CN106316127B - Medium-temperature golden plum crystal glaze and preparation method thereof - Google Patents
Medium-temperature golden plum crystal glaze and preparation method thereof Download PDFInfo
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- CN106316127B CN106316127B CN201610675014.2A CN201610675014A CN106316127B CN 106316127 B CN106316127 B CN 106316127B CN 201610675014 A CN201610675014 A CN 201610675014A CN 106316127 B CN106316127 B CN 106316127B
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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Abstract
The invention discloses a medium-temperature golden plum crystal glaze and a preparation method thereof, belonging to the technical field of ceramic glaze materials. The medium-temperature golden plum crystal glaze comprises, by weight, 30-40 parts of potash feldspar, 12-18 parts of quartz, 1-6 parts of calcite, 1-5 parts of calcined zinc oxide, 1-4 parts of calcined talc, 2-8 parts of frit, 30-38 parts of manganese carbonate and 0-10 parts of a colorant. The crystallized glaze is mainly characterized in that manganese carbonate is supersaturated in the high-temperature melting process of glaze, and is crystallized in the cooling process to generate a golden plum crystal shape, the process is simple, and the firing system is easy to control; and the cooling system has no special requirements, the ceramic is suitable for large-scale production, the product has stable property and good thermal stability, and the lead-cadmium dissolution rate, the glaze hardness and other physical and chemical properties reach the national relevant standards of daily stoneware.
Description
Technical Field
The invention relates to the technical field of ceramic glaze materials, in particular to medium-temperature golden plum crystal glaze and a manufacturing method thereof.
Background
In the colored glaze products sintered at the medium temperature of 1250-1300 ℃, a plurality of crystal glazes are available, mainly comprising zinc crystals, manganese crystals, iron crystals, titanium crystals and the like, and part of the crystal is iron-manganese-titanium mixed crystals. Most of the crystal glaze products and large-area dense crystal glaze products popular in the market at present mainly need a special firing kiln or firing system, and particularly in the crystal forming stage, the firing control requirement is very strict, so that the porcelain mainly takes the display artwork such as vases and the like, the daily porcelain products are rare, the porcelain products are mainly not suitable for large-scale production, and the product quality guarantee requirement is strict.
In general, the crystallized glaze product has strong artistry, good appreciation and high value, and is deeply appreciated by consumers. However, the crystal glaze product has poor reproducibility, namely poor stability, complex process requirements, especially strict requirements on firing system, and strict requirements on the fineness of the glaze and the thickness of the glaze layer, and some even have requirements on the composition of the blank body.
Disclosure of Invention
In view of the above, the invention aims to provide a medium-temperature golden plum crystal glaze and a manufacturing method thereof, so that a medium-temperature golden plum crystal glaze daily stoneware product not only has complete crystallization, but also has the physical and chemical properties meeting international standards, has good reproducibility, and can stably produce matched products in large batch.
Based on the purpose, the medium-temperature golden plum crystal glaze provided by the invention comprises, by weight, 30-40 parts of potassium feldspar, 12-18 parts of quartz, 1-6 parts of calcite, 1-5 parts of calcined zinc oxide, 1-4 parts of calcined talc, 2-8 parts of frit, 30-38 parts of manganese carbonate and 0-10 parts of a colorant.
According to the medium-temperature golden plum crystal glaze, the potassium feldspar is in a powdery head and is grey white; the content of silicon dioxide in the quartz is more than or equal to 98 percent, and the content of water is 1-8 percent.
According to the medium-temperature golden plum crystal glaze, the content of calcium oxide in calcite is more than or equal to 53% in percentage by weight; the calcined zinc oxide is powdery and slightly yellowish.
According to the medium-temperature golden plum crystal glaze, the content of magnesium oxide in the calcined talc is more than or equal to 34.5% in percentage by weight.
According to the medium-temperature golden plum crystal glaze, the frits are common boron, calcium and zinc frits, are granular, and have a white bluish tone.
According to the medium-temperature golden plum crystal glaze, the colorant is a coloring oxide.
The invention relates to a preparation method of medium-temperature golden plum crystal glaze, which comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula of claim 1 in parts by mass, and grinding the raw materials, ball stones and water together to prepare glaze slurry for later use;
b. glazing: glazing the stoneware blank by the glaze slurry for standby in the step a, wherein the thickness of a glaze layer is controlled to be 0.10-0.25 mm;
c. firing: drying the glazed stoneware blank obtained in the step b at the temperature of 50-60 ℃ for 1.5-2.5 hours, and then calcining in a kiln; the firing atmosphere is an oxidizing atmosphere, the temperature is 80 ℃ as an initial temperature, the temperature is raised to 245 ℃ at the speed of 3-4 ℃/min, the temperature is raised to 760 ℃ at the speed of 5-6 ℃/min, the temperature is raised to 1170 ℃ at the speed of 8-10 ℃/min, the temperature is raised to 1250-1270 ℃ at the speed of 1-3 ℃/min, the temperature is kept for 20-30 min, the temperature is lowered to 700 ℃ at the speed of 24-26 ℃/min, the temperature is lowered to 530 ℃ at the speed of 7-8 ℃/min, the temperature is lowered to 450 ℃ at the speed of 1-2 ℃/min, and the temperature;
or, the firing atmosphere is a reducing atmosphere, the temperature is increased to 500 ℃ at 80 ℃ as an initial temperature, the temperature is increased to 950 ℃ at 19-20 ℃/min, the temperature is increased to 980 ℃ at 1-2 ℃/min, the temperature is increased to 1150 ℃ at 7-8 ℃/min, the temperature is increased to 1280-1300 ℃ at 1-2 ℃/min, the temperature is maintained for 20-30 min, the temperature is decreased to 750 ℃ at 23-25 ℃/min, the temperature is decreased to 530 ℃ at 9-10 ℃/min, the temperature is decreased to 450 ℃ at 1-2 ℃/min, and the temperature is decreased to 38 ℃ at 8-10 ℃/min.
According to the preparation method of the medium-temperature golden plum crystal glaze, the ratio of the raw materials, the ball stone and the water is 1 (2-2.5) to 0.6-0.8 in parts by weight.
According to the method for manufacturing the medium-temperature golden plum crystal glaze, the concentration of the glaze slip is 30-60 baume degrees.
According to the method for manufacturing the medium-temperature golden plum crystal glaze, the fineness of the glaze slip is controlled to be 0.01-0.03% of the sieve residue of a 250-mesh sieve.
The potassium adopted in the formula of the warm golden plum crystal glaze is produced from Pingjiang county in Hubei province; quartz is produced from carignan, fine sand; calcite is produced from Guangxi; calcined zinc oxide is produced in Hunan shores; the manganese carbonate is industrial chemical pure and is produced in Shanghai; calcined talc was produced from Guangxi; the frits are produced from carica and sold in the market; the colorant is a coloring oxide, and other colorants are easily hidden by the color developed by manganese and do not develop color.
The formula combination of the warm golden plum crystal glaze is critical, and the lack of the formula combination is not necessary, so the process can be widely applied, and the glaze can be fired by medium-temperature oxidizing flame and medium-temperature reducing flame. In the formula, potassium feldspar and quartz are used as backbones to form a glaze slurry matrix; the clinker, the calcite, the calcined zinc oxide and the calcined talc are used as fluxes, so that the sintering temperature of the glaze material is ensured to reach or be kept to the required sintering temperature and crystallization temperature. Calcined zinc oxide and calcined talc promote crystallization within the ranges described herein, and beyond this range they adversely affect crystallization, i.e., do not favor crystal formation or continued crystal growth. Manganese dioxide is decomposed from manganese carbonate in the high-temperature process, and the activity of the decomposed manganese dioxide is better than that of the manganese dioxide added independently, and the purity is higher; the glaze formula is molten at high temperature, excessive manganese dioxide is dissolved in the glaze solution at high temperature, and supersaturated manganese dioxide precipitates crystals in the process of glaze layer condensation in the process of temperature reduction to form the golden plum crystal glaze.
In the manufacturing method of the wintersweet crystallized glaze, when the glaze slurry in the step a is prepared, the added ball stones are large, medium and small, the diameter of the large ball stone is 25-35 mm, the diameter of the medium ball stone is 15-25 mm, the diameter of the small ball stone is 8-15 mm, and the ratio of the large ball stone to the medium ball stone to the small ball stone is 2:5: 3. And b, glazing the stoneware blank, namely firstly screening the glaze slurry through a 120-mesh standard sieve, so that impurities, such as small crushed particles of ball stones, ball-milling linings and the like in a ball mill, impurity particles brought by a discharge port of the ball mill and the like can be prevented from being introduced in the process of discharging the slurry. According to different models, adding water to adjust the concentration of the glaze slip, adding electrolyte to adjust the thixotropy of the glaze slip to reach the optimal condition, and ensuring that the thickness of a glaze layer of a glazed blank is 0.1-0.25 mm; when the thixotropy of the glaze slip reaches the optimal condition, the glaze material is convenient to use, and glaze defects such as glaze strands, glaze ribs and the like are not generated. The effect is not good when the thickness of the glaze layer exceeds the range of 0.1-0.25 mm, if the thickness of the glaze layer is less than 0.1 mm, crystallization hardly occurs, and if the thickness of the glaze layer exceeds 0.25 mm, crystallization is excessive, and the glaze surface is rough because of all crystallization. When the sintering in the step c adopts an oxidizing atmosphere, the temperature is increased from 80 ℃ to 180 ℃ mainly for discharging steam, the temperature is reduced from 530 ℃ to 450 ℃ by adopting 1-2 ℃/min, and the quartz crystal phase transition body is changed at the temperature stage, so that the quartz crystal phase transition body is slowly cooled to avoid explosion; when the sintering adopts a reducing atmosphere, the temperature is increased from 80 ℃ to 180 ℃ mainly for discharging steam, the temperature is increased from 950 ℃ to 1150 ℃ mainly for completing the conversion from the oxidizing atmosphere to the reducing atmosphere, and the temperature is decreased from 530 ℃ to 450 ℃ by adopting 1-2 ℃/min, and the quartz crystal phase conversion volume change is carried out at the temperature stage, so the quartz crystal phase conversion volume change needs to be slowly cooled so as to avoid explosion.
From the above, it can be seen that the advantages and benefits of the present invention are:
(1) the medium-temperature golden plum crystal glaze product disclosed by the invention belongs to the category of manganese crystal glaze, has wide temperature adaptation range, and can be sintered in an oxidation flame atmosphere within a sintering period with the highest sintering temperature reaching 1250-1270 ℃; the high-temperature-resistant.
(2) The crystal flower effect of the warm prunus mume crystal glaze is that the outer ring is a yellow and reddish halo, the inner part is yellow, the middle part is a golden patch, the golden patch has a slightly convex feeling, the feeling of the hand is clear, the golden feeling is strong, and the whole glaze looks like a golden plum flower, so the product is named as the prunus mume crystal glaze. The diameter of the crystal block is between 0.5 mm and 3.5 mm, the thick part of the glaze is denser, and the thin part of the glaze is thinner. The background glaze surface is metallic luster glaze, matt and is similar to stainless steel in texture.
(3) The wintersweet crystal glaze is mainly characterized in that manganese carbonate is supersaturated in the high-temperature melting process of the glaze, and is crystallized in the cooling process to generate a wintersweet crystal shape, the process is simple, and the firing system is easy to control.
(4) The product of the invention has no special requirements on the cooling system, is suitable for large-scale production, and has stable property, good thermal stability, lead-cadmium dissolution, glaze hardness and other physical and chemical properties which reach the national relevant standards of daily stoneware.
Drawings
FIG. 1 is a medium temperature oxidizing flame firing curve of an embodiment of the present invention;
FIG. 2 is a medium-temperature reducing flame firing curve of an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Example 1
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 30 parts of potash feldspar, 12 parts of quartz, 6 parts of calcite, 5 parts of calcined zinc oxide, 4 parts of calcined talc, 2 parts of frit and 38 parts of manganese carbonate, and no colorant is added.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.01%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2:0.7, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 30 baume degrees, adding 0.08% of sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.10 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 50 ℃ for 2.5 hours, then sintering the blank in a medium-temperature oxidation flame roller kiln, wherein the sintering atmosphere is an oxidation atmosphere, the temperature is increased to 245 ℃ at the temperature of 80 ℃, is increased to 760 ℃ at the temperature of 5 ℃/min, is increased to 1170 ℃ at the temperature of 10 ℃/min, is increased to 1260 ℃ at the temperature of 3 ℃/min, is kept warm for 30min, is reduced to 700 ℃ at the temperature of 24 ℃/min, is reduced to 530 ℃ at the temperature of 8 ℃/min, is reduced to 450 ℃ at the temperature of 1 ℃/min, and is reduced to 38 ℃ at the temperature of 10 ℃/min, and the sintering is. Specifically, see a medium-temperature oxidizing flame firing curve chart 1, wherein the highest firing temperature can reach 1250-1270 ℃.
Example 2
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 40 parts of potash feldspar, 18 parts of quartz, 1 part of calcite, 1 part of calcined zinc oxide, 1 part of calcined talc, 8 parts of frit, 30 parts of manganese carbonate, 8 parts of a colorant, and the colorant is cobalt oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.03%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2.5:0.6, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 60 baume degrees, adding 0.1% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.25 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 60 ℃ for 1.5 hours, then sintering the blank in a shuttle kiln, wherein the sintering atmosphere is a reducing atmosphere, the temperature is increased to 500 ℃ at the temperature of 80 ℃, the temperature is increased to 950 ℃ at the temperature of 20 ℃/min, the temperature is increased to 980 ℃ at the temperature of 1 ℃/min, the temperature is increased to 1150 ℃ at the temperature of 8 ℃/min, the temperature is increased to 1290 ℃ at the temperature of 2 ℃/min, the temperature is kept for 20min, the temperature is decreased to 750 ℃ at the temperature of 23 ℃/min, the temperature is decreased to 530 ℃ at the temperature of 10 ℃/min, the temperature is decreased to 450 ℃ at the temperature of 10 ℃/min, and. Specifically, see the medium-temperature reducing flame firing curve 2, wherein the highest firing temperature can reach 1280-1300 ℃.
Example 3
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 35 parts of potash feldspar, 15 parts of quartz, 4 parts of calcite, 3 parts of calcined zinc oxide, 2 parts of calcined talc, 5 parts of frit, 34 parts of manganese carbonate, 8 parts of a colorant, and the colorant is cobalt oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.02%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2.3:0.8, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 45 baume degrees, adding 0.09% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.18 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 55 ℃ for 2 hours, then sintering the blank in a medium-temperature oxidation flame roller kiln, wherein the sintering atmosphere is an oxidation atmosphere, the temperature is increased to 245 ℃ at the temperature of 80 ℃ as an initial temperature, the temperature is increased to 760 ℃ at the temperature of 6 ℃/min, the temperature is increased to 1170 ℃ at the temperature of 8 ℃/min, the temperature is increased to 1270 ℃ at the temperature of 3 ℃/min, the temperature is kept for 20min, the temperature is decreased to 700 ℃ at the temperature of 26 ℃/min, the temperature is decreased to 530 ℃ at the temperature of 7 ℃/min, the temperature is decreased to 450 ℃ at the temperature of 2 ℃/min. Specifically, see a medium-temperature oxidizing flame firing curve chart 1, wherein the highest firing temperature can reach 1250-1270 ℃.
Example 4
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 35 parts of potash feldspar, 15 parts of quartz, 4 parts of calcite, 3 parts of calcined zinc oxide, 2 parts of calcined talc, 5 parts of frit, 34 parts of manganese carbonate, 10 parts of a colorant, and the colorant is cobalt oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.03%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2.5:0.6, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 60 baume degrees, adding 0.1% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.25 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 60 ℃ for 1.5 hours, then sintering the blank in a medium-temperature reduction flame roller kiln, wherein the sintering atmosphere is a reduction atmosphere, the temperature is increased to 500 ℃ at the temperature of 80 ℃, is increased to 950 ℃ at the temperature of 19 ℃/min, is increased to 980 ℃ at the temperature of 2 ℃/min, is increased to 1150 ℃ at the temperature of 7 ℃/min, is increased to 1280 ℃ at the temperature of 1 ℃/min, is kept warm for 30min, is decreased to 750 ℃ at the temperature of 25 ℃/min, is decreased to 530 ℃ at the temperature of 9 ℃/min, is decreased to 450 ℃ at the temperature of 2 ℃/min, and is decreased to 38 ℃ at the temperature of 8 ℃/min. Specifically, see the medium-temperature reducing flame firing curve 2, wherein the highest firing temperature can reach 1280-1300 ℃.
Example 5
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 32 parts of potash feldspar, 13 parts of quartz, 5 parts of calcite, 4 parts of calcined zinc oxide, 3 parts of calcined talc, 3 parts of frit, 36 parts of manganese carbonate, 2 parts of a colorant, and the colorant is nickel oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.01%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2:0.7, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 30 baume degrees, adding 0.08% of sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.10 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 50 ℃ for 2.5 hours, then sintering the blank in a medium-temperature oxidation flame roller kiln, wherein the sintering atmosphere is an oxidation atmosphere, the temperature is increased to 245 ℃ at the temperature of 80 ℃, is increased to 760 ℃ at the temperature of 6 ℃/min, is increased to 1170 ℃ at the temperature of 8 ℃/min, is increased to 1250 ℃ at the temperature of 1 ℃/min, is kept at the temperature for 30min, is reduced to 700 ℃ at the temperature of 26 ℃/min, is reduced to 530 ℃ at the temperature of 7 ℃/min, is reduced to 450 ℃ at the temperature of 2 ℃/min, is reduced to 38 ℃ at the temperature of 8 ℃/min, and the sintering. Specifically, see a medium-temperature oxidizing flame firing curve chart 1, wherein the highest firing temperature can reach 1250-1270 ℃.
Example 6
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 38 parts of potash feldspar, 16 parts of quartz, 2 parts of calcite, 2 parts of calcined zinc oxide, 2 parts of calcined talc, 6 parts of frit, 32 parts of manganese carbonate, 4 parts of a colorant, and the colorant is chromium oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.03%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2:0.7, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 60 baume degrees, adding 0.1% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.25 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 60 ℃ for 1.5 hours, then sintering the blank in a medium-temperature reduction flame roller kiln, wherein the sintering atmosphere is a reduction atmosphere, the temperature is increased to 500 ℃ at the temperature of 80 ℃, is increased to 950 ℃ at the temperature of 20 ℃/min, is increased to 980 ℃ at the temperature of 1 ℃/min, is increased to 1150 ℃ at the temperature of 8 ℃/min, is increased to 1300 ℃ at the temperature of 2 ℃/min, is kept for 20min, is decreased to 750 ℃ at the temperature of 23 ℃/min, is decreased to 530 ℃ at the temperature of 10 ℃/min, is decreased to 450 ℃ at the temperature of 1 ℃/min, and is decreased to 38 ℃ at the temperature of 10 ℃/min. Specifically, see the medium-temperature reducing flame firing curve 2, wherein the highest firing temperature can reach 1280-1300 ℃.
Comparative example 1
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 45 parts of potash feldspar, 20 parts of quartz, 0.5 part of calcite, 6 parts of calcined zinc oxide, 0.5 part of calcined talc, 1 part of frit, 28 parts of manganese carbonate, 8 parts of a colorant, and the colorant is cobalt oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.02%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2.3:0.8, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 45 baume degrees, adding 0.09% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.15 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 55 ℃ for 2 hours, then sintering the blank in a medium-temperature oxidation flame roller kiln, wherein the sintering atmosphere is an oxidation atmosphere, the temperature is increased to 245 ℃ at the temperature of 80 ℃ as an initial temperature, the temperature is increased to 760 ℃ at the temperature of 5 ℃/min, the temperature is increased to 1170 ℃ at the temperature of 10 ℃/min, the temperature is increased to 1260 ℃ at the temperature of 3 ℃/min, the temperature is maintained for 30min, the temperature is decreased to 700 ℃ at the temperature of 24 ℃/min, the temperature is decreased to 530 ℃ at the temperature of 8 ℃/min, the temperature is decreased to 450 ℃ at the temperature of 1 ℃/min. Specifically, see a medium-temperature oxidizing flame firing curve chart 1, wherein the highest firing temperature can reach 1250-1270 ℃.
Comparative example 2
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 25 parts of potash feldspar, 10 parts of quartz, 7 parts of calcite, 0.5 part of calcined zinc oxide, 5 parts of calcined talc, 10 parts of frit, 40 parts of manganese carbonate, 4 parts of a colorant, and the colorant is chromium oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.03%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2:0.7, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 60 baume degrees, adding 0.1% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.25 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 60 ℃ for 1.5 hours, then sintering the blank in a medium-temperature reduction flame roller kiln, wherein the sintering atmosphere is a reduction atmosphere, the temperature is increased to 500 ℃ at the temperature of 80 ℃, is increased to 950 ℃ at the temperature of 20 ℃/min, is increased to 980 ℃ at the temperature of 2 ℃/min, is increased to 1150 ℃ at the temperature of 8 ℃/min, is increased to 1300 ℃ at the temperature of 2 ℃/min, is kept for 20min, is decreased to 750 ℃ at the temperature of 23 ℃/min, is decreased to 530 ℃ at the temperature of 10 ℃/min, is decreased to 450 ℃ at the temperature of 1 ℃/min, and is decreased to 38 ℃ at the temperature of 10 ℃/min. Specifically, see the medium-temperature reducing flame firing curve 2, wherein the highest firing temperature can reach 1280-1300 ℃.
Comparative example 3
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 40 parts of potash feldspar, 18 parts of quartz, 1 part of calcite, 1 part of calcined zinc oxide, 1 part of calcined talc, 8 parts of frit, 30 parts of manganese carbonate, 8 parts of a colorant, and the colorant is cobalt oxide.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.03%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2.5:0.6, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 60 baume degrees, adding 0.1% sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.30 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 60 ℃ for 1.5 hours, then sintering the blank in a shuttle kiln, wherein the sintering atmosphere is a reducing atmosphere, the temperature is increased to 500 ℃ at the temperature of 80 ℃, the temperature is increased to 950 ℃ at the temperature of 19 ℃/min, the temperature is increased to 980 ℃ at the temperature of 1 ℃/min, the temperature is increased to 1150 ℃ at the temperature of 7 ℃/min, the temperature is increased to 1280 ℃ at the temperature of 1 ℃/min, the temperature is kept for 30min, the temperature is decreased to 750 ℃ at the temperature of 25 ℃/min, the temperature is decreased to 530 ℃ at the temperature of 9 ℃/min, the temperature is decreased to 450 ℃ at the temperature of 8 ℃/min, and. Specifically, see the medium-temperature reducing flame firing curve 2, wherein the highest firing temperature can reach 1280-1300 ℃.
Comparative example 4
The medium-temperature golden plum crystal glaze comprises the following components in percentage by weight: 30 parts of potash feldspar, 12 parts of quartz, 6 parts of calcite, 5 parts of calcined zinc oxide, 4 parts of calcined talc, 2 parts of frit and 38 parts of manganese carbonate, and no colorant is added.
The preparation method of the medium-temperature golden plum crystal glaze comprises the following steps:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula as claimed in claim 1 in parts by mass, putting the raw materials, high-alumina ball stones and water into a ball mill together for grinding until the balance of a standard sieve with a size of 250 meshes is 0.01%, and preparing glaze slurry for later use; wherein the ratio of the raw materials, the high alumina ball stone and the water is 1:2:0.7, and the ratio of the large ball stone, the medium ball stone and the small ball stone in the high alumina ball stone is 2:5: 3.
b. Glazing: b, screening the standby glaze slurry in the step a by a 120-mesh standard sieve, adding water to adjust the concentration of the glaze slurry to 30 baume degrees, adding 0.08% of sodium tripolyphosphate to adjust the thixotropy of the glaze slurry to the optimal state, glazing the stoneware blank, and controlling the thickness of a glaze layer to be 0.05 mm;
c. firing: and c, drying the glazed stoneware blank obtained in the step b at the temperature of 50 ℃ for 2.5 hours, then sintering the blank in a medium-temperature oxidation flame roller kiln, wherein the sintering atmosphere is an oxidation atmosphere, the temperature is increased to 245 ℃ at the temperature of 80 ℃, is increased to 760 ℃ at the temperature of 6 ℃/min, is increased to 1170 ℃ at the temperature of 8 ℃/min, is increased to 1270 ℃ at the temperature of 3 ℃/min, is kept for 20min, is reduced to 700 ℃ at the temperature of 26 ℃/min, is reduced to 530 ℃ at the temperature of 7 ℃/min, is reduced to 450 ℃ at the temperature of 2 ℃/min, is reduced to 38 ℃ at the temperature of 8 ℃/min, and the sintering is finished. Specifically, see a medium-temperature oxidizing flame firing curve chart 1, wherein the highest firing temperature can reach 1250-1270 ℃.
Detection examples
The stoneware blanks attached with the medium-temperature golden plum crystal glaze prepared in examples 1 to 6 and comparative examples 1 to 4 are subjected to heat stability, lead and cadmium dissolution, appearance quality and glaze hardness detection, and subjected to dish-washing machine test.
The thermal stability test method comprises the following steps: reference is made to BSEN1183:1997, Method B for detection.
The lead and cadmium leaching amount testing method comprises the following steps: the test was carried out with reference to ISO6486-1: 1999.
The glaze hardness detection method comprises the following steps: and (4) scribing the glaze by using a knife and a fork, and checking the scribing traces of the glaze.
Dishwasher equivalent test method: after the strong alkali solution is soaked for 4 hours at 100 ℃, the glaze surface change is observed.
The results are shown in Table 1.
Table 1.
The frit and the pigment adopted in the invention have strict requirements, and the frit and the pigment which only contain trace lead and cadmium or do not contain lead and cadmium are adopted, so that the lead and cadmium content in the product is extremely low; the matching of the glaze thermal expansion coefficient and the green body thermal expansion coefficient is ensured by adopting all the components in the glaze raw material formula, and the good thermal stability of the whole porcelain body is ensured; the potash feldspar adopted in the glaze raw material formula ensures that the glaze surface has higher hardness under the same cooling effect, and the glaze surface has golden plum crystal precipitation, so that the crystal hardness is very high, and the glaze hardness is further improved.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The medium-temperature golden plum crystal glaze is characterized by comprising, by weight, 30-40 parts of potassium feldspar, 12-18 parts of quartz, 1-6 parts of calcite, 1-5 parts of calcined zinc oxide, 1-4 parts of calcined talc, 2-8 parts of frit, 30-38 parts of manganese carbonate and 0-10 parts of a colorant.
2. The medium-temperature golden plum crystal glaze according to claim 1, wherein the potassium feldspar is powdery and grey-white.
3. A medium-temperature golden plum crystal glaze according to claim 1, characterized in that the content of calcium oxide in calcite is not less than 53% in percentage by weight; the calcined zinc oxide is powdery and slightly yellowish.
4. A medium-temperature golden plum crystal glaze according to claim 1, wherein the calcined talc contains 34.5% or more of magnesium oxide in percentage by weight.
5. A medium-temperature golden plum crystal glaze according to claim 1, wherein the frits are ordinary boron, calcium and zinc frits, block-granular and have a bluish white tone.
6. A medium-temperature golden plum crystal glaze according to claim 1, wherein the colorant is a coloring oxide.
7. A method for preparing a medium-temperature golden plum crystal glaze according to claim 1, characterized by comprising the steps of:
a. preparing glaze slip: weighing the raw materials of the medium-temperature golden plum crystal glaze formula of claim 1 in parts by mass, and grinding the raw materials, ball stones and water together to prepare glaze slurry for later use;
b. glazing: glazing the stoneware blank by the glaze slurry for standby in the step a, wherein the thickness of a glaze layer is controlled to be 0.10-0.25 mm;
c. firing: drying the glazed stoneware blank obtained in the step b at the temperature of 50-60 ℃ for 1.5-2.5 hours, and then calcining in a kiln; the firing atmosphere is an oxidizing atmosphere, the temperature is 80 ℃ as an initial temperature, the temperature is raised to 245 ℃ at the speed of 3-4 ℃/min, the temperature is raised to 760 ℃ at the speed of 5-6 ℃/min, the temperature is raised to 1170 ℃ at the speed of 8-10 ℃/min, the temperature is raised to 1250-1270 ℃ at the speed of 1-3 ℃/min, the temperature is kept for 20-30 min, the temperature is lowered to 700 ℃ at the speed of 24-26 ℃/min, the temperature is lowered to 530 ℃ at the speed of 7-8 ℃/min, the temperature is lowered to 450 ℃ at the speed of 1-2 ℃/min, and the temperature;
or, the firing atmosphere is a reducing atmosphere, the temperature is increased to 500 ℃ at 80 ℃ as an initial temperature, the temperature is increased to 950 ℃ at 19-20 ℃/min, the temperature is increased to 980 ℃ at 1-2 ℃/min, the temperature is increased to 1150 ℃ at 7-8 ℃/min, the temperature is increased to 1280-1300 ℃ at 1-2 ℃/min, the temperature is maintained for 20-30 min, the temperature is decreased to 750 ℃ at 23-25 ℃/min, the temperature is decreased to 530 ℃ at 9-10 ℃/min, the temperature is decreased to 450 ℃ at 1-2 ℃/min, and the temperature is decreased to 38 ℃ at 8-10 ℃/min.
8. The method for preparing a medium-temperature golden plum crystal glaze according to claim 7, wherein the ratio of the raw materials, the ball stone and the water is 1 (2-2.5) to (0.6-0.8) in parts by weight.
9. The method for preparing a medium-temperature golden plum crystal glaze according to claim 7, wherein the concentration of the glaze slip is 30-60 baume degrees.
10. The method for manufacturing the medium-temperature golden plum crystal glaze according to claim 7, wherein the fineness of the glaze slip is controlled to be 0.01-0.03% of the sieve residue of a 250-mesh sieve.
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