A preparation method of foil crystal diamond or microcrystalline diamond and its application

Abstract

The present invention belongs to the field of ceramics, and discloses a method for preparing foil crystal diamond or microcrystalline diamond and its application. The preparation method comprises mixing raw materials such as aluminum oxide and soda ash, melting, rolling into sheets, and crushing and screening to obtain the obtained materials. In the preparation method of some examples of the present invention, the melt obtained by melting the raw materials has a certain viscosity and a long material property. When the molten metal overflows from the overflow port, it will not harden rapidly due to sudden cooling in contact with the air. It is not easy to flow and deform during the rolling process, and the rolled material is flat and uniform. The melting point of the prepared foil crystal diamond or microcrystalline diamond is greater than 1500°C. It is not easily affected when used in combination with ceramic materials such as glazes, dry particles, and new materials, and it is difficult to react with other materials. It has a wide range of applicability, and can retain its flake or granular form in tiles, shining brightly and flickering under natural light.

Description

Technical Field

[0001] The invention belongs to the field of ceramics, and in particular relates to a preparation method of foil crystal diamond or microcrystalline diamond and application thereof. Background Art

[0002] In the prior art, the materials used in ceramics are usually in granular or powdery form. In order to facilitate the production of fabric materials, the shapes are generally prepared in a smaller size, and the effect displayed on the surface of the ceramic tile is also limited.

[0003] Sheet materials can bring unique decorative effects to ceramics. With the rapid development of materials science, various materials are increasingly used in the ceramic field, and sheet materials have become a direction of ceramic material application.

[0004] When commonly seen flaky materials such as mica and rock flakes are applied to ceramics, they often react during the firing process of tiles due to their low temperature resistance, losing their original flaky structure or causing glaze defects.

[0005] Transparent materials have broad application prospects, including optical glass, crystals, transparent polymer materials, etc. They are widely used in people's daily life and other fields. Glass, as a traditional transparent material, is simple to prepare, but its low hardness, low melting point, poor wear resistance and other disadvantages limit its application in many fields. Crystals have a long growth cycle, high cost and small size. Although optical polymer materials have the advantages of good processing performance, low cost and not easy to break, their application is also limited by their flammability, low hardness, easy scratches and easy aging. Therefore, there is still a lack of high-hardness and heat-resistant transparent materials that can be used in the ceramic field. The sheet material used in the ceramsite glaze should be well integrated into the glaze layer and show its unique decorative effect. It is required to be relatively thin and the melting point is higher than the melting temperature of the glaze. The sheet material used for the ceramic glaze should generally not exceed 1.5 mm. The thin sheet material used in the ceramic field requires a certain hardness. The thin sheet material with poor hardness is easily affected by external forces and breaks, thus affecting the application effect. At the same time, the preparation of sheet materials should adjust the formula according to the needs so that the material has a certain ductility and long material property. Therefore, when preparing sheet materials, it is necessary to consider both the material formula and the control of the sheet thickness. The characteristics of the melt have a very significant impact on the quality of calendering, and it is relatively difficult to prepare sheet materials with uniform thickness. This puts higher requirements on the preparation process of sheet materials, which is also an important reason why there are fewer types of sheet materials used in ceramics in the prior art. Summary of the invention

[0006] The object of the present invention is to overcome at least one disadvantage of the prior art and to provide a method for preparing foil crystal diamond or microcrystalline diamond and its application.

[0007] The technical solution adopted by the present invention is:

[0008] The first aspect of the present invention provides:

[0009] A method for preparing foil crystal diamond or microcrystalline diamond comprises the following steps:

[0010] Prepare raw materials: the mass composition of the raw materials is 92-95 parts of aluminum oxide, 8-11 parts of soda ash, 1-2 parts of dolomite, 5-6 parts of calcite, and 0.5-0.8 parts of lithium fluoride, and mix the raw materials evenly;

[0011] Melting: Put the mixed raw materials into the furnace and fully melt them to obtain a melt;

[0012] Calendering: The melt is introduced into a calender and calendered into a sheet material strip with a thickness of 0.2 to 1.0 mm, and then water quenched, dried, crushed, screened, and iron removed to obtain foil crystal diamond or microcrystalline diamond;

[0013] The foil crystal diamond and the microcrystalline diamond have the same chemical composition. The foil crystal diamond is in the form of flakes with an average particle size of [280, 2000] μm and a thickness of 0.2 to 1.0 mm; the microcrystalline diamond is in the form of particles with an average particle size of [75, 280) μm.

[0014] In some examples, the chemical composition of the foil diamond or microcrystalline diamond is: Al 2 O 3 :85~98%,Na 2 O: 1~8%, CaO: 0.2~4%, MgO: 0.2~1%, Li 2 O: 0.1~0.6%, the remainder is impurities.

[0015] In some examples, the melting time is 2.5 to 4 h.

[0016] In some examples, the melting temperature is 1600-1900°C.

[0017] In some examples, the calendering speed is 4-8 m / s.

[0018] In some embodiments, during calendering, the temperature of the pressing roller is controlled not to exceed 1000°C.

[0019] The above technical features can be combined arbitrarily without conflict.

[0020] The second aspect of the present invention provides:

[0021] A ceramic tile, the glaze of which is added with foil crystal diamond or microcrystalline diamond prepared by the method described in the first aspect of the present invention.

[0022] In some embodiments, the firing temperature of the ceramic tile is 1140-1200°C.

[0023] In some embodiments, the firing time of the tile is 40 to 75 minutes.

[0024] The above technical features can be combined arbitrarily without conflict.

[0025] The beneficial effects of the present invention are:

[0026] The preparation method of some examples of the present invention optimizes the ratio of raw materials so that the melt obtained by melting the raw materials has a certain viscosity and a long material property. When the melt overflows from the overflow port, it will not harden rapidly due to sudden cooling in contact with air. It is not easy to flow and deform during the calendering process, and the calendered material is flat and uniform. Experimental data show that the decrease in quartz content and the increase in soda ash and dolomite content will lead to a decrease in the viscosity of the melt obtained by melting, poor plasticity, uneven thickness during the rolling process, distortion and deformation after calendering, and difficulty in obtaining sheet foil diamonds after crushing; if the alumina content increases beyond the range and the content of other fluxes is small, the formula melting temperature will increase sharply and the viscosity will rise sharply. The melt viscosity is too large to flow out and cannot be calendered; if the dolomite and calcite content in the raw materials increases beyond the range, excessive calcium oxide and magnesium oxide content will make the material opaque during the sintering process, and calcite will produce a large amount of gas when it is decomposed by heat, which will cause a large number of bubbles in the material, affecting the hardness and permeability of the material.

[0027] The melting point of the prepared foil diamond or micro-crystal diamond in the preparation method of some examples of the present invention is greater than 1500°C, and it is not easily affected when used in combination with ceramic materials such as glaze, dry particles, new materials, and it is difficult to react with other materials, and has wide applicability. The experimental results show that the foil diamond or micro-crystal diamond prepared by the method of the present invention will retain its original flake form or particle form during the firing process of ceramic tiles, shining brightly and flickering under natural light. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a photograph of the foil crystal diamond material sample of Example 1.

[0029] Figure 2 This is a photograph of the tile sample of Example 1.

[0030] Figure 3 This is a photograph of the microcrystalline diamond material sample of Example 2.

[0031] Figure 4 This is a photograph of the tile sample of Example 2.

[0032] Figure 5 This is a photograph of the tile sample of Example 3.

[0033] Figure 6 This is a photograph of the tile sample of Example 4.

[0034] Figure 7 This is a photograph of the tile sample of Example 5.

[0035] Figure 8 This is a photograph of the tile sample of Comparative Example 1.

[0036] Fig. 9 This is a photograph of the tile sample of Comparative Example 2.

[0037] Fig.10 This is a photo of the material of Comparative Example 3 after cooling.

[0038] Fig.11 This is a photo of the material of Comparative Example 4 after cooling.

[0039] Fig.12 This is a photograph of the tile sample of Comparative Example 5. DETAILED DESCRIPTION

[0040] The first aspect of the present invention provides:

[0041] A method for preparing foil crystal diamond or microcrystalline diamond comprises the following steps:

[0042] Prepare raw materials: the mass composition of the raw materials is 92-95 parts of aluminum oxide, 8-11 parts of soda ash, 1-2 parts of dolomite, 5-6 parts of calcite, and 0.5-0.8 parts of lithium fluoride, and mix the raw materials evenly;

[0043] Melting: Put the mixed raw materials into the furnace and fully melt them to obtain a melt;

[0044] Calendering: The melt is introduced into a calender and calendered into a sheet material strip with a thickness of 0.2 to 1.0 mm, and then water quenched, dried, crushed, screened, and iron removed to obtain foil crystal diamond or microcrystalline diamond;

[0045] The foil crystal diamond and the microcrystalline diamond have the same chemical composition. The foil crystal diamond is in the form of flakes with an average particle size of [280, 2000] μm and a thickness of 0.2 to 1.0 mm; the microcrystalline diamond is in the form of particles with an average particle size of [75, 280) μm.

[0046] In some examples, the chemical composition of the foil diamond or microcrystalline diamond is: Al 2 O 3 :85~98%,Na 2 O: 1~8%, CaO: 0.2~4%, MgO: 0.2~1%, Li 2 O: 0.1~0.6%, the remainder is impurities.

[0047] In the present invention, the main components of foil crystal diamond or microcrystalline diamond are aluminum oxide, sodium oxide, and calcium oxide. The extremely high aluminum oxide content can make the material have higher mechanical strength, can withstand various external loads, and has better wear resistance and corrosion resistance. It reduces the crystallization tendency and crystallization speed of the material, reduces the expansion coefficient of the material, makes the material adaptable to the glaze, dry particles, blanks and other materials used, makes the tiles less likely to crack or deform, and thus improves the thermal stability and chemical stability of the material.

[0048] In order to adapt to production conditions and melt the formula with high aluminum components, the alkali metal oxide and alkaline earth metal oxide components are added to reduce the overall melting temperature of the material. The addition of sodium oxide and calcium oxide as flux can greatly reduce the viscosity of the material melt and help clarify the material during the melting process, but the amount added should not be too much, as too much will greatly reduce the mechanical strength and stability of the material. Adding magnesium oxide to replace part of calcium oxide flux can reduce the material's devitrification tendency and crystallization rate.

[0049] Adding a small amount of lithium fluoride to the formulation can promote melt clarification and degassing, while reducing melt viscosity.

[0050] The rapid forming characteristics of the pressure roller can effectively avoid material crystallization, the material thickness is roughly uniform, and the production efficiency is greatly improved.

[0051] In some examples, the melting time is 2.5 to 4 hours. A longer melting time can allow the material to expel as much gas as possible during the firing process. Too many bubbles in the material will reduce its hardness and permeability and affect the effect.

[0052] In some examples, the melting temperature is 1600-1900° C. At this temperature, the raw materials can be fully melted to form a uniform melt, which is conducive to calendering and shaping.

[0053] In some examples, the calendering speed is 4-8 m / s. By controlling the calendering speed, the material thickness can be better controlled to avoid accidents caused by uneven force due to too fast feeding and accumulation of melt due to too slow feeding.

[0054] In some examples, the gap width of the pressing rollers is 0.2-1.0 mm. The gap width of the pressing rollers is controlled to have a suitable material thickness, which is convenient for tile production.

[0055] In some embodiments, the sheet material strip has a thickness of 0.2-1.0 mm. After being broken into pieces, the sheet material strip of this thickness can be well applied to the glaze surface.

[0056] In some examples, the average particle size of the foil crystal diamond is [280, 2000] μm and the thickness is 0.2-1.0 mm. Foil crystal diamonds of this size can be easily laid while retaining the unique decorative effect of its sheet material.

[0057] In some examples, the average particle size of the microcrystalline diamond is [75, 280) μm. Microcrystalline diamonds of this size can be easily distributed while retaining the unique decorative effect of its granular material.

[0058] In some embodiments, during calendering, the temperature of the pressing roller is controlled not to exceed 1000°C.

[0059] The above technical features can be combined arbitrarily without conflict.

[0060] The second aspect of the present invention provides:

[0061] A ceramic tile, the glaze of which is added with foil crystal diamond or microcrystalline diamond prepared by the method described in the first aspect of the present invention.

[0062] In some embodiments, the firing temperature of the ceramic tile is 1140-1200°C.

[0063] In some embodiments, the firing time of the tile is 40 to 75 minutes.

[0064] Tiles can be laid using a variety of existing methods, including but not limited to:

[0065] Antique craft: In inkjet design, the production method of spraying or pouring materials is combined with other materials for positioning or the entire surface is applied with foil crystal diamonds or microcrystalline diamonds and fired.

[0066] Polishing process: In inkjet design, the production method of spraying or pouring materials is combined with other materials for positioning or the entire surface is applied with foil crystal diamond or micro-crystal diamond, fired, fully polished, semi-polished, soft polished or not polished.

[0067] Body process: mix foil crystal diamond or micro-crystal diamond with other materials or digitally position it into the whole body or thin layer of cloth, press it into shape, apply or not apply protective glaze, fire it, and fully polish, semi-polish, soft polish or no polish.

[0068] The above technical features can be combined arbitrarily without conflict.

[0069] The following disclosure provides various different embodiments or examples to implement different solutions of the present invention.

[0070] In the following examples, unless otherwise specified, the parts are parts by mass and the percentages are all percentages by mass.

[0071] The raw material compositions of foil crystal diamond or microcrystalline diamond in different examples are shown in Table 1.

[0072] Table 1. Raw material composition by mass of different examples of foil crystal diamond or microcrystalline diamond

[0073]

[0074] The preparation processes of different examples of foil crystal diamond or microcrystalline diamond are as follows:

[0075] The raw materials are weighed and mixed according to the proportion, put into the furnace and completely melted, and then overflow from the overflow port. The amount of molten liquid overflowing is controlled, and it continuously flows into the calender through the receiving groove, passes through the gap between a pair of water-cooled rollers, and the calendering speed and the gap width of the rollers are controlled to roll into a sheet material strip of the required thickness, and then introduced into the water tank for water quenching and drying. It is processed and crushed by a hammer crusher, and then vibrated and screened horizontally to remove iron. For crushed materials with larger particle sizes, they are further crushed. According to the use requirements, the crushed materials after iron removal are screened with screens of different specifications to obtain particles of the required particle size. Among them, the foil crystal diamond is in the form of flakes, with an average particle size of [280, 2000] μm and a thickness of 0.2-1.0 mm. The foil crystal diamond can be further screened into various specifications such as [280, 500) μm, [500, 1000) μm, [1000, 2000) μm, and [330, 600) μm; the microcrystalline diamond is in the form of particles, with an average particle size of [75, 280) μm. The microcrystalline diamond can also be further screened into various specifications such as [75, 100) μm, [100, 150) μm, [150, 200) μm, and [200, 280) μm. When in use, at least one of the foil crystal diamond and the microcrystalline diamond can be selectively used according to the needs. If necessary, foil crystal diamond and microcrystalline diamond of different specifications can be mixed. The specific preparation process parameters of foil crystal diamond or microcrystalline diamond are shown in Table 2.

[0076] Table 2. Preparation process parameters of foil crystal diamond or microcrystalline diamond in different examples

[0077]

[0078] In the table, “ / ” indicates not used.

[0079] According to tests, the melting points of different examples of foil crystal diamond or microcrystalline diamond are not less than 1500℃, which is significantly higher than the general firing temperature of ceramic tiles (around 1300℃), and has good thermal stability.

[0080] The preparation methods of different example tiles are as follows:

[0081] Example 1

[0082] Process flow: blank → glaze → inkjet design → glaze spraying → foil crystal diamond application → glue spraying to fix → protective glaze spraying → drying → firing.

[0083] Representative photos of foil diamonds obtained by crushing and screening are shown in Figure 1 As shown in the figure, it has a typical flaky structure, transparent, crystal clear, and has a strong gloss. Figure 2 As shown, from Figure 2It can be seen that there is a clearly visible flaky foil crystal effect in the glaze layer, which sparkles under natural light and retains the characteristics of the foil crystal itself.

[0084] Example 2

[0085] Process flow: blank → glaze → inkjet design → glaze spraying → micro-crystal drilling → glue spraying to fix → protective glaze spraying → drying → firing.

[0086] Representative photos of microcrystalline diamond obtained by crushing and screening are shown in Figure 3 As shown in the figure, the particles are transparent, crystal clear and have a strong gloss. Figure 4 As shown, from Figure 4 It can be seen that there is a clearly visible granular microcrystalline diamond effect in the glaze layer, which sparkles under natural light.

[0087] Example 3

[0088] Process flow: blank → glaze → inkjet design → glaze spraying → foil crystal diamond application → glue spraying to fix → protective glaze spraying → drying → firing.

[0089] Photos of fired tiles Figure 5 As shown, from Figure 5 It can be seen that there is a clearly visible flaky foil crystal effect in the glaze layer, which sparkles under natural light.

[0090] Example 4

[0091] Process flow: blank → glaze → inkjet design → glaze spraying → micro-crystal drilling → glue spraying to fix → protective glaze spraying → drying → firing.

[0092] Photos of fired tiles Figure 6 As shown, from Figure 6 It can be seen that there is a clearly visible granular microcrystalline diamond effect in the glaze layer, which sparkles under natural light.

[0093] Example 5

[0094] Process flow: green body particles → foil crystal drilling, microcrystalline drilling → pressing and molding → inkjet printing → protective glaze → drying → firing.

[0095] Photos of fired tiles Figure 7 As shown, from Figure 7 It can be seen that there are clearly visible flake foil crystal diamonds and granular micro-crystal diamond effects in the blank, which sparkle under natural light.

[0096] Comparative Example 1

[0097] Process flow: blank → glaze → inkjet design → glaze spraying → foil crystal diamond application → glue spraying to fix → protective glaze spraying → drying → firing.

[0098] Photos of fired tiles Figure 8As shown, from Figure 8 It can be seen that the foil crystal diamond is too thick, which makes it difficult to bond during the laying process and protrudes too much from the surface of the glaze layer, resulting in the laying design being offset and the surface of the fired tile being rough and uneven.

[0099] Comparative Example 2

[0100] Process flow: blank → glaze → inkjet design → glaze spraying → foil crystal diamond application → glue spraying to fix → protective glaze spraying → drying → firing.

[0101] Photos of fired tiles Fig. 9 As shown, from Fig. 9 It can be seen that the foil crystal diamond is relatively thin, the hardness is reduced, and it is easy to break during the crushing process. The yield of the obtained flaky foil crystal diamond is low and the material is relatively fine.

[0102] Comparative Example 3

[0103] Compared with Example 1, the quartz content in the formula of Comparative Example 3 is reduced, the soda ash and dolomite contents are increased beyond the range, the viscosity of the formula is reduced, the plasticity is poor, and the fluidity is poor during the roller calendering process, resulting in uneven thickness and distortion after calendering.

[0104] After the material is cooled, Fig.10 As shown, from Fig.10 It can be seen that the materials are in various shapes, few of which are in flaky form.

[0105] Comparative Example 4

[0106] Compared with Example 3, the alumina content in the formula of Comparative Example 4 increased beyond the range, the content of other fluxes was relatively small, the viscosity of the formula increased sharply as the melting temperature increased, and the viscosity of the melt was too high to flow out.

[0107] After the material is cooled, Fig.11 As shown, from Fig.11 It can be seen that the material is difficult to flow and clumps, and cannot be rolled.

[0108] Comparative Example 5

[0109] Process flow: blank → glaze → inkjet design → glaze spraying → foil crystal diamond application → glue spraying to fix → protective glaze spraying → drying → firing.

[0110] Compared with Example 1, the dolomite and calcite contents in the formula of Comparative Example 5 are increased beyond the range, and excessive contents of calcium oxide and magnesium oxide will make the material opaque during the firing process, and calcite will produce a large amount of gas when decomposed by heat, which will cause a large number of bubbles in the material.

[0111] Photos of fired tiles Fig.12 As shown, from Fig.12 It can be seen that it affects the hardness and permeability of the material.

[0112] The above is a further detailed description of the present invention, which should not be regarded as a limitation on the specific implementation of the present invention. For ordinary technicians in the technical field to which the present invention belongs, simple deduction or replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. A method for preparing foil crystal diamond or microcrystalline diamond, characterized in that: The steps include: Prepare raw materials: the mass composition of the raw materials is 92-95 parts of aluminum oxide, 8-11 parts of soda ash, 1-2 parts of dolomite, 5-6 parts of calcite, and 0.5-0.8 parts of lithium fluoride, and mix the raw materials evenly; Melting: Put the mixed raw materials into the furnace and fully melt them to obtain a melt; Calendering: The melt is introduced into a calender and calendered into a sheet material strip with a thickness of 0.2 to 1.0 mm, and then water quenched, dried, crushed, screened, and iron removed to obtain foil crystal diamond or microcrystalline diamond; The foil crystal diamond and the microcrystalline diamond have the same chemical composition. The foil crystal diamond is in the form of flakes with an average particle size of [280, 2000] μm and a thickness of 0.2 to 1.0 mm; the microcrystalline diamond is in the form of particles with an average particle size of [75, 280) μm.

2. The preparation method according to claim 1, characterized in that: The chemical mass composition of the foil crystal diamond or microcrystalline diamond is: Al2O3: 85-98%, Na2O: 1-8%, CaO: 0.2-4%, MgO: 0.2-1%, Li2O: 0.1-0.6%, and the remainder is impurities.

3. The preparation method according to claim 1, characterized in that: The melting time is 2.5 to 4 hours.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The melting temperature is 1600-1900°C.

5. The preparation method according to any one of claims 1 to 3, characterized in that: The calendering speed is 4-8 m / s.

6. The preparation method according to any one of claims 1 to 3, characterized in that: During calendering, the temperature of the pressing roller is controlled not to exceed 1000°C.

7. A ceramic tile, characterized in that: The glaze surface is added with the foil crystal diamond or microcrystalline diamond as claimed in any one of claims 1 to 6.

8. The tile according to claim 7, characterized in that: The firing temperature of the ceramic tile is 1140-1200°C.

9. The ceramic tile according to claim 7 or 8, characterized in that: The firing time of the ceramic tile is 40 to 75 minutes.

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