Positioning metal dry particles and a method for preparing the same

Abstract

The present application relates to a kind of positioning metal dry particles and its preparation method, belong to ceramic technical field.The present application provides a kind of positioning metal dry particles and its preparation method, the raw material of the positioning metal dry particles includes 60-70 parts by weight composite metal particles, 30-40 parts by weight glass glaze;The composite metal particles are obtained by compounding copper-zinc alloy powder, electrolytic manganese dioxide powder, nano bismuth oxide powder;The glass glaze is obtained by compounding SiO2, B2O3, ZnO, BaO, NaO2, K2O, CaO, MgO, Al2O3.The positioning metal dry particles prepared by the present application is not prone to produce explosion flower, microcrack and other defects after firing, simultaneously has good gloss, has good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of ceramic technology and relates to a positioning metal dry granule and its preparation method. Background Technology

[0002] Positioning metal granules is a process in ceramic tile surface treatment. Common positioning methods include adhesive positioning or using peeling ink or engraving ink on the ceramic tile surface. By fixing the metal granules to specific positions on the tile surface, a metallic texture or pattern is formed after firing. However, since positioning metal granules are mostly obtained by mixing different metal particles, the differences in thermal expansion coefficients, melting points, and sintering activities between the components of different particles are significant. During firing, these differences lead to internal stress concentration. After cooling or under the influence of temperature and humidity changes in the usage environment, defects such as "cracking" and micro-cracks are easily generated on the surface or inside of the granules, seriously affecting the product's durability and decorative effect. Summary of the Invention

[0003] The purpose of this invention is to provide a positioning metal dry granule and its preparation method. The positioning metal dry granule prepared is not prone to defects such as cracking and micro-cracks after firing, and has good gloss.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A positioning metal dry granule, wherein the raw materials of the positioning metal dry granule, by weight, include 60-70 parts of composite metal particles and 30-40 parts of glass glaze;

[0006] The raw materials for the composite metal particles, by weight, include 8.6-9.2 parts copper-zinc alloy powder, 0.5-1.1 parts electrolytic manganese dioxide powder, and 0.3-0.5 parts nano bismuth oxide powder.

[0007] Furthermore, the composite metal particles are composite metal particles whose surfaces have undergone coupling treatment, and the specific operation of the coupling treatment is as follows:

[0008] A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 20-40 rpm to obtain composite metal particles.

[0009] A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

[0010] Further, the lower rotation speed in step A2 is 200-300 rpm; the spraying time is 10-16 min; and the higher rotation speed is 500-600 rpm.

[0011] Further, the coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 8-12 wt%; and the mass of the coupling agent is 1.1-1.5 wt% of the total mass of the composite metal particles.

[0012] Further, the drying process described in step A2 involves drying in a vacuum drying oven at 86-90°C and a vacuum degree of -0.09MPa for 2.5-3.5 hours.

[0013] Further, the raw materials of the glass glaze, by weight, include 4.5-5 parts SiO2, 1.8-2.2 parts B2O3, 0.8-1.2 parts ZnO, 0.5-0.8 parts BaO, 0.2-0.3 parts NaO2, 0.2-0.3 parts K2O, 0.1-0.2 parts CaO, 0.1-0.2 parts MgO, and 0.1-0.2 parts Al2O3; after the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 400-500 mesh sieve to obtain the glass glaze.

[0014] Furthermore, the method for preparing the positioned metal dry granules includes the following steps:

[0015] B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 10-20 rpm for 6-8 hours to obtain the final product.

[0016] Furthermore, the glaze is prepared by sieving the positioning metal dry particles through an 80-100 mesh sieve, applying them to the glazed surface of a pre-set area on the brick blank, sintering, and cooling.

[0017] Furthermore, the application rate is 150-180 g / m³. 2 The sintering process refers to firing at 1150-1180℃ for 40-60 minutes, followed by holding at that temperature for 15-25 minutes.

[0018] The beneficial effects of this invention are:

[0019] This invention provides a positioning metal dry granule made from composite metal particles and glass glaze. The composite metal particles, primarily composed of copper-zinc alloy powder, provide the main metallic texture and luster. The abundant hydroxyl groups on the surface of electrolytic manganese dioxide powder provide numerous binding sites for the coupling agent, thereby improving the interfacial bonding between raw materials and synergistically promoting sintering with NaO2 and K2O, thus improving the smoothness of the glaze surface. Nano-bismuth oxide powder acts as a sintering aid, melting before other components during sintering to form a liquid phase, thereby wetting the solid surface and promoting sintering, effectively reducing defects caused by differences in sintering activity. The resulting composite metal particles can effectively disperse stress and suppress the generation of "bursting" and microcracks. Furthermore, the doping of glass glaze not only helps reduce internal stress concentration caused by particle size differences but also forms a smooth, mirror-like surface after melting, highlighting the luster of the metallic material and giving the brick a high gloss, resulting in excellent decorative effects. Detailed Implementation

[0020] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0021] In all embodiments and comparative examples of this invention, the copper-zinc alloy powder had a particle size of 600 mesh and was purchased from Hunan Zhongcai Shengte New Material Technology Co., Ltd.; the electrolytic manganese dioxide powder was purchased from Hunan Daji Environmental Protection and Energy Saving Materials Co., Ltd. and further ball-milled through an 800-mesh sieve; and the nano bismuth oxide powder had a particle size of 50 nm and was purchased from Hebei Teng Shuang Metal Materials Co., Ltd.

[0022] Example 1

[0023] A positioning metal dry granule, wherein the raw materials of the positioning metal dry granule, by weight, include 60 parts of composite metal particles and 30 parts of glass glaze;

[0024] The raw materials for the composite metal particles, by weight, include 8.6 parts copper-zinc alloy powder, 0.5 parts electrolytic manganese dioxide powder, and 0.3 parts nano bismuth oxide powder.

[0025] The composite metal particles are composite metal particles whose surfaces have undergone coupling treatment. The specific operation of the coupling treatment is as follows:

[0026] A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 20 rpm to obtain composite metal particles.

[0027] A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

[0028] The lower rotation speed in step A2 is 200 rpm; the spraying time is 10 min; and the higher rotation speed is 500 rpm.

[0029] The coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 8 wt%; the mass of the coupling agent is 1.1 wt% of the total mass of the composite metal particles.

[0030] The drying process described in step A2 involves drying the product in a vacuum drying oven at 86°C and a vacuum degree of -0.09 MPa for 2.5 hours.

[0031] The raw materials of the glass glaze, by weight, include 4.5 parts SiO2, 1.8 parts B2O3, 0.8 parts ZnO, 0.5 parts BaO, 0.2 parts NaO2, 0.2 parts K2O, 0.1 parts CaO, 0.1 parts MgO, and 0.1 parts Al2O3. After the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 400-mesh sieve to obtain the glass glaze.

[0032] The method for preparing the positioning metal dry granules includes the following steps:

[0033] B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 10 rpm for 6 hours to obtain the final product.

[0034] Example 2

[0035] A positioning metal dry granule, wherein the raw materials of the positioning metal dry granule, by weight, include 64 parts of composite metal particles and 33 parts of glass glaze;

[0036] The raw materials for the composite metal particles, by weight, include 8.7 parts copper-zinc alloy powder, 0.65 parts electrolytic manganese dioxide powder, and 0.37 parts nano bismuth oxide powder.

[0037] The composite metal particles are composite metal particles whose surfaces have undergone coupling treatment. The specific operation of the coupling treatment is as follows:

[0038] A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 20 rpm to obtain composite metal particles.

[0039] A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

[0040] The lower rotation speed in step A2 is 200 rpm; the spraying time is 12 min; and the higher rotation speed is 500 rpm.

[0041] The coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 9 wt%; and the mass of the coupling agent is 1.2 wt% of the total mass of the composite metal particles.

[0042] The drying process described in step A2 involves drying the product in a vacuum drying oven at 87°C and a vacuum degree of -0.09 MPa for 2.8 hours.

[0043] The raw materials of the glass glaze, by weight, include 4.65 parts SiO2, 1.9 parts B2O3, 0.9 parts ZnO, 0.6 parts BaO, 0.24 parts NaO2, 0.24 parts K2O, 0.13 parts CaO, 0.13 parts MgO, and 0.12 parts Al2O3. After the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 400-mesh sieve to obtain the glass glaze.

[0044] The method for preparing the positioning metal dry granules includes the following steps:

[0045] B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 10 rpm for 6.5 hours to obtain the final product.

[0046] Example 3

[0047] A positioning metal dry granule, wherein the raw materials of the positioning metal dry granule, by weight, include 65 parts of composite metal particles and 35 parts of glass glaze;

[0048] The raw materials for the composite metal particles, by weight, include 8.9 parts copper-zinc alloy powder, 0.8 parts electrolytic manganese dioxide powder, and 0.4 parts nano bismuth oxide powder.

[0049] The composite metal particles are composite metal particles whose surfaces have undergone coupling treatment. The specific operation of the coupling treatment is as follows:

[0050] A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 30 rpm to obtain composite metal particles.

[0051] A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

[0052] The lower rotation speed in step A2 is 250 rpm; the spraying time is 13 min; and the higher rotation speed is 550 rpm.

[0053] The coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 1 wt%; the mass of the coupling agent is 1.3 wt% of the total mass of the composite metal particles.

[0054] The drying process described in step A2 involves drying the product in a vacuum drying oven at 88°C and a vacuum degree of -0.09 MPa for 3 hours.

[0055] The raw materials of the glass glaze, by weight, include 4.75 parts SiO2, 2 parts B2O3, 1 part ZnO, 0.65 parts BaO, 0.25 parts NaO2, 0.25 parts K2O, 0.15 parts CaO, 0.15 parts MgO, and 0.15 parts Al2O3. After the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 450-mesh sieve to obtain the glass glaze.

[0056] The method for preparing the positioning metal dry granules includes the following steps:

[0057] B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 15 rpm for 7 hours to obtain the final product.

[0058] Example 4

[0059] A positioning metal dry granule, wherein the raw materials of the positioning metal dry granule, by weight, include 67 parts of composite metal particles and 38 parts of glass glaze;

[0060] The raw materials for the composite metal particles, by weight, include 9.1 parts copper-zinc alloy powder, 1 part electrolytic manganese dioxide powder, and 0.46 parts nano bismuth oxide powder.

[0061] The composite metal particles are composite metal particles whose surfaces have undergone coupling treatment. The specific operation of the coupling treatment is as follows:

[0062] A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 0 rpm to obtain composite metal particles.

[0063] A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

[0064] The lower rotation speed in step A2 is 300 rpm; the spraying time is 15 min; and the higher rotation speed is 600 rpm.

[0065] The coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 11 wt%; and the mass of the coupling agent is 1.4 wt% of the total mass of the composite metal particles.

[0066] The drying process described in step A2 involves drying the product in a vacuum drying oven at 89°C and a vacuum degree of -0.09 MPa for 3.3 hours.

[0067] The raw materials of the glass glaze, by weight, include 4.9 parts SiO2, 2.1 parts B2O3, 1.1 parts ZnO, 0.75 parts BaO, 0.27 parts NaO2, 0.27 parts K2O, 0.16 parts CaO, 0.16 parts MgO, and 0.16 parts Al2O3. After the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 500-mesh sieve to obtain the glass glaze.

[0068] The method for preparing the positioning metal dry granules includes the following steps:

[0069] B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 20 rpm for 7.5 hours to obtain the final product.

[0070] Example 5

[0071] A positioning metal dry granule, wherein the raw materials of the positioning metal dry granule, by weight, include 70 parts of composite metal particles and 40 parts of glass glaze;

[0072] The raw materials for the composite metal particles, by weight, include 9.2 parts copper-zinc alloy powder, 1.1 parts electrolytic manganese dioxide powder, and 0.5 parts nano bismuth oxide powder.

[0073] The composite metal particles are composite metal particles whose surfaces have undergone coupling treatment. The specific operation of the coupling treatment is as follows:

[0074] A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 40 rpm to obtain composite metal particles.

[0075] A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

[0076] The lower rotation speed in step A2 is 300 rpm; the spraying time is 16 min; and the higher rotation speed is 600 rpm.

[0077] The coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 8-12 wt%; and the mass of the coupling agent is 1.5 wt% of the total mass of the composite metal particles.

[0078] The drying process described in step A2 involves drying the product in a vacuum drying oven at 90°C and a vacuum degree of -0.09 MPa for 3.5 hours.

[0079] The raw materials of the glass glaze, by weight, include 5 parts SiO2, 2.2 parts B2O3, 1.2 parts ZnO, 0.8 parts BaO, 0.3 parts NaO2, 0.3 parts K2O, 0.2 parts CaO, 0.2 parts MgO, and 0.2 parts Al2O3. After the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 500-mesh sieve to obtain the glass glaze.

[0080] The method for preparing the positioning metal dry granules includes the following steps:

[0081] B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 20 rpm for 8 hours to obtain the final product.

[0082] Example 6

[0083] Based on Example 3, the raw material composition of the glass glaze was changed to include, by weight, 4.75 parts SiO2, 2 parts B2O3, 1 part ZnO, 0.65 parts BaO, 0.5 parts NaO2, 0.15 parts CaO, 0.15 parts MgO, and 0.15 parts Al2O3, while other conditions remained the same as in Example 3.

[0084] Example 7

[0085] Based on Example 3, the raw material composition of the glass glaze was changed to include, by weight, 4.75 parts SiO2, 2 parts B2O3, 1 part ZnO, 0.65 parts BaO, 0.5 parts K2O, 0.15 parts CaO, 0.15 parts MgO, and 0.15 parts Al2O3, while other conditions remained the same as in Example 3.

[0086] Comparative Example 1

[0087] Based on Example 3, the electrolytic manganese dioxide powder in the composite metal particles was removed and replaced with an equal weight of nano bismuth oxide powder, while other conditions remained the same as in Example 3.

[0088] Comparative Example 2

[0089] Based on Example 3, the nano-bismuth oxide powder in the composite metal particles was removed and replaced with an equal weight of electrolytic manganese dioxide powder, while other conditions remained the same as in Example 3.

[0090] Comparative Example 3

[0091] Based on Example 3, the raw material composition of the composite metal particles was changed to include, by weight, 8.9 parts copper-zinc alloy powder, 0.4 parts electrolytic manganese dioxide powder, and 0.8 parts nano bismuth oxide powder.

[0092] Comparative Example 4

[0093] Based on Example 3, no surface coupling treatment was performed on the composite metal particles, and other conditions remained the same as in Example 3.

[0094] Comparative Example 5

[0095] Based on Example 3, the raw materials for the glass glaze were mixed evenly and then ball-milled through a 300-mesh sieve to obtain the glass glaze. Other conditions remained the same as in Example 3.

[0096] Comparative Example 6

[0097] Based on Example 3, the sintering temperature was changed to 1200℃, while other conditions remained the same as in Example 3.

[0098] The positioning metal dry granules prepared in Examples 1-7 and Comparative Examples 1-6 were applied to the brick blanks. Specifically, the positioning metal dry granules were sieved through a 90-mesh sieve at a concentration of 165 g / m³. 2 The amount of glaze applied is applied to the glazed surface of the pre-set area of ​​the brick blank, and then fired at 1165℃ for 50 minutes, followed by holding for 20 minutes, and then cooled to obtain the corresponding sample.

[0099] The appearance of the sample was directly observed by illuminating it with light to evaluate whether the surface of the sample was smooth and flat, and whether there were cracks on the surface or inside. At the same time, the gloss of the sample was tested according to the CB / T13891-2008 standard. The test results are recorded in Table 1 below.

[0100]

[0101] As shown in Table 1, the positioning metal dry granules prepared by this invention are not prone to defects such as cracking and micro-cracks after firing, and have good gloss, showing good application prospects.

[0102] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A type of positioning metal dry granules, characterized in that: The raw materials for the positioning metal dry granules, by weight, include 60-70 parts of composite metal particles and 30-40 parts of glass glaze. The raw materials for the composite metal particles, by weight, include 8.6-9.2 parts copper-zinc alloy powder, 0.5-1.1 parts electrolytic manganese dioxide powder, and 0.3-0.5 parts nano bismuth oxide powder; The composite metal particles are composite metal particles whose surfaces have undergone coupling treatment. The specific operation of the coupling treatment is as follows: A1. Mix copper-zinc alloy powder, electrolytic manganese dioxide powder, and nano bismuth oxide powder evenly in a three-dimensional mixer at a speed of 20-40 rpm to obtain composite metal particles. A2. The coupling agent-ethanol solution is uniformly sprayed onto the surface of the composite metal particles at a low speed, and stirred at a higher speed until the composite metal particles are uniformly dispersed. After drying, composite metal particles with surface coupling treatment are obtained.

2. The positioning metal dry granules according to claim 1, characterized in that: The lower rotation speed in step A2 is 200-300 rpm; the spraying time is 10-16 min; and the higher rotation speed is 500-600 rpm.

3. The positioning metal dry granules according to claim 1, characterized in that: The coupling agent in the coupling agent-ethanol solution in step A2 is γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the mass concentration of the coupling agent in the coupling agent-ethanol solution is 8-12 wt%; and the mass of the coupling agent is 1.1-1.5 wt% of the total mass of the composite metal particles.

4. The positioning metal dry granules according to claim 1, characterized in that: The drying mentioned in step A2 refers to drying in a vacuum drying oven at 86-90℃ and a vacuum degree of -0.09MPa for 2.5-3.5 hours.

5. The positioning metal dry granules according to claim 1, characterized in that: The raw materials of the glass glaze, by weight, include 4.5-5 parts SiO2, 1.8-2.2 parts B2O3, 0.8-1.2 parts ZnO, 0.5-0.8 parts BaO, 0.2-0.3 parts NaO2, 0.2-0.3 parts K2O, 0.1-0.2 parts CaO, 0.1-0.2 parts MgO, and 0.1-0.2 parts Al2O3. After the raw materials of the glass glaze are mixed evenly, they are ball-milled through a 400-500 mesh sieve to obtain the glass glaze.

6. A method for preparing the positioning metal dry granules as described in any one of claims 1-5, characterized in that: The method for preparing the positioning metal dry granules includes the following steps: B1. Add the composite metal particles and glass glaze into a three-dimensional motion mixer in proportion and mix at 10-20 rpm for 6-8 hours to obtain the final product.

7. A glaze comprising the positioning metal dry particles as described in claim 1, characterized in that: The glaze is obtained by a preparation method including the following steps: positioning dry metal particles are sieved through an 80-100 mesh sieve, applied to the glazed surface of a pre-set area on the brick blank, sintered, and cooled to obtain the glaze.

8. The glaze according to claim 7, characterized in that: The application amount is 150-180 g / m2; the sintering refers to firing at 1150-1180℃ for 40-60 min and then holding at that temperature for 15-25 min.

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