Glaze with metal-like light sense and application thereof in preparation of high-fidelity metal-like light sense ceramic tile

Abstract

The application discloses a glaze with a metal-imitating light sense and application of the glaze in preparation of high-fidelity metal-imitating light sense ceramic tiles. The glaze raw material comprises, by weight, 58-75 parts of base glaze, 16-25 parts of liquid pearlescent agent, 1-2 parts of pigment, 2-5 parts of sodium chloride and 6-10 parts of suspended solvent. The liquid pearlescent agent in the glaze is coated with high-refraction-index nano-sized particles of titanium dioxide, nickel oxide and zinc oxide through a series of chemical reactions on the surface of low-refraction-index natural mica powder. When light irradiates on the surface of the liquid pearlescent agent, the light is reflected and refracted for multiple times, so that the ceramic tile sprayed with the glaze has high-fidelity metal-imitating gloss. In addition, during the firing of the ceramic tile, the sodium chloride in the glaze is volatilized and seeped out to form a glassy thin layer on the surface of the body, which prevents the ceramic tile from moisture, corrosion and pigment oxidation and discoloration, and saves the preparation cost of the ceramic tile.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal-imitating light-sensitive glaze, in particular to a metal-imitating light-sensitive glaze and its application in the preparation of high-fidelity metal-imitating light-sensitive ceramic tiles. BACKGROUND

[0002] Glazes used in building and sanitary ceramic tile products are increasingly diverse, and most enterprises use glaze products, which can be roughly classified into lead glaze and lead-free glaze, raw material glaze and fused glaze, one-time firing or twice firing glaze; according to the glazing method, it is also divided into dipping glazing, spraying glazing, and pouring glazing; there are various pursuits in terms of color patterns and light sensitivity of glaze, such as colored glaze and colorless glaze, transparent glaze and opaque glaze, glossy glaze, matte glaze, semi-matte glaze, and patterned glaze, etc.

[0003] The decorative effect of ceramic tiles with metal luster is magnificent, luxurious and beautiful, and has become a new object of pursuit. At present, the main methods to achieve metal-imitating luster on glaze surface are electroplating and paint spraying, which have certain limitations: the use of electroplating method is seriously wasteful, and the electroplating process is seriously polluting, and the plated layer is easy to wear and fall off; paint spraying treatment forms a metal texture on the glaze surface, but the treatment technology cost is high, and there is three-waste pollution to the environment, i.e. waste gas, waste water and waste paint residue, and the product will have paint film abrasion and fall off during long-term use, and is easy to be damp and oxidized, causing the metal-imitating luster of the ceramic tile to become dull. SUMMARY

[0004] In view of the defects of the prior art, the present application provides a metal-imitating light-sensitive glaze and its application in the preparation of high-fidelity metal-imitating light-sensitive ceramic tiles, which has high-fidelity metal-imitating luster, delicate and shining luster, and magnificence, and can be applied to ceramic tiles. In addition, a layer of glass salt thin layer will be formed on the glaze surface during the firing process, and no additional glass glaze protective layer is needed during glazing, which not only saves cost, but also achieves the purposes of moisture-proof and oxidation-proof.

[0005] The technical problem of the present application is solved by the following technical scheme:

[0006] The present application provides a metal-imitating light-sensitive glaze, which comprises, by weight: 58-75 parts of base glaze, 16-25 parts of liquid pearl agent, 1-2 parts of pigment, 2-5 parts of sodium chloride, and 6-10 parts of suspending solvent.

[0007] Preferably, the glaze raw material comprises, by weight: 66 parts of base glaze, 22 parts of liquid pearl agent, 1 part of pigment, 3 parts of sodium chloride, and 8 parts of suspending solvent.

[0008] The liquid pearling agent comprises by weight parts: mica 43-62 parts, white glass 11-16 parts, borax 17-19 parts, nickel oxide 1-2 parts, zinc oxide 2-5 parts, titanium dioxide 7-15 parts.

[0009] Preferably, the liquid pearling agent comprises by weight parts: mica 46-55 parts, white glass 12-16 parts, borax 17-19 parts, nickel oxide 1-2 parts, zinc oxide 3-4 parts, titanium dioxide 13-15 parts.

[0010] Preferably, the liquid pearling agent raw material comprises by weight parts: mica 50 parts, white glass 14 parts, borax 18 parts, nickel oxide 1 part, zinc oxide 3 parts, titanium dioxide 14 parts.

[0011] The inventor of the present application found that a mica titanium liquid pearling agent made of the above raw materials can make the glaze have a metal-like light sense, and the mica replaces aluminum particles. A series of chemical reactions are performed on the surface of natural mica powder with low refractive index to accurately coat nano-sized particles of titanium dioxide, nickel oxide and zinc oxide with high refractive index, simulate the negative charge electron sea of a large number of metal surface electrons wandering around cations, and when light irradiates the surface, the light undergoes multiple reflections and refractions to produce a rich metal-like luster.

[0012] The inventor also found that adding sodium chloride to the glaze enables the sodium chloride to seep out and volatilize at high temperature during the firing process of the ceramic tile, float on the surface of the body to form a glassy thin layer, and play a role in preventing moisture, corrosion and pigment oxidation discoloration of the ceramic tile. The ceramic tile does not need to be additionally coated with a glass glaze protective layer, thereby saving the preparation cost.

[0013] The borax mainly comprises sodium tetraborate pentahydrate, and the mass percentage of boron in the borax is 3%-8%. The borax can reduce the elasticity of the glaze, reduce the melting temperature of the glaze, and improve the gloss of the glaze.

[0014] The preparation method of the liquid pearling agent is as follows:

[0015] S1, grinding the mica into fine powder in a grinding machine, sieving to 200 mesh, adding 3 times the mass of deionized water to the mica and dispersing and stirring with a high-speed frame stirrer at a stirring rate of 1300-1500 r / min, and stirring while heating to 70-80℃, and then stirring for 0.5 h after the temperature is constant;

[0016] S2, adjusting the pH value to 2.0-2.5 by adding 10% hydrochloric acid solution under stirring, and then adding 5% titanium tetrachloride solution, and reacting for 1 h;

[0017] S3, slowly adding 12% sodium hydroxide solution to weak alkaline pH, adding zinc oxide and titanium dioxide, and reacting for 0.5 h, and then pouring into an ammonium chloride solution to quench, to obtain a pre-prepared liquid mixture;

[0018] S4, grinding white glass, borax and nickel oxide into powder, adding into the prepared liquid mixture, rotary evaporation at 45 DEG C for 0.5h under vacuum, cooling, and then the liquid pearlescent agent is obtained.

[0019] An enamel with metal-like light sense, and a method for preparing high-fidelity metal-like light sense ceramic tiles is provided.

[0020] S11, melting the base enamel and sodium chloride into glassy substance according to the ratio, quenching into small frits with water, and then ball milling with other raw materials to obtain the enamel with metal-like light sense;

[0021] S12, spraying the enamel on the pressed body with the thickness controlled at 0.4-0.6mm, and ultrasonicating in a closed space for 15-20min with the ultrasonic power of 100-120W;

[0022] S13, putting into the kiln for calcination at 1000-1200 DEG C, and grinding the edges, and then the high-fidelity metal-like light sense ceramic tile is obtained.

[0023] Preferably, the process for firing the ceramic tile is as follows: the heating rate is 50 DEG C / min, the highest temperature is 1200 DEG C, the temperature is kept for 10-15min, and then the product is rapidly cooled with the kiln exit temperature of 300-400 DEG C.

[0024] Preferably, the base enamel includes, by weight, calcium carbonate 7-17 parts, potassium dichromate 3-5 parts, calcined talc 10-13 parts, Longyan soil 8-11 parts, sodium feldspar 13-17 parts, clay 22-27 parts, and calcite 9-11 parts.

[0025] Preferably, the suspension solvent is ethylene glycol distearate and polyvinyl alcohol with the mass ratio of 1.5:1.

[0026] The beneficial effects of the present application are as follows:

[0027] The present application improves the composition of the enamel, adds a liquid pearlescent agent and sodium chloride, so that the ceramic tile with the enamel has rich metal-like light sense, and can show color different metal luster color through the adjustment of various pigments, and has excellent decoration effect; the sodium chloride forms a glassy film on the surface of the ceramic tile during the firing process, reduces the moisture and oxidation of the enamel, and saves the cost of additional transparent protective glaze layer in the preparation of general ceramic tiles. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with specific embodiments.

[0029] Embodiment 1.

[0030] The raw materials of the glaze of the embodiment include, by weight, 58 parts of base glaze, 25 parts of liquid pearl, 2 parts of pigment, 5 parts of sodium chloride, and 10 parts of suspension solvent.

[0031] The liquid pearl of the embodiment includes, by weight, 43 parts of mica, 16 parts of white glass, 19 parts of borax, 2 parts of nickel oxide, 5 parts of zinc oxide, and 15 parts of titanium dioxide.

[0032] The preparation method of the liquid pearl is as follows:

[0033] S1, put the mica into a grinder to grind into fine powder, sieve to 200 mesh, add 3 times the mass of deionized water to the mica and disperse and stir with a high-speed frame stirrer at a stirring rate of 1300 r / min, and heat to 70℃ while stirring; after the temperature is constant, stir for 0.5 h;

[0034] S2, adjust the pH value to 2.0 by adding 10% hydrochloric acid solution under stirring, then add 5% titanium tetrachloride solution, and react for 1 h;

[0035] S3, slowly add 12% sodium hydroxide solution to weak alkaline pH, add zinc oxide and titanium dioxide, react for 0.5 h, pour into ammonium chloride solution to quench, and obtain a pre-prepared liquid mixture;

[0036] S4, grind the white glass, borax, and nickel oxide into powder, add to the pre-prepared liquid mixture, rotary evaporate at 45℃ under vacuum for 0.5 h, and cool to obtain the liquid pearl.

[0037] The method for preparing a high-fidelity metal-imitating glaze ceramic tile of the embodiment is as follows:

[0038] S11, melt the base glaze and sodium chloride according to the ratio to form a glassy substance, quench into small frits with water, then ball mill with other raw materials to obtain a metal-imitating glaze;

[0039] S12, spray the glaze on the pressed body, control the thickness to be 0.4 mm, and ultrasonic in a closed space for 15 min at a power of 100 W;

[0040] S13, put into a kiln to calcine at 1000℃, and grind the edges to obtain a high-fidelity metal-imitating glaze ceramic tile.

[0041] The firing process of the ceramic tile of the embodiment is as follows: the heating rate is 50℃ / min, the highest temperature is 1000℃, and the temperature is kept at this temperature for 10 min, then rapidly cooled, and the product is discharged from the kiln at a temperature of 300℃.

[0042] The base glaze of the embodiment includes, by weight: calcium carbonate 7 parts, potassium dichromate 5 parts, calcined talc 13 parts, Longyan clay 11 parts, albite 17 parts, clay 27 parts, calcite 11 parts.

[0043] The suspension solvent of the embodiment is ethylene glycol distearate and polyvinyl alcohol, with a mass ratio of 1.5:1.

[0044] Embodiment 2.

[0045] The glaze with a metallic luster of the embodiment includes, by weight: base glaze 75 parts, liquid pearl 16 parts, pigment 1 part, sodium chloride 2 parts, suspension solvent 6 parts.

[0046] The liquid pearl of the embodiment includes, by weight: mica 62 parts, white glass 11 parts, borax 17 parts, nickel oxide 1 part, zinc oxide 2 parts, titanium dioxide 7 parts.

[0047] The preparation method of the liquid pearl is as follows:

[0048] S1, put the mica into a grinder to grind into fine powder, sieve to 200 mesh, add 3 times the mass of deionized water to the mica and disperse and stir with a high-speed frame stirrer, the stirring rate is 1500 r / min, and the temperature is raised to 80℃ while stirring, after the temperature is constant, stir for 0.5 h;

[0049] S2, under stirring, add 10% hydrochloric acid solution to adjust the pH value to 2.5, then add 5% titanium tetrachloride solution, and react for 1 h;

[0050] S3, slowly add 12% sodium hydroxide solution to weak alkaline pH, add zinc oxide and titanium dioxide, react for 0.5 h, pour into ammonium chloride solution to quench, and obtain a pre-prepared liquid mixture;

[0051] S4, grind the white glass, borax and nickel oxide into powder, add to the pre-prepared liquid mixture, rotary evaporate at 45℃ under vacuum for 0.5 h, and cool to obtain the liquid pearl.

[0052] The method for preparing the glaze with a metallic luster in the high-fidelity ceramic tile with a metallic luster of the embodiment is as follows:

[0053] S11, melt the base glaze and sodium chloride according to the ratio to form a glassy substance, quench into small frits with water, then ball mill with other raw materials to obtain the glaze with a metallic luster;

[0054] S12, spray the glaze on the pressed body, control the thickness to be 0.6 mm, and ultrasonic in a closed space for 20 minutes, the ultrasonic power is 120 W;

[0055] S13, put into the kiln at 1200℃ calcination, grinding edge, namely the high realistic imitation metal light sense of ceramic tile.

[0056] The firing process of the ceramic tile of the embodiment is: the temperature rising rate is 50℃ / min, the highest temperature is 1200℃, the temperature is kept for 15min at the highest temperature, and then the product is rapidly cooled, and the product out of the kiln is at a temperature of 400℃.

[0057] The base glaze of the embodiment includes, by weight: calcium carbonate 17 parts, potassium dichromate 3 parts, calcined talc 10 parts, Longyan soil 8 parts, sodium feldspar 13 parts, clay 22 parts, and calcite 9 parts.

[0058] The suspension solvent of the embodiment is ethylene glycol distearate and polyvinyl alcohol, and the mass ratio is 1.5:1.

[0059] Embodiment 3.

[0060] The glaze with the imitation metal light sense of the embodiment includes, by weight: base glaze 66 parts, liquid pearl 22 parts, pigment 1 part, sodium chloride 3 parts, and suspension solvent 8 parts.

[0061] The liquid pearl of the embodiment includes, by weight: mica 50 parts, white glass 14 parts, borax 18 parts, nickel oxide 1 part, zinc oxide 3 parts, and titanium dioxide 14 parts.

[0062] The preparation method of the liquid pearl is:

[0063] S1, put the mica into a grinding machine to grind into fine powder, sieve to 200 mesh, add 3 times the mass of deionized water to the mica and disperse and stir with a high-speed frame stirrer, the stirring rate is 1400r / min, the temperature is raised to 75℃ while stirring, and after the temperature is constant, the stirring is performed for 0.5h;

[0064] S2, under the stirring state, add 10% hydrochloric acid solution to adjust the pH value to 2.3, then add 5% titanium tetrachloride solution, and react for 1h;

[0065] S3, slowly add 12% sodium hydroxide solution to weak alkaline pH, add zinc oxide and titanium dioxide, react for 0.5h, pour into ammonium chloride solution to quench, and obtain a pre-prepared liquid mixture;

[0066] S4, grind the white glass, borax and nickel oxide into powder, add to the pre-prepared liquid mixture, rotary evaporate at 45℃ under vacuum for 0.5h, and cool to obtain the liquid pearl.

[0067] The method of the glaze with the imitation metal light sense of the embodiment in the preparation of the high realistic imitation metal light sense ceramic tile is:

[0068] S11, the base glaze and sodium chloride are melted into a glassy substance according to the ratio, quenched into small frits with water, and then ball milled with other raw materials to obtain a metal-like gloss glaze;

[0069] S12, the glaze is sprayed on the pressed body to a thickness of 0.5mm, and is ultrasonically treated in a closed space for 18 minutes at a power of 110W;

[0070] S13, put into the kiln to calcine at 1100℃, and grind the edges to obtain a high-fidelity metal-like gloss ceramic tile.

[0071] The firing process of the ceramic tile of the embodiment is as follows: the temperature rising rate is 50℃ / min, the highest temperature is 1100℃, the temperature is kept at this temperature for 12min, and then the product is rapidly cooled, and the product out of the kiln is at a temperature of 350℃.

[0072] The base glaze of the embodiment includes, by weight: calcium carbonate 12 parts, potassium dichromate 4 parts, calcined talc 12 parts, Longyan soil 10 parts, sodium feldspar 15 parts, clay 24 parts, and calcite 10 parts.

[0073] The suspension solvent of the embodiment is ethylene glycol distearate and polyvinyl alcohol, and the mass ratio is 1.5:1.

[0074] Comparative Example 1.

[0075] Different from Example 3, the titanium dioxide in the liquid pearl luster agent raw material is replaced by tin dioxide, and the rest is the same.

[0076] Comparative Example 2.

[0077] Different from Example 3, in the preparation method of the liquid pearl luster agent, the step of “adding 10% hydrochloric acid solution under stirring to adjust the pH value to 2.5, then adding 5% titanium tetrachloride solution, and reacting for 1h” is replaced by “adding 5% titanium sulfate under stirring, and reacting for 3h”, and the rest is the same.

[0078] Comparative Example 3.

[0079] Different from Example 3, the sodium chloride in the glaze raw material is replaced by potassium chloride, and the rest is the same.

[0080] In order to further prove the effect of the application, four ceramic tile samples are prepared according to Examples 1-3 and Comparative Examples 1-3 respectively to evaluate the metal gloss and oxidation resistance, and the evaluation results are as follows:

[0081]

[0082] As can be seen from Examples 1-3, the glaze prepared according to the method of the present application makes the ceramic tile have high fidelity, rich metal-like light sense, excellent decorative effect, and certain moisture resistance and oxidation resistance.

[0083] As can be seen from Comparative Example 1 and Example 3, when the titanium dioxide in the liquid pearlescent agent raw material is replaced by tin dioxide, the refractive index of the tin dioxide is lower, the adhesion to zinc oxide and nickel oxide is not strong enough, the coating degree to the mica is weaker, the light refraction is not strong enough, and the glaze metal luster is not good enough.

[0084] As can be seen from Comparative Example 2 and Example 3, in the preparation method of the liquid pearlescent agent, the step of "adding 10% hydrochloric acid solution under stirring to adjust the pH value to 2.5, and then adding 5% titanium tetrachloride solution and reacting for 1 h" is replaced by "adding 5% titanium sulfate under stirring and reacting for 3 h", the reaction is not pre-acidified, the obtained titanium dioxide crystal form is different, and the glaze luster is not good enough.

[0085] As can be seen from Comparative Example 3 and Example 3, when the sodium chloride in the glaze raw material is replaced by potassium chloride, the boiling point of the potassium chloride is 1420℃, it is difficult to form a glassy film on the glaze surface during the ceramic tile firing process, and increasing the ceramic tile firing temperature may cause the tile body to deform and crack, so the sodium chloride is more suitable.

[0086] The innovation of the present application lies in that:

[0087] The liquid pearlescent agent in the glaze coats the high-refractive-index nano-sized particles titanium dioxide, nickel oxide and zinc oxide on the surface of the low-refractive-index natural mica powder through a series of chemical reactions, when light irradiates the surface, the light is reflected and refracted through multiple layers, so that the ceramic tile sprayed with the glaze has high-fidelity metal-like luster.

[0088] In addition, during the ceramic tile firing process, the sodium chloride in the glaze volatilizes and adheres to the surface of the body to form a glassy layer, which has the effects of moisture resistance, corrosion resistance and pigment oxidation resistance, and saves the preparation cost of the ceramic tile.

[0089] It is apparent for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be regarded as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application.

[0090] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes every feature or implementation described herein. The specification can include implicit combinations of explicitly mentioned features and / or implicit combinations of implicitly mentioned features. Such combinations are also expressly included within the scope of the specification and an embodiment.

Claims

1. A glaze having a metallic-like light sensation, characterized by comprising: The enamel raw material comprises, by weight parts: base enamel 58-75 parts, liquid pearl 16-25 parts, pigment 1-2 parts, sodium chloride 2-5 parts, and suspension solvent 6-10 parts; The liquid pearl comprises, by weight parts: mica 46-55 parts, white glass 12-16 parts, borax 17-19 parts, nickel oxide 1-2 parts, zinc oxide 3-4 parts, and titanium dioxide 13-15 parts; The base enamel comprises, by weight parts: calcium carbonate 7-17 parts, potassium dichromate 3-5 parts, calcined talc 10-13 parts, Longyan soil 8-11 parts, sodium feldspar 13-17 parts, clay 22-27 parts, and calcite 9-11 parts; The preparation method of the liquid pearl is as follows: S1, put the mica into a grinding machine to grind into fine powder, sieve to 200 mesh, add 3 times the mass of deionized water to the mica and disperse and stir with a high-speed frame stirrer at a stirring rate of 1300-1500 r / min, and heat to 70-80℃ while stirring, and after the temperature is constant, stir for 0.5 h; S2, under stirring, add 10% hydrochloric acid solution to adjust the pH value to 2.0-2.5, then add 5% titanium tetrachloride solution, and react for 1 h; S3, slowly add 12% sodium hydroxide solution to weak alkaline pH, add zinc oxide and titanium dioxide, react for 0.5 h, pour into ammonium chloride solution to quench, and obtain a pre-prepared liquid mixture; S4, grind the white glass, borax and nickel oxide into powder, add to the pre-prepared liquid mixture, rotary evaporate at 45℃ under vacuum for 0.5 h, cool, and obtain the liquid pearl.

2. The glaze having a metallic luster according to claim 1, wherein The enamel raw material comprises, by weight parts: base enamel 66 parts, liquid pearl 22 parts, pigment 1 part, sodium chloride 3 parts, and suspension solvent 8 parts.

3. The glaze with a metallic luster according to claim 1, wherein The liquid pearl raw material comprises, by weight parts: mica 50 parts, white glass 14 parts, borax 18 parts, nickel oxide 1 part, zinc oxide 3 parts, and titanium dioxide 14 parts.

4. The glaze with a metallic luster according to claim 1, wherein The suspension solvent is ethylene glycol distearate and polyvinyl alcohol, and the mass ratio is 1.5:

1.

5. Use of the enamel with metal-like light sense according to any one of claims 1-4 in the preparation of high-fidelity metal-like light sense ceramic tiles.

6. Use according to claim 5, characterized in that, The specific method of the enamel in the preparation of high-fidelity metal-like light sense ceramic tiles is as follows: S11, melt the base enamel and sodium chloride according to the ratio to form a glass-like substance, quench into small clinkers with water, and then ball mill with other raw materials to obtain the metal-like light sense enamel; S12, spray the enamel on the pressed body, control the thickness to be 0.4-0.6 mm, and ultrasonic in a closed space for 15-20 minutes at an ultrasonic power of 100-120 W; S13, put into a kiln to calcine at 1000-1200℃, and grind the edges, to obtain the high-fidelity metal-like light sense ceramic tiles.

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