阅读说明：本技术 一种天然矿物-钙长石微晶釉料及其制备方法和使用方法 (Natural mineral-anorthite microcrystalline glaze and preparation method and use method thereof ) 是由 李帅值 张昊 黄菲 张长青 张志彬 常卓雅 闻昕宇 李德先 于 2019-11-25 设计创作，主要内容包括：本发明的一种天然矿物-钙长石微晶釉料及其制备方法和使用方法,釉料原料包括相应重量比的铁矿围岩,矽卡岩和乙二醇聚氧乙烯醚。制备时,将铁矿围岩和钙矽卡岩球磨后,加入乙二醇聚氧乙烯醚,研磨后调节波美度,制得微晶釉料。对光洁坯体施釉,升温至1250-1270℃,保温0.5-1h；以3-6℃/min速率冷却至1230-1250℃,保温0.2-0.5h；1-3℃/min速率冷却至1180-1200℃,保温0.2-0.5h,冷却获得钙长石微晶釉面,基底为红褐色,单个钙长石晶花密集堆叠生长聚集形成晶花聚集体,分布于釉层表面。该发明钙长石微晶釉料完全取材天然矿物,不添加任何色料和助剂,施釉过程一次成型,烧制温度低,聚集体均匀,釉色晶莹细润,透亮光滑,釉层光亮细密。(The invention relates to a natural mineral-anorthite microcrystalline glaze and a preparation method and a use method thereof. During preparation, after ball milling of iron ore surrounding rock and calcium silicalite, ethylene glycol polyoxyethylene ether is added, and the baume degree is adjusted after grinding, so that the microcrystalline glaze is prepared. Glazing the polished blank, heating to 1250-; cooling to 1230-1250 ℃ at the speed of 3-6 ℃/min, and preserving heat for 0.2-0.5 h; cooling to 1180-. The anorthite microcrystalline glaze material is completely made of natural minerals, is not added with any pigment or auxiliary agent, is formed in one step in the glazing process, and has the advantages of low firing temperature, uniform aggregate, glittering and translucent glaze color, transparency and smoothness, and bright and fine glaze layer.)

1. The natural mineral-anorthite microcrystalline glaze is characterized by comprising the following raw material components: iron ore surrounding rock, calcium silicalite and ethylene glycol polyoxyethylene ether, wherein the iron ore surrounding rock, the calcium silicalite and the ethylene glycol polyoxyethylene ether comprise the following components in percentage by weight: iron ore surrounding rock: calcium skarn: ethylene glycol polyoxyethylene ether ═ 60-75: (25-40): (25-35).

2. The natural mineral anorthite microcrystalline glaze material as claimed in claim 1, wherein the iron ore surrounding rock comprises the following components in percentage by mass: 0.75% K ₂O，0.05％Na ₂O，3.09％CaO，3.65％MgO，0.12％MnO，7.60％FeO，3.11％Al ₂O ₃，0.23％P ₂O ₅，81.4％SiO ₂。

3. The natural mineral-anorthite microcrystalline glaze material as claimed in claim 1, wherein the agasicite comprises the following components by mass percent: 1.74% K ₂O，0.76％Na ₂O，30.54％CaO，4.47％MgO，0.29％TiO ₂，0.41％MnO，13.49％Fe ₂O ₃，7.07％Al ₂O ₃，0.11％P ₂O ₅，40.24％SiO ₂。

4. The natural mineral-anorthite microcrystalline glaze material as claimed in claim 1, wherein the concentration of the natural mineral-anorthite microcrystalline glaze material is 55-65 Baume degrees.

5. The method for preparing the natural mineral-anorthite microcrystalline glaze material as claimed in claim 1, which comprises the following steps:

(1) taking the following raw materials in percentage by weight: 60-75 parts of iron ore surrounding rock and 25-40 parts of calcium silicalite;

(2) adding 250 parts of water 200 and 250 parts of calcium silicate rock into iron ore surrounding rock and calcium silicate rock according to the weight ratio, and performing wet ball milling for 3-5 hours;

(3) drying the ball-milled product, adding 25-35 parts of ethylene glycol polyoxyethylene ether, uniformly stirring, and grinding for 20-30 min;

(3) and (3) sieving the ground product by a 200-mesh sieve, and then mixing into glaze slip with 55-65 baume degrees to prepare the anorthite microcrystalline glaze material prepared from natural minerals.

6. The method for preparing the natural mineral-anorthite microcrystalline glaze material as claimed in claim 5, wherein in the step (2), the ball milling rotation speed is 50r/min, and the particle size of the ball milling product is 150-.

7. The method for preparing the natural mineral-anorthite microcrystalline glaze material as claimed in claim 5, wherein in the step (3), the grinding operation is performed in a high frequency oscillation grinding machine, the high frequency oscillation frequency is 1500r/min, and the grain size of the ground product is 30-80 μm.

8. The method of using the natural mineral-anorthite microcrystalline glaze material as set forth in claim 1, which comprises the steps of:

(1) taking a blank with a smooth surface, taking anorthite microcrystalline glaze prepared from natural minerals, glazing, and keeping the thickness of a glaze layer at 1-2 mm;

(2) after the blank body is dried after glazing, heating to 1250-; cooling to 1230-1250 ℃ at the speed of 3-6 ℃/min, and preserving heat for 0.2-0.5 h; cooling to 1180-1200 ℃ at the speed of 1-3 ℃/min, and preserving the heat for 0.2-0.5h to finish the firing; and finally, air-cooling to room temperature to obtain the anorthite microcrystalline glaze surface.

9. The method for using the natural mineral-anorthite microcrystalline glaze material as claimed in claim 8, wherein in the step (2), the specific process of raising the temperature of the dried blank to 1250-: the temperature is raised to 850-.

10. The use method of the natural mineral anorthite microcrystalline glaze material according to claim 8, wherein in the step (2), the substrate of the prepared anorthite microcrystalline glaze is reddish brown, the single anorthite crystal flower crystal whisker is in a lath shape and grows in a dense stacking manner and is aggregated to form a crystal flower aggregate, and the crystal flower aggregate is yellow and is distributed on the surface of the glaze layer; the diameter of the single anorthite crystal flower is 100-150 mu m, the aggregate is quasi-circular, and the diameter is 300-900 mu m.

The technical field is as follows:

the invention belongs to the technical field of glaze materials, and particularly relates to a natural mineral-anorthite microcrystalline glaze material, and a preparation method and a use method thereof.

Background art:

china is a big ceramic country and is called the porcelain country in history, and the produced ceramic products have long history, rich theoretical deposits, and high occupancy of daily necessities, and the glaze brilliant culture is accumulated. In recent years, the nation actively advocates energy conservation, emission reduction and innovation creation, and under the background, the calcium-magnesium silicate mineral glaze has large raw material reserves and wide sources, can be simultaneously used as a main fluxing agent and a crystallizing agent, and is particularly emphasized by the environment-friendly and healthy environment-friendly property. The natural ore is used for replacing the traditional glaze making raw material to make the glaze, the addition of various pigments and auxiliary agents is reduced, the glaze making cost is reduced, the glaze variety is enriched, the artistic expressive force of the glaze surface is enhanced, and the method has important significance for green ecological transformation of the current ceramic production enterprises.

The invention content is as follows:

the invention aims to overcome the defects in the prior art and provide the anorthite microcrystalline glaze, the raw materials of the anorthite microcrystalline glaze are natural mineral rocks completely, other color-developing agents and auxiliary agents are not doped, the glazing process is formed in one step, the firing temperature is lower, and the effect is stable; the glaze substrate is reddish brown, anorthite crystals are usually lath-shaped, densely stacked and grown, and aggregated to form aggregates of 300-900 mu m which are distributed on the surface of the glaze layer, so that the artistic effect is very strong.

In order to achieve the purpose, the invention adopts the following technical scheme:

the natural mineral-anorthite microcrystalline glaze comprises the following raw material components: iron ore surrounding rock, calcium silicalite and ethylene glycol polyoxyethylene ether, wherein the iron ore surrounding rock, the calcium silicalite and the ethylene glycol polyoxyethylene ether comprise the following components in percentage by weight: iron ore surrounding rock: calcium skarn: ethylene glycol polyoxyethylene ether ═ 60-75: (25-40): (25-35).

The iron ore surrounding rock comprises the following components in percentage by mass: 0.75% K ₂O，0.05％Na ₂O，3.09％CaO，3.65％MgO，0.12％MnO，7.60％FeO，3.11％Al ₂O ₃，0.23％P ₂O ₅，81.4％SiO ₂。

The calcium silicalite comprises the following components in percentage by mass: 1.74% K ₂O，0.76％Na ₂O，30.54％CaO，4.47％MgO，0.29％TiO ₂，0.41％MnO，13.49％Fe ₂O ₃，7.07％Al ₂O ₃，0.11％P ₂O ₅，40.24％SiO ₂。

The concentration of the natural mineral-anorthite microcrystalline glaze material is 55-65 Baume degrees.

The preparation method of the natural mineral-anorthite microcrystalline glaze material comprises the following steps:

(1) taking the following raw materials in percentage by weight: 60-75 parts of iron ore surrounding rock and 25-40 parts of calcium silicalite;

(2) adding 250 parts of water 200 and 250 parts of calcium silicate rock into iron ore surrounding rock and calcium silicate rock according to the weight ratio, and performing wet ball milling for 3-5 hours;

(3) drying the ball-milled product, adding 25-35 parts of ethylene glycol polyoxyethylene ether, uniformly stirring, and grinding for 20-30 min;

(3) and (3) sieving the ground product by a 200-mesh sieve, and then mixing into glaze slip with 55-65 baume degrees to prepare the anorthite microcrystalline glaze material prepared from natural minerals.

In the step (2), the ball milling rotation speed is 50r/min, and the particle size of the ball milling product is 150-.

In the step (3), the grinding operation is carried out in a high-frequency oscillation grinding machine, the high-frequency oscillation frequency is 1500r/min, and the grain diameter of the ground product is 30-80 μm.

In the step (3), the raw materials are subjected to low-temperature solid-phase melting reaction in the high-frequency oscillation grinding process, albite in iron ore surrounding rock is partially melted, the edges of quartz around and calcium iron garnet in calcium silicalite are promoted to be partially melted, and CaO and Al are formed on the local part of the particle edges together ₂O ₃And SiO ₂The main components are selected, and the components react to form wollastonite and gehlenite precursors:

CaO+SiO ₂＝CaSiO ₃

CaSiO ₃+CaO+Al ₂O ₃＝2CaO·Al ₂O ₃·SiO ₂

in the step (3), due to the wrapping of the ethylene glycol polyoxyethylene ether, the formed precursor mineral cannot grow continuously, and a large amount of micro precursor particles are formed.

The use method of the natural mineral-anorthite microcrystalline glaze material comprises the following steps:

(1) taking a blank with a smooth surface, wiping the surface, taking anorthite microcrystalline glaze prepared from natural minerals, and glazing by adopting a glaze dipping method, wherein the thickness of a glaze layer is kept at 1-2 mm;

(2) after the blank body is dried after glazing, heating to 1250-; cooling to 1230-1250 ℃ at the speed of 3-6 ℃/min, and preserving heat for 0.2-0.5 h; cooling to 1180-1200 ℃ at the speed of 1-3 ℃/min, and preserving the heat for 0.2-0.5h to finish the firing; and finally, air-cooling to room temperature to obtain the anorthite microcrystalline glaze surface.

In the step (2), the drying mode of the blank body after glazing is natural drying.

In the step (2), the firing operation is carried out in an electric kiln.

In the step (2), the specific process of raising the temperature of the dried blank to 1250-: the temperature is raised to 850-.

In the step (2)And in the temperature rising process: the speed of 10-15 ℃/min is increased to 850-900 ℃, a product system after one-time heating is obtained, and in the process, albite in the iron ore surrounding rock is decomposed to form Na ₂O, the temperature of the liquid phase formation of the product system after one-time heating is reduced, dolomite is decomposed to form CaO, albite and pyroxene are decomposed to form a large amount of free Al ₂O ₃. In the high-temperature reaction process, albite, dolomite and pyroxene are completely melted and disappear, and a small amount of residual crystals remain in quartz, so that a fused mass containing calcium-rich aluminum and silicon is formed.

In the step (2), through a rapid temperature rise process, wollastonite precursors in the raw materials are retained and react with free CaO and Al ₂O ₃And SiO ₂The reaction forms nanometer anorthite crystal nucleus, and the specific reaction is as follows:

CaSiO ₃+CaO+2Al ₂O ₃+3SiO ₂＝2CaAl ₂Si ₂O ₈

in the step (2), in the cooling process, the nanometer anorthite crystal nucleus becomes the center of crystal growth, and the decomposition of dolomite in iron ore surrounding rocks releases CO ₂And the gas provides a space for the growth of anorthite crystals. In the first stage of temperature reduction process, the melt temperature is higher, the viscosity is smaller, and the cooling rate is higher, so that the crystal nucleus grows up in the melt rapidly and overlaps with each other. In the second stage, the lower cooling rate enables solute ions in the melt to continue to slowly diffuse to the crystal, and promotes the further growth of anorthite crystals.

In the step (2), the dolomite is decomposed to form iron element formed by decomposing pyroxene, and the iron element is oxidized into Fe in the firing process ³⁺And remains in the matrix, so that the glazed matrix presents a reddish-brown base tone.

In the step (2), the firing process is performed in an air atmosphere.

In the step (2), the prepared anorthite microcrystalline glaze substrate is reddish brown, the single anorthite crystal flower crystal grains are lath-shaped, densely stacked and grown, and aggregated to form crystal flower aggregates which are yellow and distributed on the surface of the glaze layer; the diameter of the single anorthite crystal flower is 100-150 mu m, the aggregate is quasi-circular, and the diameter is 300-900 mu m.

In the step (2), the grain size of the single crystal flowers of the prepared anorthite microcrystalline glaze surface is measured by the longest diameter passing through the crystal nucleus, and the polycrystalline flowers are aggregated to form a roundish aggregate, wherein the diameter of the aggregate is measured by the longest diameter passing through the center of the aggregate.

The invention has the beneficial effects that:

in the natural mineral-glaze material and the preparation method and the use method thereof, the anorthite microcrystalline glaze material is completely made of natural minerals, no pigment or auxiliary agent is added, the preparation cost is low, the glazing process is formed in one step, the firing temperature is low, the aggregates are uniform and are yellow; the base of the glaze is reddish brown, the glaze color is glittering and translucent, transparent and smooth, and the glaze layer is bright and fine. The prepared anorthite crystal is usually in a lath shape, grows in a dense stacking mode, aggregates of 300-900 mu m are formed and distributed on the surface of the glaze layer, the color of the substrate and the color of the crystal flower are natural, and the artistic effect is very strong. The glaze material can well improve the appearance quality of ceramic products, so as to improve the ornamental value of the ceramic products and the service performance of the ceramic products, and has higher economic value and market competitiveness.

Description of the drawings:

fig. 1 is an SEM photograph of the anorthite microcrystalline glaze prepared in example 1, at a magnification of 160 times.

The specific implementation mode is as follows:

the present invention will be described in further detail with reference to examples.

In the following examples:

the green body is a porcelain body or a ceramic body;

the electric kiln is a German Naberterm high-temperature furnace;

the raw materials are all taken from natural geologic bodies;

the natural mineral-anorthite microcrystalline glaze comprises the following raw material components: iron ore surrounding rock, calcium silicalite and ethylene glycol polyoxyethylene ether, wherein the iron ore surrounding rock, the calcium silicalite and the ethylene glycol polyoxyethylene ether comprise the following components in percentage by weight: iron ore surrounding rock: calcium skarn: ethylene glycol polyoxyethylene ether ═ 60-75: (25-40): (25-35).

The iron ore surrounding rock comprises components and substancesThe weight percentage content is as follows: 0.75% K ₂O，0.05％Na ₂O，3.09％CaO，3.65％MgO，0.12％MnO，7.60％FeO，3.11％Al ₂O ₃，0.23％P ₂O ₅，81.4％SiO ₂。

The calcium silicalite comprises the following components in percentage by mass: 1.74% K ₂O，0.76％Na ₂O，30.54％CaO，4.47％MgO，0.29％TiO ₂，0.41％MnO，13.49％Fe ₂O ₃，7.07％Al ₂O ₃，0.11％P ₂O ₅，40.24％SiO ₂。

The concentration of the natural mineral-anorthite microcrystalline glaze material is 55-65 Baume degrees.

The preparation method of the natural mineral-anorthite microcrystalline glaze material comprises the following steps:

(1) taking the following raw materials in percentage by weight: 60-75 parts of iron ore surrounding rock and 25-40 parts of calcium silicalite;

(2) adding 250 parts of water 200 and 250 parts of calcium silicate rock into iron ore surrounding rock and calcium silicate rock according to the weight ratio, and performing wet ball milling for 3-5 hours;

(3) drying the ball-milled product, adding 25-35 parts of ethylene glycol polyoxyethylene ether, uniformly stirring, and grinding for 20-30 min;

(3) and (3) sieving the ground product by a 200-mesh sieve, and then mixing into glaze slip with 55-65 baume degrees to prepare the anorthite microcrystalline glaze material prepared from natural minerals.

In the step (2), the ball milling rotation speed is 50r/min, and the particle size of the ball milling product is 150-.

In the step (3), the grinding operation is carried out in a high-frequency oscillation grinding machine, the high-frequency oscillation frequency is 1500r/min, and the grain diameter of the ground product is 30-80 μm.

In the step (3), the raw materials are subjected to low-temperature solid-phase melting reaction in the high-frequency oscillation grinding process, albite in iron ore surrounding rock is partially melted, the edges of quartz around and calcium iron garnet in calcium silicalite are promoted to be partially melted, and CaO and Al are formed on the local part of the particle edges together ₂O ₃And SiO ₂The main components are selected, and the components react to form wollastonite and gehlenite precursors:

CaO+SiO ₂＝CaSiO ₃

CaSiO ₃+CaO+Al ₂O ₃＝2CaO·Al ₂O ₃·SiO ₂

in the step (3), due to the wrapping of the ethylene glycol polyoxyethylene ether, the formed precursor mineral cannot grow continuously, and a large amount of micro precursor particles are formed.

The use method of the natural mineral-anorthite microcrystalline glaze material comprises the following steps:

(1) taking a blank with a smooth surface, wiping the surface, taking anorthite microcrystalline glaze prepared from natural minerals, and glazing by adopting a glaze dipping method, wherein the thickness of a glaze layer is kept at 1-2 mm;

(2) after the blank body is dried after glazing, heating to 1250-; cooling to 1230-1250 ℃ at the speed of 3-6 ℃/min, and preserving heat for 0.2-0.5 h; cooling to 1180-1200 ℃ at the speed of 1-3 ℃/min, and preserving the heat for 0.2-0.5h to finish the firing; and finally, air-cooling to room temperature to obtain the anorthite microcrystalline glaze surface.

In the step (2), the drying mode of the blank body after glazing is natural drying.

In the step (2), the firing operation is carried out in an electric kiln.

In the step (2), the specific process of raising the temperature of the dried blank to 1250-: the temperature is raised to 850-.

In the step (2), in the temperature rising process: the speed of 10-15 ℃/min is increased to 850-900 ℃, a product system after one-time heating is obtained, and in the process, albite in the iron ore surrounding rock is decomposed to form Na ₂O, the temperature of the liquid phase formation of the product system after one-time heating is reduced, dolomite is decomposed to form CaO, albite and pyroxene are decomposed to form a large amount of free Al ₂O ₃. In the high-temperature reaction process, albite, dolomite and pyroxene are completely melted and disappear, and a small amount of residual crystals remain in quartz, so that a fused mass containing calcium-rich aluminum and silicon is formed.

In the step (2), through a rapid temperature rise process, wollastonite precursors in the raw materials are keptLeft in and with free CaO, Al ₂O ₃And SiO ₂The reaction forms nanometer anorthite crystal nucleus, and the specific reaction is as follows:

CaSiO ₃+CaO+2Al ₂O ₃+3SiO ₂＝2CaAl ₂Si ₂O ₈

in the step (2), in the cooling process, the nanometer anorthite crystal nucleus becomes the center of crystal growth, and the decomposition of dolomite in iron ore surrounding rocks releases CO ₂And the gas provides a space for the growth of anorthite crystals. In the first stage of temperature reduction process, the melt temperature is higher, the viscosity is smaller, and the cooling rate is higher, so that the crystal nucleus grows up in the melt rapidly and overlaps with each other. In the second stage, the lower cooling rate enables solute ions in the melt to continue to slowly diffuse to the crystal, and promotes the further growth of anorthite crystals.

In the step (2), the dolomite is decomposed to form iron element formed by decomposing pyroxene, and the iron element is oxidized into Fe in the firing process ³⁺And remains in the matrix, so that the glazed matrix presents a reddish-brown base tone.

In the step (2), the firing process is performed in an air atmosphere.

In the step (2), the prepared anorthite microcrystalline glaze substrate is reddish brown, the single anorthite crystal flower crystal grains are lath-shaped, densely stacked and grown, and aggregated to form crystal flower aggregates which are yellow and distributed on the surface of the glaze layer; the diameter of the single anorthite crystal flower is 100-150 mu m, the aggregate is quasi-circular, and the diameter is 300-900 mu m.

In the step (2), the grain size of the single crystal flowers of the prepared anorthite microcrystalline glaze surface is measured by the longest diameter passing through the crystal nucleus, and the polycrystalline flowers are aggregated to form a roundish aggregate, wherein the diameter of the aggregate is measured by the longest diameter passing through the center of the aggregate.