CN109369027A - Add the novel environment friendly glass powder and preparation method thereof of nano-metal-oxide - Google Patents
Add the novel environment friendly glass powder and preparation method thereof of nano-metal-oxide Download PDFInfo
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- CN109369027A CN109369027A CN201811346848.4A CN201811346848A CN109369027A CN 109369027 A CN109369027 A CN 109369027A CN 201811346848 A CN201811346848 A CN 201811346848A CN 109369027 A CN109369027 A CN 109369027A
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- oxide
- metal
- glass powder
- environment friendly
- novel environment
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- 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 relates to the technical field of high-temperature coatings more particularly to a kind of novel environment friendly glass powders and preparation method thereof of the addition nano-metal-oxide for high-temperature coatings.It by mass percentage include following components: Bi2O3It is 5~20%, B for 60~85%, ZnO2O3For 5~30%, Sb2O3For 0.5~5%, SiO2For 1~10%, Al2O3For 1~10%, TiO2It is 0.5~8%, MgO for 0.5~3%, CaO be 0.5~10%, BaO is 0.5~10%, Na2O is 0~5%, K2O is 0~5%, Li2O is 0~5%, Y2O3It is 0.5~5% for 0.5~5%, SrO.Low-temperature lead-free environmental protection glass powder of the invention does not contain lead oxide, and softening point is low, and adhesiveness is good, and chemical stability is good, and Deliquescence-resistant is strong, can be used for high-temperature resistant coating.
Description
Technical field
The present invention relates to a kind of addition nano-metal-oxides for high-temperature coatings, more particularly to one kind to be used for high-temperature coating
The novel environment friendly glass powder and preparation method thereof of the addition nano-metal-oxide of material.
Background technique
Currently, the glass powder with low melting point for being mostly used in high-temperature coatings is all leaded glass powder, such as PbO-B2O3-SiO2
System or PbO-ZnO-B2O3It is glass.The softening temperature of these glass is less than 400 DEG C, thermal expansion coefficient 90~100 × 10-7/
DEG C, chemical stability is preferable, and Deliquescence-resistant is good.But the oxidation lead content in glass powder is 30~80wt%, belongs to high lead glass
Glass.For flint glass in production, there are about 10~12wt%PbO to drop to ground by being volatized into atmosphere or being condensed into micronic dust,
Atmosphere, soil, river etc. are polluted.Flint glass in use also can be by contacting or by respiratory tract with application on human skin
Health is damaged in suction body；It also can contaminated soil and underground water after same lead glass is discarded.With modern society's environmental protection
The raising of consciousness, lead have caused the whole society to pay much attention to the harmfulness of human and environment, the application of lead-containing materials in world wide
Also it is increasingly restricted.Therefore, providing a kind of own pass through of lead-free sealing glass material as early as possible becomes the task of top priority, must solve
Certainly the problem of.
For the low-melting glass without lead component, it is known to phosphate glass, borosilicate glass, alkaline silicate
Glass and bismuthate glass etc., wherein bismuthate glass compared to having brilliant chemical stability for other several glass and
It attracts attention.
Summary of the invention
Present invention seek to address that drawbacks described above, a kind of the novel of the addition nano-metal-oxide for high-temperature coatings is provided
Environmentally friendly glass powder and preparation method thereof.
In order to overcome defect present in background technique, the technical solution adopted by the present invention to solve the technical problems is:
The novel environment friendly glass powder of this addition nano-metal-oxide, includes following components: Bi by mass percentage2O3For 60~
85%, ZnO are 5~20%, B2O3For 5~30%, Sb2O3For 0.5~5%, SiO2For 1~10%, Al2O3For 1~10%, TiO2It is 0.5
It is 0.5~10%, BaO is 0.5~10%, Na that~3%, CaO, which are 0.5~8%, MgO,2O is 0~5%, K2O is 0~5%, Li2O is 0
~5%, Y2O3It is 0.5~5% for 0.5~5%, SrO.
It according to another embodiment of the invention, further comprise the Bi2O3Mass percent is 65~75%, ZnO
For 7~12%, B2O3For 5~12%, Sb2O3For 1~3%, SiO2For 1~5%, Al2O3For 1~5%, TiO2It is for 0.5~3%, CaO
0.5~5%, MgO are that 0.5~5%, BaO is 2~8%, Na2O is 0~5%, K2O is 0~5%, Li2O is 0~5%, Y2O3For 0.5~
3%, SrO are 0.5~3%.
It according to another embodiment of the invention, further comprise the nanometer Y2O3It is equal with the average grain diameter of nanometer SrO
For 10~60nm.
It according to another embodiment of the invention, further comprise the nanometer Y2O3With total quality hundred of nanometer SrO
Divide than being 2.5%~8%.
It according to another embodiment of the invention, further comprise total mass percent of described CaO, MgO and BaO
It is 2%~10%.
It according to another embodiment of the invention, further comprise total quality percentage of described Na2O, K2O and Li2O
Than being 1%~8%.
The preparation method of the novel environment friendly glass powder of addition nano-metal-oxide for high-temperature coatings, the preparation method
Including,
The first step weighs each raw material according to the mass percent of each component；
The weighed raw material of institute is sufficiently mixed by second step, and wherein nanosized Y2O3 and nanometer SrO are eventually adding and mix, and are made mixed
Close material；
Mixed mixture is put into corundum crucible by third step, is then placed in the electric furnace that furnace temperature is 900 DEG C~1100 DEG C
In, keep the temperature 1~3h；
Glass metal after fusing is poured into tablet press machine and is pressed into thin slice or pours into quenching in cold water by the 4th step；
Sheet or granular glass are put into togerther ball mill ball milling by the 5th step；
Glass powder after ball milling is sieved, detection, packaging by the 6th step.
The beneficial effects of the present invention are:
(1) product of the present invention is free of lead, nontoxic, pollution-free, meets the environmental requirement of WEEE, RoHS instruction；
(2) by the way of adding nano-oxide, the problem of low-melting glass poor chemical stability, while energy are advantageously accounted for
It is effectively reduced the softening temperature of glass, improves the Deliquescence-resistant performance of glass powder and the bond properties with substrate；
(3) preparation process is simple, easy to operate；
(4) pigment can be added, generate color diversification, meet the individual demand of different clients；
(5) product of the invention not only has the thermal expansion coefficient for being suitable for and being easy to adjust, and suitable softening temperature also has excellent
Different chemical stability has extensive market development prospect in high-temperature coatings.
Specific embodiment
Surface and interfacial effect, small-size effect, quantum size effect and macroscopic quantum of the present invention using nano material
Unusual physics, chemical property that tunnel-effect etc. is showed and show certain excellent performances, such as reduce glass
Transition temperature, sintering temperature and thermal expansion coefficient, improve sintering bright property, the performance for keeping its excellent emerges from.The present invention
It is exactly the above-mentioned characteristic using nano material, nano yttrium oxide and nano oxidized strontium is added in low melting point bismuthate glass powder,
Thermal expansion coefficient, raising sintering bright property and Deliquescence-resistant is reduced to open to improve the physical and chemical performance of leadless environment-friendly glass powder
Send out to be suitable for the leadless environment-friendly glass powder of high-temperature coatings a kind of.
By mass percentage include following components:
It is 5~20%, B2O3 be 5~30%, Sb2O3 be 0.5~5%, SiO2 is 1~10%, Al2O3 that Bi2O3, which is 60~85%, ZnO,
It is 0.5~3%, CaO for 1~10%, TiO2 be 0.5~8%, MgO be 0.5~10%, BaO be 0.5~10%, Na2O is 0~5%,
It is 0~5%, Y2O3 be 0.5~5%, SrO is 0.5~5% that K2O, which is 0~5%, Li2O,.
Preference
Bi2O3Mass percent is that 65~75%, ZnO is 7~12%, B2O3For 5~12%, Sb2O3For 1~3%, SiO2It is 1~5%,
Al2O3For 1~5%, TiO2It is 0.5~5%, MgO for 0.5~3%, CaO be 0.5~5%, BaO is 2~8%, Na2O is 0~5%,
K2O is 0~5%, Li2O is 0~5%, Y2O3It is 0.5~3% for 0.5~3%, SrO.
The average grain diameter of nanosized Y2O3 and nanometer SrO are 10~60nm.
Total mass percent of nanosized Y2O3 and nanometer SrO are 2.5%~8%.
Total mass percent of CaO, MgO and BaO are 2%~10%.
Total mass percent of Na2O, K2O and Li2O are 1%~8%.
The preparation method of the novel environment friendly glass powder of addition nano-metal-oxide for high-temperature coatings, the preparation method
Including,
The first step weighs each raw material according to the mass percent of each component；
The weighed raw material of institute is sufficiently mixed by second step, and wherein nanosized Y2O3 and nanometer SrO are eventually adding and mix, and are made mixed
Close material；
Mixed mixture is put into corundum crucible by third step, and it is 900 DEG C~1100 DEG C that beautiful crucible, which is then put into furnace temperature,
Electric furnace in, keep the temperature 1~3h；
Glass metal after fusing is poured into tablet press machine and is pressed into thin slice or pours into quenching in cold water by the 4th step；
Sheet or granular glass are put into togerther ball mill ball milling by the 5th step；
Glass powder after ball milling is sieved, detection, packaging by the 6th step.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
Raw material forms by mass percentage are as follows:
Bi2O3 is 69%, ZnO 7.2%, and B2O3 7.7%, Sb2O3 2.5%, SiO2 1.5%, Al2O3 1.5%, TiO2 are
1.5%, CaO 1%, MgO 1%, BaO 2.1%, Na2O 0.5%, K2O 0.5%, Li2O 0.5%, Y2O3 1.5%, SrO
It is 2%.
Raw material introduces
Each raw material is the pure grade raw material of chemistry in addition to Al2O3, and wherein Bi2O3, ZnO, Sb2O3, SiO2, TiO2 are drawn with oxide
Enter, B2O3 is introduced with boric acid, and CaO, MgO, BaO, Na2O, K2O, Li2O are introduced in the form of carbonate, and Y2O3 is using average
The nano yttrium oxide that partial size is 30nm introduces, and SrO uses average grain diameter to introduce for the nano oxidized strontium of 20nm.
Preparation method
The first step weighs each raw material according to the mass percent of each component；
The weighed raw material of institute is sufficiently mixed by second step, and wherein nano yttrium oxide and nano oxidized strontium are eventually adding and mix, system
At mixture；
Mixed mixture is put into corundum crucible by third step, is then placed in the electric furnace that furnace temperature is 1000 DEG C, heat preservation
2h；
Glass metal after fusing is poured into tablet press machine and is pressed into thin slice or pours into quenching in cold water by the 4th step；
Sheet or granular glass are put into togerther ball mill ball milling by the 5th step；
Glass powder after ball milling is sieved, detection, packaging by the 6th step.
Properties of product compare sintering bright property Deliquescence-resistant
| Performance | T(DEG C of glass transformation temperature) | Sintering temperature (DEG C) | Thermal expansion coefficient (10-7/ DEG C) | It is sintered bright property | Deliquescence-resistant |
| Chemistry pure Y2O3, SrO | 367 | 498 | 171 | It is bright | Well |
| Nanosized Y2O3, SrO | 349 | 479 | 155 | It is bright | It is excellent |
Embodiment 2
Raw material forms by mass percentage are as follows:
Bi2O3 is 64%, ZnO 7%, B2O3 11%, Sb2O3 1.5%, SiO2 2.5%, Al2O3 2%, TiO2 1%,
CaO is 1%, MgO 2%, BaO 3.8%, Na2O 0.7%, K2O 0.5%, Li2O 0.5%, Y2O3 1.5%, SrO 1%.
Raw material introduces
Each raw material is the pure grade raw material of chemistry in addition to Al2O3, and wherein Bi2O3, ZnO, Sb2O3, SiO2, TiO2 are drawn with oxide
Enter, B2O3 is introduced with boric acid, and CaO, MgO, BaO, Na2O, K2O, Li2O are introduced in the form of carbonate, and Y2O3 is using average
The nano yttrium oxide that partial size is 30nm introduces, and SrO uses average grain diameter to introduce for the nano oxidized strontium of 20nm.
Preparation method
The first step weighs each raw material according to the mass percent of each component；
The weighed raw material of institute is sufficiently mixed by second step, and wherein nano yttrium oxide and nano oxidized strontium are eventually adding and mix, system
At mixture；
Mixed mixture is put into corundum crucible by third step, is then placed in the electric furnace that furnace temperature is 1050 DEG C, heat preservation
2h；
Glass metal after fusing is poured into tablet press machine and is pressed into thin slice or pours into quenching in cold water by the 4th step；
Sheet or granular glass are put into togerther ball mill ball milling by the 5th step；
Glass powder after ball milling is sieved, detection, packaging by the 6th step.
Properties of product compare
| Performance | T(DEG C of glass transformation temperature) | Sintering temperature (DEG C) | Thermal expansion coefficient (10-7/ DEG C) | It is sintered bright property | Deliquescence-resistant |
| Chemistry pure Y2O3, SrO | 345 | 483 | 137 | It is bright | Well |
| Nanosized Y2O3, SrO | 328 | 465 | 120 | It is bright | It is excellent |
Embodiment 3
Raw material forms by mass percentage are as follows:
Bi2O3 is 73%, ZnO 8.2%, and B2O3 5%, Sb2O3 2%, SiO2 2%, Al2O3 1%, TiO2 1%, CaO are
0.5%, MgO 0.5%, BaO 2%, Na2O 0.5%, K2O 0.8%, Li2O 0.5%, Y2O3 1%, SrO 2%.
Raw material introduces
Each raw material is the pure grade raw material of chemistry in addition to Al2O3, and wherein Bi2O3, ZnO, Sb2O3, SiO2, TiO2 are drawn with oxide
Enter, B2O3 is introduced with boric acid, and CaO, MgO, BaO, Na2O, K2O, Li2O are introduced in the form of carbonate, and Y2O3 is using average
The nano yttrium oxide that partial size is 30nm introduces, and SrO uses average grain diameter to introduce for the nano oxidized strontium of 20nm.
Preparation method
The first step weighs each raw material according to the mass percent of each component；
The weighed raw material of institute is sufficiently mixed by second step, and wherein nano yttrium oxide and nano oxidized strontium are eventually adding and mix, system
At mixture；
Mixed mixture is put into corundum crucible by third step, is then placed in the electric furnace that furnace temperature is 1100 DEG C, heat preservation
2h；
Glass metal after fusing is poured into tablet press machine and is pressed into thin slice or pours into quenching in cold water by the 4th step；
Sheet or granular glass are put into togerther ball mill ball milling by the 5th step；
Glass powder after ball milling is sieved, detection, packaging by the 6th step.
Properties of product compare
| Performance | T(DEG C of glass transformation temperature) | Sintering temperature (DEG C) | Thermal expansion coefficient (10-7/ DEG C) | It is sintered bright property | Deliquescence-resistant |
| Chemistry pure Y2O3, SrO | 358 | 516 | 152 | It is bright | Well |
| Nanosized Y2O3, SrO | 337 | 496 | 136 | It is bright | It is excellent |
Claims (7)
1. a kind of novel environment friendly glass powder for adding nano-metal-oxide, it is characterised in that: by mass percentage include following
Component: Bi2O3It is 5~20%, B for 60~85%, ZnO2O3For 5~30%, Sb2O3For 0.5~5%, SiO2For 1~10%, Al2O3For
1~10%, TiO2It is 0.5~8%, MgO for 0.5~3%, CaO be 0.5~10%, BaO is 0.5~10%, Na2O is 0~5%, K2O
For 0~5%, Li2O is 0~5%, Y2O3It is 0.5~5% for 0.5~5%, SrO.
2. the novel environment friendly glass powder of addition nano-metal-oxide as described in claim 1, it is characterised in that: described
Bi2O3Mass percent is that 65~75%, ZnO is 7~12%, B2O3For 5~12%, Sb2O3For 1~3%, SiO2For 1~5%, Al2O3
For 1~5%, TiO2It is 0.5~5%, MgO for 0.5~3%, CaO be 0.5~5%, BaO is 2~8%, Na2O is 0~5%, K2O is 0
~5%, Li2O is 0~5%, Y2O3It is 0.5~3% for 0.5~3%, SrO.
3. the novel environment friendly glass powder of addition nano-metal-oxide as described in claim 1, it is characterised in that: described receives
Rice Y2O3Average grain diameter with nanometer SrO is 10~60nm.
4. the novel environment friendly glass powder of addition nano-metal-oxide as described in claim 1, it is characterised in that: described receives
Rice Y2O3Total mass percent with nanometer SrO is 2.5%~8%.
5. the novel environment friendly glass powder of addition nano-metal-oxide as described in claim 1, it is characterised in that: described
Total mass percent of CaO, MgO and BaO are 2%~10%.
6. the novel environment friendly glass powder of addition nano-metal-oxide as described in claim 1, it is characterised in that: described
Na2O、K2O and Li2Total mass percent of O is 1%~8%.
7. the preparation for the novel environment friendly glass powder of the addition nano-metal-oxide of high-temperature coatings as described in claim 1
Method, it is characterised in that: the preparation method includes,
The first step weighs each raw material according to the mass percent of each component；
The weighed raw material of institute is sufficiently mixed by second step, wherein nanometer Y2O3It is eventually adding and mixes with nanometer SrO, mixing is made
Material；
Mixed mixture is put into corundum crucible by third step, is then placed in the electric furnace that furnace temperature is 900 DEG C~1100 DEG C
In, keep the temperature 1~3h；
Glass metal after fusing is poured into tablet press machine and is pressed into thin slice or pours into quenching in cold water by the 4th step；
Sheet or granular glass are put into togerther ball mill ball milling by the 5th step；
Glass powder after ball milling is sieved, detection, packaging by the 6th step.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811346848.4A CN109369027A (en) | 2018-11-13 | 2018-11-13 | Add the novel environment friendly glass powder and preparation method thereof of nano-metal-oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811346848.4A CN109369027A (en) | 2018-11-13 | 2018-11-13 | Add the novel environment friendly glass powder and preparation method thereof of nano-metal-oxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111028975A (en) * | 2019-12-03 | 2020-04-17 | 南京汇聚新材料科技有限公司 | Low-temperature coefficient resistor paste and preparation method and application thereof |
| CN115893853A (en) * | 2023-01-08 | 2023-04-04 | 西北工业大学 | Lead-free glass powder for resistance paste and preparation method thereof |
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| CN101456674A (en) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | Rare-earth doped leadless and low-melting point sealing glass and its preparation method |
| CN101863622A (en) * | 2009-04-15 | 2010-10-20 | 李胜春 | Nanooxide-doped red solder glass and preparation method thereof |
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2018
- 2018-11-13 CN CN201811346848.4A patent/CN109369027A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456674A (en) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | Rare-earth doped leadless and low-melting point sealing glass and its preparation method |
| CN101863622A (en) * | 2009-04-15 | 2010-10-20 | 李胜春 | Nanooxide-doped red solder glass and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111028975A (en) * | 2019-12-03 | 2020-04-17 | 南京汇聚新材料科技有限公司 | Low-temperature coefficient resistor paste and preparation method and application thereof |
| CN111028975B (en) * | 2019-12-03 | 2022-07-08 | 南京汇聚新材料科技有限公司 | Low-temperature coefficient resistor paste and preparation method and application thereof |
| CN115893853A (en) * | 2023-01-08 | 2023-04-04 | 西北工业大学 | Lead-free glass powder for resistance paste and preparation method thereof |
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Application publication date: 20190222 |