CN114920464A - Automobile glass slurry suitable for high-curvature processing and preparation method thereof - Google Patents
Automobile glass slurry suitable for high-curvature processing and preparation method thereof Download PDFInfo
- Publication number
- CN114920464A CN114920464A CN202210619615.7A CN202210619615A CN114920464A CN 114920464 A CN114920464 A CN 114920464A CN 202210619615 A CN202210619615 A CN 202210619615A CN 114920464 A CN114920464 A CN 114920464A
- Authority
- CN
- China
- Prior art keywords
- powder
- glass
- spodumene
- reinforcing
- main phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 99
- 239000002002 slurry Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000003672 processing method Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 82
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 34
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 32
- 239000000049 pigment Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 238000010304 firing Methods 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000001023 inorganic pigment Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052709 silver Inorganic materials 0.000 abstract description 7
- 239000004332 silver Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 6
- 238000005496 tempering Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000003484 crystal nucleating agent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000006121 base glass Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 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 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005401 pressed glass Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- 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
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)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses an automobile glass slurry suitable for large-curvature processing and a preparation method thereof, belonging to the technical field of glass slurry and comprising the following steps: according to the mass percentage, 35-60% of main phase glass powder, 4-24% of reinforcing powder, 5-20% of spodumene and 10-30% of black pigment, wherein the particle sizes D90 of the crushed main phase glass powder, reinforcing powder, spodumene and black pigment are respectively 1-9 μm, 1-3 μm and 1-5 μm; the reinforcing powder comprises: by mass percent, SiO 2 30～80％,B 2 O 3 5～20％，Al 2 O 3 2～8％,P 2 O 5 4～9％,Na 2 O 2～4％,K 2 1-3% of O and 0-2% of fluorine-containing compound, and the slurry for the automobile glass has excellent anti-sticking performance under a tempering and pressing process and can be suitable for being used in a tempering and pressing processThe glass slurry has wide sintering performance, excellent chemical corrosion resistance and excellent silver paste affinity.
Description
Technical Field
The invention relates to the field of glass paste, in particular to automobile glass paste suitable for large-curvature processing and a preparation method thereof.
Background
The sizing agent for the automobile glass is mainly used for printing a certain width on the periphery of the automobile glass, drying and then carrying out baking bending or toughening. The printing width of the front windshield of the automobile is smaller than that of the rear windshield of the automobile, and the two types of glass are assembled with the automobile body frame after forming a certain radian after being baked and bent or toughened. The automobile glass has two processes of self-weight forming and press forming during forming, and the process efficiency of self-weight forming is gradually replaced by the press forming process. During press forming, different pressures are selected according to the shape of a vehicle body frame for pressing, and the pressed glass substrate needs to be quickly separated from a mold so as to ensure the shape of the glass substrate, so that glass slurry printed on base glass needs to have certain anti-sticking performance. At present, automobile glass used by a plurality of automobile types has large curvature, and has extremely high requirement on the anti-sticking performance of glass slurry in a tempering and pressing process. Existing glass paste on the market has numerous shortcomings, the sintering temperature of the paste with good anti-sticking performance is high, and meanwhile, the silver paste is easy to crack, so that performance defects of other performances are easy to occur when the anti-sticking performance is met.
Disclosure of Invention
In view of the technical defects, the invention aims to provide the automotive glass paste suitable for large-curvature processing and the preparation method thereof, which can improve other problems of the glass paste, such as higher sintering temperature and silver paste cracking, on the premise of ensuring the anti-sticking performance of the glass paste.
In order to solve the technical problems, the invention provides an automobile glass slurry suitable for large-curvature processing, which is characterized by comprising the following components: according to the mass percentage, 35-60% of main phase glass powder, 4-24% of reinforcing powder, 5-20% of spodumene and 10-30% of black pigment, wherein the particle sizes D90 of the crushed main phase glass powder, reinforcing powder, spodumene and black pigment are respectively 1-9 μm, 1-3 μm and 1-5 μm; the reinforcing powder comprises: by mass percent, SiO 2 30～80％,B 2 O3 5～20％，Al 2 O3 2～8％,P 2 O 5 4～9％,Na 2 O 2～4％,K 2 1-3% of O and 0-2% of fluorine-containing compound.
Preferably, the main phase glass frit comprises: by mass percent, SiO 2 20～50％，B 2 O 3 5～25％，Bi 2 O 3 5～40％，Nb 2 O 5 0～5％，P 2 O 5 0.5～4％，SnO 2 0.5～2％，TiO 2 1～8％，ZrO 2 0.5～4％，ZnO 5-30％，BaO 1～7％，MgO 0～2％，Na 2 O 0.5～2％，K 2 0.5-4% of O and 0-3% of fluorine-containing compound.
Preferably, the spodumene is commercially available spodumene.
Preferably, the fluorine-containing compound is one or more of sodium fluoride and potassium fluoride.
Preferably, the black pigment comprises one or more of spinel type metal oxide mixed phase black inorganic pigments of copper chromium black, iron chromium black and manganese chromium black.
Preferably, the firing temperature of the reinforcing powder is 1200-1300 ℃, and the firing time is 2-8 h.
Preferably, the firing temperature of the main phase glass powder is 1000-1300 ℃, and the firing time is 0.5-3 h.
Another object of the present invention is to provide a method for preparing an automotive glass paste suitable for large-curvature processing, wherein the preparation of the glass paste comprises the steps of:
s1, weighing the main-phase glass powder, the reinforcing powder, spodumene and the black pigment according to the proportion, and uniformly mixing by using a high-speed mixer to obtain a mixed material;
s2, placing the mixed material obtained in the step S1 into a stirrer, adding an organic carrier according to the proportion of 1: 0.2-1: 0.3, and stirring into paste to obtain a paste material;
and S3, placing the paste material obtained in the step S2 into a three-roll grinder, and grinding for 3-5 times to obtain the finished product of the slurry for the automobile glass.
Preferably, the preparation of the glass paste further comprises: respectively prefabricating main phase glass powder and reinforcing powder before the step S1, wherein the method for prefabricating the main phase glass powder and the reinforcing powder comprises the following steps:
weighing raw materials in proportion, uniformly mixing the raw materials by using a high-speed mixer, and putting the uniformly mixed raw materials into a high-temperature furnace for melting and firing; and (3) performing water quenching on the fired molten liquid, and crushing the water-quenched particles for 1-4 h in a planetary ball mill by using 1-10 mm agate balls to obtain finished powder.
Preferably, the method further comprises respectively pretreating the spodumene and the black pigment before the step S1; the pretreatment steps of spodumene and black pigment comprise: crushing 1-10 mm agate balls for 1-4 h in a planetary ball mill.
The invention has the beneficial effects that:
1) the sizing agent for the automobile glass has excellent anti-sticking performance under the toughening pressing process, can be suitable for manufacturing automobile glass with various curvature forming, is particularly suitable for manufacturing automobile glass with deep bending forming, and has wide sintering performance and excellent chemical performance.
2) The main phase glass powder mainly plays a role of a skeleton and a connection role in the system, and has lower melting temperature and excellent chemical corrosion resistance under the synergistic action of oxides. The reinforcing powder is glass powder with a more compact network framework, the basic network structure is further reinforced by regulating and controlling the relative proportions of the components in the reinforcing powder and combining with controlling the granularity of the powder, and the basic network structure can be reinforced to the maximum extent by smaller granularity. When the automobile glass slurry is used, the automobile glass slurry and the conductive silver paste can be overprinted, and the heating and defrosting effects of the automobile windshield are achieved. The conductive silver paste is a material with a large expansion coefficient, the phenomenon that the silver paste is cracked and the like due to mismatching of the expansion coefficient is very easy to occur when the conductive silver paste is overprinted with glass paste, the reinforcing powder is glass powder with a compact network structure, and in the glass paste toughening process, the mismatching of the expansion coefficient between the conductive silver paste and other components can be eliminated by the component, so that the integrity and the functionality of the conductive silver paste are ensured.
By adding spodumene, the main function of the spodumene is that fine spodumene can be used as a crystal nucleating agent to promote the crystallization performance of the main phase glass powder, so that the spodumene has excellent anti-sticking performance. The crystallization of the glass slurry is promoted by introducing crystal nucleating agents such as zinc silicate and bismuth silicate in a conventional glass slurry system, but the melting temperature of the glass slurry is also increased after the crystal nucleating agents are introduced, so that the silver paste shielding performance is poor. Because the spodumene component is close to the base glass component and has a slightly lower melting temperature, the introduction of spodumene can further increase the shading performance of the conductive silver paste.
3) By introducing black pigments such as copper chromium black, iron chromium black and the like containing metal oxide spinel structures such as Cu, Cr, Fe, Ni, Mn and the like, the glass slurry has excellent covering performance, different spinel structure interfaces can release different stresses in the toughening process, and the strength of the glass slurry is improved. The spinel structure interface can promote the crystallization capacity of the main phase glass powder, thereby improving the anti-sticking performance.
4) The granularity of each group of powder is controlled to ensure that the powder has the optimal bulk density, thereby improving the mechanical property, the covering property and the chemical corrosion resistance of the glass slurry.
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:
preparing main phase glass powder:
the main phase glass powder comprises: by mass percent, SiO 2 20～50％，B 2 O 3 5～25％，Bi 2 O 3 5～40％，Nb 2 O 5 0～5％，P 2 O 5 0.5～4％，SnO 2 0.5～2％，TiO 2 1～8％，ZrO 2 0.5～4％，ZnO 5-30％，BaO 1～7％，MgO 0～2％，Na 2 O 0.5～2％，K 2 0.5-4% of O and 0-3% of fluorine-containing compound, wherein the fluorine-containing compound is one or more of sodium fluoride and potassium fluoride, and F is introduced into the glass powder.
(1) Use high-speed blendor misce bene after weighing above raw and other materials according to the ratio, in this embodiment, each component proportion of main looks glass powder is: SiO 2 2 38％，B 2 O 3 10％，Bi 2 O 3 17％，Nb 2 O 5 3％，P 2 O 5 2％，SnO 2 1％，TiO 2 3％，ZrO 2 2％，ZnO 14％，BaO 3％，MgO 1％，Na 2 O 2％，K 2 O3%, and 1% of fluorine-containing compound; and (3) putting the uniformly mixed raw materials into a high-temperature furnace for melting and firing, wherein the firing temperature is 1000-1300 ℃, and the firing time is 0.5-3 h.
(2) And (3) performing water quenching on the melt obtained after the firing in the last step, and crushing the water-quenched particles for 1-4 hours in a planetary ball mill by using 1-10 mm agate balls to obtain finished powder, namely main-phase glass powder, wherein the particle size D90 of the main-phase glass powder of the finished powder is 1-9 mu m.
Preparing reinforced powder and pretreating materials:
the reinforcing powder comprises: by mass percent, SiO 2 30～80％,B 2 O 3 5～20％，Al 2 O 3 2～8％,P 2 O 5 4～9％,Na 2 O 2～4％,K 2 1-3% of O and 0-2% of fluorine-containing compound.
(1) After weighing above raw and other materials according to the ratio, use high-speed blendor misce bene, in this embodiment, each component ratio of reinforcing powder is: SiO 2 2 69％；B 2 O 3 12％；Al 2 O 3 5％；P 2 O 5 5％；Na 2 O 5％；K 2 O3 percent; 1% of fluorine-containing compound. And (3) putting the uniformly mixed raw materials into a high-temperature furnace for melting and firing, wherein the firing temperature is 1200-1300 ℃, and the firing time is 2-8 h.
(2) And (3) performing water quenching on the melt obtained after the firing in the previous step, and crushing the water-quenched particles for 1-4 h in a planetary ball mill by using 1-10 mm agate balls to obtain finished powder, namely the reinforced powder, wherein the particle size D90 of the finished powder reinforced powder is 1-3 mu m.
Preparing glass slurry:
the spodumene used in the embodiment is commercially available spodumene, the commercially available spodumene is crushed for 1-4 hours in a planetary ball mill by using 1-10 mm agate balls to obtain finished powder, and the granularity D90 of the finished powder is 1-3 μm.
The black pigment used in the present embodiment is one or more of spinel type metal oxide inorganic pigment copper chromium black and iron chromium black, the black pigment contains metal oxides such as Cu, Cr, Fe, Ni, Mn, etc., and the black pigment is crushed for 1-4 hours in a planetary ball mill by using 1-10 mm agate balls to obtain a finished powder material, wherein the particle size D90 of the finished powder material is 1-5 μm.
(1) Weighing the main phase glass powder, the reinforcing powder, the spodumene and the black pigment according to the proportion, and uniformly mixing by using a high-speed mixer, wherein the sum of the proportions of the main phase glass powder, the reinforcing powder, the spodumene and the black pigment is 100%, and the proportion of each component in the embodiment is as follows: 59% of main phase glass powder, 9% of reinforcing powder, 7% of spodumene and 25% of black pigment.
(2) Putting the powder uniformly mixed in the step (1) into a stirrer, and mixing the powder according to the proportion of 1: 0.24 adding organic carrier and stirring into paste;
(3) and (3) putting the paste semi-finished product material obtained in the step (2) into a three-roll grinder, and grinding for 3-5 times to obtain the finished product of the slurry for the automobile glass.
Example 2:
different from the embodiment 1, the ratio of each component in the embodiment is as follows: 50% of main phase glass powder, 16% of reinforcing powder, 9% of spodumene and 25% of black pigment, the rest being the same as in example 1.
Example 3:
different from the embodiment 1, the ratio of each component in the embodiment is as follows: 44% of main phase glass powder, 17% of reinforcing powder, 14% of spodumene and 25% of black pigment, the rest being the same as in example 1.
Example 4:
different from the embodiment 1, the ratio of each component in the embodiment is as follows: 35% of main phase glass powder, 20% of reinforcing powder, 20% of spodumene and 25% of black pigment, wherein the ratio of the mixed material to the organic carrier is 1: 0.26, the rest being the same as in example 1.
Example 5:
different from the embodiment 1, the ratio of each component in the embodiment is as follows: 54% of main phase glass powder, 4% of reinforcing powder, 17% of spodumene and 25% of black pigment, the rest being the same as in example 1.
Example 6:
different from the embodiment 1, the ratio of each component in the embodiment is as follows: 52% of main phase glass powder, 6% of reinforcing powder, 17% of spodumene, 25% of black coloring material, and the rest were the same as in example 1.
Comparative example 1:
different from the embodiment 1, in the embodiment, the ratio of each component is as follows: 55% of main phase glass powder, 20% of spodumene and 25% of black pigment, wherein the ratio of the mixed material to the organic carrier is 1: 0.26, the rest being the same as in example 1.
Comparative example 2:
example 1 is different from example 1 in that the particle size D90 of the reinforcing powder is 3 to 9 μm, and the rest is the same as example 1.
Comparative example 3:
example 1 is different from the following, the ratio of each component in this example is: 51% of main phase glass powder, 24% of reinforcing powder, 25% of black coloring material, and the balance of the mixture were the same as in example 1.
Comparative example 4: commercially available glass paste 1, the main components were: the main components are as follows: SiO 2 2 ，B 2 O 3 ,ZnO,Na 2 O,K 2 O，CaO，Fe 2 O 3 ，TiO 2 And the like.
Comparative example 5: commercially available glass paste 2, the main components were: SiO 2 2 ，B 2 O 3 ,ZnO,ZrO 2 ,K 2 O,Li 2 O,Na 2 O,Al 2 O 3 And the like.
The glass pastes of examples 1 to 6 and comparative examples 1 to 5 were subjected to performance tests:
printing the finished glass slurry on plate glass, and testing various performances after tempering for 150-200s at the temperature of 620-720 ℃, wherein various data of the performance test are shown in Table 2.
Table 1: the component data for examples 1-6 and comparative examples 1-5 are as follows:
table 2: data of performance test of glass pastes of examples 1 to 6 and comparative examples 1 to 5
As shown in the table 1 and the table 2, the slurry for the automobile glass, which is prepared by the invention and is suitable for large-curvature forming, has a lower sintering temperature due to the synergistic effect of the components, and the change range of the gloss value of the slurry after tempering at different temperatures is small. The surface gloss is related to the roughness of the surface, the surface of the glass slurry gradually tends to be flat due to melting when the tempering temperature is raised, the raising amplitude of the surface gloss value is large, and the larger the surface roughness is, the better the anti-sticking performance is. The slurry for the automobile glass has small surface state change along with the increase of the toughening temperature, namely, the surface roughness change is small, and the slurry has excellent anti-sticking performance in a wider sintering temperature range.
The automobile glass slurry has excellent chemical corrosion resistance and silver paste affinity. The addition of alkali and alkaline earth metals lowers the melting temperature of the glass paste and also the chemical resistance. The glass slurry has low alkali metal content and alkaline earth metal content, and forms eutectic glass slurry through the synergistic effect of mixed multiple groups of powder materials, so that the glass slurry has low melting temperature, and has excellent chemical corrosion resistance, safety performance and silver slurry affinity performance due to compact network structure.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. An automotive glass paste suitable for high-curvature processing, comprising: according to the mass percentageIn terms of ratio, 35-60% of main phase glass powder, 4-24% of reinforcing powder, 5-20% of spodumene and 10-30% of black pigment, wherein the particle sizes D90 of the main phase glass powder, the reinforcing powder, the spodumene and the black pigment after crushing are respectively 1-9 microns, 1-3 microns and 1-5 microns; the reinforcing powder comprises: by mass percent, SiO 2 30～80％,B 2 O 3 5～20％，Al 2 O 3 2～8％,P 2 O 5 4～9％,Na 2 O 2～4％,K 2 1-3% of O and 0-2% of fluorine-containing compound.
2. The automotive glass paste suitable for high curvature processing according to claim 1, wherein the main phase glass frit comprises: by mass percent, SiO 2 20～50％，B 2 O 3 5～25％，Bi 2 O 3 5～40％，Nb 2 O 5 0～5％，P 2 O 5 0.5～4％，SnO 2 0.5～2％，TiO 2 1～8％，ZrO 2 0.5～4％，ZnO 5-30％，BaO 1～7％，MgO 0～2％，Na 2 O 0.5～2％，K 2 0.5-4% of O and 0-3% of fluorine-containing compound.
3. The automotive glass paste suitable for high-curvature processing according to claim 1, wherein the spodumene is commercially available spodumene.
4. The automotive glass paste suitable for large curvature processing according to claim 1, wherein the black pigment comprises one or more of spinel type metal oxide mixed phase black inorganic pigments of copper chromium black, iron chromium black and manganese chromium black.
5. The automotive glass paste suitable for high-curvature processing according to claim 1, wherein the firing temperature of the reinforcing powder is 1200 to 1300 ℃ and the firing time is 2 to 8 hours.
6. The automotive glass paste suitable for high-curvature processing according to claim 2, wherein the firing temperature of the main phase glass powder is 1000 to 1300 ℃ and the firing time is 0.5 to 3 hours.
7. A method of preparing an automotive glass paste suitable for high-curvature processing according to any one of claims 1 to 6, comprising the steps of:
s1, weighing the main-phase glass powder, the reinforcing powder, spodumene and the black pigment according to the proportion, and uniformly mixing by using a high-speed mixer to obtain a mixed material;
s2, placing the mixed material obtained in the step S1 into a stirrer, adding an organic carrier according to the proportion of 1: 0.2-1: 0.3, and stirring into paste to obtain a paste material;
and S3, placing the paste material obtained in the step S2 into a three-roll grinder, and grinding for 3-5 times to obtain the finished product of the slurry for the automobile glass.
8. The method of claim 7, further comprising performing the main phase glass frit and the reinforcing frit separately before the step S1, wherein the steps of performing the main phase glass frit and the reinforcing frit each comprise the steps of:
weighing raw materials in proportion, uniformly mixing the raw materials by using a high-speed mixer, and putting the uniformly mixed raw materials into a high-temperature furnace for melting and firing; and (3) performing water quenching on the fired molten liquid, and crushing the water-quenched particles for 1-4 hours in a planetary ball mill by using 1-10 mm agate balls to obtain finished powder.
9. The method for preparing an automotive glass paste suitable for large curvature processing according to claim 7, further comprising pretreating the spodumene, black pigment, etc. before said step S1; the pretreatment steps of spodumene and black pigment comprise: crushing 1-10 mm agate balls for 1-4 h in a planetary ball mill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210619615.7A CN114920464B (en) | 2022-06-02 | 2022-06-02 | Automobile glass slurry suitable for large-curvature processing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210619615.7A CN114920464B (en) | 2022-06-02 | 2022-06-02 | Automobile glass slurry suitable for large-curvature processing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114920464A true CN114920464A (en) | 2022-08-19 |
| CN114920464B CN114920464B (en) | 2023-08-11 |
Family
ID=82811651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210619615.7A Active CN114920464B (en) | 2022-06-02 | 2022-06-02 | Automobile glass slurry suitable for large-curvature processing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114920464B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11157873A (en) * | 1997-11-28 | 1999-06-15 | Okuno Chem Ind Co Ltd | Ceramic color composition, molded flat glass and its forming method |
| CN101767936A (en) * | 2008-12-31 | 2010-07-07 | 西安宏星电子浆料科技有限责任公司 | Medium slurry for glass substrate |
| WO2016008848A1 (en) * | 2014-07-14 | 2016-01-21 | Schott Ag | Ceramic ink jet printing ink for low-expansion glass and/or low-expansion glass-ceramic and use 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 |
| CN110240407A (en) * | 2019-07-02 | 2019-09-17 | 黄山市晶特美新材料有限公司 | Impact-resistant glass ink, which is used, contains Nb2O5Low-temperature lead-free glass powder and preparation method thereof |
| CN110683769A (en) * | 2019-10-25 | 2020-01-14 | 赣州中瓷科技有限公司 | Reinforced calcium-boron-silicon glass-ceramic composite material and preparation method thereof |
| CN110845153A (en) * | 2019-12-03 | 2020-02-28 | 深圳市东丽华科技有限公司 | Reinforced microcrystalline glass with high-pressure stress layer depth and preparation method thereof |
| CN112125517A (en) * | 2019-06-24 | 2020-12-25 | 湖南衡义材料科技有限公司 | Anti-sticking shielding silver paste ink for high-acid-resistance automobile rear windshield 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 |
| CN114466828A (en) * | 2020-09-04 | 2022-05-10 | Ａｇｃ株式会社 | Glass ceramics and chemically strengthened glass |
-
2022
- 2022-06-02 CN CN202210619615.7A patent/CN114920464B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11157873A (en) * | 1997-11-28 | 1999-06-15 | Okuno Chem Ind Co Ltd | Ceramic color composition, molded flat glass and its forming method |
| CN101767936A (en) * | 2008-12-31 | 2010-07-07 | 西安宏星电子浆料科技有限责任公司 | Medium slurry for glass substrate |
| WO2016008848A1 (en) * | 2014-07-14 | 2016-01-21 | Schott Ag | Ceramic ink jet printing ink for low-expansion glass and/or low-expansion glass-ceramic and use thereof |
| CN112125517A (en) * | 2019-06-24 | 2020-12-25 | 湖南衡义材料科技有限公司 | Anti-sticking shielding silver paste ink for high-acid-resistance automobile rear windshield 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 |
| CN110240407A (en) * | 2019-07-02 | 2019-09-17 | 黄山市晶特美新材料有限公司 | Impact-resistant glass ink, which is used, contains Nb2O5Low-temperature lead-free glass powder and preparation method thereof |
| CN110683769A (en) * | 2019-10-25 | 2020-01-14 | 赣州中瓷科技有限公司 | Reinforced calcium-boron-silicon glass-ceramic composite material and preparation method thereof |
| CN110845153A (en) * | 2019-12-03 | 2020-02-28 | 深圳市东丽华科技有限公司 | Reinforced microcrystalline glass with high-pressure stress layer depth and preparation method thereof |
| CN114466828A (en) * | 2020-09-04 | 2022-05-10 | Ａｇｃ株式会社 | Glass ceramics and chemically strengthened glass |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114920464B (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102643023B (en) | Environmental-friendly black glaze for automotive glass and preparation method of black glaze | |
| CN1056127C (en) | Reduction of nickel sulfide stones in a glass melting operation | |
| CN105753328B (en) | A kind of windshield ink lead and cadmium free composite glass powder and preparation method thereof | |
| JP2024012353A (en) | Crystallized glass, crystallized glass product, and production method | |
| WO2008130747A1 (en) | Frits and obscuration enamels for automotive applications | |
| CN111807706B (en) | Glass ceramics and glass ceramics product | |
| CN111908793B (en) | Glass-ceramic and glass-ceramic article with spinel crystal phase | |
| CN113121109A (en) | Blue-light-proof high-strength lithium aluminum silicon cover plate glass and preparation method and application thereof | |
| CN111807705A (en) | Glass ceramics, glass ceramics product and manufacturing method thereof | |
| CN112573829A (en) | Glass slurry for automobile press-formed front windshield and preparation method thereof | |
| CN105244073B (en) | A kind of core-through capacitor silver paste and preparation method thereof | |
| CN113402172A (en) | Glass-ceramic and glass-ceramic article | |
| CN112456793A (en) | Lithium-aluminum silicate glass for float production | |
| CN102875021A (en) | Solar super-white and super-strong float glass | |
| CN110683764B (en) | Glass powder for environment-friendly high-acid-resistance automobile glass slurry and preparation method thereof | |
| CN114920464B (en) | Automobile glass slurry suitable for large-curvature processing and preparation method thereof | |
| CN111333335B (en) | High-acid-resistance automobile glass printing ink and preparation method thereof | |
| CN115259675B (en) | Glass powder for positive silver main grid slurry of N-type TOPCON crystalline silicon solar cell and preparation method thereof | |
| CN113233761B (en) | Glass capable of improving thermal shock resistance and preparation method thereof | |
| CN109851224B (en) | Low-temperature low-alkali metal lead-free glaze and preparation process thereof | |
| CN114590999A (en) | Low-melting-point lead-free glass powder and preparation method thereof | |
| CN103011605A (en) | Lead-free glass powder for automobile glass printing ink and preparation method of lead-free glass powder | |
| CN113651529B (en) | Glass composition, glass powder, glass ink and application of glass ink | |
| CN115784621B (en) | Glass product for connecting mobile phone rear cover and lens part and use method | |
| CN114773044B (en) | Mount Taishan jadeite porcelain body and color porcelain and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A car glass slurry suitable for large curvature processing and its preparation method Effective date of registration: 20231220 Granted publication date: 20230811 Pledgee: Huangshan Huangshan SME Financing Guarantee Co.,Ltd. Pledgor: Huangshan Jingtemei New Materials Co.,Ltd. Registration number: Y2023980072865 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |