Lead-free and antimony-free gray glaze, glaze surface, glaze surface product and preparation method

Abstract

The invention discloses a lead-free and antimony-free gray glaze, a glaze surface, a glaze surface product and a preparation method, traditional harmful elements such as lead, antimony and the like are not used, bismuth oxide is used as a coloring agent, the gray glaze surface can be successfully obtained through calcination treatment, and the harm to human and nature in the production and use process is greatly reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramic glazes, and specifically relates to a lead-free and antimony-free gray glaze, glaze surface, glazed article and preparation method thereof. Background Art

[0002] Ceramic glazes are key elements for enhancing the appearance and functionality of ceramic products. In recent years, due to its neutral and versatile characteristics, the gray tone can be harmoniously matched with various colors and styles. At the same time, its calm and elegant psychological effects are in line with the design trends of modern minimalist and industrial styles, and it has gradually become popular in the decoration field. However, compared with other colors, the glaze formula of the gray tone is relatively single, and usually uses lead and antimony as colorants.

[0003] For traditional gray glazes, lead, antimony and their compounds are toxic to the human body and have certain carcinogenicity, and at the same time, they will cause a certain degree of pollution to the environment during the production process. Therefore, it is necessary to develop a novel, stable, efficient and environmentally friendly gray glaze. Summary of the Invention

[0004] 1. Problems to be Solved

[0005] In order to solve the problems such as single products and poor environmental friendliness in the current gray glaze field, the present invention provides a lead-free and antimony-free gray glaze, and based on this raw material, the corresponding glaze surface and glazed article are obtained.

[0006] 2. Technical Solutions

[0007] In order to solve the above problems, the technical solutions adopted by the present invention are as follows:

[0008] The first aspect of the present invention provides a lead-free and antimony-free gray glaze base material, which includes, by weight:

[0009]

[0010] The lead-free and antimony-free gray glaze base material according to any implementation scheme of the first aspect of the present invention includes, by weight:

[0011]

[0012]

[0013] The lead-free and antimony-free gray glaze base material according to any implementation scheme of the first aspect of the present invention includes, by weight:

[0014] Kaolin 13 - 25 parts;

[0015]

[0016] The lead-free and antimony-free grey glaze base material according to any embodiment of the first aspect of the present invention comprises, by weight:

[0017] 15-25 parts of kaolin;

[0018]

[0019] The lead-free and antimony-free grey glaze base material according to any embodiment of the first aspect of the present invention comprises, by weight:

[0020] 15-25 parts of kaolin;

[0021]

[0022]

[0023] According to any one of the embodiments of the first aspect of the present invention, the lead-free and antimony-free grey glaze base material contains particles, and the particle size of the particles does not exceed 50 μm.

[0024] The second aspect of the present invention provides a lead-free, antimony-free grey glaze slurry, wherein the lead-free, antimony-free grey glaze slurry comprises the lead-free, antimony-free grey glaze base material according to any embodiment of the first aspect of the present invention.

[0025] The third aspect of the present invention provides a method for preparing a lead-free and antimony-free gray glaze slurry, comprising the steps of:

[0026] Preparing a wet material containing a glaze base material, wherein the glaze base material comprises the lead-free and antimony-free gray glaze base material according to any embodiment of the first aspect of the present invention;

[0027] Aging of wet mix containing glaze base.

[0028] According to the method for preparing the lead-free and antimony-free gray glaze slurry described in any embodiment of the third aspect of the present invention, the aging treatment temperature is 10 to 30° C., and the aging treatment time is 12 to 48 hours;

[0029] The method for preparing the lead-free and antimony-free gray glaze slurry according to any embodiment of the third aspect of the present invention comprises the steps of: grinding the glaze base material to obtain a wet material containing the glaze base material with the participation of water, and the water content of the wet material needs to be not less than 30%; preferably, the water content of the wet material is 30-50%.

[0030] As described herein, one of the reference methods is to proportion various raw materials of the glaze base material by quantity, and then perform wet grinding (such as wet ball milling) using a solvent (such as water) to obtain a wet material containing the glaze base material that meets the particle size requirements; on this basis, the mass ratio of m (material): m (ball): m (solvent) for the conditions of wet ball milling is 1: (1-3): (0.8-1.5);

[0031] Alternatively, it is also possible to first prepare a gray glaze base material that meets the quantity and particle size requirements, and then add a solvent that meets the quantity requirements to obtain a wet material containing the glaze base material.

[0032] The fourth aspect of the present invention provides a lead-free and antimony-free gray glaze surface, which uses the lead-free and antimony-free gray glaze base material described in any one of the embodiments of the first aspect of the present invention, or the lead-free and antimony-free gray glaze slurry described in any one of the embodiments of the second aspect of the present invention, or the lead-free and antimony-free gray glaze slurry prepared by the method described in any one of the embodiments of the third aspect of the present invention.

[0033] For the lead-free and antimony-free gray glaze surface according to any one of the embodiments of the fourth aspect of the present invention, the Lab values of the glaze surface are respectively: L = 20-29, a = 0.8-1.2, b = 1.2-1.4.

[0034] The fifth aspect of the present invention provides a method for preparing a lead-free and antimony-free gray glaze surface, which can prepare the lead-free and antimony-free gray glaze surface described in any one of the embodiments of the fourth aspect of the present invention.

[0035] For the method for preparing a lead-free and antimony-free gray glaze surface according to any one of the embodiments of the fifth aspect of the present invention, it includes the steps:

[0036] (1) Prepare the lead-free and antimony-free gray glaze slurry described in any one of the embodiments of the second aspect of the present invention, or the lead-free and antimony-free gray glaze slurry described in any one of the embodiments of the third aspect of the present invention;

[0037] (2) Apply the glaze (generally glaze slurry) to the surface of the green body, and dry it after glazing;

[0038] (3) Place the dried sample in a kiln under a reducing atmosphere for sintering.

[0039] For the method for preparing a lead-free and antimony-free gray glaze surface according to any one of the embodiments of the fifth aspect of the present invention, the holding temperature for sintering is 1150-1350 °C, and the holding time for sintering is 30-90 min.

[0040] The sixth aspect of the present invention provides a lead-free and antimony-free grey glazed product, which comprises a glazed surface formed by using the lead-free and antimony-free grey glaze base material according to any embodiment of the first aspect of the present invention, or the lead-free and antimony-free grey glaze slurry according to any embodiment of the second aspect of the present invention, or the lead-free and antimony-free grey glaze slurry according to any embodiment of the third aspect of the present invention.

[0041] The lead-free and antimony-free grey glazed product according to any embodiment of the sixth aspect of the present invention includes any one of ceramic products, glass products, metal products and fine ceramic products.

[0042] Beneficial effects

[0043] (1) Compared with other colors, the glaze formula of the grey tone is relatively simple. Usually, lead and antimony are used as colorants, and lead, antimony and their compounds are toxic to the human body and have certain carcinogenicity. At the same time, they will cause a certain degree of pollution to the environment during the production process. The lead-free and antimony-free grey glaze provided by the present invention does not use traditional harmful elements such as lead and antimony, uses bismuth oxide as a colorant, and can successfully obtain a grey glazed surface after calcination treatment, greatly reducing the harm to humans and nature during the production and use processes.

[0044] (2) The preparation process flow of the lead-free and antimony-free grey glazed surface or glazed product provided by the present invention is simple and easy to control, which can ensure the stable performance and high yield rate of the products obtained by production, helps to improve production efficiency, and reduces the production cost of traditional grey glazes. Description of the drawings

[0045] Figure 1 The glaze surface picture of the glazed product prepared in Example 1;

[0046] Figure 2 The ultraviolet-visible diffuse reflectance spectrum of the glaze surface of the glazed product prepared in Example 1;

[0047] Figure 3 The glaze surface picture of the glazed product prepared in Comparative Example 1;

[0048] Figure 4 The glaze surface picture of the glazed product prepared in Comparative Example 2;

[0049] Figure 5 The glaze surface picture of the glazed product prepared in Comparative Example 3. Detailed implementation manners

[0050] The present disclosure can be more readily understood by reference to the following description in conjunction with the accompanying drawings and examples, all of which form a part of the present disclosure. It should be understood that the present disclosure is not limited to the specific products, methods, conditions or parameters described and / or illustrated herein. Further, the terms used herein are for the purpose of describing particular embodiments by way of example only and are not intended to be limiting unless otherwise specified.

[0051] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to 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 terms used in the embodiments of the present invention are for describing specific embodiments and not for limiting the scope of protection of the present invention. If the experimental methods are not specified with specific conditions in the following specific embodiments, they are generally carried out according to the conventional methods and conditions of molecular biology in the art, and such techniques and conditions are fully explained in the literature.

[0052] It should also be understood that, for the sake of clarity, certain features of the present disclosure may be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, unless clearly incompatible or specifically excluded, each individual embodiment is considered combinable with any other embodiment, and such combination is considered to represent another distinct embodiment. Conversely, for the sake of brevity, the various features of the present disclosure described in the context of a single embodiment may also be provided individually or in any sub-combination. Finally, although a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or sub-structure itself may also be considered an independent embodiment.

[0053] Unless otherwise specified, it should be understood that each individual element in a list and each combination of the individual elements in the list will be construed as a different embodiment. For example, a list of embodiments represented as "A, B, or C" should be construed as including the embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0054] In this document, the endpoints and any values of the disclosed ranges are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this document. Unless the context clearly indicates otherwise, the singular forms "a", "an", and "the" as used herein include singular and plural referents. Numerical ranges expressed by endpoints include all the numerical values and fractions within the corresponding ranges, as well as the expressed endpoints, unless the context clearly states otherwise.

[0055] In this document, the reference to "substance" refers to at least one of such substance and its equivalents.

[0056] When describing items by using associative terms such as "……and / or……", etc., the description should be understood to include any one of the associated listed items and all combinations of one or more of them.

[0057] Generally, the use of the term "about" indicates an approximate value that can vary according to the desired characteristics obtained from the disclosed subject matter, and will be interpreted in a context-dependent manner based on the function. Therefore, those of ordinary skill in the art will be able to interpret a certain degree of difference on a case-by-case basis. In some cases, the number of significant digits used to express a specific value can be a representative technique for determining the difference allowed by the term "about". In other cases, the gradient in a series of values can be used to determine the range of differences allowed by the term "about". Further, all ranges in this disclosure are inclusive and combinable, and the reference to the values stated in the ranges includes each value within the range.

[0058] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field 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.

[0059] 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. The described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Therefore, they do not impose any limitations on the present invention. Those skilled in the art make some non-essential improvements and adjustments based on the content of the present invention, which all fall within the protection scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention. In the following embodiments, the experimental methods are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0060] Example 1

[0061] (1) The lead-free and antimony-free gray glaze base material provided in this embodiment is as follows:

[0062]

[0063] (2) The preparation of the lead-free and antimony-free gray glaze slurry provided in this embodiment is as follows:

[0064] S1. Prepare raw materials according to the ratio of the base material in the previous part of this embodiment

[0065] S2. Place the raw materials in a ball mill for wet ball milling to obtain a wet material containing the glaze base material; the mass ratio of m(material):m(ball):m(water) for the conditions of wet ball milling is 1:1:1, and ball mill for 20 minutes to make the raw materials pass through a sieve to meet a particle size <50 μm;

[0066] S3. Subject the obtained wet material containing the glaze base material to aging treatment to obtain a lead-free and antimony-free gray glaze slurry; the conditions of the aging treatment are a temperature of 12 °C and a time of 36 hours.

[0067] (3) The preparation of the lead-free and antimony-free gray glaze surface and glazed products provided in this embodiment is as follows:

[0068] A1. Apply the lead-free and antimony-free gray glaze slurry obtained in the previous part (2) of this embodiment to the surface of the green body;

[0069] A2. Place the sample after glazing in step A1 at a temperature of 75 °C and dry for 8 hours;

[0070] A3. Place the dried sample obtained in step A2 in a reducing atmosphere kiln for sintering, and then cool naturally with the furnace to obtain Figure 1 、 2The gray glaze with extremely high color saturation as shown and the products with such glaze; the heating rate is 5 °C / min, the highest temperature of the sintering process is 1350 °C, and at 1350 °C, the holding time is 60 minutes.

[0071] Among them, the green body is a ceramic green body prepared from ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Material Co., Ltd.

[0072] The Lab values of the glaze surface of the product are respectively: L = 22.54, a = 0.80, b = 1.39.

[0073] In addition, further conduct a yield test on the production process of the gray glaze in the present invention, and it is obtained that the glaze products are smooth without defects such as bubbles, the defect rate is less than 1%, and the yield rate reaches 98%.

[0074] In addition, it is calculated that the color difference of the samples is less than 0.5, and the Lab values of each test sample are shown in Table 1 below.

[0075] Among them, the calculation of the sample color difference is shown in Equation (1):

[0076] In the formula, take the L, a, and b of Sample 1 as the standard values L 标准 、a 标准 、b 标准 ;

[0077] ΔE represents the color difference;

[0078] ΔL represents the lightness difference, ΔL = L 样品 -L 标准 ;

[0079] Δa represents the color difference on the red-green axis, Δa = a 样品 -a 标准 ;

[0080] Δb represents the color difference on the yellow-blue axis, Δb = b 样品 -b 标准 ;

[0081] Table 1 Lab values of each test sample

[0082] L a b Sample 1 22.54 0.80 1.39 Sample 2 22.47 0.83 1.41 Sample 3 22.57 0.77 1.37 Sample 4 22.53 0.81 1.42 Sample 5 22.59 0.79 1.38 Sample 6 22.49 0.81 1.36

[0083] Example 2

[0084] (1) The lead-free and antimony-free gray glaze base material provided in this example is as follows:

[0085]

[0086] (2) The preparation of the lead-free and antimony-free gray glaze slurry provided in this example is as follows:

[0087] S1. Prepare raw materials according to the proportion of the base materials in the foregoing part of this embodiment;

[0088] S2. Place the raw materials in a ball mill for wet ball milling to obtain wet materials containing the glaze base materials; the mass ratio of m(materials):m(balls):m(water) for the conditions of wet ball milling is 1:1.7:0.8, and ball mill for 20 minutes to make the raw materials pass through a sieve to meet a particle size <50 μm;

[0089] S3. Subject the obtained wet materials containing the glaze base materials to a retting treatment to obtain a lead-free and antimony-free gray glaze slurry; the conditions for the retting treatment are a temperature of 15 °C and a time of 36 hours.

[0090] (3) The preparation of the lead-free and antimony-free gray glaze surface and the glazed article provided in this embodiment is as follows:

[0091] A1. Apply the lead-free and antimony-free gray glaze slurry obtained in the foregoing part (2) of this embodiment to the surface of the green body;

[0092] A2. Place the sample after glazing in step A1 at a temperature of 75 °C and dry for 8 hours;

[0093] A3. Place the dried sample obtained in step A2 in a reducing atmosphere kiln for sintering, and then naturally cool with the furnace to obtain a gray glaze surface with extremely high color saturation and the article with this glaze surface; the heating rate is 5 °C / min, the highest temperature in the sintering process is 1150 °C, and at 1150 °C, the holding time is 60 minutes.

[0094] Among them, the green body is a ceramic body prepared from ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Material Co., Ltd.

[0095] The Lab values of the glaze surface of the article are: L = 20.0, a = 0.95, b = 1.40.

[0096] Example 3

[0097] (1) The lead-free and antimony-free gray glaze base materials provided in this embodiment are as follows:

[0098]

[0099] (2) The preparation of the lead-free and antimony-free gray glaze slurry provided in this embodiment is as follows:

[0100] S1. Prepare raw materials according to the proportion of the base materials in the foregoing part of this embodiment

[0101] S2. Place the raw materials in a ball mill for wet ball milling to obtain wet materials containing the base glaze materials. The conditions for wet ball milling are as follows: the mass ratio of m(materials):m(balls):m(water) is 1:1.6:1.2, and ball mill for 20 minutes to enable the raw materials to pass through a sieve and meet the particle size <50 μm;

[0102] S3. Subject the obtained wet materials containing the base glaze materials to aging treatment to obtain a lead-free and antimony-free gray glaze slurry. The conditions for the aging treatment are a temperature of 25°C and a time of 36 hours.

[0103] (3) The preparation of the lead-free and antimony-free gray glaze surface and the glazed article provided in this embodiment is as follows:

[0104] A1. Apply the lead-free and antimony-free gray glaze slurry obtained in the aforementioned part (2) of this embodiment to the surface of the green body;

[0105] A2. Place the sample after glazing in step A1 at a temperature of 75°C and dry for 8 hours;

[0106] A3. Place the dried sample obtained in step A2 in a reduction atmosphere kiln for sintering, and then naturally cool with the furnace to obtain a gray glaze surface with extremely high color saturation and the article with this glaze surface. The heating rate is 5°C / min, the highest temperature during the sintering process is 1250°C, and at 1250°C, the holding time is 60 minutes.

[0107] Among them, the green body is a ceramic body prepared from ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Material Co., Ltd.

[0108] The Lab values of the glaze surface of the article are: L = 22.37, a = 1.08, b = 1.37.

[0109] Example 4

[0110] (1) The lead-free and antimony-free gray glaze base materials provided in this embodiment are as follows:

[0111]

[0112] (2) The preparation of the lead-free and antimony-free gray glaze slurry provided in this embodiment is as follows:

[0113] S1. Prepare the raw materials according to the ratio of the base materials in the aforementioned part of this embodiment

[0114] S2. Place the raw materials in a ball mill for wet ball milling to obtain wet materials containing the base glaze materials. The conditions for wet ball milling are as follows: the mass ratio of m(materials):m(balls):m(water) is 1:1.5:1.1, and ball mill for 20 minutes to enable the raw materials to pass through a sieve and meet the particle size <50 μm;

[0115] S3. The obtained wet material containing the glaze base material is subjected to aging treatment to obtain a lead-free and antimony-free gray glaze slurry; the conditions for the aging treatment are a temperature of 30°C and a time of 36 hours.

[0116] (3) The preparation of the lead-free and antimony-free gray glaze surface and the glazed product provided in this embodiment is as follows:

[0117] A1. Apply the lead-free and antimony-free gray glaze slurry obtained in the aforementioned part (2) of this embodiment to the surface of the green body.

[0118] A2. Place the sample after glazing in step A1 at a temperature of 75°C and dry for 8 hours.

[0119] A3. Place the dried sample obtained in step A2 in a reducing atmosphere kiln for sintering, and then naturally cool with the furnace to obtain a gray glaze surface with extremely high color saturation and the product with this glaze surface; the heating rate is 5°C / min, the highest temperature in the sintering process is 1300°C, and at 1300°C, the holding time is 60 minutes.

[0120] Among them, the green body is a ceramic body prepared from ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Material Co., Ltd.

[0121] The Lab values of the glaze surface of the product are: L = 29.0, a = 0.95, b = 1.37.

[0122] Example 5

[0123] (1) The lead-free and antimony-free gray glaze base material provided in this embodiment is as follows:

[0124]

[0125] (2) The preparation of the lead-free and antimony-free gray glaze slurry provided in this embodiment is as follows:

[0126] S1. Prepare raw materials according to the ratio of the base material in the aforementioned part of this embodiment.

[0127] S2. Place the raw materials in a ball mill for wet ball milling to obtain a wet material containing the glaze base material; the conditions for wet ball milling are a mass ratio of m(material):m(ball):m(water) of 1:1:0.9, and ball milling for 20 minutes to make the raw materials pass through a sieve to meet a particle size <50μm.

[0128] S3. The obtained wet material containing the glaze base material is subjected to aging treatment to obtain a lead-free and antimony-free gray glaze slurry; the conditions for the aging treatment are a temperature of 10°C and a time of 36 hours.

[0129] (3) The preparation of the lead-free and antimony-free gray glaze surface and the glazed product provided in this embodiment is as follows:

[0130] A1. Apply the lead-free and antimony-free gray glaze slurry obtained in the aforementioned part (2) of this embodiment to the surface of the biscuit body;

[0131] A2. Place the sample after glazing in step A1 at a temperature of 75 °C and dry for 8 hours;

[0132] A3. Place the dried sample obtained in step A2 in a reducing atmosphere kiln for sintering, and then naturally cool with the furnace to obtain a gray glaze surface with extremely high color saturation and a product with this glaze surface; the heating rate is 5 °C / min, the highest temperature of the sintering process is 1200 °C, and at 1200 °C, the holding time is 60 minutes.

[0133] Among them, the biscuit body is made of ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Material Co., Ltd.

[0134] The Lab values of the glaze surface of the product are: L = 25.68, a = 0.98, b = 1.29.

[0135] Example 6

[0136] (1) The lead-free and antimony-free gray glaze base material provided in this embodiment is as follows:

[0137]

[0138] (2) The preparation of the lead-free and antimony-free gray glaze slurry provided in this embodiment is as follows:

[0139] S1. Prepare raw materials according to the ratio of the base material in the aforementioned part of this embodiment

[0140] S2. Place the raw materials in a ball mill for wet ball milling to obtain a wet material containing the glaze base material; the conditions for wet ball milling are that the mass ratio of m(material):m(ball):m(water) is 1:1.5:1.4, and ball mill for 20 minutes to make the raw materials pass through a sieve to meet a particle size <50 μm;

[0141] S3. Subject the obtained wet material containing the glaze base material to a retting treatment to obtain a lead-free and antimony-free gray glaze slurry; the conditions for the retting treatment are a temperature of 20 °C and a time of 36 hours.

[0142] (3) The preparation of the lead-free and antimony-free gray glaze surface and glaze product provided in this embodiment is as follows:

[0143] A1. Apply the lead-free and antimony-free gray glaze slurry obtained in the aforementioned part (2) of this embodiment to the surface of the biscuit body;

[0144] A2. Place the sample after glazing in step A1 at 75 °C for 8 hours of drying;

[0145] A3. Place the dried sample obtained in step A2 in a reducing atmosphere kiln for sintering, and then naturally cool with the furnace to obtain a gray glaze with extremely high color saturation and the product with this glaze; the heating rate is 5 °C / min, the highest temperature in the sintering process is 1210 °C, and at 1210 °C, the holding time is 60 minutes.

[0146] Among them, the green body is a ceramic green body prepared from ordinary white clay purchased from Jingdezhen Shengyi Ceramic Raw Material Co., Ltd.

[0147] The Lab values of the glaze of the product are respectively: L = 26.55, a = 0.94, b = 1.28.

[0148] Comparative Example 1

[0149] This comparative example is basically the same as Example 1, the difference is only that in step A3, the obtained dried sample is placed in an air atmosphere kiln for sintering, and then naturally cooled with the furnace to obtain a colorless and transparent glaze and the product with this glaze (as Figure 3 shown), it can be found from the figure that the glaze is transparent and the green body can be directly observed.

[0150] The Lab values of the glaze of the product are respectively: L = 60.97, a = 0.76, b = 10.82.

[0151] Comparative Example 2

[0152] This comparative example is basically the same as Example 1, the difference is only that the amount of bismuth oxide is adjusted to 3 parts, and the rest is the same as Example 1.

[0153] The glazed product prepared in this comparative example has a sky blue glaze (as Figure 4 shown).

[0154] The Lab values of the glaze of the product are respectively: L = 64.92, a = -4.96, b = 0.15.

[0155] Comparative Example 3

[0156] This comparative example is basically the same as Example 1, the difference is only that the amount of bismuth oxide is adjusted to 17 parts, and the rest is the same as Example 1.

[0157] The glazed product prepared in this comparative example has a grayish-white glaze and the glaze is very rough (as Figure 5 shown).

[0158] The Lab values of the glaze of the product are respectively: L = 66.93, a = 0.05, b = -1.47.

Claims

1. A lead-free, antimony-free grey glaze base material, characterized in that: Calculated by weight:

2. The lead-free and antimony-free grey glaze base material according to claim 1, characterized in that: Calculated by weight: 10-28 parts of kaolin; 3. The lead-free and antimony-free grey glaze base material according to claim 1 or 2, characterized in that: The base material contains particles, and the particle size of the particles does not exceed 50 μm.

4. Lead-free and antimony-free grey glaze slurry, characterized in that: The invention comprises the base material described in any one of claims 1 to 3.

5. A method for preparing a lead-free and antimony-free gray glaze slurry, characterized in that: Includes steps: Preparing a wet material containing a glaze base material, wherein the glaze base material is as described in any one of claims 1 to 3; Aging of wet mix containing glaze base.

6. The method for preparing the lead-free and antimony-free grey glaze slurry according to claim 5, characterized in that: The method comprises the following steps: grinding the glaze base material, and obtaining a wet material containing the glaze base material with the participation of water.

7. Lead-free and antimony-free grey glaze, characterized in that: The glaze surface is prepared by using the glaze base material according to any one of claims 1 to 3, or the glaze slurry according to any one of claims 4 to 5; And / or, the Lab values ​​of the glaze are: L=20-29, a=0.8-1.2, b=1.2-1.

4.

8. A method for preparing a lead-free and antimony-free grey glaze, characterized in that: Includes steps: (1) preparing a lead-free, antimony-free gray glaze slurry as described in any one of claims 4 to 6; (2) applying the glaze to the surface of the blank and drying after the glazing is completed; (3) The dried sample is placed in a kiln with a reducing atmosphere for sintering.

9. The method for preparing lead-free and antimony-free grey glaze according to claim 8, characterized in that: The sintering heat preservation temperature is 1150-1350° C., and the sintering heat preservation time is 30-90 minutes.

10. Lead-free and antimony-free grey glazed products, characterized in that: The glazed product comprises a glaze surface prepared by using the glaze base material described in any one of claims 1 to 3, or the glaze slurry described in any one of claims 4 to 5; The product includes any one of ceramic products, glass products, metal products and fine ceramic products.

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