High-hardness glass slurry and preparation process thereof

Abstract

The invention discloses a high-hardness glass paste and a preparation process thereof, and belongs to the technical field of glass pastes.The high-hardness glass paste is composed of solid-phase powder and varnish, and the varnish accounts for 15-35% of the weight of the solid-phase powder; the solid-phase powder is prepared from the following components in percentage by weight: 50 to 68 percent of main-phase glass powder, 2 to 5 percent of reinforcing powder and 30 to 45 percent of black pigment. After being tempered, the high-hardness glass slurry prepared by the preparation method disclosed by the invention has the properties of black brightness, high glossiness, good shielding capability, high hardness and the like, and is suitable for surface coating of household appliance glass products, automobiles and building glass.

Description

Technical Field

[0001] This invention relates to a high-hardness glass slurry and its preparation process, belonging to the field of glass slurry technology. Background Technology

[0002] With rapid technological advancements and improved living standards, both the home appliance and automotive industries are experiencing a boom. Smart appliances and various functional appliances, such as microwave ovens, electric ovens, and range hoods, have become deeply integrated into daily life, while the automotive industry is seeing the emergence of intelligent technologies that enhance the driving experience. To meet the aesthetic and durability demands of home appliances, the performance of glass products is constantly improving, and the automotive industry also has high requirements for the scratch resistance and shielding capabilities of glass.

[0003] Nowadays, home appliances and automobiles have high requirements for the opacity and scratch resistance of glass inks. Although existing glass ink products on the market can basically meet the application requirements, they still generally have performance defects in the key performance aspects of high opacity, high hardness and scratch resistance. Summary of the Invention

[0004] In response to at least one problem existing in the prior art, the present invention provides a high-hardness glass slurry and its preparation process. After tempering, the glass slurry has properties such as high gloss, good shielding ability, and high hardness.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: a high-hardness glass paste, composed of solid phase powder and ink oil, wherein the weight of the ink oil accounts for 15-35% of the weight of the solid phase powder; the solid phase powder is composed of main phase glass powder, reinforcing powder, and black pigment, and by weight percentage: main phase glass powder 50-68%, reinforcing powder 2-5%, and pigment 30-45%.

[0006] Preferably, the main phase glass powder comprises the following raw materials and their weight percentages: 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide; and the weight percentage of silicon dioxide is less than 53% of the sum of the weights of bismuth oxide, silicon dioxide, and boric acid, and at least one of sodium fluorosilicate, barium carbonate, zinc oxide, and iron oxide is contained.

[0007] Preferably, the weight of silicon dioxide accounts for 10-45% of the total weight of bismuth oxide, silicon dioxide, and boric acid.

[0008] Preferably, the main phase glass powder contains at least one of barium carbonate or zinc oxide.

[0009] Preferably, the weight of barium carbonate accounts for 0-3% of the total weight of the main phase glass powder.

[0010] Preferably, the reinforcing powder comprises at least two of zirconium silicate, silicon nitride, silicon carbide, or aluminum oxide.

[0011] Preferably, the weight percentage of each of the zirconium silicate, silicon nitride, silicon carbide, or alumina in the total weight of the solid powder is between 0 and 3%.

[0012] Preferably, the particle size D90 of the main phase glass powder is 1~6μm.

[0013] Preferably, the particle size D90 of the reinforcing powder is 1~7μm.

[0014] Preferably, the particle size D90 of the black pigment is 1~5μm.

[0015] Preferably, the black pigment includes at least one of copper-chromium melanin or manganese-iron melanin.

[0016] Preferably, the ink oil is a water-based ink oil.

[0017] Preferably, the preparation process of the main phase glass powder is as follows: (1) Weigh out 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide according to the weight percentage of the raw materials to obtain the base material; (2) Place the base material from step (1) into a crucible and heat it at 1100~1250℃ for 0.5~2h to form molten glass. Then quench the molten glass with water to obtain glass frit. (3) Add water to the glass molten block from step (2) and ball mill it to form a suspension with a particle size of 3~10μm. After drying, pulverize it to a particle size D90 of 1~6μm to obtain the main phase glass powder.

[0018] Preferably, the ball milling conditions in step (3) are: agate balls or high-alumina balls with a diameter of 10mm to 15mm.

[0019] This invention provides a process for preparing a high-hardness glass slurry, comprising the following steps: S1. According to the above components and their weight percentages, the main phase glass powder with a particle size D90 of 1~6μm, the strengthening powder with a particle size D90 of 1~7μm, and the black pigment with a particle size D90 of 1~5μm are mixed and pretreated to obtain solid phase powder. S2. According to the above weight ratio, the solid powder and ink oil are mixed, and after mixing, they are ground to obtain glass paste.

[0020] Preferably, the pretreatment in step S1 involves adding water and ball milling to form a mixed powder suspension with a particle size of less than 5 μm, followed by drying and pulverizing.

[0021] Preferably, the ball milling conditions for pretreatment in step S1 are: agate balls or high-alumina balls with a diameter of 10mm to 15mm.

[0022] Preferably, the grinding in step S2 is performed using a three-roll mill.

[0023] Preferably, the high-hardness glass slurry prepared by the present invention, after being tempered at 580℃~720℃, has a scratch resistance greater than 18N and a hiding power OD value greater than 4.2.

[0024] The beneficial effects of this invention are: 1. The high-hardness glass slurry prepared by the present invention, through reasonable control of the metal oxides, alkaline earth metals and other components of the main phase glass powder and the synergistic effect of an appropriate ratio of reinforcing powder phase, further enhances the hardness and wear resistance of the slurry, effectively improves the chemical stability of the glass slurry, and gives it a higher hardness level and shielding ability.

[0025] 2. The high-hardness glass slurry prepared by the present invention has a dense network structure formed by adjusting Bi2O3, H3BO3 and SiO2 in the main phase glass powder.

[0026] 3. The high-hardness glass paste prepared by this invention, after being tempered at 580℃~720℃, not only has high hardness and scratch resistance, but also has high black gloss and high opacity.

[0027] 4. The high-hardness glass slurry prepared by this invention uses readily available raw materials and has a simple process, making it particularly suitable for surface coating of household appliance glass products and automotive and architectural glass. Detailed Implementation

[0028] The following is a clear and complete description of the technical solutions in the implementation of this invention. The described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents, instruments, or components used that do not specify the manufacturer are all conventional products that can be purchased commercially.

[0029] The present invention provides a high-hardness glass paste, which is composed of solid phase powder and ink oil, wherein the weight of the ink oil accounts for 15-35% of the weight of the solid phase powder; the solid phase powder is composed of main phase glass powder, reinforcing powder and black pigment, and by weight percentage: main phase glass powder 50-68%, reinforcing powder 2-5%, pigment 30-45%; the ink oil is a water-based ink oil.

[0030] A further technical solution involves the following preparation process for the main phase glass powder: (1) Weigh out 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide according to the weight percentage of the raw materials to obtain the base material; (2) Place the base material from step (1) into a crucible and heat it at 1100~1250℃ for 0.5~2h to form molten glass. Then quench the molten glass with water to obtain glass frit. (3) Add water to the glass molten block from step (2) and ball mill it. The ball milling conditions are: agate balls or high-alumina balls with a diameter of 10 mm to 15 mm to form a suspension with a particle size of 3 to 10 μm. After drying, the suspension is crushed to a particle size D90 of 1 to 6 μm to obtain the main phase glass powder.

[0031] A further technical solution is that the main phase glass powder contains at least one of barium carbonate or zinc oxide; the weight of barium carbonate accounts for 0 to 3% of the total weight of the main phase glass powder.

[0032] A further technical solution includes a reinforcing powder comprising at least two of zirconium silicate, silicon nitride, silicon carbide, or aluminum oxide; and a black pigment comprising at least one of copper chromium melanin or manganese iron melanin.

[0033] A further advanced technical solution is that the weight percentage of each of zirconium silicate, silicon nitride, silicon carbide, or alumina in the total weight of the solid powder is between 0 and 3%.

[0034] This invention provides a process for preparing a high-hardness glass slurry, comprising the following steps: S1. According to the above components and their weight percentages, the main phase glass powder with a particle size D90 of 1~6μm, the strengthening powder with a particle size D90 of 1~7μm, and the black pigment with a particle size D90 of 1~5μm are mixed and pretreated: water is added and ball milling is performed to form a mixed powder suspension with a particle size of less than 5μm, which is then dried and pulverized to obtain solid phase powder. S2. Mix the solid powder and water-based ink, wherein the weight of the ink accounts for 15-35% of the weight of the solid powder. After mixing, grind and mix the mixture using a three-roll mill to obtain a glass slurry.

[0035] The high-hardness glass paste prepared by this invention, after being tempered at 580℃~720℃, exhibits a scratch resistance greater than 18N and a hiding power OD value greater than 4.2.

[0036] I. Preparation of Solid Powder in Examples Specific process: Step 1, Preparation of main phase glass powder: 1) Weigh bismuth oxide, silicon dioxide, boric acid, sodium oxide, potassium oxide, sodium fluoride, titanium dioxide, sodium fluorosilicate, barium carbonate, zinc oxide and iron oxide according to the weight percentage of raw materials in Table 1 to obtain the base material; 2) Place the base material from step 1) into a crucible and heat it at 1100~1250℃ for 0.5~2 hours to form molten glass. Then, quench the molten glass with water to obtain glass frit. 3) Add water to the glass molten block from step 2) and ball mill it. The ball milling conditions are: agate balls or high alumina balls with a diameter of 10 mm to 15 mm to form a suspension with a particle size of 3 to 10 μm. After drying, pulverize it to a particle size D90 of 1 to 6 μm to obtain the main phase glass powder. Step 2: Weigh zirconium silicate, silicon nitride, silicon carbide and alumina according to Table 2 below, mix them, and pulverize them to a particle size D90 of 1~7μm to obtain reinforced powder; Step 3: Weigh out copper chromium melanin or manganese iron melanin, and pulverize it to a particle size D90 of 1~5μm to obtain black pigment; Step 4: Weigh the main phase glass powder from Step 1, the strengthening powder from Step 2, and the black pigment from Step 3 according to Table 2 below, mix them, and perform pretreatment: add water and ball milling. The ball milling conditions are: agate balls or high-alumina balls with a diameter of 10mm~15mm to form a mixed powder suspension with a particle size of less than 5μm. After drying, the mixture is pulverized to obtain solid phase powder.

[0037] Table 1 Content of each raw material in the main phase glass powder of the embodiment

[0038] In Table 1, the sum of the masses of bismuth oxide, silicon dioxide, and boric acid is T.

[0039] Table 2 Contents of each component in the solid powder of the examples

[0040] II. Preparation of Glass Slurry in Examples Specific process: Solid powder and water-based ink are mixed, with the ink accounting for 15-35% of the weight of the solid powder. After thorough mixing, the mixture is ground and blended using a three-roll mill to obtain a glass slurry. Among other things: Examples 1-18 Glass Slurry The solid powders of Examples 1 to 18 were mixed with water-based ink oil, and the weight of the ink oil accounted for 20% of the weight of the solid powder, to form the glass pastes of Examples 1 to 18.

[0041] Example 19 Glass Slurry The solid powder of Example 18 was mixed with water-based ink oil, and the weight of the ink oil accounted for 15% of the weight of the solid powder, to form the glass paste of Example 19.

[0042] Example 20 Glass Slurry The solid powder of Example 18 was mixed with water-based ink oil, and the weight of the ink oil accounted for 35% of the weight of the solid powder, to form the glass paste of Example 20.

[0043] III. Comparative Solid Powder Preparation Specific process: Step 1, Preparation of main phase glass powder: 1) Weigh bismuth oxide, silicon dioxide, boric acid, sodium oxide, potassium oxide, sodium fluoride, titanium dioxide, sodium fluorosilicate, barium carbonate, zinc oxide and iron oxide according to the weight percentage of raw materials in Table 3 to obtain the base material; 2) Place the base material from step 1) into a crucible and heat it at 1100~1250℃ for 0.5~2 hours to form molten glass. Then, quench the molten glass with water to obtain glass frit. 3) Add water to the glass molten block from step 2) and ball mill it. The ball milling conditions are: agate balls or high alumina balls with a diameter of 10 mm to 15 mm to form a suspension with a particle size of 3 to 10 μm. After drying, pulverize it to a particle size D90 of 1 to 6 μm to obtain the main phase glass powder. Step 2: Weigh zirconium silicate, silicon nitride, silicon carbide and alumina according to Table 4 below, mix them, and pulverize them to a particle size D90 of 1~7μm to obtain reinforced powder; Step 3: Weigh out copper chromium melanin or manganese iron melanin, and pulverize it to a particle size D90 of 1~5μm to obtain black pigment; Step 4: Weigh the main phase glass powder from Step 1, the strengthening powder from Step 2, and the black pigment from Step 3 according to Table 4 below, mix them, and perform pretreatment: add water and ball milling. The ball milling conditions are: agate balls or high-alumina balls with a diameter of 10mm~15mm to form a mixed powder suspension with a particle size of less than 5μm. After drying, the mixture is pulverized to obtain solid phase powder.

[0044] Table 3 Content of each raw material in the main phase glass powder of the comparative example

[0045] Table 4. Content of each raw material in the main phase glass powder of the comparative example

[0046] IV. Preparation of Comparative Glass Slurry Specific process: Solid powder and water-based ink are mixed, with the ink accounting for 15-35% of the weight of the solid powder. After thorough mixing, the mixture is ground and blended using a three-roll mill to obtain a glass slurry. Among other things: Comparative Examples 1-12 Glass Slurry The solid powders of Comparative Examples 1 to 12 were mixed with water-based ink oil, and the weight of the ink oil accounted for 20% of the weight of the solid powder, to form glass pastes of Comparative Examples 1 to 12.

[0047] The glass slurries of Examples 1-20 and Comparative Examples 1-12 were tempered at 580℃-720℃ and their performance was tested. The results are shown in Table 5 below. Standard requirements: the larger the N value, the better the scratch resistance, greater than 18N; the larger the OD value, the better the shielding performance, ranging from 4.2 to 6.

[0048] Table 5. Properties of Glass Slurry

[0049] As shown in Table 5, in the solid phase powder of the glass slurry used in Examples 1 to 20 of the present invention, the main phase glass powder, strengthening powder and black pigment of appropriate particle size are combined with their suitable proportion system. After tempering at 580℃ to 720℃, the OD value range is suitable, the shielding is better, the black gloss is high, the N value increases, the scratch resistance is good, the hardness and wear resistance of the material are enhanced, and the glass slurry has excellent shielding ability and high hardness.

[0050] Compared to Examples 1-20, in Comparative Examples 1-6, Comparative Examples 10, and Comparative Example 12, the content of reinforcing powder in the solid phase powder of the glass slurry was either too high or too low, which affected the surface gloss and scratch resistance after tempering. Excessive reinforcing powder resulted in a higher sintering temperature, lower surface gloss, a matte finish, and reduced scratch resistance after tempering. Conversely, insufficient reinforcing powder weakened the structural reinforcement after tempering, also reducing scratch resistance. Furthermore, Comparative Examples 1, 2, and 3 contained excessive or insufficient amounts of silicon dioxide, boric acid, and bismuth oxide; Comparative Example 4 contained zinc oxide exceeding the acceptable range; Comparative Examples 5 and 6 contained excessive alkali metals; Comparative Example 7 contained excessive alkaline earth metals; and Comparative Example 8 contained excessive titanium dioxide. In such systems, excessive or insufficient amounts of silicon dioxide, boric acid, and bismuth oxide disrupted the balance of the network structure, leading to a decrease in structural strength after tempering and affecting scratch resistance and surface gloss. Comparative Example 9, lacking any of sodium fluorosilicate, barium carbonate, zinc oxide, or iron oxide, resulted in reduced opacity and scratch resistance of the tempered surface. In Comparative Examples 11 and 12, excessive or insufficient amounts of main phase glass powder, reinforcing powder, and black pigment significantly impacted the opacity and scratch resistance of the tempered surface. In contrast, the solid-phase powders in Examples 1-20, through the synergistic effect of containing appropriate amounts of metal oxides and alkaline earth metal main phase glass powder, and appropriate amounts of reinforcing powder, contribute to the glass slurry's high opacity and high hardness.

[0051] Furthermore, the presence of either barium carbonate or zinc oxide in Examples 12, 16, and 17 improved the masking and scratch resistance of the tempered surface. The combination of at least one of barium carbonate or zinc oxide with at least one of sodium fluorosilicate or barium carbonate in Examples 1-9 further enhanced the masking and scratch resistance of the tempered surface. In Examples 11 and 14, the barium carbonate content was 6%; in Example 10, the weight percentage of silicon oxide relative to the sum of bismuth oxide, silicon oxide, and boric acid was 7.8%, less than 10%; and in Example 11, the weight percentage of silicon oxide relative to the sum of bismuth oxide, silicon oxide, and boric acid was 52.2%, greater than 45%. This resulted in a slight decrease in the masking and scratch resistance of the tempered surface, although the OD value remained in the range of 4.2-6 and the N value remained greater than 18. Examples 1-9, 13, 15, and 18 showed that the presence of at least two of zirconium silicate, silicon nitride, silicon carbide, or aluminum oxide in the reinforcing powder further improved the masking and scratch resistance of the tempered surface. In this invention, the glass pastes of Examples 1-9 and Example 13 are preferred, as they have superior shielding ability and hardness performance.

[0052] In summary, the high-hardness glass slurry prepared by this invention, through reasonable control of the metal oxides, alkaline earth metals and other components of the main phase glass powder and the synergistic effect of an appropriate ratio of reinforcing powder, further enhances the hardness and wear resistance of the slurry, effectively improves the chemical stability of the glass slurry, and gives it a higher hardness level and shielding ability; the raw materials are readily available and the process is simple, making it particularly suitable for surface coating of household appliance glass products and automotive and architectural glass.

[0053] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit and essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0054] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A high-hardness glass paste, characterized in that, It is composed of solid powder and ink oil, and the weight of the ink oil accounts for 15-35% of the weight of the solid powder; the solid powder is composed of main phase glass powder, reinforcing powder and black pigment, and by weight percentage: main phase glass powder 50-68%, reinforcing powder 2-5%, pigment 30-45%.

2. The high-hardness glass slurry according to claim 1, characterized in that, The main phase glass powder comprises the following raw materials and their weight percentages: 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide; and the weight percentage of silicon dioxide is less than 53% of the sum of the weights of bismuth oxide, silicon dioxide, and boric acid, and at least one of sodium fluorosilicate, barium carbonate, zinc oxide, and iron oxide is contained.

3. The high-hardness glass slurry according to claim 2, characterized in that, The weight percentage of silicon dioxide is 10-45% of the sum of the weights of bismuth oxide, silicon dioxide, and boric acid.

4. The high-hardness glass slurry according to claim 2, characterized in that, The main phase glass powder contains at least one of barium carbonate or zinc oxide.

5. The high-hardness glass slurry according to claim 2, characterized in that, The weight of barium carbonate accounts for 0-3% of the total weight of the main phase glass powder.

6. The high-hardness glass slurry according to claim 1, characterized in that, The reinforcing powder includes at least two of zirconium silicate, silicon nitride, silicon carbide, or alumina; the weight percentage of each of zirconium silicate, silicon nitride, silicon carbide, or alumina in the total weight of the solid powder is between 0 and 3%.

7. The high-hardness glass slurry according to claim 1, characterized in that, The black pigment includes at least one of copper-chromium melanin or manganese-iron melanin.

8. The high-hardness glass slurry according to claim 1, characterized in that, The preparation process of the main phase glass powder is as follows: (1) Weigh out 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide according to the weight percentage of the raw materials to obtain the base material; (2) Place the base material from step (1) into a crucible and heat it at 1100~1250℃ for 0.5~2h to form molten glass. Then quench the molten glass with water to obtain glass frit. (3) Add water to the glass molten block from step (2) and ball mill it to form a suspension with a particle size of 3~10μm. After drying, pulverize it to a particle size D90 of 1~6μm to obtain the main phase glass powder.

9. The high-hardness glass slurry according to claim 1, characterized in that, The particle size D90 of the main phase glass powder is 1~6μm; the particle size D90 of the reinforcing powder is 1~7μm; and the particle size D90 of the black pigment is 1~5μm.

10. A process for preparing a high-hardness glass slurry according to any one of claims 1 to 9, characterized in that, The steps include the following: S1. According to the above components and their weight percentages, the main phase glass powder with a particle size D90 of 1~6μm, the strengthening powder with a particle size D90 of 1~7μm, and the black pigment with a particle size D90 of 1~5μm are mixed and pretreated to obtain solid phase powder. S2. According to the above weight ratio, the solid powder and the ink oil are mixed, and then ground and mixed to obtain the glass paste. The pretreatment in step S1 involves adding water and ball milling to form a mixed powder suspension with a particle size of less than 5 μm, followed by drying and pulverization.

Images