Iridescence white glaze base, glaze slurry, glaze surface, glaze surface product and preparation method

Abstract

The present application discloses a rainbow color white glaze base material, a glaze slurry, a glaze surface, a glaze surface product and a preparation method. The present application does not use traditional harmful elements such as lead and vanadium as the formula of the rainbow color glaze. After high-temperature sintering treatment, the rainbow color white glaze surface can be successfully obtained. By controlling the microstructure of the glaze layer and the glaze formula, the harm to human beings and nature during production and use is greatly reduced.

Description

Technical Field

[0001] This invention belongs to the field of ceramic iridescent glaze technology, specifically relating to an iridescent white glaze base material, glaze slurry, glaze surface, glaze surface products, and preparation method. Background Technology

[0002] Rainbow glaze is a special ceramic glaze that can display multi-colored interference light like a rainbow under different viewing angles. It can present different color effects depending on the viewing angle.

[0003] Most commercially available ceramic iridescent glazes are lead-based, utilizing lead's high refractive index to create optical interference and thus produce an iridescent color-changing effect. However, lead is a harmful substance; it slowly leaches from the glaze surface under weak acid, high temperature, or prolonged contact, leading to unstable iridescent effects and potential health risks. While the International Agency for Research on Cancer (IARC) has not classified lead as a Group 1 carcinogen, it is classified as "possibly carcinogenic," so long-term exposure requires caution. Furthermore, the addition of lead lowers the glaze's firing temperature, resulting in slower or incomplete iridescent formation. Vanadium is often added to lead-zinc systems to promote crystallization, but vanadium may also be harmful to health and affect the iridescent effect. Therefore, there is a need to find an environmentally friendly glaze that can create a stable iridescent effect. Summary of the Invention

[0004] 1. The problem to be solved To address the problem of unstable iridescent effect in existing lead-containing iridescent glazes, the primary objective of this invention is to provide a base material for iridescent white glazes. A second objective of the present invention is to provide an iridescent white glaze slurry comprising the aforementioned glaze base material; A third objective of this invention is to provide a method for preparing the aforementioned iridescent white glaze slurry; A fourth objective of the present invention is to provide a glaze surface obtained using the above-described iridescent white glaze slurry; The fifth objective of this invention is to provide glazed products obtained using the above-mentioned iridescent white glaze slurry.

[0005] 2. Technical Solution To solve the above problems, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides an iridescent white glaze base material, comprising, by weight: 1-10 parts of kaolin; 26-34 parts of quartz; 1-12 parts talc; 14-24 parts zinc oxide; 2-19 parts of albite; 12-21 parts of calcite; Borax 12-19 parts.

[0006] According to any embodiment of the first aspect of the present invention, the iridescent white glaze base material comprises, by weight: 5-9 parts of kaolin; 26-30 parts of quartz; 4-8 parts talc; 18-21 parts zinc oxide; 8-12 parts of albite; 13-19 parts of calcite; Borax 12-19 parts.

[0007] According to any embodiment of the first aspect of the present invention, the iridescent white glaze base material comprises, by weight: 3-10 parts of kaolin; 26-30 parts of quartz; 4-8 parts talc; 14-21 parts zinc oxide; 8-19 parts of albite; 12-19 parts of calcite; Borax 12-19 parts.

[0008] In the aforementioned iridescent white glaze base material, quartz serves as the core network forming agent, constituting the basic framework of the glaze layer, and also acts as a key regulator of the rheological properties of the high-temperature melt. Boron acts as both a network forger and a network modifier. It can form BO trihedrons, improving chemical stability, and also efficiently flux in the low-temperature region (<1150℃), lowering the melting point, saving energy, and being more environmentally friendly. Introducing boron into glazes has several advantages. First, during the high-temperature melting stage, the boron-rich phase formed by the enrichment of boron components exhibits low viscosity. This significantly reduces the overall surface tension and viscosity of the high-temperature melt, resulting in better migration ability of SiO2 units within the system. This promotes their movement under gravity settling and interfacial energy, thus facilitating the formation of a highly ordered microstructure. Second, during cooling... During the curing stage, cations such as Ca, Mg, and Na in the glaze tend to accumulate at the interface between the already formed silicon-rich and boron-rich phases. This behavior, driven by the minimization of interfacial energy, forms a transitional interfacial layer with a gradual change in composition. This effectively alleviates the interfacial stress caused by the mismatch in the thermal expansion coefficients of the two phases during subsequent cooling, thereby significantly suppressing the generation of microcracks and the destruction of the ordered photonic crystal structure. Under the migration of different ions, films with different compositional gradients are formed on the glaze surface. These films together constitute a photonic crystal structure that satisfies the Bragg diffraction conditions, giving the glaze a bright iridescent effect.

[0009] Zinc oxide serves both as a flux and an increase in refractive index. By introducing zinc oxide, the refractive index of the glaze layer is increased, resulting in a higher gloss and stronger iridescent effect in the iridescent glaze, and making it more environmentally friendly.

[0010] The key to forming iridescent colors lies in the formation of nanoscale crystals or crystalline films within the glaze layer, creating a special photonic crystal structure. This structure is a regular structure composed of two or more substances with different dielectric constants arranged in an orderly manner according to certain rules, resulting in photonic bandgap characteristics. Light waves within the bandgap cannot propagate through the crystal and are strongly reflected. If the reflected wave is within the visible light range, structural colors, i.e., photonic crystal structural colors, will be generated. The optical path difference is generated by the refractive index difference between the film layers in the glaze layer, further triggering optical interference. After the visible light undergoes both reflection and interference, an iridescent effect is caused, thus giving the glaze surface an iridescent color-changing effect.

[0011] According to any embodiment of the first aspect of the present invention, the mass ratio of borax:zinc oxide:quartz is (12~19):(14~24):(26~34).

[0012] The mass ratio of borax, zinc oxide, and quartz described herein affects the refractive index and interlayer spacing of the glaze, resulting in a photonic crystal structure without a fixed single reflected color. Under normal conditions, the multi-band reflected light in the visible light spectrum appears as white, but when the viewing angle is changed, an optical interference effect is generated, exhibiting a dynamic iridescent luster, thus forming the base material for iridescent white glaze.

[0013] Specifically, the mass ratio of borax to quartz affects the interlayer spacing, and thus the iridescent effect. The mass ratio of borax to quartz is (12~19):(26~34). Adding excessive borax partially acts as a flux, and secondly, due to the significant difference in the field strength between silicon and boron ions, it causes phase separation, forming a quasi-periodic phase-separated structure at the microscale. If this ratio is too high, the borax content is too high, resulting in excessive B2O3 in the glaze layer. This leads to excessively low melt viscosity, excessive phase separation, and easy disorder or disappearance of the layered structure, causing the glaze surface to turn blue or shift in hue, thus weakening or eliminating the iridescent effect. If the content is too low, the quartz content is too high, resulting in insufficient melting and increased residual quartz. This residual quartz will crystallize during firing and cooling, increasing the number of glaze grains, roughening the surface, and reducing transparency, thus weakening or eliminating the iridescent effect.

[0014] The mass ratio of zinc oxide to quartz affects the refractive index, and the ratio is (14~24):(26~34). Zinc oxide provides a high refractive index, creating a strong contrast with the low refractive index of quartz, thus producing an iridescent effect. If this ratio is too high, the zinc oxide content is too high, which will reduce the melt viscosity and make it difficult for gases to escape during firing, resulting in bubbles and pinholes on the fired glaze surface, thus weakening or eliminating the iridescent effect. If the content is too low, when the quartz content is too high, melting is insufficient, and the amount of residual quartz increases, which will cause crystallization during firing and cooling, increasing the number of glaze grains, making the surface rough and reducing transparency, thus weakening or eliminating the iridescent effect.

[0015] The second aspect of the present invention provides an iridescent white glaze slurry, comprising the iridescent white glaze base material described in the first aspect of the present invention.

[0016] A third aspect of this invention provides a method for preparing an iridescent white glaze slurry, comprising the steps of: Prepare a wet material containing a glaze base material, wherein the glaze base material includes the iridescent white glaze base material described in any embodiment of the first aspect of the present invention; The wet material containing the glaze base material is aged.

[0017] According to any embodiment of the third aspect of the present invention, the method for preparing iridescent white glaze slurry, wherein the aging treatment temperature is 10~30℃ and the treatment time is 12~36h.

[0018] The method for preparing an iridescent white glaze slurry according to any embodiment of the third aspect of the present invention includes the steps of: grinding the glaze base material, obtaining a wet material containing the glaze base material with the participation of water, wherein the moisture content of the wet material is not less than 40%, preferably 40% to 50%.

[0019] As described herein, one possible approach is to prepare the various raw materials of the glaze base material in the specified amounts, and then wet-mill the prepared glaze base material using a solvent (e.g., water) (e.g., wet ball milling) to obtain a wet material containing the glaze base material that meets the particle size requirements; in this case, the mass ratio of glaze, balls, and solvent used for wet milling is 1:(1~3):(0.8~1.2). Alternatively, one can first prepare a suitable amount of iridescent white glaze base material, and then add a suitable amount of water to obtain a wet material containing the glaze base material.

[0020] The iridescent white glaze surface according to any embodiment of the fourth aspect of the present invention comprises the iridescent white glaze base material according to any embodiment of the first aspect of the present invention, or the iridescent white glaze slurry according to any embodiment of the second aspect of the present invention, or the iridescent white glaze slurry obtained by the preparation method according to any embodiment of the third aspect of the present invention.

[0021] According to any embodiment of the fourth aspect of the present invention, the iridescent white glaze has Lab values ​​of L=89~95, a=-4~0, and b=0~3.

[0022] Where L represents the brightness value; a represents the value on the red-green axis; and b represents the value on the yellow-blue axis.

[0023] According to any embodiment of the fourth aspect of the present invention, the iridescent white glaze comprises: at least one layered structure and a phase-separated structure; and / or, The glaze depth is ≤2μm, and the iridescent white glaze includes a layered structure; and / or, The glaze depth is >2μm, and the iridescent white glaze includes a phase-separated structure; and / or, The thickness of the iridescent white glaze is 1-3 mm.

[0024] According to any embodiment of the fourth aspect of the present invention, the iridescent white glaze has a quasi-periodic layered structure; and / or, The interlayer spacing of the layered structure is 100nm-800nm.

[0025] The term "quasi-periodicity" as used here is defined as a phenomenon that exhibits a certain regularity of repetition, but does not strictly follow a regular pattern of repetition.

[0026] According to any embodiment of the fourth aspect of the present invention, the iridescent white glaze surface comprises a first phase and a second phase, wherein the first phase is wrapped around the surface of the second phase; the second phase is particles; and / or the particle size is <2μm.

[0027] According to any embodiment of the fourth aspect of the present invention, the second phase comprises at least one of Ca, Zn, Mg, Na, and B; The first phase is a glass phase, which contains at least one of Si and Al.

[0028] After being fired at high temperature, the base material of the iridescent white glaze forms a granular second phase with a particle size of <2μm. These particles are rich in Ca, Zn, Mg, Na, and B ions, surrounded by a glassy phase rich in Si and Al. These droplet-like particles are enriched particles of the second phase formed during liquid-liquid phase separation in the glaze layer during firing. During firing, the B-rich and Si-rich phases separate in the glaze melt, while Ca, Mg, Zn, and Na cations enrich in localized areas of the B-rich phase, forming droplet-like dispersed phases. Subsequently, during cooling, the melt viscosity increases, and the droplet morphology is fixed, thus manifesting as droplet-like particles in the microstructure.

[0029] The fifth aspect of this invention provides a method for preparing an iridescent white glaze, comprising the steps of: (1) Prepare the iridescent white glaze slurry according to any embodiment of the second aspect of the present invention, or the iridescent white glaze slurry obtained by the preparation method according to any embodiment of the third aspect of the present invention; (2) Apply the above-mentioned glaze slurry to the surface of the unglazed body and dry it after glazing; (3) The dried sample is sintered at high temperature.

[0030] According to any embodiment of the fifth aspect of the present invention, the method for preparing an iridescent white glaze is wherein the sintering holding temperature is 1100℃~1250℃ and the sintering holding time is 30~100min.

[0031] The temperature effect on the layering effect described above specifically refers to the changes in the fluidity of the glaze melt, the component diffusion rate, and the phase separation kinetics as the sintering temperature increases within the aforementioned temperature range. These changes affect the formation and stability of the layered phase separation structure in the borosilicate system. When the temperature is too low, the glaze melts insufficiently, and the microstructure is difficult to spread uniformly, resulting in an indistinct layering effect. When the temperature is moderate, the melt undergoes phase separation at an appropriate viscosity and freezes during cooling, forming a clearer quasi-periodic layered structure, which is beneficial for the generation of iridescent effects. When the temperature is too high, the melt flows excessively and tends to homogenize, causing the original layered structure to become disordered or merge and disappear, thus weakening or eliminating the iridescent effect.

[0032] During the sintering process, due to the significant difference in the field strength of silicon and boron ions, phase separation occurs in the glaze, forming liquid phase separation. This results in the formation of micron-sized spherical particles in the glaze. Through Stokes migration, droplets of the same density float or sink, thus forming a continuous and flat optical thin film layer—an interference layer. The thin film interference caused by the continuous film with uniform thickness generated by this phase separation results in an angle-dependent iridescent effect on the glaze surface. The photonic micro-nano structure of the glaze layer generated by this in-situ self-assembly method has higher density and higher color gloss, resulting in a higher saturation of angle-dependent iridescent colors on the glaze surface. This structure can remain unchanged for a long time during product use, with better optical stability, and the color is durable, stable, and not easy to fade.

[0033] In addition, the phase-separated particles precipitated in the glaze layer are micron-sized, which will cause Mie scattering effect. Furthermore, since the outer layer of the phase-separated particles is enriched with high-refractive-index cations such as Ca, Zn, and Mg, while the inner layer is a low-refractive-index material, the reflection of incident light is further enhanced, resulting in the glaze surface appearing milky white.

[0034] The sixth aspect of the present invention provides an iridescent white glazed product, the glazed product comprising a glaze made using an iridescent white glaze base material as described in any embodiment of the first aspect of the present invention, an iridescent white glaze slurry as described in any embodiment of the second aspect of the present invention, or an iridescent white glaze slurry obtained by a preparation method as described in any embodiment of the third aspect of the present invention.

[0035] According to the sixth aspect of the present invention, the iridescent white glaze product includes, but is not limited to, any one of ceramic products, glass products and fine ceramic products.

[0036] Because boron forms a stable BO trihedron, the leaching amount of boron glaze is <0.01 mg / L (national standard limit 0.05 mg / L), so the finished products made using this glaze can be directly placed in microwave ovens and dishwashers.

[0037] Meanwhile, the boron network exhibits high chemical stability; when placed in 4% acetic acid for 24 hours, its acid-resistant weight loss is only 0.2 mg / cm², which is an order of magnitude better than lead enamel.

[0038] This invention produces an iridescent effect by adding harmless substances such as boron oxides to the base material formula, thereby replacing heavy metals such as lead, manganese, and vanadium and eliminating the harm of heavy metals to human health during glaze preparation, glazing, firing, and finished product use. Boron is a special network forming agent that can play an excellent role in phase separation and fluxing, while also saving costs and being environmentally friendly. Furthermore, it can flexibly control the thermal expansion coefficient of the glaze layer, making the body better resistant to cracking or peeling, and at the same time, it can better promote the formation of the structure required to produce iridescence, resulting in a better iridescent effect.

[0039] 3. Beneficial Effects Compared with the prior art, the beneficial effects of the present invention are as follows: (1) In this invention, borax, zinc oxide and quartz are added to the base material of iridescent white glaze and the mass ratio is limited. During the high-temperature sintering process, based on the significant difference in the field strength of silicon and boron ions, phase separation behavior is easy to occur, forming a microscale quasi-periodic layered phase separation structure. This special photonic structure will form a certain degree of interference and scattering effect on visible light, and promote the formation of a controllable iridescent effect on the surface of the glaze layer. (2) In this invention, borax and quartz are added to the base material of iridescent white glaze and the mass ratio is limited. During the cooling and solidification stage, cations such as Ca, Mg, and Na in the glaze tend to accumulate at the interface between the already formed silicon-rich phase and the boron-rich phase. This behavior is driven by the minimization of interfacial energy to form a transitional interface layer with gradually changing composition. This effectively alleviates the interfacial stress caused by the mismatch of the thermal expansion coefficients of the two phases during the subsequent cooling process, thereby significantly suppressing the generation of microcracks and the destruction of the ordered photonic crystal structure, and improving the integrity of the glaze surface. (3) The glaze surface formed by the iridescent white glaze of the present invention has a layered structure. Micron-sized droplet-shaped particles are formed in the glaze. Then, through Stokes migration, droplets of the same density float or sink to form a continuous and flat optical thin film layer, i.e., an interference layer. Different film layers have different compositions and different refractive indices, which not only makes the glaze surface exhibit angle-dependent iridescence, but also enhances the overall texture and iridescence presentation effect of the glaze surface by enhancing the scattered light. The photonic crystal particles are formed by in-situ self-assembly, which has higher density and higher color gloss. The inherent density also has a reinforcing effect, making the angle-dependent iridescent saturation of the glaze surface higher, the optical stability better, and the color more durable and stable and less prone to fading. (4) The iridescent white glaze of the present invention does not use heavy metal elements such as lead and vanadium as raw materials for iridescent glaze, and does not contain harmful substances. By controlling the microstructure of the glaze melt during the sintering process, the optical path difference is formed by the refractive index difference between the film layers, resulting in the interference effect of light, thereby forming an iridescent effect on the glaze surface. The iridescent color meets the color needs of consumers, the preparation process is simple, easy to operate, low cost, green and environmentally friendly, and easy to promote on a large scale. It has a wide market demand in the ceramic industry. Attached Figure Description

[0040] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. However, it should be understood that these drawings are designed for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless specifically indicated, these drawings are intended only to conceptually illustrate the structural construction described herein and are not necessarily drawn to scale.

[0041] Figure 1 The image shows the glaze surface of the glazed product prepared in Example 1, tilted at a 35° angle. o ; Figure 2 The image shows the glaze surface of the glazed product prepared in Example 1, tilted at an angle of 40°. o ; Figure 3 The image shows the glaze surface of the glazed product prepared in Example 1, tilted at an angle of 55 degrees. o ; Figure 4 Here is a SEM image of the glazed product prepared in Example 1; Figure 5 The image shows the glaze surface of the glazed product prepared in Comparative Example 1. Figure 6 The image shows the glaze surface of the glazed product prepared in Comparative Example 3. Figure 7 The image shows the glaze surface of the glazed product prepared in Comparative Example 5. Figure 8 The image shows the glaze surface of the glazed product prepared in Comparative Example 7. Detailed Implementation

[0042] The following detailed description of exemplary embodiments of the invention is taken with reference to the accompanying drawings, which form part of the description and illustrate exemplary embodiments in which the invention may be practiced. While these exemplary embodiments have been described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be implemented and various changes may be made to the invention without departing from the spirit and scope thereof. The more detailed description of embodiments of the invention below is not intended to limit the scope of the claimed invention, but is merely illustrative and not restrictive of the description of the features and characteristics of the invention, to suggest the best mode for carrying out the invention, and is sufficient to enable those skilled in the art to practice the invention. Therefore, the scope of the invention is defined only by the appended claims.

[0043] This disclosure will be more readily understood by referring to the following description, taken in conjunction with the accompanying drawings and examples, all of which form part of this disclosure. It should be understood that this disclosure is not limited to the specific products, methods, conditions, or parameters described and / or illustrated herein. Furthermore, the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting, unless otherwise stated.

[0044] It should be noted that the terminology used herein is for describing specific embodiments only and is not intended to limit the exemplary embodiments of the present invention. It should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Experimental methods in the following specific embodiments, unless otherwise specified, generally follow conventional methods and conditions of molecular biology in the art, which are fully explained in the literature.

[0045] It should also be understood that, for clarity, certain features of this disclosure may be described herein in the context of individual embodiments, but may also be provided in combination with each other in individual embodiments. That is, unless obviously incompatible or specifically excluded, each individual embodiment is considered to be combinable with any other embodiment, and such combination is considered to represent another different embodiment. Conversely, for brevity, various features of this disclosure described in the context of individual embodiments may also be provided individually or in any sub-combination. Finally, while a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure may also be considered an independent embodiment in itself.

[0046] Unless otherwise stated, it should be understood that each individual element in the list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments denoted as "A, B, or C" should be interpreted as including embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0047] In this document, the endpoints and any values ​​of the disclosed ranges are not limited to the precise ranges or values, which should be understood to include values ​​close to those ranges or values. For numerical ranges, one or more new numerical ranges can be obtained by combining the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges with individual point values, and individual point values ​​with each other, and these numerical ranges should be considered as specifically disclosed herein. Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “described” as used herein include both singular and plural indicators. Numerical ranges expressed by endpoints include all numerical values ​​and fractions within the corresponding range, as well as the expressed endpoints, unless the context clearly indicates otherwise.

[0048] In this article, references to “substance” are references to at least one of the substance and its equivalents.

[0049] When an item is described using the combined terms “...and / or ...", the description should be understood to include any one of the listed items and all combinations thereof.

[0050] Generally, the use of the term "about" indicates an approximation that can vary depending on the desired characteristics obtained from the disclosed subject matter and will be interpreted in a context-dependent manner based on function. Therefore, those skilled in the art will be able to interpret a degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term "about." In other cases, a gradient within a range of values ​​can be used to determine the range of differences allowed by the term "about." Furthermore, all ranges in this disclosure are inclusive and composable, and references to values ​​described within a range include every value within that range.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0052] The present invention will be described below through specific embodiments to make the technical solutions of the present invention easier to understand and master. However, the present invention is not limited thereto, and the described embodiments are only some embodiments of the present invention, not all embodiments. Therefore, they do not limit the present invention in any way. Any non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are all within the scope of protection of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should be within the scope of protection of the present invention. Unless otherwise specified, the experimental methods described in the following embodiments are conventional methods; the reagents and materials described, unless otherwise specified, can be obtained commercially.

[0053] The ceramic blanks used in the examples and comparative examples were all ceramic blanks prepared from ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Materials Co., Ltd.

[0054] Example 1 (1) The base material of the iridescent white glaze provided in this embodiment is as follows: 5 parts of kaolin; 30 samples of quartz; 5 parts talc; 20 parts zinc oxide; 10 parts of albite; 16 portions of calcite; 14 parts of borax.

[0055] The ratio of borax:zinc oxide:quartz is 14:20:30.

[0056] (2) The preparation method of the iridescent white glaze slurry provided in this embodiment is as follows: S1. Prepare raw materials according to the proportion of the glaze base material in the aforementioned part of this embodiment; S2. Place the raw material in a ball mill for wet ball milling to obtain a wet material containing glaze base material; wherein, the mass ratio of glaze base material, balls and water is 1:1.5:1.2, ball mill for 60 min, and sieve to ensure that the raw material has a particle size <50μm. S3. The wet material containing the glaze base material is aged to obtain an iridescent white glaze slurry; the aging temperature is 25℃ and the time is 36h.

[0057] (3) The preparation method of the iridescent white glaze provided in this embodiment is as follows, including the following steps: A1. Apply the iridescent white glaze slurry obtained in part (2) above in this embodiment to the surface of the unglazed body; A2. After glazing in step A1, place the sample at 75℃ and dry for 8 hours; A3. The dried sample obtained in step A2 is placed in a high-temperature electric furnace for sintering, and then naturally cooled with the furnace to obtain a bright iridescent white glaze and its glaze products; the heating rate is 4.25℃ / min, the maximum temperature of the sintering process is 1200℃, and it is held at 1200℃ for 90min.

[0058] (4) The iridescent white glaze provided in this embodiment is as follows: The glazed products, such as Figure 1 , 2 As shown in Figures 3 and 4, the Lab values ​​of the glaze of the product are: L=94, a=-2, b=2.8.

[0059] The electron microscope image of the glaze of the product is shown below. Figure 4As shown, a layered structure and a droplet-like phase separation structure are formed in the glaze. Specifically, during high-temperature firing, after the glaze forms a melt, due to the compatibility and refractive index differences between different components, liquid-liquid phase separation occurs, forming enriched phase droplets. These droplets tend to spherize under interfacial tension and are solidified during heat preservation and subsequent cooling, thus forming the spherical droplets and layered structure shown in the figure. The droplet-like micro-regions are rich in Ca, Zn, Mg, Na, and B ions, and the size of the droplets is submicron to micrometer, preferably 0.5 μm-2 μm. The layered structure is preferably located in the surface or near-surface region of the glaze layer, forming several quasi-periodic layered structures with an interlayer thickness of 100 nm-800 nm, preferably 200 nm-400 nm. The corresponding optical thickness is within the visible light interference range, satisfying the Bragg diffraction condition, thus enabling constructive interference at specific wavelengths and exhibiting bright iridescent colors.

[0060] Example 2 This embodiment is basically the same as Embodiment 1, except that the number of quartz parts is adjusted to 26 parts, and the rest is the same as Embodiment 1, wherein borax:zinc oxide:quartz = 14:20:26.

[0061] The white glazed product prepared in this embodiment has a pearly white glaze with obvious iridescence.

[0062] The Lab values ​​of the glaze of the product are: L=92.56, a=-3.45, b=1.05.

[0063] Example 3 This embodiment is basically the same as Embodiment 1, except that the amount of zinc oxide is adjusted to 14 parts, and the rest is the same as Embodiment 1, wherein the ratio of borax:zinc oxide:quartz is 14:14:30.

[0064] The white glazed product prepared in this embodiment exhibits a pearly white glaze effect and angle-dependent iridescence.

[0065] The Lab values ​​of the glaze of the product are: L=93.25, a=-2.22, b=1.35.

[0066] Example 4 This embodiment is basically the same as Embodiment 1, except that the amount of zinc oxide is adjusted to 24 parts, and the rest is the same as Embodiment 1, wherein the ratio of borax:zinc oxide:quartz is 14:24:30.

[0067] The white glazed product prepared in this embodiment exhibits a pearly white glaze effect and angle-dependent iridescence.

[0068] The Lab values ​​of the glaze of the product are: L=92.61, a=-1.75, b=2.56.

[0069] Example 5 This embodiment is basically the same as Embodiment 1, except that the amount of borax is adjusted to 12 parts, and the rest is the same as Embodiment 1, wherein the ratio of borax:zinc oxide:quartz is 12:20:30.

[0070] The white glazed product prepared in this embodiment exhibits a pearly white glaze effect and angle-dependent iridescence.

[0071] The Lab values ​​of the glaze of the product are: L=92.42, a=-2.42, b=2.94.

[0072] Example 6 This embodiment is basically the same as Embodiment 1, except that the amount of borax is adjusted to 19 parts, and the rest is the same as Embodiment 1, wherein the ratio of borax:zinc oxide:quartz is 19:20:30.

[0073] The white glazed product prepared in this embodiment exhibits a pearly white glaze effect and angle-dependent iridescence.

[0074] The Lab values ​​of the glaze of the product are: L=94.03, a=-1.81, b=2.78.

[0075] Example 7 This embodiment is basically the same as Embodiment 1, except that the highest temperature during the sintering process is 1100℃, and the rest is the same as Embodiment 1.

[0076] The white glazed product prepared in this embodiment exhibits a pearly white glaze effect and angle-dependent iridescence.

[0077] The Lab values ​​of the glaze of the product are: L=90.51, a=-1.45, b=1.89.

[0078] Example 8 This embodiment is basically the same as Embodiment 1, except that the highest temperature during the sintering process is 1250℃, and the rest is the same as Embodiment 1.

[0079] The white glazed product prepared in this embodiment exhibits a pearly white glaze effect and angle-dependent iridescence.

[0080] The Lab values ​​of the glaze of the product are: L=91.24, a=-2.01, b=2.67.

[0081] Example 9 (1) The base material of the iridescent white glaze provided in this embodiment is as follows: 1 part kaolin; 32 samples of quartz; 1 part talc; 24 parts zinc oxide; Two parts of albite; 21 portions of calcite; 19 parts of borax.

[0082] The ratio of borax:zinc oxide:quartz is 19:24:32.

[0083] (2) The preparation of the iridescent white glaze slurry provided in this embodiment is as follows, including the following steps: S1. Prepare raw materials according to the proportion of the glaze base material in the aforementioned part of this embodiment; S2. Place the raw material in a ball mill for wet ball milling to obtain a wet material containing glaze base material; wherein, the mass ratio of glaze base material, balls and water is 1:1:0.8, and the ball milling is performed for 60 minutes so that the raw material can be sieved to meet the particle size requirement of <50μm. S3. The wet material containing the glaze base material is aged to obtain an iridescent white glaze slurry; the aging temperature is 10℃ and the time is 48h.

[0084] (3) The preparation of the iridescent white glaze and glaze products provided in this embodiment is as follows, including the following steps: A1. Apply the iridescent white glaze slurry obtained in part (2) of this embodiment to the surface of the unglazed body; A2. After glazing in step A1, place the sample at 75℃ and dry for 8 hours; A3. The dried sample obtained in step A2 is placed in a high-temperature electric furnace for sintering, and then naturally cooled with the furnace to obtain a bright iridescent white glaze and a product with the glaze; the heating rate is 4.25℃ / min, the maximum temperature of the sintering process is 1150℃, and it is held at 1150℃ for 90min.

[0085] The Lab values ​​of the glaze of the product are: L=93.13, a=-2.10, b=1.88.

[0086] Example 10 (1) The base material of the iridescent white glaze provided in this embodiment is as follows: 10 parts of kaolin; 26 samples of quartz; 7 parts talc; 14 parts zinc oxide; 19 parts of albite; 12 parts of calcite; 12 parts of borax.

[0087] The ratio of borax:zinc oxide:quartz is 12:14:26.

[0088] (2) The preparation of the iridescent white glaze slurry provided in this embodiment is as follows: S1. Prepare the raw materials according to the proportion of the glaze base material described in the preceding part of this embodiment; S2. Place the raw material in a ball mill for wet ball milling to obtain a wet material containing glaze base material; wherein, the mass ratio of glaze base material, balls and water is 1:1.5:1, and the ball milling is performed for 60 minutes so that the raw material can be sieved to meet the particle size requirement of <50μm; S3. The wet material containing the glaze base material is aged to obtain an iridescent white glaze slurry; the aging temperature is 30℃ and the time is 36h.

[0089] (3) The preparation of the iridescent white glaze and glaze products provided in this embodiment is as follows: A1. Apply the iridescent white glaze slurry obtained in part (2) of this embodiment to the surface of the unglazed body; A2. After glazing in step A1, place the sample at 75℃ and dry for 8 hours; A3. The dried sample obtained in step A2 is placed in a high-temperature electric furnace for sintering, and then naturally cooled with the furnace to obtain an iridescent white glaze and a product with the glaze; the heating rate is 4.25℃ / min, the maximum temperature of the sintering process is 1250℃, and the temperature is held at 1250℃ for 90min.

[0090] The Lab values ​​of the glaze of the product are: L=90.78, a=-1.96, b=2.66.

[0091] Example 11 (1) The base material for the iridescent white glaze provided in this example is as follows: 2 parts of kaolin; 34 samples of quartz; 12 parts talc; 16 parts zinc oxide; 6 parts of albite; 14 portions of calcite; 16 parts of borax.

[0092] The ratio of borax:zinc oxide:quartz is 16:16:34.

[0093] (2) The preparation of the iridescent white glaze slurry provided in this embodiment is as follows, including the following steps: S1. Prepare raw materials according to the proportion of the glaze base material in the aforementioned part of this embodiment; S2. Place the raw material in a ball mill for wet ball milling to obtain a wet material containing glaze base material; wherein, the mass ratio of glaze base material, balls and water is 1:1.6:0.9, and the ball milling is performed for 60 minutes so that the raw material can be sieved to meet the particle size requirement of <50μm; S3. The wet material containing the glaze base material is aged to obtain an iridescent white glaze slurry; the aging temperature is 25℃ and the time is 36h.

[0094] (3) The preparation of the iridescent white glaze and glaze products provided in this embodiment is as follows: A1. Apply the iridescent white glaze slurry obtained in part (2) of the above-mentioned part of this embodiment to the surface of the unglazed body; A2. After glazing in step A1, place the sample at 75℃ and dry for 8 hours; A3. The dried sample obtained in step A2 is placed in a high-temperature electric furnace for sintering, and then naturally cooled with the furnace to obtain a bright iridescent white glaze and a product with the glaze; the heating rate is 4.25℃ / min, the maximum temperature of the sintering process is 1100℃, and it is held at 1100℃ for 90min.

[0095] The Lab values ​​of the glaze of the product are: L=89.97, a=-1.80, b=1.65.

[0096] Example 12 (1) The base material of the iridescent white glaze provided in this embodiment is as follows: 6.5 parts of kaolin; 27 samples of quartz; 8 parts talc; 21 parts zinc oxide; 12 parts of albite; 13 portions of calcite; 12.5 parts of borax.

[0097] The ratio of borax:zinc oxide:quartz is 12.5:21:27.

[0098] (2) The preparation of the iridescent white glaze slurry provided in this embodiment is as follows, including the following steps: S1. Prepare raw materials according to the proportion of the glaze base material in the aforementioned part of this embodiment; S2. Place the raw material in a ball mill for wet ball milling to obtain a wet material containing glaze base material; wherein, the mass ratio of glaze base material, balls and water is 1:1.7:1.1, and the ball milling is performed for 60 minutes so that the raw material can be sieved to meet the particle size requirement of <50μm; S3. The wet material containing the glaze base material is aged to obtain an iridescent white glaze slurry; the aging conditions are a temperature of 15°C and a time of 36 hours.

[0099] (3) The preparation of the iridescent white glaze and glaze products provided in this embodiment is as follows: A1. Apply the iridescent white glaze slurry obtained in part (2) above in this embodiment to the surface of the unglazed body; A2. After glazing in step A1, place the sample at 75℃ and dry for 8 hours; A3. The dried sample obtained in step A2 is placed in a high-temperature electric furnace for sintering, and then naturally cooled with the furnace to obtain a bright iridescent white glaze and a product with the glaze; the heating rate is 4.25℃ / min, the maximum temperature of the sintering process is 1100℃, and it is held at 1100℃ for 60min.

[0100] The Lab values ​​of the glaze of the product are: L=90.45, a=-2.30, b=2.40.

[0101] Example 13 (1) The base material of the iridescent white glaze provided in this embodiment is as follows: 9 parts of kaolin; 29 samples of quartz; 4 parts talc; 18 parts zinc oxide; 8 parts of sodium feldspar; 19 portions of calcite; 13 parts of borax.

[0102] The ratio of borax:zinc oxide:quartz is 13:18:29.

[0103] (2) The preparation of the iridescent white glaze slurry provided in this embodiment is as follows, including the following steps: S1. Prepare the raw materials according to the proportion of the iridescent white glaze base material described in the preceding part of this embodiment; S2. Place the raw material in a ball mill for wet ball milling to obtain a wet material containing glaze base material; wherein, the mass ratio of glaze base material, balls and water is 1:1:1, and the ball milling is performed for 60 minutes to ensure that the raw material can be sieved to meet the particle size requirement of <50μm. S3. The wet material containing the glaze base material is aged to obtain an iridescent white glaze slurry; the aging conditions are a temperature of 12°C and a time of 36 hours.

[0104] (3) The preparation of the iridescent white glaze and glaze products provided in this embodiment is as follows: A1. Apply the iridescent white glaze slurry obtained in part (2) of this embodiment to the surface of the unglazed body; A2. After glazing in step A1, place the sample at 75℃ and dry for 8 hours; A3. The dried sample obtained in step A2 is placed in a high-temperature electric furnace for sintering, and then naturally cooled with the furnace to obtain a bright iridescent white glaze and a product with the glaze; the heating rate is 4.25℃ / min, the maximum temperature of the sintering process is 1250℃, and it is held at 1250℃ for 90min.

[0105] The Lab values ​​of the glaze of the product are: L=92.05, a=-1.94, b=1.90.

[0106] Comparative Example 1 This comparative example is basically the same as Example 1, except that in step A3, the dried sample is placed in a high-temperature electric furnace for sintering. The maximum temperature of the sintering process is 1350°C, and the sample is held at 1350°C for 120 minutes. Then, the sample is naturally cooled in the furnace to obtain the sample as shown in Example 1. Figure 5 The white glaze shown and the products with the glaze are rough with crystal precipitation, a small amount of iridescence, and no vitreous luster. The Lab values ​​of the glaze of the product are: L=83.18, a=4.25, b=3.11.

[0107] Comparative Example 2 This comparative example is basically the same as Example 1, except that the highest temperature during the sintering process is 1000℃, and the rest is the same as Example 1.

[0108] The white glazed product prepared in this comparative example has a dark glaze surface and no iridescence.

[0109] The Lab values ​​of the glaze of the product are: L=85.12, a=-5.49, b=4.37.

[0110] Comparative Example 3 This comparative example is basically the same as Example 1, except that the number of quartz parts is adjusted to 35 parts, and the rest is the same as Example 1, wherein borax:zinc oxide:quartz = 14:20:35.

[0111] The white glazed product prepared in this comparative example is as follows: Figure 6 As shown, its glaze has a large number of white crystals precipitated out and no iridescence.

[0112] The Lab values ​​of the glaze of the product are: L=84.19, a=2.58, b=5.49.

[0113] Comparative Example 4 This comparative example is basically the same as Example 1, except that the number of quartz parts is adjusted to 19 parts, and the rest is the same as Example 1, wherein borax:zinc oxide:quartz = 14:20:19.

[0114] The white glazed product prepared in this comparative example has a transparent glaze with a faint light blue edge and no iridescence.

[0115] The Lab values ​​of the glaze of the product are: L=51.46, a=0.24, b=-7.25.

[0116] Comparative Example 5 This comparative example is basically the same as Example 1, except that the amount of zinc oxide is adjusted to 13 parts, and the rest is the same as Example 1, wherein the ratio of borax:zinc oxide:quartz is 14:13:30.

[0117] The white glazed product prepared in this comparative example is as follows: Figure 7 As shown, its glaze is rough, porous, and lacks iridescence.

[0118] The Lab values ​​of the glaze of the product are: L=87, a=-4.89, b=4.59.

[0119] Comparative Example 6 This comparative example is basically the same as Example 1, except that the amount of zinc oxide is adjusted to 27 parts, and the rest is the same as Example 1, wherein the ratio of borax:zinc oxide:quartz is 14:27:30.

[0120] The white glazed product prepared in this comparative example has a large number of pores on its glaze surface, a light blue edge, and no iridescence.

[0121] The Lab values ​​of the glaze of the product are: L=96.20, a=1.09, b=6.89.

[0122] Comparative Example 7 This comparative example is basically the same as Example 1, except that the amount of borax is adjusted to 20 parts, and the rest is the same as Example 1, wherein the ratio of borax:zinc oxide:quartz is 20:20:30.

[0123] The blue-white glazed product prepared in this comparative example is as follows: Figure 8 As shown, its glaze is light blue and white, and the glaze is transparent, has cracks, and no iridescence.

[0124] The Lab values ​​of the glaze of the product are: L=71, a=-4.71, b=-14.

[0125] Comparative Example 8 This comparative example is basically the same as Example 1, except that the amount of borax is adjusted to 8 parts, and the rest is the same as Example 1, wherein the ratio of borax:zinc oxide:quartz is 8:20:30.

[0126] The white glazed product prepared in this comparative example has a rough glaze surface, a large amount of crystallization, and no iridescence.

[0127] The Lab values ​​of the glaze of the product are: L=79, a=-5.57, b=6.45.

[0128] The above description is merely a preferred embodiment of this application and an explanation of the technical principles used. Those skilled in the art should understand that the scope involved in this application is not limited to the technical solutions formed by a specific combination of the above-mentioned technical features, but should also cover other technical solutions formed by any combination of the above-mentioned technical features or their equivalent features without departing from the inventive concept. For example, technical solutions formed by replacing the above-mentioned features with technical features with similar functions disclosed in this application (but not limited to) each other.

[0129] Apart from the technical features described in the specification, the other technical features are known to those skilled in the art. To highlight the innovative features of this invention, the other technical features will not be described in detail here.

Claims

1. A base material for iridescent white glazes, characterized in that, Calculated by weight, including: 1-10 parts of kaolin; 26-34 parts of quartz; 1-12 parts talc; 14-24 parts zinc oxide; 2-19 parts of albite; 12-21 parts of calcite; Borax 12-19 parts.

2. The iridescent white glaze base of claim 1, wherein, The mass ratio of borax:zinc oxide:quartz is (12~19):(14~24):(26~34).

3. An iridescent white glaze slurry, characterized by, Includes the glaze base material as described in any one of claims 1 to 2.

4. A method for preparing an iridescent white glaze slurry, characterized by, Including the following steps: Prepare a wet material containing a glaze base material, wherein the glaze base material is as described in any one of claims 1 to 2; The wet material containing the glaze base material is aged. And / or, The glaze base material is ground to obtain a wet material containing the glaze base material in the presence of water; and / or, The aging process is carried out at a temperature of 10~30℃ for 12~36 hours.

5. A white glaze with iridescent color, characterized in that, The glaze is prepared using the glaze base material according to any one of claims 1 to 2, or the glaze slurry according to claim 3, or the glaze slurry obtained by the preparation method according to claim 4. And / or, the Lab value of the glaze is: L=89~95, a=-4~0, b=0~3.

6. The iridescent white glazed body of claim 5 wherein, The iridescent white glaze includes: at least one layered structure and a phase-separated structure; and / or, The glaze depth is ≤2μm, and the iridescent white glaze includes a layered structure; and / or, The glaze depth is >2μm, and the iridescent white glaze includes a phase-separated structure; and / or, The thickness of the iridescent white glaze is 1-3 mm.

7. The iridescent white glazed surface of claim 6, wherein, The layered structure is a quasi-periodic layered structure; and / or, The interlayer spacing of the layered structure is 100nm-800nm.

8. The iridescent white glazed surface of claim 6, wherein, The phase-separated structure contains a first phase and a second phase. The first phase is wrapped around the surface of the second phase; The second phase contains at least one of the elements Ca, Zn, Mg, Na, and B; The first phase is a glassy phase, which contains at least one of Si and Al elements; and / or, The second phase consists of particles with a size of <2μm.

9. A method for producing a white glaze with iridescent color, characterized by, Including the following steps: (1) Prepare the glaze slurry as described in claim 3; (2) Apply the glaze slurry to the surface of the unglazed body and dry it after glazing; (3) The dried sample is placed in a kiln under an oxidizing atmosphere for sintering; and / or, In step (3), the sintering temperature is 1100℃~1250℃ and the holding time is 30~100min.

10. A white iridescent glazed article, characterized in that, The glazed product comprises the glaze base material as described in any one of claims 1 to 2, or the glaze slurry as described in claim 3, or a glaze surface prepared from the glaze slurry obtained by the preparation method described in claim 4; and / or, The products include any one of ceramic products, glass products, metal products, and fine ceramic products.

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