Iron gray metallic glaze and preparation method thereof

Abstract

The application provides a metal luster glaze, raw materials for preparing the metal luster glaze are composed of the following components with mass percentage: SiO2: 46-49%; Al2O3: 10-13%; CaO: 3-5%; MgO: 1-3%; BaO: 5-7%; K2O: 1-3%; Na2O: 0-2%; Li2O: 0-2%; TiO2: 6-8%; Fe2O3: 1-3%; CuO: 2-4%; MnO2: 7-9%; Cr2O3: 0-1%; CoO: 0-1%. The application can make the product present soft iron gray metal luster, be completely matched with a blank body, have high thermal stability, be resistant to acid and alkali, have low cost and be suitable for large-scale production by regulating the mass ratio of SiO2 / Al2O3, the content of flux components CaO and MgO and introducing appropriate Li2O.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of sanitary ceramics, and particularly relates to a grayish iron metal glaze and a preparation method thereof. BACKGROUND

[0002] Metal luster glaze refers to a kind of ceramic luster glaze which can produce color and luster similar to the surface of a certain metal by adding one or more transition metal oxides in the glaze. In recent years, it has been widely used in the production of wall and floor tiles as a special decorative art glaze. It is also applied to daily-use porcelain or art porcelain. The glaze surface emits a metallic luster, which adds a lot of thick and elegant charm to the porcelain, and is favored by consumers in the ceramic industry.

[0003] At present, there are still few products on the market that use metal luster glaze decoration on sanitary ceramics, and the colors are relatively monotonous. In the new era, people's pursuit of life quality and individuality is becoming stronger and stronger. In addition to the basic cleaning function, people will pay more attention to the quality of life and the feelings in their hearts when using bathroom products, and pay more attention to the space atmosphere created by bathroom products. Therefore, the development of diversified metal luster glaze can provide a wider space for the decoration of sanitary ceramics and greatly enrich the single color glaze at the present stage. Therefore, it is urgent to develop a sanitary ceramic metal luster glaze and a preparation method thereof at the present stage.

[0004] In the research on metal luster glaze (Wang Xufen. Research on metal luster glaze [D]. South China University of Technology), by adding TiO2, Fe2O3, CuO, MnO2 and other oxides in the base glaze, a good steel gray metal luster glaze is obtained after firing at 1155 DEG C in an oxidizing atmosphere. However, the crystal of the glaze surface is coarse, the glaze surface is rough, and the firing temperature is too low, which is not consistent with the firing temperature of the current sanitary porcelain. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a grayish iron metal glaze, which has a smooth and flat glaze surface, a soft color, and a more intense metal luster, and can be completely matched with the production body.

[0006] To achieve the above purpose, the present application adopts the following technical solutions.

[0007] A metal luster glaze, the preparation raw materials of the metal luster glaze consist of the following components with mass percentage: SiO2: 46-49%; Al2O3: 10-13%; CaO: 3-5%; MgO: 1-3%; BaO: 5-7%; K2O: 1-3%; Na2O: 0-2%; Li2O: 0-2%; TiO2: 6-8%; Fe2O3: 1-3%; CuO: 2-4%; MnO2: 7-9%; Cr2O3: 0-1%; CoO: 0-1%.

[0008] In some embodiments, the mass ratio of SiO2 and Al2O3 is (3.5-4.5):1.

[0009] In some embodiments, the sum of the mass percentage of CaO and MgO in the preparation raw material is 5%-7%.

[0010] The application also provides a preparation method of the metallic luster glaze as described above, comprising the following steps:

[0011] 1) ingredients are weighed according to the formula and mixed uniformly to obtain a material;

[0012] 2) the material, balls, water and carboxymethyl cellulose are simultaneously loaded into a rapid ball mill tank for wet ball milling to obtain a glaze slurry, and the glaze slurry is sieved through a 120-mesh sieve;

[0013] 3) a clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body;

[0014] 4) after the glaze surface is dried, it is fired in an oxidizing atmosphere.

[0015] In some embodiments, the mass ratio of the material, balls and water in step 2) is 1:2:0.65; and the mass of the carboxymethyl cellulose accounts for 0.5% of the total mass of the material, balls and water.

[0016] In some embodiments, the concentration of the glaze slurry after sieving in step 2) is 1.4g / cm 3 ~1.5g / cm 3 .

[0017] In some embodiments, the firing in step 4) is performed in a box muffle furnace at 1200℃.

[0018] The application also provides a ceramic containing the metallic luster glaze as described above or prepared by the preparation method as described above.

[0019] The application optimizes to obtain an iron-gray metallic glaze. In the preparation raw material, the content of SiO2 and Al2O3 has a great influence on the high-temperature viscosity of the glaze, thereby affecting the precipitation and growth of crystals; the flux components Li2O, Na2O, K2O, CaO, MgO and BaO can reduce the high-temperature viscosity of the melt and promote crystallization; TiO2, Fe2O3, CuO, MnO2, Cr2O3 and CoO can not only reduce the high-temperature viscosity of the glaze melt, but also TiO2, Fe2O3, CuO and MnO2 can form Fe3Ti3O 10The two crystals of CuMn2O4 and Fe3Ti3O7 make the glaze surface present metallic luster. By adjusting the mass ratio of SiO2 / Al2O3, the content of flux components CaO and MgO, and introducing appropriate Li2O on this basis, the metallic glaze can be matched with the sanitary porcelain body, and the firing temperature of the metallic glaze can be controlled within the allowable range of the sanitary porcelain production temperature. In addition, appropriate Cr2O3, CoO and other metal oxides are added in the metallic glaze of the application, which can effectively promote the growth of Fe3Ti3O7 crystal and CuMn2O4 crystal, and the two crystals can be effectively combined to form a new crystal structure. 10 The two crystals of CuMn2O4 and Fe3Ti3O7 are nucleated and grown, the two crystals are massively precipitated and directionally grown on the surface of the glaze layer, and the two crystals are combined to form a new crystal structure. 10 The crystal structure is distributed in parallel to the surface of the glaze layer, and the two crystals grow together and restrict each other, which avoids the roughness of the glaze surface caused by the excessive growth of a certain crystal in a certain direction, and the multiple crystals play a synergistic role to produce strong reflection of light, greatly enhances the metallic luster of the glaze surface, and makes the glaze surface present the characteristics of smoothness, soft color, warm and delicate, and dignified and elegant, which enriches the color types of the metallic glaze to a certain extent. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The firing effect diagram of the iron gray metallic luster glaze prepared in Example 1 of the application and a steel gray metallic luster glaze prepared in Comparative Example 1; wherein A: Example 1, B: Comparative Example.

[0021] Figure 2 The firing curve diagram of the iron gray metallic luster glaze prepared in Example 1 of the application.

[0022] Figure 3 The X-ray diffraction (XRD) spectrum of the glaze surface of the iron gray metallic luster glaze prepared in Example 1 of the application. DETAILED DESCRIPTION

[0023] The experimental methods not specified in the following examples of the application are usually carried out according to the conventional conditions, or according to the conditions suggested by the manufacturers. The various common chemical reagents used in the examples are all commercially available products.

[0024] Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0025] The terms "comprising" and "having" and any variations thereof herein are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of steps or modules is not necessarily limited to those listed steps or modules, but can include additional or alternative steps or modules not expressly listed or inherent to such process, method, article, or apparatus.

[0026] The following will be described in conjunction with specific embodiments.

[0027] Embodiment 1

[0028] The embodiment provides an iron-gray metallic luster glaze, and chemical compositions of components of a glaze used by the iron-gray metallic luster glaze are as follows: SiO2: 48.73%; Al2O3: 11.62%; CaO: 4.3%; MgO: 1.4%; BaO: 6.07%; K2O: 2.96%; Na2O: 1.02%; Li2O: 1%; TiO2: 7.55%; Fe2O3: 2.26%; CuO: 3.28%; MnO2: 8.81%; Cr2O3: 0.7%; and CoO: 0.3%.

[0029] The iron-gray metallic luster glaze is prepared by the following method.

[0030] 1) Weigh various raw materials according to components and masses of the components and mix uniformly;

[0031] 2) In a proportion of 1:2:0.65 of material: ball: water, 0.5% of CMC is additionally added, and then the mixture is loaded into a rapid ball mill tank for wet ball milling for 30 min; the glaze slurry after ball milling is passed through a 120-mesh screen, so that the concentration of the glaze slurry is controlled to be 1.5 g / cm 3 ;

[0032] 3) A clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body by using a spraying method, and the thickness of the glaze layer is controlled to be between 0.3-0.5 mm;

[0033] 4) After the glaze surface is dried, the glaze surface is placed in a box muffle furnace for firing at 1200 ℃, and the firing atmosphere is an oxidizing atmosphere.

[0034] The glaze surface obtained by the embodiment has an intense iron-gray metallic luster, and the glaze surface is flat and smooth, and has soft and warm and delicate color and luster.

[0035] Embodiment 2

[0036] The embodiment provides an iron-gray metallic luster glaze, and the chemical composition of each component of the glaze is as follows: SiO2: 48.73%; Al2O3: 11.87%; CaO: 4.3%; MgO: 1.15%; BaO: 6.07%; K2O: 2.96%; Na2O: 1.02%; Li2O: 1%; TiO2: 7.55%; Fe2O3: 2.26%; CuO: 3.28%; MnO2: 8.81%; Cr2O3: 0.7%; and CoO: 0.3%.

[0037] The iron-gray metallic luster glaze is prepared by the following method.

[0038] 1) various raw materials are weighed according to components and the mass of each component and uniformly mixed;

[0039] 2) in a proportion of 1:2:0.65 of material:ball:water, 0.5% of CMC is additionally added, and then the materials are loaded into a rapid ball mill tank for wet ball milling for 30 min; the glaze slurry after ball milling is sieved through a 120-mesh screen, so that the concentration of the glaze slurry is controlled to be 1.5 g / cm 3 ;

[0040] 3) a clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body by using a spraying method, and the thickness of the glaze layer is controlled to be between 0.3-0.5 mm;

[0041] 4) after the glaze surface is dried, the glaze surface is placed in a box muffle furnace for firing at 1200 DEG C, and the firing atmosphere is an oxidizing atmosphere.

[0042] The glaze surface obtained in the embodiment has strong iron-gray metallic luster, a small amount of pinholes, soft color, and warm and delicate delicacy.

[0043] Embodiment 3

[0044] The embodiment provides an iron-gray metallic luster glaze, and the chemical composition of each component of the glaze is as follows: SiO2: 46.73%; Al2O3: 12.87%; CaO: 4.3%; MgO: 2.15%; BaO: 6.07%; K2O: 2.96%; Na2O: 1.02%; Li2O: 1%; TiO2: 7.55%; Fe2O3: 2.26%; CuO: 3.28%; MnO2: 8.81%; Cr2O3: 0.7%; and CoO: 0.3%.

[0045] The iron-gray metallic luster glaze is prepared by the following method.

[0046] 1) various raw materials are weighed according to components and the mass of each component and uniformly mixed;

[0047] 2) with the ratio of material: ball: water being 1:2:0.65, plus 0.5% CMC, and then loaded into a rapid ball mill tank for wet ball milling for 30 min, and the glaze slurry after ball milling is passed through a 120-mesh screen to control the glaze slurry concentration at 1.5 g / cm 3 ;

[0048] 3) a clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body in a spraying manner, and the glaze layer thickness is controlled between 0.3-0.5 mm;

[0049] 4) after the glaze surface is dried, it is placed in a box muffle furnace for firing at 1200°C, and the firing atmosphere is an oxidizing atmosphere.

[0050] The glaze surface obtained in this example has a weak iron-gray metallic luster, and the glaze surface is flat and smooth, and the color is relatively soft.

[0051] Example 4

[0052] This example provides an iron-gray metallic luster glaze, and the chemical composition of each component of the glaze material used is as follows: SiO2: 49%; Al2O3: 10.46%; CaO: 4.54%; MgO: 2.05%; BaO: 6.07%; K2O: 2.96%; Na2O: 1.02%; Li2O: 1%; TiO2: 7.55%; Fe2O3: 2.26%; CuO: 3.28%; MnO2: 8.81%; Cr2O3: 0.7%; CoO: 0.3%.

[0053] The iron-gray metallic luster glaze is prepared by the following method:

[0054] 1) each raw material is weighed according to the component and the mass of each component, and mixed uniformly;

[0055] 2) with the ratio of material: ball: water being 1:2:0.65, plus 0.5% CMC, and then loaded into a rapid ball mill tank for wet ball milling for 30 min, and the glaze slurry after ball milling is passed through a 120-mesh screen to control the glaze slurry concentration at 1.5 g / cm 3 ;

[0056] 3) a clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body in a spraying manner, and the glaze layer thickness is controlled between 0.3-0.5 mm;

[0057] 4) after the glaze surface is dried, it is placed in a box muffle furnace for firing at 1200°C, and the firing atmosphere is an oxidizing atmosphere.

[0058] The glaze surface obtained in this example has almost no metallic feeling, and is more similar to a rubbery feeling, and only has a shiny feeling visually, and the glaze surface has many pinholes.

[0059] Example 5

[0060] The embodiment provides an iron-gray metallic luster glaze, and the chemical composition of each component of the glaze is as follows: SiO2: 47.85%; Al2O3: 10.51%; CaO: 4.84%; MgO: 2.85%; BaO: 6.07%; K2O: 2.96%; Na2O: 1.02%; Li2O: 1%; TiO2: 7.55%; Fe2O3: 2.26%; CuO: 3.28%; MnO2: 8.81%; Cr2O3: 0.7%; and CoO: 0.3%.

[0061] The iron-gray metallic luster glaze is prepared by the following method.

[0062] 1) The various raw materials are weighed according to the components and the mass of each component and uniformly mixed;

[0063] 2) The ratio of material: ball: water is 1:2:0.65, 0.5% of CMC is additionally added, and then the mixture is loaded into a rapid ball mill tank for wet ball milling for 30 min; the glaze slurry after ball milling is sieved through a 120-mesh screen, and the concentration of the glaze slurry is controlled to be 1.5 g / cm 3 ;

[0064] 3) A clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body by using a spraying method, and the thickness of the glaze layer is controlled to be between 0.3-0.5 mm;

[0065] 4) After the glaze surface is dried, the glaze surface is placed in a box muffle furnace for firing at 1200 DEG C, and the firing atmosphere is an oxidizing atmosphere.

[0066] The glaze surface obtained in the embodiment has a strong metallic feeling, but the crystals precipitated are coarse, the glaze surface is relatively rough in vision, and the bottom of the fired body has "glaze accumulation".

[0067] Comparative Example 1

[0068] The comparative example provides a steel-gray metallic luster glaze, and the mass of each component of the glaze is as follows: sodium feldspar: 10%; kaolin: 18%; quartz: 30%; talc: 6%; limestone: 14%; TiO2: 7%; Fe2O3: 5%; CuO: 1%; MnO2: 9%; and ZnO: 5%.

[0069] The steel-gray metallic luster glaze is prepared by the following method: the glaze slurry is prepared by introducing an appropriate amount of CuO into the base formula, and is applied to the body, and is fired at the highest firing temperature of 1150 DEG C, and is kept for 5 min, and the temperature is selected to be between 1000-1050 DEG C during the cooling process, and is kept for 30 min, and finally is cooled with the furnace.

[0070] Comparative Example 2

[0071] The embodiment provides a kind of iron gray metal luster glaze, the chemical composition mass percentage of each component of glaze used in it is as follows: SiO2: 50.3%; Al2O3: 9.58%; CaO: 4.77%; MgO: 1.4%; BaO: 6.07%; K2O: 2.96%; Na2O: 1.02%; Li2O: 1%; TiO2: 7.55%; Fe2O3: 2.26%; CuO: 3.28%; MnO2: 8.81%; Cr2O3: 0.7%; CoO: 0.3%.

[0072] The iron gray metal luster glaze is prepared by the following method:

[0073] 1) the various raw materials are weighed according to the components and the mass of each component and mixed uniformly;

[0074] 2) with the ratio of material: ball: water being 1:2:0.65, 0.5% of CMC is additionally added, and then it is loaded into a rapid ball mill tank for wet ball milling for 30 min; the glaze slurry after ball milling is sieved through a 120-mesh sieve, so that the concentration of the glaze slurry is controlled to be 1.5 g / cm 3 ;

[0075] 3) a clean body is taken, and the glaze slurry is sprayed on the inner and outer surfaces of the body by using the spraying method, and the thickness of the glaze layer is controlled to be between 0.3-0.5 mm;

[0076] 4) after the glaze surface is dried, it is placed in a box muffle furnace for firing at 1200 DEG C, and the firing atmosphere is an oxidizing atmosphere.

[0077] Compared with examples 2-3, the total amount of SiO2 and Al2O3 and the total amount of CaO and MgO in example 1 are between those in examples 2-3, but the mass ratio of SiO2 / Al2O3 is the largest.Combined with the firing effect description of examples 1-3, it can be illustrated that when the total amount of SiO2 and Al2O3 and the total amount of CaO and MgO are within a suitable range, with the increase of the mass ratio of SiO2 / Al2O3, it is beneficial for the glaze melt to have a suitable viscosity at high temperature, and the diffusion and migration of crystal nucleation points in the melt are easier to proceed, so as to be beneficial for the crystal to grow and enhance the metal luster effect of the glaze surface.

[0078] Compared with example 1, the mass ratio of SiO2 / Al2O3 in example 4 is 4.68:1, which is not within the range of (3.5-4.5):1, resulting in that the obtained glaze surface has almost no metal feeling, is more similar to rubber feeling, has only luster feeling in vision, and has more pinholes on the glaze surface.

[0079] Compared with example 1, the total amount of CaO and MgO in example 5 accounts for 7.69% of the total amount of glaze slurry glaze, which is not within the range of 5%-7%, resulting in that the obtained glaze surface has strong metal feeling, but the crystals precipitated are coarse, the glaze surface is relatively rough in vision, and the bottom of the fired body has "glaze accumulation".

[0080] Compared with Example 1, the steel gray metallic luster glaze in Comparative Example 1 has coarse crystals precipitated on the glaze surface, the glaze surface is rough, and the metallic luster is poor. Figure 1 B); while the iron gray metallic luster glaze prepared in Example 1 has a smooth and even glaze surface, soft color, warm and delicate, and solemn and elegant, which basically meets the research and development requirements (A). Figure 1

[0081] Figure 2 is the firing curve diagram of the metallic glaze surface of Example 1; Figure 3 is the XRD pattern of the metallic glaze surface of Example 1. As shown in Figure 3 , the diffraction peaks of the precipitated Fe3Ti3O 10 crystals and CuMn2O4 crystals mainly show the diffraction peaks of (200) crystal face and (311) crystal face, respectively. It can be inferred that the reason for the metallic luster of the glaze surface is that the (200) crystal face of the Fe3Ti3O 10 crystals is parallel to the glaze surface, and the two kinds of crystals grow in the direction of the glaze surface and restrict each other. The existence of CuMn2O4 crystals avoids the excessive growth of Fe3Ti3O 10 crystals along the (200) crystal face, which causes the size to be too large and the glaze surface to be rough, thereby jointly enhancing the light reflection ability of the glaze surface and making the metallic luster of the glaze surface more intense.

[0082] Compared with Example 1, the glaze melt has a relatively small high-temperature viscosity in Comparative Example 1 even at a lower firing temperature, and the precipitated crystals cause the metallic glaze glaze surface to be rough due to excessive growth, which seriously affects the aesthetic appearance of the glaze surface.

[0083] Compared with Example 1, the amount of SiO2 and Al2O3 in Comparative Example 2 is not within the range of the present application, resulting in a glaze surface without metallic texture, similar to the luster of ordinary bright color glaze.

[0084] In summary, by adjusting the mass ratio of SiO2 / Al2O3, the content of CaO and MgO in the flux component, and introducing an appropriate amount of Li2O on this basis, the product can present a soft iron gray metallic luster, which is completely matched with the production blank, has high thermal stability, is resistant to acid and alkali, has low cost, and is suitable for large-scale production. In the process of bathroom decoration, if other light color matching products are matched, the artistic effect of perfect coordination of light and shade, soft and warm color, and ancient style can be achieved.

[0085] The technical features of the above-described embodiments can be combined in any manner. In order to make the description concise, all possible combinations of the technical features in the above embodiments are not described, but as long as the combinations of the technical features do not exist, they should be considered as the scope of the present disclosure. ​

[0086] The above embodiments only express several implementation manners of the present application, which are described in a more specific and detailed manner, but cannot be understood as a limitation on the patent scope of the present application. It should be noted that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A metallic luster glaze, characterized by, The preparation raw material of the metal luster glaze is composed of the following components with mass percentage: SiO2: 46-49%; Al2O3: 10-13%; CaO: 3-5%; MgO: 1-3%; BaO: 5-7%; K2O: 1-3%; Na2O: 0-2%; Li2O: 0-2%; TiO2: 6-8%; Fe2O3: 1-3%; CuO: 2-4%; MnO2: 7-9%; Cr2O3: 0-1%; CoO: 0-1%; the mass ratio of SiO2 and Al2O3 is (3.5~4.5):

1.

2. The metallic luster glaze of claim 1, wherein The sum of mass percentage of CaO and MgO in the preparation raw material is 5%~7%.

3. The method of producing a metallic luster glaze according to any one of claims 1 to 2, wherein The method comprises the following steps: 1) weighing each component according to the formula and mixing uniformly to obtain material; 2) loading the material, ball, water and carboxymethyl cellulose into a rapid ball mill tank simultaneously for wet ball milling to obtain glaze slurry, and passing the glaze slurry through a 120-mesh screen; 3) taking clean body, and spraying the glaze slurry on the inner and outer surface of the body; 4) after the glaze surface is dried, firing it in an oxidizing atmosphere.

4. The production method according to claim 3, wherein In step 2), the mass ratio of the material, ball and water is 1:2:0.65; the mass of the carboxymethyl cellulose accounts for 0.5% of the total mass of the material, ball and water.

5. The production method according to claim 3, wherein Step 2) The concentration of the sieved slip was 1.4 g / cm 3 1.5 g / cm 3 .

6. The production method according to claim 3, wherein In step 4), firing in a 1200℃ box muffle furnace.

7. A ceramic, characterized by, The ceramic contains the metal luster glaze as claimed in any one of claims 1~2 or the metal luster glaze prepared by the preparation method as claimed in any one of claims 3~6.

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