CN114014546A - High-strength corrosion-resistant glass glaze for automobiles and preparation method thereof - Google Patents
High-strength corrosion-resistant glass glaze for automobiles and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 139
- 230000007797 corrosion Effects 0.000 title claims abstract description 42
- 238000005260 corrosion Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 34
- 230000004907 flux Effects 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 19
- 238000007499 fusion processing Methods 0.000 claims abstract description 16
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000000049 pigment Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 74
- 238000000498 ball milling Methods 0.000 claims description 35
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000006060 molten glass Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- VKOBVWXKNCXXDE-UHFFFAOYSA-N ethyl stearic acid Natural products CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 9
- 238000010902 jet-milling Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000000156 glass melt Substances 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005341 toughened glass Substances 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000001939 inductive effect Effects 0.000 abstract 1
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- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 239000001023 inorganic pigment Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a high-strength corrosion-resistant glass glaze for automobiles and a preparation method thereof, relating to the field of glass glaze, through the research on a ternary glass system, lead-free environment-friendly low-melting-point glass fusing agent is prepared by introducing lead-free low-melting-point raw materials as a glass binder, thereby reducing the melting temperature of the glass flux, inducing the low-melting-point glass powder to crystallize during the automobile glass toughening by pre-crystallizing bismuth silicate crystal nucleus, leading the toughened glass glaze layer to have good anti-sticking property and acid resistance, by adding the copper-chromium black as a black pigment, the copper-chromium black has the advantages of good black tone, excellent durability, high temperature resistance, very stable chemical property, sun resistance, weather resistance, acid and alkali resistance, solvent resistance, no migration, easy dispersion and the like, the low expansion coefficient raw material is introduced into the low melting point glass system to achieve the adjustability of the expansion coefficient, thereby realizing high adaptability with the automobile glass.
Description
Technical Field
The invention relates to the field of glass glaze, in particular to high-strength corrosion-resistant glass glaze for automobiles and a preparation method thereof.
Background
The automobile glass ink is black glass slurry printed on the edge of an automobile windshield or the whole surface of the automobile windshield, and is mainly prepared by uniformly mixing, dispersing and grinding low-melting-point glass powder, inorganic pigment, ink mixing oil, a dispersing agent, a flatting agent and other auxiliaries. Printing ink on a glass substrate through screen printing, drying and sintering, finishing the volatilization and decomposition of other components in the ink basically, melting low-melting-point glass powder and inorganic pigment and covering the glass on a windshield to form a black glass ink layer, and playing the roles of preventing the chemical change of glue for bonding the windshield and a vehicle body, shielding conductive silver paste, decorating the appearance of the vehicle and absorbing ultraviolet rays.
With the rapid development of the automobile industry, great demands for the automobile glass ink appear, and research and innovation of the automobile glass ink are driven. However, at present, the preparation and performance of the automobile glass ink in China lack systematic research data, and most of the produced automobile glass inks have the problems of insufficient acid and alkali resistance, poor adhesion resistance and mismatched expansion coefficients.
After the glass glaze is coated on the surface of the glass substrate, the glass glaze needs to be fired at a certain temperature to be firmly combined with the glass substrate. If the expansion coefficients of the glass glaze and the glass substrate are not matched, stress is generated in the cooling process after the firing, and the compressive strength of the glass is 10 times higher than the tensile strength, so that the expansion coefficient of the glaze layer is expected to be slightly smaller than that of the blank body, so that the compressive stress is formed on the surface, and the difference between the two is generally 3 multiplied by 10-7/℃-5×10-7If the temperature is in the range of/DEG C, the glass substrate is subjected to excessive tensile force after cooling, and the glaze layer is pushed away from the substrate to fall off or the product bends towards the substrate; if the expansion coefficient of the glaze is larger than that of the substrate, the glaze layer is subjected to tensile stress, and the glaze surface cracks or the product bends towards the glaze surface.
Therefore, a high-strength corrosion-resistant glass glaze for automobiles and a preparation method thereof are needed to solve the above problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a high-strength corrosion-resistant glass glaze for automobiles and a preparation method thereof, wherein the glass glaze comprises the following steps: by the pair of Bi2O3-B2O3-SiO2The research of the ternary glass system introduces the lead-free low-melting-point raw material to prepare the lead-free environment-friendly melting temperatureThe low-melting-point glass fusing agent with the temperature of 520-620 ℃ is used as a glass binder, and the problems of insufficient acid and alkali resistance, poor anti-sticking property and unmatched expansion coefficient of the existing automobile glass ink are solved.
The purpose of the invention can be realized by the following technical scheme:
the high-strength corrosion-resistant glass glaze for the automobile comprises the following components in parts by weight: 100-200 parts of glass fusing agent, 5-25 parts of black agent and 50-150 parts of ink mixing oil;
the glass fusing agent comprises the following components in parts by weight:
Na21-3 parts of O, 4-8 parts of ZnO and B2O310 to 14 portions of Bi2O350-55 parts of SiO221-29 parts of TiO21-3 parts of Li20-12 parts of O;
the black agent is copper-chromium black, and the ink mixing oil is water-soluble ink mixing oil.
As a further scheme of the invention: a preparation method of high-strength corrosion-resistant glass glaze for automobiles comprises the following steps:
the method comprises the following steps: weighing Na according to parts by weight21-3 parts of O, 4-8 parts of ZnO and B2O310 to 14 portions of Bi2O350-55 parts of SiO221-29 parts of TiO21-3 parts and Li20-12 parts of O for later use;
step two: mixing Na2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2Mixing the materials evenly to obtain a mixture;
step three: melting the mixture at the temperature of 520-620 ℃ to obtain glass melt;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20-25 ℃ to obtain low-melting-point glass;
step five: crushing the low-melting-point glass to obtain a glass fusing agent;
step six: weighing 200 parts of glass flux, 5-25 parts of black agent and 50-150 parts of ink mixing oil according to the parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling time is 30-60min, and the ball milling material is sieved by a sieve with 500 meshes of 300-fold sand after the ball milling is finished, so that the ball milling material is obtained;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1-3, mixing uniformly to obtain a blending agent;
step ten: according to the weight ratio of 2: 1-3, adding the semi-finished glaze powder and a blender into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
As a further scheme of the invention: the grain diameter of the semi-finished glaze powder is 1-2.5 mu m.
As a further scheme of the invention: the expansion coefficient of the high-strength corrosion-resistant glass glaze for the automobile is less than 8.6 multiplied by 10-6/℃。
The invention has the beneficial effects that:
the invention relates to a high-strength corrosion-resistant glass glaze for automobiles and a preparation method thereof, which is prepared by subjecting Bi to2O3-B2O3-SiO2The research of ternary glass system, introduce lead-free low melting point raw materials (zinc oxide, lithium oxide, sodium oxide) and prepare lead-free environment-friendly low melting point glass flux with the melting temperature of 520 ℃ -620 ℃ as the glass binder, thus reducing the melting temperature of the glass flux, and induce the low melting point glass powder to crystallize during automobile glass toughening by pre-crystallizing bismuth silicate crystal nucleus, the toughened glass glaze layer has good anti-sticking property and acid resistance, copper chromium black is added as a black pigment, the copper chromium black is prepared from CuO and Cr2O3The synthesized novel spinel pigment has the advantages of good black color tone, excellent durability, high temperature resistance up to 1000 ℃, very stable chemical property, sun resistance, weather resistance, acid and alkali resistance, solvent resistance, no migration, easy dispersion and the like. The coefficient of expansion of automotive glass is generally 8.6X 10-6/℃-9.0×10-6Between/° c, in low melting glass systemsThe raw materials with low expansion coefficient (lithium oxide and zinc oxide) are introduced to achieve the adjustability of the expansion coefficient, so that the expansion coefficient of the automobile glass glaze is less than 8.6 multiplied by 10 < -6 >/DEG C, and high adaptability with the automobile glass is realized.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an XRD spectrum of an enamel layer of a high strength corrosion resistant glass frit for automobiles in example 12 of the present invention;
FIG. 2 is a SEM image of 5000 times the glaze layer of the high-strength corrosion-resistant glass glaze for automobiles in example 12 of the present invention;
FIG. 3 is a 10000 times SEM image of an enamel layer of a high-strength corrosion-resistant glass glaze for an automobile in example 12 of the invention;
fig. 4 is an SEM image of 20000 times of the glaze layer of the high-strength corrosion-resistant glass frit for automobile in example 12 of the present invention;
fig. 5 is a 30000 times SEM image of an enamel layer of a high-strength corrosion-resistant glass frit for an automobile in example 12 of the present invention.
FIG. 6 shows TiO in the present invention2Is plotted against the glass solvent onset temperature.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this embodiment is a method for producing a glass flux, including the steps of:
the method comprises the following steps: weighing Na according to parts by weight2O2 parts, ZnO 6 parts, B2O312 parts of Bi2O353 parts of SiO225 parts of TiO22 parts and Li2O0 part for later use;
step two: will be provided withNa2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2Mixing the materials evenly to obtain a mixture;
step three: melting the mixture to obtain molten glass;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20 ℃ to obtain low-melting-point glass;
step five: and crushing the low-melting-point glass to obtain the glass fusing agent.
Example 2:
this embodiment is a method for producing a glass flux, including the steps of:
the method comprises the following steps: weighing Na according to parts by weight2O2 parts, ZnO 6 parts, B2O312 parts of Bi2O353 parts of SiO225 parts of TiO22 parts and Li2O3, for later use;
step two: mixing Na2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2Mixing the materials evenly to obtain a mixture;
step three: melting the mixture to obtain molten glass;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20 ℃ to obtain low-melting-point glass;
step five: and crushing the low-melting-point glass to obtain the glass fusing agent.
Example 3:
this embodiment is a method for producing a glass flux, including the steps of:
the method comprises the following steps: weighing Na according to parts by weight2O2 parts, ZnO 6 parts, B2O312 parts of Bi2O353 parts of SiO225 parts of TiO22 parts and Li2O6, for later use;
step two: mixing Na2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2And the mixture of the oxygen and the water is uniform,obtaining a mixture;
step three: melting the mixture to obtain molten glass;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20 ℃ to obtain low-melting-point glass;
step five: and crushing the low-melting-point glass to obtain the glass fusing agent.
Example 4:
this embodiment is a method for producing a glass flux, including the steps of:
the method comprises the following steps: weighing Na according to parts by weight2O2 parts, ZnO 6 parts, B2O312 parts of Bi2O353 parts of SiO225 parts of TiO22 parts and Li2O9 parts for later use;
step two: mixing Na2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2Mixing the materials evenly to obtain a mixture;
step three: melting the mixture to obtain molten glass;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20 ℃ to obtain low-melting-point glass;
step five: and crushing the low-melting-point glass to obtain the glass fusing agent.
Example 5:
this embodiment is a method for producing a glass flux, including the steps of:
the method comprises the following steps: weighing Na according to parts by weight2O2 parts, ZnO 6 parts, B2O312 parts of Bi2O353 parts of SiO225 parts of TiO22 parts and Li2O12 parts for later use;
step two: mixing Na2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2Mixing the materials evenly to obtain a mixture;
step three: melting the mixture to obtain molten glass;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20 ℃ to obtain low-melting-point glass;
step five: and crushing the low-melting-point glass to obtain the glass fusing agent.
The glass solvents of examples 1 to 5 were tested for onset temperature at 1300 ℃ to determine TiO2The effect of the amount of (2) on the onset melting temperature of the glass solvent is shown in FIG. 6.
From the above figure, it can be seen that Li is added2O can obviously reduce the initial melting temperature of the glass fusing agent, thereby reducing the production difficulty of the glass fusing agent from 1350 ℃ to 1200-1250 ℃.
Example 6:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 100 parts of glass flux, 5 parts of copper-chromium black and 50 parts of WGH-801 water-based glass varnish from example 1 in parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling for 30min, and sieving the ball milled material by a 300-mesh sieve to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 1, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
Example 7:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 100 parts of glass flux, 5 parts of copper-chromium black and 50 parts of WGH-801 water-based glass varnish from example 2 in parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling for 30min, and sieving the ball milled material by a 300-mesh sieve to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 1, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
Example 8:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 100 parts of glass flux, 5 parts of copper-chromium black and 50 parts of WGH-801 water-based glass varnish from example 3 in parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling for 30min, and sieving the ball milled material by a 300-mesh sieve to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 1, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
Example 9:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 100 parts of glass flux, 5 parts of copper-chromium black and 50 parts of WGH-801 water-based glass varnish from example 4 in parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling for 30min, and sieving the ball milled material by a 300-mesh sieve to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 1, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
Example 10:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 100 parts of glass flux, 5 parts of copper-chromium black and 50 parts of WGH-801 water-based glass varnish from example 5 in parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling for 30min, and sieving the ball milled material by a 300-mesh sieve to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 1, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
Example 11:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 150 parts of glass flux, 15 parts of copper-chromium black and 100 parts of WGH-801 aqueous glass varnish from example 5 in parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling for 45min, and sieving with a 400-mesh sieve after ball milling to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 2, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 2, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding the mixture into a three-roller machine for rolling to obtain a finished product, thereby obtaining the high-strength corrosion-resistant glass glaze for the automobile.
Example 12:
the embodiment is a preparation method of a high-strength corrosion-resistant glass glaze for automobiles, which comprises the following steps:
step six: weighing 200 parts of glass flux, 25 parts of copper-chromium black and 150 parts of WGH-801 water-based glass varnish from example 5 in parts by weight for later use;
step seven: mixing the glass fusing agent, the black toner and the ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, the ball milling time is 60min, and after the ball milling is finished, sieving the mixture through a 500-mesh sieve to obtain a ball grinding material;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 3, uniformly mixing to obtain a blending agent;
step ten: according to the weight ratio of 2: 3, adding the semi-finished glaze powder and a blending agent into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thereby obtaining the high-strength corrosion-resistant glass glaze for the automobile.
The performance of the high-strength corrosion-resistant glass glaze for automobiles of examples 6 to 12 was tested, and the test results were as follows:
by referring to the data, the expansion coefficient of the prepared high-strength corrosion-resistant glass glaze is less than 8.6 multiplied by 10-6/° c, acid resistance > 48 h; from the comparison of examples 6 to 10, it can be seen that Li2The expansion coefficient of the high-strength corrosion-resistant glass glaze for automobiles can be effectively reduced by increasing the addition amount of O, and the comparison of examples 10 to 12 shows that the proportion of the glass flux is increased, so that Li is increased2O is added to further react Li2The expansion coefficient of the high-strength corrosion-resistant glass glaze for the automobile can be influenced by the O, so that the expansion coefficient of the high-strength corrosion-resistant glass glaze can be controlled.
The anti-sticking performance test of the high-strength corrosion-resistant glass glaze is shown in figures 1-5:
to impart blocking resistance to the ink, the presently available process starts in three ways, with additive systems, reactive systems and crystalline systems providing blocking resistance. The additive system is formed by adding high-melting-point oxide or mixture of oxides, and the high-melting-point oxide does not melt when the glass glaze is melted and stays on the surface of the glaze layer, so that the effect of separating the glaze layer and the glass mould cloth is achieved, and the anti-sticking effect is achieved. The reaction type system is characterized in that simple metal or low-valence metal oxide or sulfide is added, and the simple metal or low-valence metal oxide or sulfide is oxidized into non-molten metal oxide or high-valence oxide in the process that the glass printing ink is heated to be molten and stays on the surface of the glaze layer, so that the glaze layer and the glass cloth are separated, and the anti-sticking effect is achieved. The crystalline system is formed by separating out a layer of crystals on the surface of the glass during hot bending, so that the effects of blocking a glaze layer and glass mould cloth are achieved, the anti-sticking effect is achieved, and the acid resistance and other properties can be improved by the dense crystal layer.
The three anti-sticking methods have advantages and disadvantages, the addition of high-melting point oxides into an additive system is simple and convenient, the cost is reduced, and a good anti-sticking effect is achieved, but the common high-melting point oxides are white and other light-colored substances, and when the high-melting point oxides are applied to black toughened glass printing ink, the surface of a sintered oil layer is grayed, and meanwhile, the acid resistance of a glaze layer is greatly reduced; the reaction type system is added with metal simple substances or sulfides, and the like, and has the characteristics of simplicity, easiness in use and the like, but the acid resistance of a sintered glaze layer is also seriously reduced, and the sulfides can cause air pollution and harm health; the crystallization system utilizes the crystallization of the low-melting-point glass powder in the glass hot bending process to achieve the anti-sticking property, and has the defects of high process difficulty, high cost and the like.
The invention adopts a crystalline system, mainly because the crystalline system does not influence the acid resistance of the glaze layer, the color, the shielding degree and other properties of the glaze layer. The existence of more bismuth silicate in the glaze layer is analyzed in XRD and SEM pictures, clear crystals can be seen from the sections with different magnifications in figures 2-5, the shapes of the crystals are leaf-shaped, and the number of the crystals is more, so that the anti-sticking fresh fruit can be well played.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (4)
1. The high-strength corrosion-resistant glass glaze for the automobile is characterized by comprising the following components in parts by weight: 100-200 parts of glass fusing agent, 5-25 parts of black agent and 50-150 parts of ink mixing oil;
the glass fusing agent comprises the following components in parts by weight:
Na21-3 parts of O, 4-8 parts of ZnO and B2O310 to 14 portions of Bi2O350-55 parts of SiO221-29 parts of TiO21-3 parts of Li20-12 parts of O;
the black agent is copper-chromium black, and the ink mixing oil is water-soluble ink mixing oil.
2. The preparation method of the high-strength corrosion-resistant glass glaze for the automobile is characterized by comprising the following steps of:
the method comprises the following steps: weighing Na according to parts by weight21-3 parts of O, 4-8 parts of ZnO and B2O310 to 14 portions of Bi2O350-55 parts of SiO221-29 parts of TiO21-3 parts and Li20-12 parts of O for later use;
step two: mixing Na2O、ZnO、B2O3、Bi2O3、SiO2、TiO2And Li2Mixing the materials evenly to obtain a mixture;
step three: melting the mixture at the temperature of 520-620 ℃ to obtain glass melt;
step four: pouring the molten glass into a copper mold, and naturally cooling to 20-25 ℃ to obtain low-melting-point glass;
step five: crushing the low-melting-point glass to obtain a glass fusing agent;
step six: weighing 200 parts of glass flux, 5-25 parts of black agent and 50-150 parts of ink mixing oil according to the parts by weight for later use;
step seven: mixing glass flux, black pigment and ink mixing oil, adding the mixture into a ball mill for ball milling, wherein the material-ball ratio is 1:3, ball milling time is 30-60min, and the ball milling material is sieved by a sieve with 500 meshes of 300-fold sand after the ball milling is finished, so that the ball milling material is obtained;
step eight: drying the ball-milling material, and then performing jet milling to form powder, thereby obtaining semi-finished glaze powder;
step nine: mixing water, absolute ethyl alcohol and stearic acid according to the weight ratio of 30: 10: 1-3, mixing uniformly to obtain a blending agent;
step ten: according to the weight ratio of 2: 1-3, adding the semi-finished glaze powder and a blender into a kneader for dispersion, and then adding into a three-roller machine for rolling to obtain a finished product, thus obtaining the high-strength corrosion-resistant glass glaze for the automobile.
3. The method for preparing a high-strength corrosion-resistant glass glaze material for automobiles according to claim 2, wherein the particle size of the semi-finished glaze powder is 1-2.5 μm.
4. The method for preparing the high-strength corrosion-resistant glass glaze for the automobile according to claim 2, wherein the expansion coefficient of the high-strength corrosion-resistant glass glaze for the automobile is less than 8.6 x 10-6/℃。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252595.6A CN114014546A (en) | 2021-10-27 | 2021-10-27 | High-strength corrosion-resistant glass glaze for automobiles and preparation method thereof |
| PCT/CN2022/089220 WO2022156831A2 (en) | 2021-10-27 | 2022-04-28 | High-strength corrosion-resistant glass glaze for automobile, and preparation method therefor |
| ZA2022/05996A ZA202205996B (en) | 2021-10-27 | 2022-05-30 | High-strength corrosion-resistant glass glaze for automobiles and preparation method thereof |
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| CN202111252595.6A CN114014546A (en) | 2021-10-27 | 2021-10-27 | High-strength corrosion-resistant glass glaze for automobiles and preparation method thereof |
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| CN (1) | CN114014546A (en) |
| WO (1) | WO2022156831A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115159851A (en) * | 2022-08-12 | 2022-10-11 | 江苏拜富科技股份有限公司 | Anti-sticking glass glaze for automobiles and preparation method thereof |
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| CN109133641A (en) * | 2018-10-31 | 2019-01-04 | 江苏拜富科技有限公司 | High covering power black environmental protection tempered glass ink and preparation method thereof |
| CN110028831A (en) * | 2019-04-23 | 2019-07-19 | 郑州知淘信息科技有限责任公司 | A kind of tempered glass of automobile crown glass ink and preparation method thereof |
| CN112573829A (en) * | 2020-12-15 | 2021-03-30 | 黄山市晶特美新材料有限公司 | Glass slurry for automobile press-formed front windshield and preparation method thereof |
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| JP2010116541A (en) * | 2008-10-16 | 2010-05-27 | Nissei Kogyo Kk | Ink for inorganic material |
| CN104893409A (en) * | 2015-07-03 | 2015-09-09 | 陈养生 | Light-resistant glass printing ink and preparation method thereof |
| CN104893410A (en) * | 2015-07-03 | 2015-09-09 | 陈养生 | High-temperature tempered glass ink and preparation method thereof |
| CN108384312B (en) * | 2018-04-04 | 2021-05-07 | 佛山市高明绿色德化工有限公司 | High-temperature cutting-resistant black ink and preparation method thereof |
| CN110229555A (en) * | 2019-07-02 | 2019-09-13 | 黄山市晶特美新材料有限公司 | A kind of halogen-free high acid and alkali-resistance environmental protection black ink of no boron and preparation method thereof |
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2021
- 2021-10-27 CN CN202111252595.6A patent/CN114014546A/en active Pending
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2022
- 2022-04-28 WO PCT/CN2022/089220 patent/WO2022156831A2/en unknown
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133641A (en) * | 2018-10-31 | 2019-01-04 | 江苏拜富科技有限公司 | High covering power black environmental protection tempered glass ink and preparation method thereof |
| CN110028831A (en) * | 2019-04-23 | 2019-07-19 | 郑州知淘信息科技有限责任公司 | A kind of tempered glass of automobile crown glass ink and preparation method thereof |
| CN112573829A (en) * | 2020-12-15 | 2021-03-30 | 黄山市晶特美新材料有限公司 | Glass slurry for automobile press-formed front windshield and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115159851A (en) * | 2022-08-12 | 2022-10-11 | 江苏拜富科技股份有限公司 | Anti-sticking glass glaze for automobiles and preparation method thereof |
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| WO2022156831A2 (en) | 2022-07-28 |
| WO2022156831A3 (en) | 2022-09-15 |
| ZA202205996B (en) | 2022-10-26 |
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