface characteristic, proof voltage, acid-alkali-corrosive-resisting, adherence after 3~5 minutes the unleaded aluminum or aluminum alloy substrate of finished product is used dielectric material.
Embodiment three: all kinds of raw materials according to mass ratio are in the unleaded aluminum or aluminum alloy substrate use medium base mateiral: 29% SiO
2, 14% B
2O
3, 8% TiO
2, 2% Al
2O
3, 6% ZnO, 3% MgO, 9% K
2O, 16% Na
2O, 3% Li
2O and 10% Bi
2O
3Mix; Place the process furnace about 1000 ℃ to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is 1: (1~1.2): placed corundum ball grinder ball milling one hour after (1~1.2) mixed, cross 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtains printing slurry in the corundum ball grinder about 2 hours; Use correct printing process to be printed on the surface-treated aluminium base with 60 mesh sieves; Through about 80 ℃ oven dry, 600 ℃ of sintering can be met requirements such as surface characteristic, proof voltage, acid-alkali-corrosive-resisting, adherence after 3~5 minutes the unleaded aluminum or aluminum alloy substrate of finished product is used dielectric material.
Embodiment four: all kinds of raw materials according to mass ratio are in the unleaded aluminum or aluminum alloy substrate use medium base mateiral: 32% SiO
2, 12% B
2O
3, 14% TiO
2, 1% Al
2O
3, 5% ZnO, 1% MgO, 6% K
2O, 18% Na
2O, 2% Li
2O and 9% Bi
2O
3Mix; Place the process furnace about 1000 ℃ to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is 1: (1~1.2): placed corundum ball grinder ball milling one hour after (1~1.2) mixed, cross 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtains printing slurry in the corundum ball grinder about 2 hours; Use correct printing process to be printed on the surface-treated aluminium base with 60 mesh sieves; Through about 80 ℃ oven dry, 600 ℃ of sintering can be met requirements such as surface characteristic, proof voltage, acid-alkali-corrosive-resisting, adherence after 3~5 minutes the unleaded aluminum or aluminum alloy substrate of finished product is used dielectric material.
The above embodiment that lifts only uses to conveniently illustrating the present invention; Be merely the present invention's preferred embodiment; Be not that the present invention is implemented any pro forma restriction; Have common knowledge the knowledgeable in the technical field under any,, utilize disclosed technology contents to make local more should equalization the variation or the equivalent embodiment of modification if in the scope that does not break away from technical characterictic that the present invention carries; And do not break away from technical characterictic content of the present invention, all still belong in the covering scope of technical characterictic of the present invention.
Claims (7)
1. a unleaded aluminum or aluminum alloy substrate is characterized in that with the preparation method of dielectric material,
Comprise the steps:
1., at first prepare unleaded aluminum or aluminum alloy substrate and use the medium base mateiral, raw material is by quality
Per-cent comprises following each component:
Silicon-dioxide SiO
2: 25%~35%
Boron oxide B
2O
3: 11%~18%
Titanium oxide TiO
2: 8%~14%
Aluminium sesquioxide Al
2O
3: 1%~5%
Zinc oxide ZnO:5%~10%
Natural manganese dioxide MgO:0.5%~3%
Potassium oxide K
2O:5%~9%
Sodium oxide Na
2O:15%~22%
Lithium Oxide 98min Li
2O:0.5%~3%
Bismuthous oxide bismuth trioxide Bi
2O
3: 9%~15%;
2., the unleaded aluminum or aluminum alloy substrate with above-mentioned mass percent mixes with the medium base mateiral; Then this mixture is thrown in 1000 ℃ process furnace and melted one hour; Pass through shrend again; According to material after the shrend: ball: the water ratio is to place corundum ball grinder ball milling one hour after 1: 1~1.2: 1~1.2 mixed, crosses 200 mesh sieves then, can obtain dielectric material through oven dry again;
3., dielectric material that above-mentioned steps is obtained, be placed on according to 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin that ball milling promptly obtained printing slurry in 2 hours in the corundum ball grinder;
4., before slurry prints, to the surface treatment of carrying out of aluminium base,, pass through hot alkali treatment more earlier, behind the clean aluminium base of high temperature washed with de-ionized water, dry then and get final product through the zone of oxidation that hot acid cleans aluminium base in printing;
5., at last will print slurry and be printed on the aluminium base with 60 mesh sieves, through 80 ℃ of oven dry, 600 ℃ of sintering can obtain the unleaded aluminum or aluminum alloy substrate of finished product and use dielectric material after 3~5 minutes.
2. unleaded aluminum or aluminum alloy substrate according to claim 1 is with the preparation method of dielectric material, and it is characterized in that: step 3. each constituent mass per-cent of described organic solvent is:
Terpineol 350: 60~80%, TKK 021: 1~8%
Hydrocerol A tri butyl ester: 10~30% THIXCINs: 0.5~3%
Flow agent: 0.5~1% skimmer: 0~0.5%
Regulating various ratios makes viscosity at 100~200mPas.
3. unleaded aluminum or aluminum alloy substrate according to claim 1 is with the preparation method of dielectric material, and it is characterized in that: said unleaded aluminum or aluminum alloy substrate is used the medium base mateiral, and all kinds of raw materials and mass percent thereof are: 32% SiO
2, 12% B
2O
3, 14% TiO
2, 1% Al
2O
3, 5% ZnO, 1% MgO, 6% K
2O, 18% Na
2O, 2% Li
2O and 9% Bi
2O
3Mix; Place 1000 ℃ process furnace to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is to place corundum ball grinder ball milling one hour after 1: 1~1.2: 1~1.2 mixed, crosses 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtained printing slurry in 2 hours in the corundum ball grinder; The printing slurry is printed on the surface-treated aluminium base with 60 mesh sieves, and through 80 ℃ of oven dry, 600 ℃ of sintering can obtain the unleaded aluminum or aluminum alloy substrate of finished product and use dielectric material after 3~5 minutes.
4. unleaded aluminum or aluminum alloy substrate according to claim 1 is with the preparation method of dielectric material, and it is characterized in that: said unleaded aluminum or aluminum alloy substrate is used the medium base mateiral, and all kinds of raw materials and mass ratio thereof are: 25% SiO
2, 16% B
2O
3, 10% TiO
2, 4.5% Al
2O
3, 7% ZnO, 1.5% MgO, 8% K
2O, 15% Na
2O, 1% Li
2O and 12% Bi
2O
3Mix; Place 1000 ℃ process furnace to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is to place corundum ball grinder ball milling one hour after 1: 1~1.2: 1~1.2 mixed, crosses 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtained printing slurry in 2 hours in the corundum ball grinder; The printing slurry is printed on the surface-treated aluminium base with 60 mesh sieves, and through 80 ℃ of oven dry, 600 ℃ of sintering can obtain the unleaded aluminum or aluminum alloy substrate of finished product and use dielectric material after 3~5 minutes.
5. unleaded aluminum or aluminum alloy substrate according to claim 1 is with the preparation method of dielectric material, and it is characterized in that: said unleaded aluminum or aluminum alloy substrate is used the medium base mateiral, and all kinds of raw materials and mass ratio thereof are: 29% SiO
2, 14% B
2O
3, 8% TiO
2, 2% Al
2O
3, 6% ZnO, 3% MgO, 9% K
2O, 16% Na
2O, 3% Li
2O and 10% Bi
2O
3Mix; Place 1000 ℃ process furnace to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is to place corundum ball grinder ball milling one hour after 1: 1~1.2: 1~1.2 mixed, crosses 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtained printing slurry in 2 hours in the corundum ball grinder; The printing slurry is printed on the surface-treated aluminium base with 60 mesh sieves, and through 80 ℃ of oven dry, 600 ℃ of sintering can obtain the unleaded aluminum or aluminum alloy substrate of finished product and use dielectric material after 3~5 minutes.
6. unleaded aluminum or aluminum alloy substrate according to claim 1 is with the preparation method of dielectric material, and it is characterized in that: said unleaded aluminum or aluminum alloy substrate is used the medium base mateiral, and all kinds of raw materials and mass ratio thereof are: 26% SiO
2, 15% B
2O
3, 12% TiO
2, 1.5% Al
2O
3, 8.5% ZnO, 0.5% MgO, 5% K
2O, 17% Na
2O, 0.5% Li
2O and 14% Bi
2O
3Mix; Place 1000 ℃ process furnace to melt one hour in this mixture then; Pour the material after the fusing in cold water shrend; With the material after the shrend according to shrend after material: ball: the water ratio is to place corundum ball grinder ball milling one hour after 1: 1~1.2: 1~1.2 mixed, crosses 200 mesh sieves then, can obtain dielectric material through oven dry again; 100 parts of dielectric materials, 32 parts of organic solvents, 2 parts of mixing of kaolin are placed on ball milling promptly obtained printing slurry in 2 hours in the corundum ball grinder; The printing slurry is printed on the surface-treated aluminium base with 60 mesh sieves, and through 80 ℃ of oven dry, 600 ℃ of sintering can obtain the unleaded aluminum or aluminum alloy substrate of finished product and use dielectric material after 3~5 minutes.
7. a unleaded aluminum or aluminum alloy substrate is used the medium base mateiral, and its composition comprises following each component by weight percentage:
Silicon-dioxide SiO
2: 25%~35%
Boron oxide B
2O
3: 11%~18%
Titanium oxide TiO
2: 8%~14%
Aluminium sesquioxide Al
2O
3: 1%~5%
Zinc oxide ZnO:5%~10%
Natural manganese dioxide MgO:0.5%~3%
Potassium oxide K
2O:5%~9%
Sodium oxide Na
2O:15%~22%
Lithium Oxide 98min Li
2O:0.5%~3%
Bismuthous oxide bismuth trioxide Bi
2O
3: 9%~15%.
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US6624104B2 (en) * | 1998-04-27 | 2003-09-23 | Ferro Glass & Color Corporation | High durability low temperature lead-free glass and enamel compositions with low boron content |
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Granted publication date: 20120523 Termination date: 20200423 |