Colored microcrystalline glass with textures as well as preparation method, preparation system and application of colored microcrystalline glass

Abstract

The invention relates to the field of glass manufacturing and glass processing, relates to colored microcrystalline glass with textures as well as a preparation method, a preparation system and application of the colored microcrystalline glass, and in particular relates to a preparation method of high-strength mixed-color textured microcrystalline glass. The invention provides a method for preparing high-strength mixed-color texture glass ceramics based on a controllable unsteady state melting two-step method. The method has the core advantages that controllable color mixing of glass melts with various colors can be realized in the melting stage, and then the glass melts with various colors can be obtained through an innovative casting molding process (particularly different from a vertical molding process of traditional horizontal casting). And a high-strength mixed-color glass ceramic blank with unique and adjustable texture effects (such as natural, gradual change and flowing texture) is cast at one time.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass manufacturing and glass processing, and relates to a colored microcrystalline glass with texture and a preparation method, a preparation system and an application thereof, in particular to a preparation method of high-strength mixed-color textured microcrystalline glass. BACKGROUND

[0002] Under the background of continuous and rapid iteration of intelligent terminal devices, microcrystalline glass is increasingly becoming the core material in the field of mobile terminal protection due to its excellent mechanical strength and other characteristics. At the same time, the user demand in the consumer electronics field has undergone profound changes, extending from basic functional demand to sensory experience. As an important carrier of tactile interaction and visual expression, the mobile phone back cover glass is also undergoing a transformation from pure protection to comprehensive aesthetic design. Therefore, the current intelligent terminal back cover glass is facing dual and closely related challenges: not only to meet the demanding high-strength performance requirements, but also to respond to the growing demand for deep aesthetic design.

[0003] In view of these needs, the existing solutions present significant limitations: the colored glass commonly used in the building field can provide rich color selection, but its material is mostly soda-lime glass, which is much lower in strength than the requirements of mobile terminal devices; the scheme of realizing color texture on a transparent strengthened glass substrate through a film pasting process introduces additional process cost, sacrifices real tactile feeling (hand feeling distortion), and may cause a decrease in environmental tolerance; and the microcrystalline glass obtained by homogeneous coloring technology to obtain a single uniform color, or the scheme of obtaining different regional color effects by splicing and melting colored and colorless glass, although solving the problem of single color or block color, is limited by the process itself, and cannot form natural, gradual and flowing advanced texture effects in the microcrystalline glass, making it difficult to meet the stringent demand of high-end market for personalized and artistic design.

[0004] Especially crucial is that in the technical route of exploring texture effect control, the existing technology has a significant focus deviation: it mainly focuses on the influence of chemical or thermal factors such as temperature regulation and component optimization on texture formation (which is important and basic), for example, CN115772001A discloses a color transparent glass composition, and US2024 / 0025801A1 discloses a microcrystalline glass with a haze of less than 0.6%, but generally ignores the direct influence of the casting (pouring) forming process itself in the production line on the texture form, distribution and performance effect of the final microcrystalline glass. This lack of attention to the key physical process (i.e. casting method) in the process conditions is one of the bottlenecks for realizing the above-mentioned advanced texture effect.

[0005] In view of the above technical status quo, the present application proposes a method for preparing high-strength mixed-color textured glass-ceramics based on controllable non-steady melting. The core advantage of this method is that it can achieve controllable mixing of multiple color glass melts during the melting stage, and then through an innovative vertical forming process (different from the traditional horizontal casting), a high-strength mixed-color glass-ceramic blank with unique and controllable texture effects (such as natural, gradual, and flowing texture) can be cast in one step. In particular, compared to the traditional horizontal casting process, the vertical forming process used in the present application can significantly reduce the melting stripe defects caused by the traditional casting method, while simultaneously improving the final strength and optical consistency of the glass. This method can effectively bridge the gap in existing technology and perfectly meet the stringent requirements of the 5G era and future intelligent terminals for high strength and deep aesthetic dual demands of structural components.

[0006] In addition, on the one hand, there are differences in understanding among those skilled in the art; on the other hand, the inventors have studied a large number of literatures and patents when making the present application, but due to space limitations, all details and contents have not been listed in detail. However, this does not mean that the present application does not have these features of the prior art, on the contrary, the present application already has all the features of the prior art, and the applicant reserves the right to add relevant prior art in the background art. SUMMARY

[0007] In view of the above technical problems, the present application relates to a colored glass-ceramic with texture and its preparation method, preparation system and application, in particular to a method for preparing high-strength mixed-color textured glass-ceramics.

[0008] One of the purposes of the present application is to provide a method for preparing a colored glass-ceramic with texture, which comprises the following steps: S1 Put the base component A and the coloring component B into two containers respectively and melt them; S2 Pour the coloring component B into the coloring component B, stir clockwise for 2-4 full circles, and control the rotation speed at 20-50 rpm to form a silk or strip texture; S3 After mixing and stirring, immediately control the temperature, holding and discharging of the mixed glass liquid based on the preparation process of glass-ceramics; S4 Pour the mixture into the mold at an inclination angle θ and a crucible moving rate v.

[0009] According to a preferred embodiment, the preparation process of the glass comprises the following steps: S3-1 respectively take the raw materials of the base component A and the coloring component B, mix the two raw materials respectively, put the uniform mixture into two platinum or quartz crucibles A and B, melt the mixture in the electric furnace or gas furnace at the temperature range of 1400~1600℃ for 5~24 hours according to the melting difficulty of the glass composition, and obtain the glass liquid by clarification and homogenization; S3-2 before casting, take out the base component A and the coloring component B, pour the coloring glass liquid in the B crucible into the A crucible, immediately stir the coloring glass liquid with the platinum stirrer, use the platinum stirrer, stir 2~4 whole circles in the clockwise direction, and control the rotation speed at 20~50 rpm; put the A crucible containing the base component and the coloring component back into the electric furnace or gas furnace at 500℃, and keep the temperature for 4 hours.

[0010] Preferably, the melting temperature in S3-1 is 1580℃. The melting time is 5 hours.

[0011] According to a preferred embodiment, in S3, the preparation process of the glass is the preparation process of the glass-ceramics, which comprises the following steps: After the mixing and stirring, immediately keep the mixed glass liquid at the melting temperature of not less than 1620℃; Then keep the temperature at 1520℃; Cool down to 1480℃ and keep the temperature.

[0012] According to a preferred embodiment, the base component A comprises one or more of SiO2, Al2O3, Na2O, Li2O, BaO, ZrO2 and P2O5.

[0013] According to a preferred embodiment, the coloring component B comprises one or more of Co3O4, Fe2O3, Nd2O3, V2O5, MnO2, CuO and TiO2.

[0014] According to a preferred embodiment, the base component A and the coloring component B can be set according to the proportion in Table 4.

[0015] According to a preferred embodiment, the texture regularity factor is not less than 1.2.

[0016] One of the purposes of the present application is also to provide a method for building a glass mold, which comprises the following steps: based on the limitation and requirement of the texture regularity factor of the glass product, pour the mixture into the mold at the inclination angle θ and the crucible moving speed v.

[0017] According to a preferred embodiment, the conditions for pouring into the mold refer to the following formula:

[0018] Wherein, is the texture regularity factor; is a regularity factor; is a melt density, unit: kg / m 3 ; is a gravity acceleration, unit: m / s 2 ; is a crucible inclination, unit: °; is a gate height, unit: m; is an optimal shear rate, unit: s -1 ; is a pouring temperature, unit: ℃; is a glass transition temperature, unit: ℃; is a zero shear viscosity, unit: Pa·s; …(2) wherein, is a crucible moving rate, unit: m / s; E is a rate coefficient; is an optimal shear rate, unit: s -1 ; L is a mold length, unit: mm; W is a mold width, unit: mm; H is a gate height, unit: m.

[0019] One of the purposes of the present application is also to provide a colored microcrystalline glass with texture, which is prepared based on the above preparation method.

[0020] One of the purposes of the present application is also to provide a preparation device of colored microcrystalline glass with texture, which comprises an information input module, an information processing module in signal connection with the information input module, and a mold set controlled by the information processing module. The information processing module is configured to: based on the texture regularity factor parameters and the regularity factor confirmed by the information input module, refer to the following formula:

[0021] wherein, is a texture regularity factor; is a regularity factor; is a melt density, unit: kg / m 3 ; is a gravity acceleration, unit: m / s 2 ; is a crucible inclination, unit: °; is a gate height, unit: m; is an optimal shear rate, unit: s -1 ; is a pouring temperature, unit: ℃; is a glass transition temperature, unit: ℃; is a zero shear viscosity, unit: Pa·s; the crucible inclination of the mold set is calculated.

[0022] One of the purposes of the present application is also to provide a use of the colored microcrystalline glass prepared by the above preparation method in the back plate or other appearance shell of electronic equipment.

[0023] One of the purposes of the present application is also to provide a method for building a glass mold, comprising the following steps: Based on the limitation and requirement of the texture regularity factor of the glass product, the mixture is poured into the mold at an inclination angle θ and a crucible moving rate v, and the pouring condition of the mold is referred to the following formula:

[0024] wherein, is the texture regularity factor; is the regularity coefficient; is the melt density, unit: kg / m 3 ; is the gravity acceleration, unit: m / s 2 ; is the inclination angle of the crucible, unit: °; is the gate height, unit: m; is the optimal shear rate, unit: s -1 ; is the pouring temperature, unit: ℃; is the glass transition temperature, unit: ℃; is the zero shear viscosity, unit: Pa·s; …(2) wherein, is the crucible moving rate, unit: m / s; E is the rate coefficient; is the optimal shear rate, unit: s -1 ; L is the mold length, unit: mm; W is the mold width, unit: mm; H is the gate height, unit: m.

[0025] The beneficial effects of the technical solution are: The mixed-color microcrystalline glass prepared by the technical solution of this invention differs from ordinary homogeneous colored glass, exhibiting rich colors and unique textures, significantly enhancing the aesthetic appeal of the product and better meeting the diverse and personalized needs of high-end customized designs. Crucially, this solution systematically optimizes key process steps such as multiple strengthening processes for different color combinations, and combines precise calculations of the mold-building tilting angle and pouring speed to achieve effective control over the final product's texture, ensuring the controllability of texture properties and the precise realization of design intent. Furthermore, the microcrystalline glass prepared using this molding method maintains a strength performance comparable to that of similar microcrystalline glass systems in the industry, fully demonstrating that this invention achieves complex texture effects without negatively impacting the core mechanical properties of the microcrystalline glass. Attached Figure Description

[0026] Figure 1 The casting mold involved in this invention; Figure 2 This refers to the process flow involved in this invention; Figure 3 This is a schematic diagram of the molten glass involved in the present invention after it has been poured into a casting mold. Detailed Implementation

[0027] In the description of this invention, terminology is used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly defined.

[0028] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the materials, reagents or instruments used, unless otherwise specified by the manufacturer, are all commercially available reagents and materials; the conditions not specified in the examples are all carried out according to conventional conditions or conditions recommended by the manufacturer. At the same time, the present invention does not limit the source of the raw materials used. Unless otherwise specified, the raw materials used in the present invention are all commercially available products in this technical field.

[0029] The texture regularity factor is a parameter strongly correlated with glass texture. The quantitative correspondence between the texture regularity factor and texture features is shown in Table 2.

[0030] The regularity coefficient is a core quantitative indicator for measuring the quality of glass surface texture. Its value directly determines the width, spacing, and quantity distribution characteristics of the texture.

[0031] Melt density refers to the mass per unit volume of molten glass in its molten state, and its unit is kg / m³. 3 .

[0032] The stress layer depth of colored microcrystalline glass was measured using electron probe microanalysis. This method utilizes electron microbeams to perform non-destructive chemical analysis on tiny samples, and can obtain precise quantitative elemental analysis results in the range of 1~2 μm. The crystal phase, crystal size, and crystallinity of colored microcrystalline glass were calculated by comparing X-ray diffraction with spectra in the Jade database.

[0033] The hardness of the colored microcrystalline glass was measured using a Vickers hardness tester according to standard GB / T 16534-2009. The specific testing procedure involved using a diamond pyramidal indenter with a 136° angle between the two faces to press a pyramid-shaped indentation into the test surface. The load (N) was divided by the surface area (mm) calculated from the length of the indentation. 2 The value of ) indicates that the experimental load is 100 (N) and the holding time is 20 (s).

[0034] The four-point bending strength of the colored microcrystalline glass was measured using a universal testing machine in accordance with standard JC / T 676-1997. The test conditions were: upper / lower span 20 / 40 cm, lowering speed 10 mm / min, and rod diameter 6 mm.

[0035] The impact resistance of colored microcrystalline glass was measured using a drop ball tester. Specifically, the glass sample to be tested was placed on a fixture, and a 130 g steel ball was dropped from a specified height. The maximum drop height from which the glass sample could withstand the impact without breaking was measured. Specifically, the test was conducted starting from a height of 15 cm, with the center point dropped three times, each time rising 10 mm, until the glass broke. The breakage height was recorded.

[0036] The whole machine sandpaper drop test for colored microcrystalline glass can be conducted using a mobile phone controlled drop tester of model GP 2112. The test conditions are: 180 grit sandpaper, 170 g total weight, 60 cm base height, increasing by 10 cm, once per height, until it breaks.

[0037] It should be understood that the above-mentioned testing methods and equipment are common methods for evaluating glass-related performance in this industry. They are only one means of characterizing or evaluating the technical solution and technical effect of this invention. Other testing methods and equipment may also be used, which will not affect the final result.

[0038] The features and performance of the present invention will be further described in detail below with reference to the embodiments. The present invention will be described in detail below through embodiments. According to the component ratios of each group in Examples 1 to 5 in Table 1 below, the raw materials corresponding to each component are calculated and weighed, and after being thoroughly stirred and mixed, they are put into the float glass furnace. After melting, clarifying, forming, annealing, cutting and other processes, a base glass with a thickness of 0.6 mm is obtained.

[0039] Example 1 A method for preparing colored microcrystalline glass, using the proportions described in Table 3, wherein SiO2, Al2O3, Na2O, K2O, ZrO2, BaO, and Li2O refer to compounds containing Si, Al, Na, Li, K, Zr, or Ba (such as carbonates, nitrates, sulfates, oxides, etc. containing the aforementioned elements) in the composition. Depending on the glass preparation method, the composition contains a clarifying agent; there are no particular limitations on the specific selection of the clarifying agent, which can be SO4. 2- NO 3- F - Cl - One or more of the following are used. Under heating conditions, SiO2, Al2O3, Na2O, K2O, ZrO2, BaO, and Li2O are mixed evenly and then melted at high temperature (1520~1680℃), clarified and homogenized, shaped, and annealed to obtain a base glass. Nucleation crystallization treatment is carried out according to the corresponding process to obtain microcrystalline glass. Then, deep processing such as cutting, CNC machining, and chemical strengthening is carried out according to the required size.

[0040] The casting method for colored microcrystalline glass adopts vertical casting, and the casting mold is arranged according to... Figure 1 As shown, the molten glass is placed in the mold and cooled in the mold, eventually yielding a glass ingot with dimensions of 160 mm * 20 mm * 80 mm. The mold is composed of four L-shaped cast iron workpieces, each with a thickness of 20 mm.

[0041] Specifically, the preparation method of the mixed-color textured glass-ceramic includes the following steps: S1 Weigh the raw materials of basic component A and coloring component B according to the aforementioned ratio, mix the two raw materials evenly, and put the uniform mixture into two platinum or quartz crucibles A and B. Depending on the melting difficulty of the glass composition, melt it in an electric furnace or gas furnace at a temperature range of 1580°C for 5 hours to clarify and homogenize the glass liquid. Before casting, S2 removes the base component A and the coloring component B, and pours the molten glass from crucible B into crucible A. Immediately stir with a platinum stirring rod until homogeneous, and use a platinum stirring paddle to stir clockwise for 2-4 full revolutions at a speed of 20-50 rpm. Place crucible A containing the base component and the coloring component back into an electric furnace or gas furnace at 500℃ and keep it at that temperature for 4 hours. After the S3 heat treatment is completed, the mixed glass liquid in crucible A is poured into the furnace at an angle θ and a moving speed v. Figure 1 In the mold shown, as Figure 3 As shown.

[0042] According to a preferred embodiment, the tilt angle θ and movement speed v are set under different conditions based on the requirements for the texture regularity factor of different color textures. The setting conditions are shown in the following formula:

[0043] The meanings of the symbols in the formula are shown in Table 1 below: Table 1

[0044]

[0045] The optimal shear rate is determined by the following formula:

[0046] The crucible tilt angle θ is determined by the following formula:

[0047] The crucible moving speed is determined by the following formula:

[0048] The quantitative correspondence between the Γ value and texture features is shown in Table 2 below: Table 2

[0049] After annealing, the glass is cooled to room temperature in the furnace and removed to obtain a workable mixed-color glass product with color texture.

[0050] Examples 2-5 were prepared using the same method as Example 1, except for the proportions of the compounds used, as shown in Table 3.

[0051] Example 6 The process steps that differ from those in Example 1 are S1 and S2, while the other process steps are the same.

[0052] S1 Weigh the raw materials of basic component A and coloring component B according to the aforementioned proportions, mix the two raw materials evenly, and put the uniform mixture into two platinum or quartz crucibles A and B. According to the melting difficulty of the glass composition, melt it in an electric furnace or gas furnace using the heating and holding methods described in Table 3, and clarify and homogenize to obtain glass melt. Before casting, S2 removes the base component A and the coloring component B, and pours the molten glass from crucible B into crucible A. Maintain a constant temperature of 1520℃, and immediately stir evenly with a platinum stirring rod. Use a platinum stirring paddle to stir clockwise for 2-4 full revolutions, with the speed controlled at 20-50 rpm. Cool crucible A containing the base component and the coloring component to 1480℃ and hold for 8 minutes.

[0053] Table 3

[0054] Comparative Example 1 This comparative example uses the same proportions as Example 1.

[0055] The preparation method includes the following steps: S1 Weigh the raw materials of the basic component and the coloring component according to the above proportion, mix all the raw materials evenly, put the uniform mixture into a platinum or quartz crucible, and melt it in an electric furnace or gas furnace at a temperature range of 1580°C for 5 hours according to the melting difficulty of the glass composition, clarify and homogenize to obtain colored glass liquid. After stirring S2 until homogeneous, the mixture is cooled to an appropriate temperature and poured into a mold. It is then slowly cooled to obtain a basic colored glass ingot. The colored glass ingot is placed in an annealing furnace and annealed at 500℃ for 4 hours. After annealing, it is cooled to room temperature in the furnace and removed to obtain a processable colored glass product.

[0056] Comparative Example 2 This comparative example uses the same proportions as Example 2.

[0057] The preparation method of this comparative example is the same as that of comparative example 1.

[0058] Table 4

[0059] Pre-test treatment like Figure 2 As shown in the process, the molded colored glass ingots (without grains) of the examples and comparative examples were subjected to microcrystallization treatment as shown in Table 5 to obtain colored microcrystalline glass ingots.

[0060] Table 5

[0061] Then, the microcrystalline glass ingots treated with microcrystallization in the examples and comparative examples were cut, ground, and polished to obtain a 140*70*0.6 mm colored microcrystalline glass substrate. For example... Figure 2 As shown, the colored microcrystalline glass substrate was chemically strengthened using the process parameters described in Table 6. After the process, the substrate was rapidly annealed in an annealing furnace to obtain the strengthened colored microcrystalline glass, which is then ready for further testing.

[0062] Table 6

[0063] The strengthening expansion of a 0.6 mm thick colored microcrystalline glass after chemical strengthening is 7.5%. The strengthening expansion (under the above strengthening conditions) is related to the machining dimensional parameters in actual applications and can be used as a reference for CNC machining.

[0064] Test results The performance of the colored microcrystalline glasses prepared in Examples 1-5 and Comparative Examples 1-2 was tested. The test results are shown in Table 7.

[0065] Table 7

[0066] It can be seen that, based on the process involved in this invention, especially the improvement of the injection molding process, the regularity of the texture can be effectively stabilized and controlled, and the compressive and crack resistance of the glass can be maintained while improving the color richness and aesthetics of the glass products, and some properties are even improved.

[0067] It should be noted that the specific embodiments described above are exemplary, and those skilled in the art can devise various solutions inspired by the disclosure of this invention. These solutions all fall within the scope of this invention and its protection. Those skilled in the art should understand that this specification and its accompanying drawings are illustrative and not intended to limit the scope of the claims. The scope of protection of this invention is defined by the claims and their equivalents.

Claims

1. A method for preparing textured colored glass, characterized in that, Includes the following steps: S1 base component A and coloring component B are melted in two separate containers; Pour coloring component B into coloring component B and stir clockwise for 2-4 full rotations at a speed of 20-50 rpm to form filamentous or strip-like textures. After mixing and stirring S3, the mixed glass liquid is immediately subjected to heating, heat preservation and discharge control based on the glass preparation process; S4 pours the mixture into the mold at an angle θ and a crucible moving speed v.

2. The preparation method according to claim 1, characterized in that, The basic component A includes one or more of SiO2, Al2O3, Na2O, Li2O, BaO, ZrO2, and P2O5.

3. The preparation method according to claim 1, characterized in that, The coloring component B contains one or more of Co3O4, Fe2O3, Nd2O3, V2O5, MnO2, CuO, and TiO2.

4. The preparation method according to claim 1, characterized in that, In step S3, the glass preparation process includes the following steps: After mixing and stirring, the mixed molten glass is immediately kept at a melting temperature of 1580℃; Then anneal to 500℃ and hold.

5. The preparation method according to claim 1, characterized in that, In step S3, the glass preparation process includes the following steps: After mixing and stirring, immediately keep the mixed glass liquid at a melting temperature of not less than 1620℃; Then keep warm at 1520℃; Cool down to 1480℃ and keep warm.

6. A textured colored microcrystalline glass, characterized in that, The colored microcrystalline glass is a colored microcrystalline glass prepared according to any one of the preparation methods described in claims 1 to 5.

7. The colored microcrystalline glass according to claim 6, characterized in that, The texture regularity factor of colored microcrystalline glass is not less than 1.

2.

8. The use of colored microcrystalline glass in the back panel or other exterior housing of electronic devices, characterized in that, The colored microcrystalline glass is prepared by any of the preparation methods described in claims 1 to 5, prepared by the preparation apparatus described in claim 6, or the colored microcrystalline glass described in claim 7.

9. A method for glass molding, characterized in that, It includes the following steps: Based on the constraints and requirements for the texture regularity factor of glass products, the mixture is poured into the mold at an inclination angle θ and a crucible moving speed v. The conditions for pouring into the mold are based on the following formula: in, This is the texture regularity factor; The regularity coefficient; This refers to the melt density, expressed in kg / m³. 3 ; This is the acceleration due to gravity, measured in m / s². 2 ; The angle of inclination of the crucible is expressed in degrees (°). This refers to the gate height, in meters (m). The optimal shear rate is expressed in seconds. -1 ; The pouring temperature is expressed in °C. Glass transition temperature, expressed in °C; Zero shear viscosity, measured in Pa·s; …（2） in, The crucible moving speed is expressed in m / s; E is the speed coefficient. The optimal shear rate is expressed in seconds. -1 L is the mold length in mm; W is the mold width in mm; H is the gate height in m.

10. An apparatus for preparing textured colored microcrystalline glass, characterized in that, The system includes an information input module, an information processing module connected to the information input module via a signal, and a mold assembly controlled by the information processing module. The information processing module is configured to: based on the texture regularity factor parameter and regularity coefficient confirmed by the information input module, refer to the following formula: in, This is the texture regularity factor; The regularity coefficient; This refers to the melt density, expressed in kg / m³. 3 ; This is the acceleration due to gravity, measured in m / s². 2 ; The angle of inclination of the crucible is expressed in degrees (°). This refers to the gate height, in meters (m). The optimal shear rate is expressed in seconds. -1 ; The pouring temperature is expressed in °C. Glass transition temperature, expressed in °C; Zero shear viscosity, measured in Pa·s; …（2） in, The crucible moving speed is expressed in m / s; E is the speed coefficient. The optimal shear rate is expressed in seconds. -1 L is the mold length in mm; W is the mold width in mm; H is the gate height in m. The crucible tilt angle and moving speed of the mold assembly were calculated.

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