Silver-white metal dry granular glaze and preparation method and application thereof

Abstract

The present application relates to the technical field of building ceramics, and particularly relates to a silver-white metal dry particle glaze and a preparation method and application thereof, and comprises the following steps: A. under an inert atmosphere, completely melting silicon, aluminum, iron, chromium, manganese, vanadium and nickel, and obtaining alloy liquid drops after liquid crushing; under a natural environment, cooling the alloy liquid drops to obtain alloy dry particles; B. uniformly mixing kaolin, quartz, calcite, dolomite, barium carbonate and zinc oxide, and obtaining crystal frit after calcination, water quenching, ball milling and sieving; C. uniformly mixing the alloy dry particles, the crystal frit and a suspending agent to obtain the silver-white metal dry particle glaze. The preparation method of the silver-white metal dry particle glaze can not only have excellent silver-white metal texture effect, transparency and stain resistance, but also has high wear resistance and hardness under the premise of ensuring uniform silver-white metal texture effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building ceramics, in particular to a silver-white metal dry particle glaze and a preparation method and application thereof. BACKGROUND

[0002] Metallic glaze is a special glaze, which can make the surface of ceramic tiles present a metallic texture effect after being applied on the surface of the body and fired at high temperature, and is widely used in the building decoration industry. The existing metallic glaze is mainly composed of metal dry particles and frits. However, the frits usually need to add fluxes such as lithium oxide (Li2O), boron oxide (B2O3), potassium oxide (K2O) and sodium oxide (Na2O) to reduce the melting temperature. However, the chemical activity of the above-mentioned fluxes is very high, which will gradually dissolve the metal oxides on the surface of the metal dry particles, forming pores and micro-cracks on the surface. Subsequently, the fluxes penetrate into the interior of the metal dry particles through the pores and cracks, react with them, and finally cause the metal dry particles to completely corrode and discolor, losing the original metallic texture effect.

[0003] In order to prevent the metal dry particles from being corroded and discolored, the existing frits usually use feldspathic frits with low flux content and high silicon-aluminum content, and the feldspathic frits use kaolin and quartz as the main aluminum and silicon sources. However, due to the high melting temperature of quartz and the relatively insufficient content of fluxes, the proportion of un-melted quartz remaining in the frits is relatively high. The refractive index of un-melted quartz (about 1.65) is significantly different from that of the glass phase (about 1.50), and the above-mentioned refractive index mismatch easily causes strong light scattering effect, thereby reducing the transparency of the glaze surface. With the increase of the content of un-melted quartz, the light scattering phenomenon is intensified, further affecting the transparency of the glaze surface.

[0004] At the same time, due to the insufficient content of fluxes in the system, the aluminum oxide generated by the decomposition of kaolin at high temperature (> 950℃) is difficult to completely melt, which will exist in the form of inert α-Al2O3 and mullite crystals. The refractive index of inert α-Al2O3 (corundum phase, refractive index of 1.76) and mullite crystals (refractive index of 1.64) is significantly different from that of the glass phase (about 1.50), further intensifying the light scattering, and thus further reducing the transparency of the glaze surface. The reduction of transparency will cover the original pattern of the ceramic tile decoration layer, affecting the overall decoration effect of the ceramic tile. In addition, due to the serious lack of fluxes in the feldspathic frits, the glass phase generated in the feldspathic frits is seriously insufficient, and the glass phase is difficult to completely wrap the un-melted quartz, un-melted α-Al2O3 and mullite crystals, so that there are pores between the un-melted quartz, un-melted α-Al2O3 and mullite crystals, resulting in high porosity of the glaze surface after calcination of the metallic glaze added with the feldspathic frits, and pollutants are easy to penetrate, and the stain resistance is poor.

[0005] Since the transparent glaze generally has high transparency and stain resistance, in order to effectively improve the transparency and stain resistance, the glaze formed after the frit added with the feldspathic frit is calcined has high stain resistance on the premise of not affecting the pattern effect of the original decorative layer of the ceramic tile. The prior art attempts to add a large amount of transparent glaze in the metal glaze formula, but due to the large amount of transparent glaze added, the content of the fluxing agent in the formula is also large, so that the metal dry particles are also easily completely corroded, so that the original metal texture effect is lost. In addition, since the transparent glaze generally contains a certain amount of water, the metal glaze obtained by compounding the metal dry particles, the feldspathic frit and the transparent glaze also contains water. Since the specific gravity of the metal dry particles is very large, it is very easy to precipitate in the above-mentioned water-containing metal glaze, resulting in poor uniformity of the distribution of the metal dry particles of the calcined glaze, affecting the uniformity of the metal texture effect.

[0006] In summary, the existing metal glaze cannot simultaneously have excellent metal texture effect, transparency and stain resistance, and also cannot ensure the uniformity of the metal texture effect. SUMMARY

[0007] The first object of the present application is to provide a preparation method of a silver-white metal dry particle glaze, which is simple in preparation method and strong in operability, and can not only have excellent silver-white metal texture effect, transparency and stain resistance simultaneously on the premise of ensuring the uniformity of the silver-white metal texture effect, but also has high wear resistance and hardness, so as to overcome the shortcomings of the prior art.

[0008] The second object of the present application is to provide a silver-white metal dry particle glaze, which can not only have excellent silver-white metal texture effect, transparency and stain resistance simultaneously on the premise of ensuring the uniformity of the silver-white metal texture effect, but also has high wear resistance and hardness, so as to make the silver-white metal dry particle glaze have both decoration and practicability.

[0009] The third object of the present application is to provide an application of a silver-white metal dry particle glaze, which is applied to prepare a silver-white metal texture ceramic tile, so as to ensure that the obtained silver-white metal texture ceramic tile can not only have excellent silver-white metal texture effect, transparency and stain resistance simultaneously on the premise of realizing the uniformity of the silver-white metal texture effect, but also has high wear resistance and hardness, so as to make the silver-white metal texture ceramic tile have both decoration and practicability.

[0010] To achieve this object, the present application adopts the following technical solutions:

[0011] A preparation method of a silver-white metal dry particle glaze, comprising the following steps:

[0012] A. Under inert atmosphere, 6-7 parts of silicon element, 0.1-0.2 parts of aluminum element, 60-65 parts of iron element, 25-30 parts of chromium element, 2-3 parts of manganese element, 0.1-0.5 parts of vanadium element and 0.1-0.2 parts of nickel element are completely melted according to mass fraction, and after liquid crushing, alloy liquid droplets are obtained;

[0013] Under natural environment, the alloy liquid droplets are cooled to obtain alloy dry particles;

[0014] B. 30-40 parts of kaolin, 28-35 parts of quartz, 18-25 parts of calcite, 3-10 parts of dolomite, 2-10 parts of barium carbonate and 3-8 parts of zinc oxide are uniformly mixed, calcined, water quenched, ball milled and sieved to obtain crystal frit;

[0015] The calcination temperature curve of the crystal frit is as follows:

[0016] From room temperature to 300℃, the time is 1.5-3h;

[0017] From 300℃ to 1530℃, the time is 1.5-2.5h;

[0018] 1530℃, the holding time is 0.5-1h;

[0019] C. The alloy dry particles, the crystal frit and the suspending agent are uniformly mixed to obtain silver-white metal dry particle glaze.

[0020] Further, in step A, the raw materials of the alloy dry particles include 6.4 parts of silicon element, 0.11 parts of aluminum element, 62.59 parts of iron element, 27.77 parts of chromium element, 2.54 parts of manganese element, 0.24 parts of vanadium element and 0.11 parts of nickel element according to mass fraction.

[0021] Further, in step A, the melting temperature of the melting is 1100-1200℃.

[0022] Further, in step A, the particle gradation of the alloy dry particles is as follows according to mass percentage: the residue on 100 mesh screen is 0.1-0.5%, the residue on 160 mesh screen is 65-70%, the residue on 200 mesh screen is 83-87%, the residue on 250 mesh screen is 90-95%, and the residue on 325 mesh screen is 97-99%.

[0023] Further, in step B, the calcination temperature curve of the crystal frit is as follows:

[0024] From room temperature to 300℃, the time is 2h;

[0025] From 300℃ to 1530℃, the time is 2.5h;

[0026] 1530℃, holding for 1h.

[0027] Further, in step B, the raw materials of the crystalline frit include kaolin 35 parts, quartz 30 parts, calcite 21 parts, dolomite 5 parts, barium carbonate 5 parts and zinc oxide 5 parts, in terms of mass fraction.

[0028] Further, in step B, the particle size distribution of the crystalline frit is as follows: the residue on a 150-mesh screen is 0.1-0.5%, the residue on a 180-mesh screen is 40-50%, and the residue on a 200-mesh screen is 70-80%.

[0029] Further, in step C, the silver-white metal dry granular glaze is composed of alloy dry granules 7-10 parts, crystalline frit 90-93 parts and suspending agent 180-200 parts, in terms of mass fraction.

[0030] A silver-white metal dry granular glaze is prepared by the above method.

[0031] The application of the silver-white metal dry granular glaze in the preparation of silver-white metal texture ceramic tiles, using the above silver-white metal dry granular glaze, the application method is as follows: the silver-white metal dry granular glaze is applied on the surface of the body layer to form a silver-white metal dry granular glaze layer, and then dried and calcined at a temperature of 1100-1250℃, and then polished to obtain a silver-white metal texture ceramic tile.

[0032] The technical solution provided by the application can have the following beneficial effects:

[0033] 1. The melting degree of quartz is related to the calcination curve of the crystalline frit and the total content of the quaternary composite flux (i.e. calcium oxide, magnesium oxide, barium oxide and zinc oxide), etc. When the calcination temperature is lower than the complete melting temperature of quartz (about 1700℃) and the calcination time is insufficient, especially when the total content of the quaternary composite flux is insufficient, the quartz cannot be completely melted. The insufficient total content of the quaternary composite flux will significantly increase the eutectic point of the crystalline frit formula system, and the insufficient calcination temperature and time cannot provide sufficient thermodynamic driving force and kinetic conditions to complete the transformation of quartz to glass phase. The above factors jointly affect the melting degree of quartz. Therefore, the technical solution optimizes the calcination temperature curve of the crystalline frit (the highest calcination temperature of the calcination temperature curve is 1530℃, which is lower than the melting point of quartz 1700℃), and sets the ratio of "quartz supersaturation-quaternary composite flux under-proportioning" in the crystalline frit, so that the quartz in the crystalline frit cannot be completely melted, so that the crystalline frit contains un-melted quartz.

[0034] 2. Because current building ceramic production lines generally adopt a high-temperature rapid firing process of 1100-1250℃, and the body and glaze are fired simultaneously, the calcination temperature of the silver-white metallic dry granule glaze is also 1100-1250℃. When a crystalline frit containing unmelted quartz, anorthite, and cordierite crystals is added to the silver-white metallic dry granule glaze, at the calcination temperature of 1100-1250℃, the anorthite and cordierite crystals in the crystalline frit are basically unmelted, while the unmelted quartz, although partially melted, is still difficult to completely melt, thus the silver-white metallic dry granule glaze may still contain unmelted quartz. Therefore, the glaze surface of the silvery-white metallic dry granule glaze after calcination contains three types of crystals: anorthite, cordierite, and quartz. These three crystals not only form a physical "armor" on the surface of the alloy dry granules, directly blocking the directional migration of alkali metal ions from the quaternary composite flux to the alloy dry granules, but also, the random distribution of these three crystals transforms the diffusion path of alkali metal ions in the quaternary composite flux from linear to three-dimensional serrated. This geometric path extension strengthens the diffusion barrier, effectively inhibiting the corrosion of the alloy dry granules by alkali metal ions in the quaternary composite flux. In other words, these three crystals inhibit the corrosion of the alloy dry granules by alkali metal ions in the quaternary composite flux through physical barrier and extended diffusion path, which is beneficial to maintaining the stability of the alloy dry granule performance.

[0035] 3. The glassy phase within the crystalline frit completely enters the liquid molten state, and through melting, it causes the unmelted quartz particles to partially melt. The molten glassy phase and the melted quartz components interpenetrate and diffuse uniformly at high temperatures, ultimately forming a continuous and dense glaze glassy phase. This glaze glassy phase significantly reduces the porosity of the glaze by encapsulating the alloy dry particles and unmelted quartz, filling grain boundary voids, and strengthening the bonding of crystal particles, thus blocking the channels for stain penetration and giving the silver-white metallic dry particle glaze excellent anti-fouling properties. It should be noted that although the total content of the quaternary composite flux is insufficient to completely melt the quartz, its total content ensures that the amount of glaze glassy phase generated is sufficient to achieve the multiple functions of alloy dry particle encapsulation, grain boundary filling, and particle bonding, maintaining its anti-fouling performance while ensuring the dense structure of the glaze. Attached Figure Description

[0036] Figure 1 This is a glaze effect image of a silver-white metallic textured ceramic tile made using the silver-white metallic dry granule glaze in Embodiment 1 of the present invention. Detailed Implementation

[0037] This technical solution provides a method for preparing a silver-white metallic dry granule glaze, including the following steps:

[0038] A. Under inert atmosphere, 6-7 parts of silicon element, 0.1-0.2 parts of aluminum element, 60-65 parts of iron element, 25-30 parts of chromium element, 2-3 parts of manganese element, 0.1-0.5 parts of vanadium element and 0.1-0.2 parts of nickel element are completely fused in mass fraction, and after liquid crushing, alloy liquid droplets are obtained;

[0039] The alloy liquid droplets are cooled in a natural environment to obtain alloy dry particles;

[0040] B. 30-40 parts of kaolin, 28-35 parts of quartz, 18-25 parts of calcite, 3-10 parts of dolomite, 2-10 parts of barium carbonate and 3-8 parts of zinc oxide are mixed uniformly in mass fraction, and after calcination, water quenching, ball milling and sieving, a crystal frit is obtained;

[0041] The calcination temperature curve of the crystal frit is:

[0042] From room temperature to 300 DEG C, the time is 1.5-3h;

[0043] From 300 DEG C to 1530 DEG C, the time is 1.5-2.5h;

[0044] 1530 DEG C, 0.5-1h of holding time;

[0045] C. The alloy dry particles, the crystal frit and the suspending agent are mixed uniformly to obtain silver-white metal dry particle glaze.

[0046] In order to overcome the technical defects existing in the prior art, the technical scheme puts forward a preparation method of silver-white metal dry particle glaze, by optimizing the preparation method and raw materials, it is beneficial to ensure the uniformity of the silver-white metal texture effect, not only can have excellent silver-white metal texture effect, transparency and anti-fouling performance, but also has high wear resistance and hardness, to meet the actual use requirement.

[0047] Specifically, the technical solution adopts silicon single element (the silicon single element is a metalloid), aluminum single element, iron single element, chromium single element, manganese single element, vanadium single element and nickel single element as raw materials, forms alloy liquid drops after melting and liquid crushing in an inert atmosphere, and prepares alloy dry particles through natural cooling. In the natural cooling process, the surface of the alloy liquid drops exposed to air reacts with oxygen and generates a composite oxide protective film containing aluminum oxide, chromium oxide and silicon dioxide, etc. Finally, the alloy dry particles with a "core-shell" structure are formed, and the inner core is a multi-element alloy matrix mainly composed of iron, chromium and manganese, and the outer shell is a composite oxide protective film. It should be noted that the metalloid, also known as semimetal, has both metallic and non-metallic properties. In addition, the liquid crushing of the technical solution refers to that the alloy melt obtained by melting silicon single element, aluminum single element, iron single element, chromium single element, manganese single element, vanadium single element and nickel single element is accelerated by a high-pressure pump and then passes through a microporous nozzle, and the high-speed jet stream is rubbed or impacted on a target plate to crush the metal melt into alloy liquid drops.

[0048] The composite oxide protective film is composed of an inner layer film and an outer layer film, and the inner layer film is composed of aluminum oxide, chromium oxide and silicon dioxide. The combined action of aluminum oxide and chromium oxide forms a dense and continuous barrier layer, which can effectively block the invasion of corrosion media such as fluxing agents. Silicon dioxide further enhances the denseness of the film layer by filling the grain boundary defects. At the same time, chromium oxide also gives the material good chemical passivation effect. The outer layer film is composed of iron oxide, manganese dioxide, vanadium pentoxide and nickel oxide, and has a porous structure and sacrificial protection characteristics, which can preferentially react with corrosion media such as fluxing agents to delay the erosion process of the inner layer film. That is, the composite oxide protective film of the technical solution has the above-mentioned "dense inner layer barrier + porous outer layer buffer" synergistic protection mechanism, which not only ensures the reliability of the inner layer film, but also protects the outer layer film by sacrificing, so that the composite oxide protective film has excellent corrosion resistance in the glaze environment, and it is not easy to be corroded by corrosion media such as fluxing agents, thereby helping to maintain the stability of the performance of the alloy dry particles.

[0049] Further, the alloy dry particles of the technical solution achieve excellent high-temperature stability through the following effects: (1) high chromium content and iron single element form an iron-chromium solid solution matrix, the solidus temperature of which breaks through the 1300℃ threshold, constructing a high-temperature-resistant crystal framework; (2) silicon single element and chromium single element generate chromium trisilicide and other intermetallic compounds (high-temperature phases) in situ, the high-temperature phases with a melting point of more than 1500℃ pass through the grain boundary network in a dispersion strengthening form, forming a three-dimensional support structure; (3) the addition of silicon single element and aluminum single element promotes the formation of a dense inner film of aluminum oxide-chromium oxide-silicon dioxide, and the melting point of the inner film can be as high as 2000℃, which is conducive to improving the high-temperature stability of the alloy dry particles; (4) a small amount of vanadium single element can improve the high-temperature strength by refining the grains. Based on the high-temperature stability of the alloy dry particles, the alloy dry particles are introduced into the glaze system, and the alloy dry particles can still maintain the stability of their properties after high-temperature calcination of the glaze.

[0050] Secondly, kaolin, quartz, calcite, dolomite, barium carbonate and zinc oxide are uniformly mixed, calcined, water quenched, ball milled and sieved to obtain the crystalline frit. Firstly, during the calcination of the crystalline frit, calcite (mainly composed of calcium carbonate) and dolomite (mainly composed of calcium magnesium carbonate) can both decompose to generate calcium oxide under heating, and dolomite can also decompose to generate magnesium oxide under heating, and barium carbonate can decompose to generate barium oxide under high temperature. The calcium oxide, magnesium oxide, barium oxide and zinc oxide in the crystalline frit cooperate with each other to form a calcium oxide-magnesium oxide-barium oxide-zinc oxide quaternary composite flux. Since calcium ions, magnesium ions, barium ions and zinc ions are all low-polarizability ions with large radii and weak polarization ability, the lattice energy is high and the bond strength is large, and higher energy is required to destroy the flux network structure, so the initial melting point of the above-mentioned quaternary composite flux is relatively high. In addition, there is a size matching effect between calcium ions, magnesium ions, barium ions and zinc ions (for example, the radius ratio of barium ions and zinc ions meets the Hume-Rothery rule), which can form a high-temperature limited solid solution. The solid solution destroys the low eutectic point formation condition through atomic-level mutual solubility, so that the initial melting point of the formed quaternary composite flux is higher than that of the single flux. That is, the quaternary composite flux in the technical solution has a relatively high initial melting point through the above-mentioned multiple effects.

[0051] Further, kaolin decomposes to generate aluminum oxide and silicon dioxide under high temperature, and quartz can also provide silicon dioxide, and the calcium oxide generated by the decomposition of calcite and dolomite under heating reacts with aluminum oxide and silicon dioxide in the formula system to form anorthite crystals (CaAl2Si2O8); at the same time, the magnesium oxide generated by the decomposition of calcite and dolomite under heating reacts with aluminum oxide and silicon dioxide in the formula system to form cordierite crystals (Mg2Al2Si2O 18 )。

[0052] Meanwhile, the melting degree of the quartz is related to the calcination curve of the crystalline frit and the total content of the quaternary composite flux (i.e., calcium oxide, magnesium oxide, barium oxide, and zinc oxide). When the calcination temperature is lower than the temperature at which the quartz is completely melted (about 1700℃), the calcination time is insufficient, and especially when the total content of the quaternary composite flux is insufficient, the quartz cannot be completely melted. Among them, the insufficient total content of the quaternary composite flux can significantly increase the eutectic point of the crystalline frit formula system, and the insufficient calcination temperature and time cannot provide sufficient thermodynamic driving force and kinetic conditions to complete the transformation of the quartz into a glass phase. The above factors jointly affect the melting degree of the quartz. Therefore, the technical solution optimizes the calcination temperature curve of the crystalline frit (wherein the highest calcination temperature of the calcination temperature curve is 1530℃, which is less than the melting point 1700℃ of the quartz), and sets the ratio design of "quartz supersaturation-quaternary composite flux under-proportioning" in the crystalline frit, so that the quartz in the crystalline frit cannot be completely melted, so that the crystalline frit contains un-melted quartz.

[0053] As can be seen from the above, the crystalline frit of the technical solution includes three crystals of calcium feldspar crystals, cordierite crystals, and un-melted quartz, and the melting point of the calcium feldspar crystals is 1553℃, the melting point of the cordierite crystals is 1760℃, and the melting point of the quartz is 1700℃. The above three crystals make the crystalline frit have a high melting point.

[0054] Therefore, the technical solution improves the initial melting temperature of the crystalline frit through the mutual cooperation of the above-mentioned multiple aspects, thereby overall improving the melting threshold of the silver-white metal dry particle glaze, significantly shortening the contact time of the quaternary composite flux (i.e., fluxing agent) and the alloy dry particles in the high-temperature firing stage, thereby effectively inhibiting the corrosion of the fluxing agent on the alloy dry particles, and being conducive to maintaining the stability of the performance of the alloy dry particles.

[0055] Further, since the current building ceramic production line generally adopts high-temperature fast firing process of 1100-1250℃, and the body and glaze are fired synchronously, the calcination temperature of the silver-white metal dry particle glaze is also 1100-1250℃. When the crystal frit containing the three crystals of un-melted quartz, anorthite crystal and cordierite crystal is added to the silver-white metal dry particle glaze, the anorthite crystal and cordierite crystal in the crystal frit are basically not melted at the calcination temperature of 1100-1250℃ of the silver-white metal dry particle glaze, and although the un-melted quartz can be further dissolved, it is still difficult to completely melt, so that the silver-white metal dry particle glaze still contains un-melted quartz. Therefore, the glaze surface of the silver-white metal dry particle glaze after calcination contains the three crystals of anorthite crystal, cordierite crystal and quartz. The above three crystals not only form a physical “armor” on the surface of the alloy dry particle, thereby directly blocking the directional migration of alkali metal ions in the quaternary complex flux to the alloy dry particle, but also convert the diffusion path of alkali metal ions in the quaternary complex flux from linear to three-dimensional zigzag, thereby realizing diffusion potential barrier enhancement through geometric path lengthening, and effectively inhibiting the corrosion of alkali metal ions in the quaternary complex flux to the alloy dry particle. That is, the above three crystals inhibit the corrosion of alkali metal ions in the quaternary complex flux to the alloy dry particle through physical blocking and diffusion path lengthening, which is beneficial to maintaining the stability of the performance of the alloy dry particle.

[0056] In summary, the technical scheme prevents the corrosion of the alloy dry particle, maintains the stability of its performance, and makes the multi-element alloy matrix (the color of the multi-element alloy matrix is silver-white) mainly composed of iron, chromium and manganese in the interior of the alloy dry particle exposed when the silver-white metal dry particle glaze is applied on the surface of the body, so as to present a silver-white metallic texture effect after only polishing treatment to remove the composite oxide protective film on the surface of the alloy dry particle.

[0057] It should be noted that since the glaze surface of the silver-white metal dry particle glaze after calcination contains the three crystals of anorthite crystal, cordierite crystal and un-melted quartz, and the above three crystals have high hardness and wear resistance, the silver-white metal dry particle glaze has high hardness and wear resistance.

[0058] In addition, the raw material zinc oxide in the crystalline frit can not only act as a fluxing agent, but also as a crystal nucleus forming agent, which can reduce the crystallization activation energy and crystallization peak temperature, and is conducive to the crystallization of the anorthite crystals, thereby further improving the transparency of the silver-white metal dry particle glaze.

[0059] Further, the anorthite crystals generated by the technical scheme are triclinic crystals with a dense structure, and the refractive index of the anorthite crystals is close to the refractive index of the glass phase, so that the anorthite crystals have no significant light scattering center and have extremely high transparency. Therefore, by adjusting the addition amount of kaolin, calcite and dolomite in the crystalline frit, the technical scheme induces the generation of a high content of anorthite crystals, and the crystalline frit has relatively high transparency. When the crystalline frit is added to the silver-white metal dry particle glaze, the transparency of the silver-white metal dry particle glaze is improved.

[0060] In addition, the raw material zinc oxide in the crystalline frit can not only act as a fluxing agent, but also as a crystal nucleus forming agent, which can reduce the crystallization activation energy and crystallization peak temperature, and is conducive to the crystallization of the anorthite crystals, thereby further improving the transparency of the silver-white metal dry particle glaze.

[0061] Therefore, the technical scheme has the above two effects, so that the glaze surface obtained by firing the silver-white metal dry particle glaze has relatively high transparency. It should be noted that although the glaze surface obtained by firing the silver-white metal dry particle glaze according to the technical scheme contains un-melted quartz with relatively low transparency, the amount of un-melted quartz is limited and is not enough to affect the transparency of the glaze surface, so that the glaze surface still has relatively high transparency.

[0062] In addition, since the content of the anorthite crystal in the calcined crystal frit is significant, when the crystal frit with high anorthite crystal content is introduced into the silver-white metal dry particle glaze system, the anorthite crystal is uniformly distributed in the glaze layer structure in the form of a rigid skeleton. The skeleton structure inhibits the high-temperature softening rate of the glass phase through physical constraint, effectively slows down the fluidity of the silver-white metal dry particle glaze during the high-temperature firing stage, thereby widening the calcination temperature range of the silver-white metal dry particle glaze.

[0063] Finally, the alloy dry particles are dispersed without water by using the suspending agent, which solves the technical problem that the alloy dry particles are prone to sedimentation in the glaze containing water, and makes the alloy dry particles uniformly dispersed in the silver-white metal dry particle glaze, so that the silver-white metal dry particle glaze has a high uniformity of metallic luster effect on the glaze surface.

[0064] It should be noted that the manufacturer of the suspending agent is Jiangxi Qiantao New Material Co., Ltd., and the model is 6122A. It should be further noted that the inert atmosphere can be argon and nitrogen, and the specific type is not limited herein.

[0065] It should be further explained that in step A, the raw materials of the alloy dry particles include 6.4 parts of silicon, 0.11 parts of aluminum, 62.59 parts of iron, 27.77 parts of chromium, 2.54 parts of manganese, 0.24 parts of vanadium and 0.11 parts of nickel, calculated by mass fraction.

[0066] By optimizing the ratio of the raw materials of the alloy dry particles, the thickness ratio of the multi-element alloy matrix and the composite oxide protective film is accurately controlled, so that under the premise that the composite oxide protective film is sufficient to prevent the alloy dry particles from being corroded, the multi-element alloy matrix retains a larger volume after the composite oxide protective film on the surface of the alloy dry particles is polished and removed, forming a continuous and highly exposed metal phase, and improving the metallic luster effect of the glaze surface.

[0067] It should be further explained that in step A, the melting temperature of the molten is 1100-1200℃.

[0068] By limiting the melting temperature, the silicon, aluminum, iron, chromium, manganese, vanadium and nickel are completely melted and doped with each other, thereby facilitating to ensure the performance of the final obtained alloy dry particles. It should be noted that although the melting point of silicon is 1410-1414℃, the melting point of aluminum is 660℃, the melting point of iron is 1538-1539℃, the melting point of chromium is 1907℃, the melting point of manganese is 1907℃, the melting point of vanadium is 1244℃, and the melting point of nickel is 1917℃, but the above-mentioned elements can trigger low melting point eutectic reaction during melting, so that the above-mentioned elements are completely melted and composition homogenized by eutectic dissolution and atomic diffusion at a temperature of 1100-1200℃. In addition, due to the effects of high melting point intermetallic compounds (such as iron-solids, chromium trisilicon, etc.) and the film layer formed by surface oxides in the obtained alloy dry particles, even if the calcination temperature of the glaze added with the alloy dry particles is higher than the melting temperature, the alloy dry particles can still maintain the solid lattice structure and surface integrity, thereby avoiding the performance degradation of the alloy dry particles caused by high temperature melting.

[0069] Further, in step A, the particle size distribution of the alloy dry particles is as follows: the residue on the 100 mesh screen is 0.1-0.5%, the residue on the 160 mesh screen is 65-70%, the residue on the 200 mesh screen is 83-87%, the residue on the 250 mesh screen is 90-95%, and the residue on the 325 mesh screen is 97-99%.

[0070] By optimizing the particle size distribution of the alloy dry particles, not only the suspension stability is improved, thereby improving the uniformity of the metallic texture effect, but also the flowability of the silver-white metal dry particle glaze after high temperature calcination is improved, thereby ensuring the flatness of the glaze surface after calcination of the silver-white metal dry particle glaze, and improving the stain resistance.

[0071] According to the mass percentage, the particle size distribution of the alloy dry particles is as follows: the residue on the 100 mesh screen is 0.1%, the residue on the 160 mesh screen is 70%, the residue on the 200 mesh screen is 86.2%, the residue on the 250 mesh screen is 92.6%, and the residue on the 325 mesh screen is 98%.

[0072] Further, in step B, the calcination temperature curve of the crystalline frit is as follows:

[0073] From room temperature to 300℃, it takes 2h;

[0074] From 300℃ to 1530℃, it takes 2.5h;

[0075] 1530℃, holding for 1h.

[0076] The technical scheme further optimizes the calcination temperature curve of the crystal frit, so that the temperature curve of calcination is optimal, and the performance of the crystal frit is ensured to be optimal.

[0077] Further, in step B, the raw materials of the crystal frit include kaolin 35 parts, quartz 30 parts, calcite 21 parts, dolomite 5 parts, barium carbonate 5 parts and zinc oxide 5 parts in terms of mass fraction.

[0078] The performance of the silver-white metal dry particle glaze is further ensured by further optimizing the ratio of the raw materials of the crystal frit.

[0079] Further, in step B, the particle size distribution of the crystal frit is as follows: the residue on a 150-mesh screen is 0.1-0.5%, the residue on a 180-mesh screen is 40-50%, and the residue on a 200-mesh screen is 70-80%.

[0080] The particle size distribution of the crystal frit is optimized, so that the silver-white metal dry particle glaze obtained by mixing the crystal frit, the suspending agent and the alloy dry particle has high fluidity, the flatness of the glaze surface obtained after calcination of the silver-white metal dry particle glaze is ensured, and the crystal frit can be fully melted during calcination of the silver-white metal dry particle glaze, so that the glaze surface obtained after calcination of the silver-white metal dry particle glaze has high density, and the anti-fouling performance is further improved.

[0081] Further, in step C, the silver-white metal dry particle glaze is composed of 7-10 parts of alloy dry particle, 90-93 parts of crystal frit and 180-200 parts of suspending agent in terms of mass fraction.

[0082] The 7-10 parts of alloy dry particle can ensure that the glaze surface has a full metal texture effect and avoid loose glaze surface structure caused by excessive addition; the 90-93 parts of crystal frit as a base glass phase can not only fully wrap the alloy dry particle to form a stable combination but also maintain sufficient fluidity to achieve a flat glaze surface; and the 180-200 parts of suspending agent can give the glaze a desired rheological property, which can not only prevent the alloy dry particle with a large specific gravity from settling but also ensure uniform coating during glazing. Therefore, the addition amounts of the alloy dry particle, the crystal frit and the suspending agent are limited in the technical scheme, so that the performance of the product is optimal, and the quality and stability of the product are improved.

[0083] Preferably, in step C, the silver-white metal dry particle glaze is composed of 10 parts of alloy dry particle, 90 parts of crystal frit and 200 parts of suspending agent in terms of mass fraction.

[0084] The addition amounts of the alloy dry particle, the crystal frit and the suspending agent are further limited, so that the performance of the silver-white metal dry particle glaze is optimal, and the quality and stability of the product are improved.

[0085] A silver-white metal dry granular glaze prepared by the method for preparing a silver-white metal dry granular glaze.

[0086] The present application also provides a silver-white metal dry granular glaze which, while ensuring uniformity of the silver-white metal texture effect, can simultaneously have excellent silver-white metal texture effect, transparency and stain resistance, and has high wear resistance and hardness, so as to overcome the shortcomings of the prior art.

[0087] The present application also provides a silver-white metal dry granular glaze which, while ensuring uniformity of the silver-white metal texture effect, can simultaneously have excellent silver-white metal texture effect, transparency and stain resistance, and has high wear resistance and hardness, so as to overcome the shortcomings of the prior art.

[0088] The present application also provides a silver-white metal dry granular glaze which, while ensuring uniformity of the silver-white metal texture effect, can simultaneously have excellent silver-white metal texture effect, transparency and stain resistance, and has high wear resistance and hardness, so as to overcome the shortcomings of the prior art.

[0089] The technical solutions of the present application will be further described below through specific embodiments.

[0090] The production factory of the suspending agent in the embodiments and comparative examples of the present application is Jiangxi Qiantao New Material Co., Ltd., and the model is 6122A.

[0091] Embodiment 1

[0092] A. Under an argon atmosphere, 6.4 parts of silicon, 0.11 parts of aluminum, 62.59 parts of iron, 27.77 parts of chromium, 2.54 parts of manganese, 0.24 parts of vanadium and 0.11 parts of nickel were completely melted at a temperature of 1100-1200℃, and the alloy liquid droplets were obtained after liquid crushing; the alloy liquid droplets were cooled under a natural environment to obtain alloy dry particles; wherein, according to the mass percentage, the particle gradation of the alloy dry particles is as follows: the sieve residue of the 100 mesh screen is 0.1%, the sieve residue of the 160 mesh screen is 70%, the sieve residue of the 200 mesh screen is 86.2%, the sieve residue of the 250 mesh screen is 92.6%, and the sieve residue of the 325 mesh screen is 98%.

[0093] B. Mix 35 parts of kaolin, 30 parts of quartz, 21 parts of calcite, 5 parts of dolomite, 5 parts of barium carbonate and 5 parts of zinc oxide by mass fraction uniformly, and after calcination, water quenching, ball milling and sieving, a crystal frit is obtained; wherein, the calcination temperature curve of the crystal frit is: from room temperature to 300℃, time consumption is 2h; from 300℃ to 1530℃, time consumption is 2.5h; 1530℃, heat preservation is 1h; the particle size distribution of the crystal frit is: the residue on a 150 mesh screen is 0.3%, the residue on a 180 mesh screen is 44.6%, the residue on a 200 mesh screen is 75.3%;

[0094] C. Mix the silver-white metal dry granular glaze including 10 parts of alloy dry granules, 90 parts of crystal frit and 200 parts of suspending agent by mass fraction uniformly to obtain a silver-white metal dry granular glaze.

[0095] The silver-white metal dry granular glaze obtained in Example 1 is applied on the surface of the body layer to form a silver-white metal dry granular glaze layer, and after drying, calcination at a temperature of 1180℃, and full polishing treatment, a silver-white metal texture ceramic tile is obtained, and the glaze surface effect diagram is shown in FIG. 1. Figure 1 As can be seen from FIG. 1, the glaze surface can present a strong and uniform silver-white metal texture effect under light conditions. Figure 1

[0096] Example 2

[0097] A. Under a nitrogen atmosphere, 6.6 parts of silicon, 0.1 parts of aluminum, 62.3 parts of iron, 27.5 parts of chromium, 2 parts of manganese, 0.2 parts of vanadium and 0.18 parts of nickel are completely melted at a temperature of 1150℃, and after liquid crushing, alloy liquid droplets are obtained; the alloy liquid droplets are cooled in a natural environment to obtain alloy dry granules; wherein, according to mass percentage, the particle size distribution of the alloy dry granules is: the residue on a 100 mesh screen is 0.3%, the residue on a 160 mesh screen is 66.8%, the residue on a 200 mesh screen is 85.5%, the residue on a 250 mesh screen is 92.5%, and the residue on a 325 mesh screen is 97.8%;

[0098] B. Mix 35 parts of kaolin, 30 parts of quartz, 22 parts of calcite, 5 parts of dolomite, 6 parts of barium carbonate and 5 parts of zinc oxide by mass fraction uniformly, and after calcination, water quenching, ball milling and sieving, a crystal frit is obtained; wherein, the calcination temperature curve of the crystal frit is: from room temperature to 300℃, time consumption is 2h; from 300℃ to 1530℃, time consumption is 1.8h; 1530℃, heat preservation is 0.8h; the particle size distribution of the crystal frit is: the residue on a 150 mesh screen is 0.3%, the residue on a 180 mesh screen is 48.2%, the residue on a 200 mesh screen is 73.5%;

[0099] ​C. Mix uniformly silver-white metal dry particle glaze including alloy dry particle 8 parts, crystal frit 93 parts and suspending agent 180 parts calculated by mass fraction to obtain silver-white metal dry particle glaze.

[0100] Example 3

[0101] A. Under argon atmosphere, melt completely silicon element 7 parts, aluminum element 0.2 parts, iron element 64.2 parts, chromium element 28.1 parts, manganese element 2.7 parts, vanadium element 0.33 parts and nickel element 0.18 parts calculated by mass fraction at temperature of 1200℃, get alloy liquid drops after liquid crushing; cool alloy liquid drops under natural environment to get alloy dry particle; wherein, particle gradation of alloy dry particle is: 0.3% of 100 mesh screen residue, 70% of 160 mesh screen residue, 85% of 200 mesh screen residue, 92% of 250 mesh screen residue, 98% of 325 mesh screen residue calculated by mass percentage;

[0102] B. Mix uniformly kaolin 35 parts, quartz 32 parts, calcite 21 parts, dolomite 8 parts, barium carbonate 6 parts and zinc oxide 5 parts calculated by mass fraction, get crystal frit after calcination, water quenching, ball milling and sieving; wherein, calcination temperature curve of crystal frit is: from normal temperature to 300℃, time consumption is 3h; from 300℃ to 1530℃, time consumption is 1.5h; 1530℃, keep temperature for 1h; particle gradation of crystal frit is: 0.3% of 150 mesh screen residue, 45.8% of 180 mesh screen residue, 75.4% of 200 mesh screen residue;

[0103] C. Mix uniformly silver-white metal dry particle glaze including alloy dry particle 8 parts, crystal frit 92 parts and suspending agent 190 parts calculated by mass fraction to obtain silver-white metal dry particle glaze.

[0104] Comparative Example 1

[0105] Comparative Example 1 has same preparation method and raw materials with Example 1, except that raw materials in alloy dry particle of Comparative Example 1 only include iron element, chromium element and manganese element, without adding silicon element, aluminum element, vanadium element and nickel element.

[0106] Comparative Example 2

[0107] Comparative Example 2 has same preparation method and raw materials with Example 1, except that quartz is not added in crystal frit of Comparative Example 2.

[0108] Comparative Example 3

[0109] Comparative Example 3 has same preparation method and raw materials with Example 1, except that calcite is not added in crystal frit of Comparative Example 3.

[0110] Comparative Example 4

[0111] Comparative Example 4 is prepared by the same method and raw materials as Example 1, except that no dolomite is added to the crystalline frit in Comparative Example 4.

[0112] The silver-white metal dry particle glaze prepared in the examples and comparative examples is applied on the surface of the body layer to form a silver-white metal dry particle glaze layer, which is dried and then calcined at a temperature of 1180°C, and then the silver-white metal texture ceramic tiles are obtained after full polishing treatment. The surface effect of the silver-white metal texture ceramic tiles prepared by the silver-white metal dry particle glazes in the examples and comparative examples is observed, and the obtained silver-white metal texture ceramic tiles are subjected to the conventional glossiness test, hardness and stain resistance grade test in the field of architectural ceramics, and the results are shown in Table 1 below:

[0113] Table 1 Performance test results of the ceramic tiles of the examples and comparative examples

[0114]

[0115] It can be seen from the performance test results in Table 1 that the silver-white metal texture ceramic tiles prepared by the silver-white metal dry particle glazes of the technical solution not only have excellent silver-white metal texture effect, transparency and stain resistance, but also have high wear resistance and hardness, and have both decorative and practical properties, which is more conducive to meeting the use requirements of consumers.

[0116] In Comparative Example 1, since the raw materials in the alloy dry particles only include iron, chromium and manganese, and no silicon, aluminum, vanadium and nickel are added, only the oxides formed by the oxidation of iron, chromium and manganese in the air can be used as the composite oxide protective layer in the system. The structure of the composite oxide protective layer is not dense enough, and the corrosion resistance is limited, which not only leads to limited metal texture effect of the ceramic tiles obtained in Comparative Example 1, but also causes a certain degree of corrosion of the alloy dry particles, which introduces impurity color on the surface of the ceramic tiles.

[0117] In Comparative Example 2, since no quartz is added to the crystalline frit, the effect of inhibiting the corrosion of the alloy dry particles by the alkali metal ions in the quaternary composite flux by using the unfused quartz cannot be achieved in Comparative Example 2, so that the metal texture effect of the ceramic tiles is reduced, and the obtained ceramic tiles have impurity color. At the same time, since no quartz is added to the raw materials in the crystalline frit of Comparative Example 2, the glaze surface of the silver-white metal dry particle glaze after calcination does not contain unfused quartz, which cannot increase the hardness and wear resistance by using the unfused quartz, so that the hardness and wear resistance of the ceramic tiles prepared in Comparative Example 2 are reduced.

[0118] The following effects will be caused due to the fact that no calcite is added in the crystalline frit in Comparative Example 3: (1) the amount of anorthite crystals separated out during calcination of the silver-white metal dry particle glaze is reduced, and the characteristics of the anorthite crystals in increasing the hardness and wear resistance cannot be utilized, so that the hardness and wear resistance of the ceramic tile obtained by using Comparative Example 3 are reduced; (2) the total content of the quaternary compound flux in the silver-white metal dry particle glaze is reduced, and the amount of the glass phase generated after calcination is reduced, and the glass phase is difficult to completely wrap the un-melted quartz, anorthite crystals and cordierite crystals, so that pores exist between the un-melted quartz, anorthite crystals and cordierite crystals, resulting in the reduction of the stain resistance of the glaze surface; (3) the amount of the anorthite crystals separated out after calcination of the silver-white metal dry particle glaze is reduced, resulting in the reduction of the transparency of the glaze surface. It should be noted that although the amount of the anorthite crystals generated in Comparative Example 3 is reduced, the anorthite crystals cannot play the role of inhibiting the corrosion of the alkali metal ions in the quaternary compound flux to the alloy dry particles, but due to the reduction of the total content of the quaternary compound flux in the silver-white metal dry particle glaze, the tendency of the corrosion of the alkali metal ions in the quaternary compound flux to the alloy dry particles is reduced.

[0119] The following effects will be caused due to the fact that no calcite is added in the crystalline frit in Comparative Example 3: (1) the amount of anorthite crystals separated out during calcination of the silver-white metal dry particle glaze is reduced, and the characteristics of the anorthite crystals in increasing the hardness and wear resistance cannot be utilized, so that the hardness and wear resistance of the ceramic tile obtained by using Comparative Example 3 are reduced; (2) the total content of the quaternary compound flux in the silver-white metal dry particle glaze is reduced, and the amount of the glass phase generated after calcination is reduced, and the glass phase is difficult to completely wrap the un-melted quartz, anorthite crystals and cordierite crystals, so that pores exist between the un-melted quartz, anorthite crystals and cordierite crystals, resulting in the reduction of the stain resistance of the glaze surface; (3) the amount of the anorthite crystals separated out after calcination of the silver-white metal dry particle glaze is reduced, resulting in the reduction of the transparency of the glaze surface. It should be noted that although the amount of the anorthite crystals generated in Comparative Example 3 is reduced, the anorthite crystals cannot play the role of inhibiting the corrosion of the alkali metal ions in the quaternary compound flux to the alloy dry particles, but due to the reduction of the total content of the quaternary compound flux in the silver-white metal dry particle glaze, the tendency of the corrosion of the alkali metal ions in the quaternary compound flux to the alloy dry particles is reduced.

[0120] The technical principles of the present application are described above in combination with specific embodiments. These descriptions are only for explaining the principles of the present application, and cannot be interpreted as limiting the protection scope of the present application in any way. Based on the explanations herein, other specific embodiments of the present application can be conceived by those skilled in the art without creative efforts, and these embodiments will all fall within the protection scope of the present application.

Claims

1. A method for preparing a silver-white metallic dry granular glaze, characterized by, It comprises the following steps: A. Under inert atmosphere, melt completely silicon 6-7 parts by mass fraction, aluminum 0.1-0.2 parts by mass fraction, iron 60-65 parts by mass fraction, chromium 25-30 parts by mass fraction, manganese 2-3 parts by mass fraction, vanadium 0.1-0.5 parts by mass fraction and nickel 0.1-0.2 parts by mass fraction, and get alloy liquid drops after liquid crushing; Cool the alloy liquid drops under natural environment to get alloy dry particles; The method of liquid crushing is as follows: melt silicon, aluminum, iron, chromium, manganese, vanadium and nickel to get alloy melt, accelerate the alloy melt by high-pressure pump, and then pass through micro-porous nozzle, high-speed jet flow rubs against air or hits target plate to crush the metal melt into alloy liquid drops; B. Mix kaolin 30-40 parts by mass fraction, quartz 28-35 parts by mass fraction, calcite 18-25 parts by mass fraction, dolomite 3-10 parts by mass fraction, barium carbonate 2-10 parts by mass fraction and zinc oxide 3-8 parts by mass fraction uniformly, and get crystal frit after calcination, water quenching, ball milling and sieving; The calcination temperature curve of the crystal frit is as follows: From room temperature to 300℃, time consumption is 1.5-3h; From 300℃ to 1530℃, time consumption is 1.5-2.5h; 1530℃, keep temperature for 0.5-1h; C. Mix the alloy dry particles, the crystal frit and the suspending agent uniformly to get silver-white metal dry particle glaze.

2. The method of preparing a silver-white metal dry granular glaze according to claim 1, characterized in that, In step A, the raw materials of the alloy dry particles include silicon 6.4 parts by mass fraction, aluminum 0.11 parts by mass fraction, iron 62.59 parts by mass fraction, chromium 27.77 parts by mass fraction, manganese 2.54 parts by mass fraction, vanadium 0.24 parts by mass fraction and nickel 0.11 parts by mass fraction.

3. The method of preparing a silver-white metal dry granular glaze according to claim 1, characterized in that, In step A, the melting temperature of the melting is 1100-1200℃.

4. The method of preparing a silver-white metal dry granular glaze according to claim 1, characterized in that, In step A, the particle gradation of the alloy dry particles is as follows: 100 mesh screen residue is 0.1-0.5%, 160 mesh screen residue is 65-70%, 200 mesh screen residue is 83-87%, 250 mesh screen residue is 90-95% and 325 mesh screen residue is 97-99% by mass percentage.

5. The method of preparing a silver-white metal dry granular glaze according to claim 1, characterized in that, In step B, the calcination temperature curve of the crystal frit is as follows: From room temperature to 300℃, time consumption is 2h; From 300℃ to 1530℃, time consumption is 2.5h; 1530℃, keep temperature for 1h.

6. The method of making a silver-white metal dry granular glaze according to claim 1, wherein, In step B, the raw materials of the crystal frit include kaolin 35 parts by mass fraction, quartz 30 parts by mass fraction, calcite 21 parts by mass fraction, dolomite 5 parts by mass fraction, barium carbonate 5 parts by mass fraction and zinc oxide 5 parts by mass fraction.

7. The method of making a silver-white metal dry granular glaze according to claim 1, wherein, In step B, the particle gradation of the crystal frit is as follows: 150 mesh screen residue is 0.1-0.5%, 180 mesh screen residue is 40-50% and 200 mesh screen residue is 70-80%.

8. The method of making a silver-white metal dry granular glaze according to claim 1, wherein, In step C, the silver-white metal dry particle glaze is composed of alloy dry particles 7-10 parts by mass fraction, crystal frit 90-93 parts by mass fraction and suspending agent 180-200 parts by mass fraction.

9. A silver-white metallic dry granular enamel, characterized by, The silver-white metal dry particle glaze is prepared by the preparation method of any one of claims 1-8.

10. Use of a silver-white metallic dry granular glaze in the preparation of silver-white metallic texture ceramic tiles, characterized by the fact that, The silver-white metal dry granular glaze is used as follows: the silver-white metal dry granular glaze is applied on the surface of the body layer to form a silver-white metal dry granular glaze layer, and then the silver-white metal dry granular glaze layer is dried and calcined at a temperature of 1100-1250 DEG C, and then polished to obtain a silver-white metal texture ceramic tile.

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