CN113185126B - High-wear-resistance sanitary ceramic and preparation method thereof - Google Patents
High-wear-resistance sanitary ceramic and preparation method thereof Download PDFInfo
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Abstract
The application relates to a high wear-resistant sanitary ceramic and a preparation method thereof, which belong to the technical field of ceramic production and comprise a sanitary ceramic blank and a glazed layer; the glaze material of the glaze layer comprises the following components in parts by weight: 27-32 parts of quartz, 23-28 parts of potash feldspar, 3-5 parts of zinc oxide, 12-15 parts of calcite, 7-8 parts of dolomite, 7-9 parts of zirconium silicate, 1.5-2.5 parts of alumina, 5-7 parts of Suzhou soil, 2.5-3.5 parts of clinker and 10-15 parts of modified pyrophyllite powder. This application has the effect that improves ceramic sanitary ware glazed layer's wearability.
Description
Technical Field
The application relates to the field of ceramic technology, in particular to high-wear-resistance sanitary ceramic and a preparation method thereof.
Background
The sanitary ceramics are glazed ceramic products used in places such as toilets, kitchens, laboratories and the like, and also become sanitary wares.
Sanitary ceramics play an important role in building decoration materials, and are well received by people due to the characteristics of mild color, smooth surface, compact texture, no permeability and the like. However, the sanitary ceramics are different from decorative ceramics, and are often washed and abraded in the using process, the aging phenomenon is obvious, the glossiness of the sanitary ceramics is reduced, the color of the sanitary ceramics is lightened, and the service life of the sanitary ceramics is seriously shortened. The quality of the sanitary ceramics is most critical to the glaze layer, and the composition of the glaze has great influence on the performance of the glaze layer. Therefore, it is important to improve the wear resistance of sanitary ceramics by improving the glaze for ceramics.
Disclosure of Invention
In order to improve the wear resistance of the glazed layer of the sanitary ceramic, the application provides the high-wear-resistance sanitary ceramic and the preparation method thereof.
In a first aspect, the high wear-resistant sanitary ceramic and the preparation method thereof provided by the application adopt the following technical scheme:
a high wear-resistant sanitary ceramic comprises a sanitary ceramic blank and a glaze layer;
the glaze material of the glaze layer comprises the following components in parts by weight: 27-32 parts of quartz, 23-28 parts of potassium feldspar, 3-5 parts of zinc oxide, 12-15 parts of calcite, 7-8 parts of dolomite, 7-9 parts of zirconium silicate, 1.5-2.5 parts of alumina, 5-7 parts of Suzhou soil, 2.5-3.5 parts of frit and 10-15 parts of modified pyrophyllite powder.
Through adopting above-mentioned technical scheme, adopt quartzy principal ingredients as the frit in this application, constitute the glass state skeleton, play the chemical stability and the thermal stability of adjustment glazed layer, simultaneously, can also increase glazed layer's hardness, improve wear resistance. The zirconium silicate has good chemical stability, is not influenced by the ceramic firing atmosphere, is beneficial to improving the hardness of a glaze layer and the wear resistance, can form baddeleyite and the like after being fired, and can scatter incident light waves, thereby achieving the effects of opacification and whitening. Meanwhile, the zirconium silicate and the zinc oxide are matched for use, so that the abrasion loss of the glaze layer of the sanitary ceramic can be further reduced, and the glossiness is improved, so that the abrasion resistance of the glaze layer is improved; calcite and dolomite mainly play a role in fluxing, magnesium carbonate is contained in the dolomite, the sintering temperature is favorably widened, and the dissolution of quartz and the formation of mullite crystals can be effectively promoted by the cooperation of the calcite and the dolomite; the zinc oxide can also play a role in fluxing, and can be used in combination with calcite and dolomite to effectively improve the glossiness and wear resistance of a glaze layer.
In addition, modified pyrophyllite powder is added in the method, because the aluminum content in the pyrophyllite is rich, the application is wide, impurities in the pyrophyllite are removed through modifying the pyrophyllite, the problem that glaze is easy to get turbid is solved, the hardness of the pyrophyllite is increased, and the wear resistance of a glaze layer is improved. Meanwhile, the pyrophyllite has compact structure and greasy feeling, the powder has lubricating property, is easy to be mixed with other raw materials, and has good dispersibility, so that the fired glaze layer has better wear resistance.
Preferably, the preparation method of the modified pyrophyllite powder comprises the following steps:
a. crushing pyrophyllite, removing iron, adding water, ball-milling and drying to obtain pyrophyllite powder;
b. calcining the pyrophyllite powder obtained in the step a at the temperature of 500-700 ℃, and then putting the pyrophyllite powder into an acid washing tank for precipitation;
c. mixing the upper layer slurry obtained in the step b with magnesium stearate and nano hydrotalcite, and stirring at 75-85 ℃ to obtain a mixture; wherein the weight ratio of the pyrophyllite powder to the magnesium stearate to the nano hydrotalcite is (3-4) to 1 (0.8-1.2);
d. and c, carrying out suction filtration and drying on the mixture in the step c to obtain the modified pyrophyllite powder.
By adopting the technical scheme, the iron powder in the pyrophyllite powder is removed through iron removal treatment, so that the purity of the pyrophyllite powder is improved; then, impurities of the pyrophyllite powder are further reduced through calcination, and magnesium stearate and nano hydrotalcite are introduced, so that the hardness of the pyrophyllite is increased, and the wear resistance of the glazed layer is improved.
Preferably, the particle size of the modified pyrophyllite powder obtained in the step d is 150-200 meshes.
Preferably, the calcite is modified calcite, and the modification method comprises the following steps:
(1) preparing powder slurry: calcite and titanate coupling agent are mixed according to the weight ratio of 1: (0.5-0.7%) to form a mixture, adding water to prepare slurry with the mass concentration of 70-75%, and grinding to form powder slurry;
(2) preparing titanium dioxide slurry: titanium dioxide, titanate coupling agent and silica sol are mixed according to the weight ratio of 1: (0.5-0.8%): (2-6%) and adding water and stirring to prepare titanium dioxide slurry with the mass concentration of 60-70%;
(3) and (2) mixing the powder slurry prepared in the step (1) and the titanium dioxide slurry prepared in the step (2) according to the weight ratio of (1.5-2.5): 1 to obtain a mixed slurry, stirring at the rotating speed of 1000-1500r/min, filtering and drying to obtain the modified calcite.
By adopting the technical scheme, the titanium dioxide is adopted to modify calcite, which is beneficial to inducing the titanium dioxide to react with calcium oxide, so that the titanium dioxide is inhibited from generating rutile phase, and further the yellowing of a glaze layer is eliminated, and the service life of the sanitary ceramic is prolonged.
Preferably, the specific conditions for drying in step (3) are as follows: filtering the mixed slurry in the step (3), adding the filtered mixed slurry into water, performing ultrasonic dispersion for 8-10min, and performing freeze drying for 4-5h under the conditions that the temperature is minus 25 to minus 20 ℃ and the vacuum degree is 130 and 140 pa.
By adopting the technical scheme, the dispersion of the modified calcite is facilitated through ultrasonic treatment, and the agglomeration phenomenon of the modified calcite is reduced, so that the drying efficiency in the later period is improved, and meanwhile, the moisture in the modified calcite can be fully removed.
Preferably, the glaze further comprises 0.6-1.2 parts of montmorillonite and 0.5-0.8 part of sodium humate.
By adopting the technical scheme, the montmorillonite and the sodium humate are added, the montmorillonite and the sodium humate can cooperate and act together, and the inorganic-organic combination mode is adopted, so that the strength and the wear resistance of the glaze layer are increased.
Preferably, the weight ratio of the montmorillonite to the sodium humate is (1.0-2.0): 1.
By adopting the technical scheme, a large number of tests prove that when the weight ratio of the montmorillonite to the sodium humate is (1.0-2.0):1, the strength and the wear resistance of the glaze layer can be further improved.
Preferably, the glaze also comprises 0.2-0.3 part of gelatin.
By adopting the technical scheme, the addition of the gelatin can greatly improve the bonding property among the raw materials of the glaze, so that the sintered glaze is smooth and compact in texture, and the strength and the wear resistance of the glaze layer are improved.
Preferably, the pug of the sanitary ceramic blank comprises the following components in parts by weight: 10-14 parts of Zhangvillage soil, 5-7 parts of Zhangwu soil, 5-7 parts of Chengde soil, 10-14 parts of Tangshan mountain wood knot, 7-9 parts of Shanxi mountain wood knot, 8-12 parts of Qinyang soil, 7-9 parts of Xuanhua soil, 6-8 parts of Funing china stone, 3-5 parts of ball soil, 3-5 parts of white clay, 4-6 parts of coked gray powder, 1-3 parts of porcelain powder, 28390and 16-20 parts of county sandstone.
In a second aspect, the application provides a preparation method of high-wear-resistance sanitary ceramic, which adopts the following technical scheme:
a preparation method of high wear-resistant sanitary ceramics comprises the following steps:
s1: preparing a sanitary ceramic blank:
s11: mixing the pug of the sanitary ceramic blank, and then adding water accounting for 40-45wt% of the pug for ball milling to obtain slurry;
s12: standing and ageing the slurry in the step S11, grouting, demolding and drying to obtain a green body sample, and firing at 1100-1200 ℃ to obtain a sanitary ceramic blank;
s2: preparing glaze slip of the glaze layer:
s21: ball-milling the frit in advance, then mixing the rest raw materials in the glaze with the frit, and adding 40-50wt% of water into the glaze for ball-milling to obtain glaze slurry of a glaze layer;
s23: sieving the glaze layer glaze obtained in the step S21 through a 180-mesh and 200-mesh sieve, and removing iron;
s3: glazing: spraying the glaze slurry prepared in the step S23 on the sanitary ceramic blank obtained in the step S12 by adopting a glaze spraying method to prepare a glazed blank;
s4: and (4) carrying out glaze firing on the glazed blank to obtain the sanitary ceramic.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the modified pyrophyllite powder is added into the glaze material and is matched with other raw materials in a synergistic manner, so that the prepared glaze layer has good wear resistance;
2. the titanium dioxide is adopted to modify calcite, which is beneficial to inducing the titanium dioxide to react with calcium oxide, so that the titanium dioxide is inhibited from generating rutile phase, and further the yellowing of a glaze layer is eliminated, and the service life of the sanitary ceramic is prolonged;
3. montmorillonite and sodium humate are added to be matched with each other synergistically, and an inorganic-organic combination mode is adopted, so that the strength and the wear resistance of a glaze layer are improved.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
The following preparations and examples:
qinyang soil was purchased from Hongda clay dealings in Boai county, and the specification is as follows: al (aluminum) 2 O 3 : 34.5-39%, loss on ignition: 11 to 14 percent;
the shanxi wood knots are purchased from Jianhua porcelain soil dealings in Tangshan City, and have the following specifications: fe 2 O 3 ：21%，Al 2 O 3 Is more than 34 percent; the loss on ignition is less than 12 percent;
the ball clay is purchased from Taihe Zhenjiang refined pottery raw material Jingzhe in Qing and Yun markets, and the specification is as follows: al (Al) 2 O 3 : 12 percent and the ignition loss is less than 12 percent;
xuanhua soil is purchased from Xuanhua county jade white porcelain stone ore, and the specification is as follows: al (Al) 2 O 3 : 13-15%, NaK > 4%, loss on ignition: 4 percent;
the funing china stone is purchased from the full dragon commercial and trade company Limited in Tangshan city, and has the specification: al (Al) 2 O 3 : 13-15%, NaK > 4%, loss on ignition: less than 3 percent;
zhangwu soil is purchased from the Lu area rich source porcelain stone field, and the specification is as follows: al (Al) 2 O 3 : 12-14%, NaK > 3%, loss on ignition: less than 3 percent;
the Zhangvillage soil is purchased from a China soil selling place in the northern mountain of Shahe city, and the specification is as follows: al (Al) 2 O 3 : 32-35%, NaK > 4%, loss on ignition: less than 5 percent;
the Chengde soil is purchased from Venus magnetotelluric ore in Shahe city, and the specification is as follows: al (Al) 2 O 3 : 13-15%, NaK > 4%, loss on ignition: less than 4 percent;
the wood knot of Tangshan mountain is purchased from the ceramic raw material selling place of Tangshan Kaihu Pingbao, and the specification is as follows: al (Al) 2 O 3 : 31%, loss on ignition: less than 13 percent;
\28390, purchasing county sandstone from \28390, selling county Mingbo ceramic raw material dealerships, and measuring the specifications: SiO 2 2 More than 97 percent, and the ignition loss is less than 0.5 percent;
white mud Lushan xing De ceramic raw material factory, specification: al (aluminum) 2 O 3 : more than 35 percent, loss on ignition: < 14%;
the coke ash is purchased from Hongda clay dealings in Boai county, and the specification is as follows: al (Al) 2 O 3 : 34.5-39%, loss on ignition: less than 13 percent;
quartz is purchased from east chuan of tangshan, commerce ltd, specifications: SiO 2 2 ＞99%，Fe 2 O 3 ：＜0.2%；
The potassium feldspar is purchased from a Yingjiang euphoria ceramic raw material warp beam part, and has the specification: fe 2 O 3 ，KN 2 O is more than 9 percent, and the ignition loss is less than 0.5 percent;
calcite was purchased from east chuan commercial ltd, tangshan, with specifications: SiO 2 2 ：＜1%，CaO＞52%；
Dolomite is purchased from the ceramic raw material distribution place of Changshan Fengxin, and has the specification: SiO 2 2 ：4-6%，MgO＞52%；
Porcelain powder was purchased from the tang mountain reynolds porcelain industry ltd, specifications: caustic soda is less than 0.44, Al 2 O 3 ＜24.11，Fe 2 O 3 ＜1.02；
Suzhou soil was purchased from Suzhou sorghum soil Co., Ltd, and the specifications were as follows: caustic soda is less than 15.54, Al 2 O 3 ＜37，Fe 2 O 3 ＜0.26；
The frit is purchased from the raw materials of the compound fertilizer ceramic glaze production company Limited, and has the specification: caustic soda is less than 0.43, Al 2 O 3 ＜4.52/3.0，Fe 2 O 3 ＜0.14/3.02；
Zirconium silicate is purchased from auspicious zirconium industry, and has the following specifications: caustic soda is less than 0.44, Al 2 O 3 ＜0.2，Fe 2 O 3 ＜0.1；
Pyrophyllite was purchased from Ningbo Jia and New materials science and technology, Inc.;
magnesium stearate was purchased from zhengzhou dragon biochemical products ltd;
the nano hydrotalcite is purchased from Jida plastics Co., Ltd, Shunde district of Foshan city;
the titanate coupling agent is purchased from Guangdong green Wei New Material science and technology Limited;
titanium dioxide was purchased from Ningbo Mingnan New materials science and technology, Inc.;
the silica sol is purchased from Jiangyin gentle flying chemical Co., Ltd, and the model is pH1.5-8;
montmorillonite was purchased from Guangzhou hundred million kurtosis Industrial technologies, Inc.;
sodium humate was purchased from Zhengzhou Jiajie chemical Co., Ltd;
gelatin was purchased from Hengshui Wanding gelatin science and technology Co.
Preparation example 1
The preparation method of the modified pyrophyllite powder comprises the following steps:
a. crushing pyrophyllite, adding the crushed pyrophyllite into an iron remover for iron removal, adding water, ball-milling, drying, and obtaining pyrophyllite powder through airflow homogenization equipment;
b. b, calcining and converting the pyrophyllite powder obtained in the step a at 500 ℃, then putting the pyrophyllite powder into an acid washing tank for precipitation, and taking the upper slurry;
c. mixing the upper layer slurry obtained in the step b with magnesium stearate and nano hydrotalcite, and stirring for 40min at 75 ℃ to obtain a mixture; wherein the weight ratio of the pyrophyllite powder to the magnesium stearate to the nano hydrotalcite is 3:1: 1.2;
d. and d, carrying out reduced pressure distillation, suction filtration and drying on the mixture obtained in the step c to obtain modified pyrophyllite powder, wherein the particle size of the modified pyrophyllite powder is 150-200 meshes.
Preparation example 2
The preparation method of the modified pyrophyllite powder comprises the following steps:
a. crushing pyrophyllite, adding the crushed pyrophyllite into an iron remover for iron removal, adding water, ball-milling, drying, and obtaining pyrophyllite powder through airflow homogenization equipment;
b. b, calcining and converting the pyrophyllite powder obtained in the step a at 600 ℃, then putting the pyrophyllite powder into an acid pickling tank for precipitation, and taking the upper slurry;
c. mixing the upper layer slurry obtained in the step b with magnesium stearate and nano hydrotalcite, and stirring for 40min at 80 ℃ to obtain a mixture; wherein the weight ratio of the pyrophyllite powder to the magnesium stearate to the nano hydrotalcite is 3.5:1: 1;
d. and d, carrying out reduced pressure distillation, suction filtration and drying on the mixture obtained in the step c to obtain modified pyrophyllite powder, wherein the particle size of the modified pyrophyllite powder is 150-mesh and 200-mesh.
Preparation example 3
The preparation method of the modified pyrophyllite powder comprises the following steps:
a. crushing pyrophyllite, adding the crushed pyrophyllite into an iron remover for iron removal, adding water, ball-milling, drying, and obtaining pyrophyllite powder through airflow homogenization equipment;
b. calcining and converting the pyrophyllite powder obtained in the step a at 700 ℃, then putting the pyrophyllite powder into an acid pickling tank for precipitation, and taking the upper slurry;
c. mixing the upper layer slurry obtained in the step b with magnesium stearate and nano hydrotalcite, and stirring at 85 ℃ for 40min to obtain a mixture; wherein the weight ratio of the pyrophyllite powder to the magnesium stearate to the nano hydrotalcite is 4:1: 0.8;
d. and d, carrying out reduced pressure distillation, suction filtration and drying on the mixture obtained in the step c to obtain modified pyrophyllite powder, wherein the particle size of the modified pyrophyllite powder is 150-mesh and 200-mesh.
Preparation example 4
A process for preparing modified calcite, comprising the steps of:
(1) preparing powder slurry: calcite and titanate coupling agent are mixed according to the weight ratio of 1: mixing the components in a ratio of 0.5% to form a mixture, adding water to prepare slurry with the mass concentration of 75%, and grinding to form powder slurry;
(2) preparing titanium dioxide slurry: titanium dioxide, titanate coupling agent and silica sol are mixed according to the weight ratio of 1: 0.5%: mixing the components according to the proportion of 6 percent, adding water and stirring to prepare titanium dioxide slurry with the mass concentration of 70 percent;
(3) mixing the powder slurry prepared in the step (1) and the titanium dioxide slurry prepared in the step (2) according to the weight ratio of 1.5:1 to obtain mixed slurry, and stirring at the rotating speed of 1500 r/min; then filtering, adding water, performing ultrasonic dispersion for 8min, and performing freeze drying for 4h at the temperature of-25 ℃ and the vacuum degree of 140pa to obtain the modified calcite.
Preparation example 5
A process for preparing modified calcite, comprising the steps of:
(1) preparing powder slurry: calcite and titanate coupling agent are mixed according to the weight ratio of 1: mixing the components in a ratio of 0.6% to form a mixture, adding water to prepare slurry with the mass concentration of 72%, and grinding the slurry to form powder slurry;
(2) preparing titanium dioxide slurry: titanium dioxide, titanate coupling agent and silica sol are mixed according to the weight ratio of 1: 0.6%: mixing the components in a proportion of 4 percent, adding water and stirring to prepare titanium dioxide slurry with the mass concentration of 65 percent;
(3) mixing the powder slurry prepared in the step (1) and the titanium dioxide slurry prepared in the step (2) in a weight ratio of 2:1 to obtain mixed slurry, and stirring at a rotating speed of 1200 r/min; then filtering, adding water, performing ultrasonic dispersion for 9min, and performing freeze drying for 4.5h at the temperature of-23 ℃ and the vacuum degree of 135pa to obtain the modified calcite.
Preparation example 6
A process for preparing modified calcite, comprising the steps of:
(1) preparing powder slurry: calcite and titanate coupling agent are mixed according to the weight ratio of 1: mixing the components in a ratio of 0.7% to form a mixture, adding water to prepare slurry with the mass concentration of 70%, and grinding the slurry to form powder slurry;
(2) preparing titanium dioxide slurry: titanium dioxide, titanate coupling agent and silica sol are mixed according to the weight ratio of 1: 0.8%: 2 percent of the components are mixed, and then water is added for stirring to prepare titanium dioxide slurry with the mass concentration of 60 percent;
(3) mixing the powder slurry prepared in the step (1) and the titanium dioxide slurry prepared in the step (2) according to the weight ratio of 2.5:1 to obtain mixed slurry, and stirring at the rotating speed of 1000 r/min; then filtering, adding water, performing ultrasonic dispersion for 10min, and freeze-drying for 5h at the temperature of-20 ℃ and the vacuum degree of 130pa to obtain the modified calcite.
Example 1
A high wear-resistant sanitary ceramic prepared by the following method comprises the following steps:
s1: preparing a sanitary ceramic blank:
s11: 10kg of Zhangvillage soil, 7kg of Zhangwu soil, 5kg of Chengdu soil, 14kg of Tangshan mountain wood knot, 7kg of Shanxi wood knot, 12kg of Qinyang soil, 7kg of Xuanning soil, 8kg of Funing porcelain stone, 3kg of ball clay, 5kg of white mud, 4kg of coke ash, 3kg of porcelain powder, 283900 and 16kg of county sandstone are mixed and stirred uniformly to obtain a pug, and then 40wt% of water is added into the pug for ball milling to obtain slurry;
s12: standing and ageing the slurry obtained in the step S11, performing grouting, demolding and drying to obtain a green body sample, and firing at 1100 ℃ to obtain a sanitary ceramic blank;
s2: preparing glaze slip of the glaze layer:
s21: adding 2.5kg of frit into a ball mill for ball milling in advance, adding 27kg of quartz, 28kg of potash feldspar, 3kg of zinc oxide, 15kg of calcite, 7kg of dolomite, 9kg of zirconium silicate, 1.5kg of alumina, 7kg of Suzhou soil and 15kg of modified pyrophyllite powder prepared in preparation example 1 into the ball mill for mixing with the frit, and adding water with glaze content of 40wt% for ball milling to obtain glaze slurry of a glaze layer;
s23: sieving the glaze of the glaze layer obtained in the step S21 through a 180-mesh sieve, and removing iron;
s3: glazing: spraying the glaze slurry prepared in the step S23 on the sanitary ceramic blank obtained in the step S12 by adopting a glaze spraying method to prepare a glazed blank, wherein the thickness of the glaze layer is 0.8-1.2 mm;
s4: drying and firing: and (3) putting the glazed blank body into a drying chamber at 50 ℃ for drying, and putting the dried blank body into a kiln for high-temperature glaze firing at 1200 ℃ to obtain the high-wear-resistance sanitary ceramic.
Example 2
A high wear-resistant sanitary ceramic prepared by the following method comprises the following steps:
s1: preparing a sanitary ceramic blank:
s11: 12kg of Zhangvillage soil, 6kg of Zhangwu soil, 6kg of Chengdu soil, 12kg of Tangshan mountain wood knot, 8kg of Shanxi seed wood knot, 10kg of Qinyang soil, 8kg of Xuanning soil, 7kg of Funing porcelain stone, 4kg of ball soil, 4kg of white mud, 5kg of coke ash, 2kg of porcelain powder, 283900 and 18kg of county sandstone are mixed and stirred uniformly to obtain a pug, and then 42wt% of water of the pug is added into the pug for ball milling to obtain slurry;
s12: standing and ageing the slurry obtained in the step S11, performing grouting, demolding and drying to obtain a green body sample, and firing at 1150 ℃ to obtain a sanitary ceramic green body;
s2: preparing glaze slip of the glaze layer:
s21: adding 3kg of frit into a ball mill for ball milling in advance, then adding 30kg of quartz, 25kg of potash feldspar, 4kg of zinc oxide, 13kg of calcite, 7.5kg of dolomite, 8kg of zirconium silicate, 2kg of alumina, 6kg of Suzhou soil and 12kg of modified pyrophyllite powder prepared in preparation example 2 into the ball mill for mixing with the frit, and adding 45wt% of glaze material into the mixture for ball milling to obtain glaze slurry of a glaze layer;
s23: sieving the glaze of the glaze layer obtained in the step S21 through a 190-mesh sieve, and removing iron;
s3: glazing: spraying the glaze slurry prepared in the step S23 on the sanitary ceramic blank obtained in the step S12 by adopting a glaze spraying method to prepare a glazed blank, wherein the thickness of the glaze layer is 0.8-1.2 mm;
s4: drying and firing: and (3) placing the glazed blank body in a drying chamber at 50 ℃ for drying, and placing the glazed blank body in a kiln for high-temperature glaze firing at 1200 ℃ to obtain the high-wear-resistance sanitary ceramic.
Example 3
A high wear-resistant sanitary ceramic prepared by the following method comprises the following steps:
s1: preparing a sanitary ceramic blank:
s11: 14kg of Zhangvillage soil, 5kg of Zhangwu soil, 7kg of Chengdu soil, 10kg of Tangshan mountain wood knot, 9kg of Shanxi seed wood knot, 8kg of Qinyang soil, 9kg of Xuanning soil, 6kg of Funing porcelain stone, 5kg of ball soil, 3kg of white mud, 6kg of coke ash, 1kg of porcelain powder, 283900 and 20kg of county sandstone are mixed and stirred uniformly to obtain a pug, and then 45wt% of water is added into the pug for ball milling to obtain slurry;
s12: standing and ageing the slurry obtained in the step S11, performing grouting, demolding and drying to obtain a green body sample, and firing at 1200 ℃ to obtain a sanitary ceramic blank;
s2: preparing glaze slip of the glaze layer:
s21: adding 3.5kg of frit into a ball mill for ball milling in advance, adding 32kg of quartz, 23kg of potash feldspar, 5kg of zinc oxide, 12kg of calcite, 8kg of dolomite, 7kg of zirconium silicate, 2.5kg of alumina, 5kg of Suzhou soil and 10kg of modified pyrophyllite powder prepared in preparation example 3 into the ball mill for mixing with the frit, and adding 50wt% of glaze material water for ball milling to obtain glaze slurry of a glaze layer;
s23: sieving the glaze of the glaze layer obtained in the step S21 through a 200-mesh sieve, and removing iron;
s3: glazing: spraying the glaze slurry prepared in the step S23 on the sanitary ceramic blank obtained in the step S12 by adopting a glaze spraying method to prepare a glazed blank, wherein the thickness of the glaze layer is 0.8-1.2 mm;
s4: drying and firing: and (3) placing the glazed blank body in a drying chamber at 50 ℃ for drying, and placing the glazed blank body in a kiln for high-temperature glaze firing at 1200 ℃ to obtain the high-wear-resistance sanitary ceramic.
Example 4
A highly wear-resistant sanitary ceramic manufactured by the following method is different from example 2 in that calcite is modified calcite manufactured in preparation example 4.
Example 5
A highly wear-resistant sanitary ceramic manufactured by the following method is different from example 2 in that calcite is modified calcite manufactured in preparation example 5.
Example 6
A high wear-resistant sanitary ceramic produced by the following method is different from example 2 in that calcite is modified calcite produced in production example 6.
Example 7
A highly abrasion-resistant sanitary ware produced by the following method differs from example 2 in that 0.6kg of montmorillonite and 0.8kg of sodium humate are further added in step S21.
Example 8
A highly wear-resistant sanitary ware produced by the following method differs from example 2 in that 1.2kg of montmorillonite and 0.5kg of sodium humate are further added in step S21.
Example 9
A highly wear-resistant sanitary ceramic was obtained by the following method, except that 0.6kg of montmorillonite and 0.6kg of sodium humate were added, as in example 7.
Example 10
A highly wear-resistant sanitary ceramic was obtained by the following method, except that 1.2kg of montmorillonite and 0.6kg of sodium humate were added to the ceramic in example 7.
Example 11
A sanitary ceramic having high wear resistance, which is manufactured by the following method, is different from example 7 in that 0.2kg of gelatin is further added in step S21.
Example 12
A sanitary ceramic having high wear resistance, which is manufactured by the following method, is different from example 7 in that 0.25kg of gelatin is further added in step S21.
Example 13
A sanitary ceramic having high wear resistance, which is manufactured by the following method, is different from example 7 in that 0.3kg of gelatin is further added in step S21.
Comparative example 1
A highly wear-resistant sanitary ceramic produced by the following method, which is different from example 2 in that the modified pyrophyllite powder is replaced by the same amount of pyrophyllite powder.
Comparative example 2
A highly wear-resistant sanitary ceramic manufactured by the following method is different from example 2 in that pyrophyllite powder is not contained.
Performance detection
(1) The wear resistance and gloss of the high wear-resistant sanitary ceramics prepared in examples 1-13 and comparative examples 1-2 were measured by the method for measuring the wear resistance of the surface of the glazed tile in the test method of GB/T3810.7-2016 ceramic tile, and the results are shown in Table 1.
(2) Mohs hardness determination: the high-wear-resistance sanitary ceramic is stably placed on a hard support, and the glaze layer faces upwards. The surface of a sample is scribed by selecting standard ores with different Mohs values from small to large, the surface of the sample is scribed by uniformly and vertically applying force by using a new ore cutting edge, attention is paid to the moderate application of force, and the cutting edge of the standard ore cannot form double-line or multi-line scribing traces due to excessive crushing of the standard ore. The lowest hardness value that gave just a noticeable scratch was used as the test result and the results are shown in Table 1.
TABLE 1 abrasion resistance and gloss measurement
| Item | Mohs hardness (grade) | Average abrasion loss (mg) | Glossiness (GU) |
| Example 1 | 5 | 80 | 95 |
| Example 2 | 4 | 79 | 97 |
| Example 3 | 5 | 81 | 96 |
| Example 4 | 5 | 76 | 104 |
| Example 5 | 5 | 77 | 102 |
| Example 6 | 4 | 75 | 105 |
| Example 7 | 5 | 73 | 102 |
| Example 8 | 5 | 70 | 101 |
| Example 9 | 5 | 68 | 98 |
| Example 10 | 5 | 67 | 100 |
| Example 11 | 5 | 65 | 103 |
| Example 12 | 5 | 63 | 102 |
| Example 13 | 5 | 64 | 99 |
| Comparative example 1 | 3 | 87 | 85 |
| Comparative example 2 | 3 | 94 | 84 |
Combining examples 1-13 and comparative examples 1-2, and combining Table 1, it can be seen that the hardness, wear resistance and gloss of the high wear resistant sanitary ceramics of examples 1-13 are better than those of comparative examples 1-2, indicating that the high wear resistant sanitary ceramics prepared by the formulation of the present application have better wear resistance and contribute to the improvement of gloss.
Combining examples 4-6 with example 2 and combining table 1, it can be seen that the abrasion performance and the glossiness of examples 4-6 are better than those of example 2, which shows that the modification of calcite by titanium dioxide is helpful to increase the abrasion resistance of the glaze layer, remove the yellow color of the glaze layer and improve the glossiness of the glaze layer.
Combining examples 7-8 with example 2 and combining table 1, it can be seen that the hardness and wear resistance of examples 7-8 are better than those of example 2, which shows that the addition of montmorillonite and sodium humate increases the strength and wear resistance of the glaze layer by inorganic-organic combination. In addition, combining examples 9-10 and example 7, the hardness and abrasion resistance in examples 9-10 are superior to example 7, demonstrating that the strength and abrasion resistance of the glaze layer can be further increased when the weight ratio of montmorillonite to sodium humate is in the range of (1.0-2.0): 1.
Combining examples 11-13 with example 7, and combining table 1, it can be seen that the properties of examples 11-13 are superior to those of example 7, which shows that the addition of gelatin can greatly improve the adhesion between the raw materials of glaze, so that the sintered glaze has smooth and compact texture, and at the same time, the gelatin, montmorillonite and sodium humate act synergistically to further improve the strength and wear resistance of the glaze layer.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (6)
1. The high wear-resistant sanitary ceramic is characterized by comprising a sanitary ceramic blank and a glazed layer;
the glaze material of the glaze layer comprises the following components in parts by weight: 27-32 parts of quartz, 23-28 parts of potassium feldspar, 3-5 parts of zinc oxide, 12-15 parts of calcite, 7-8 parts of dolomite, 7-9 parts of zirconium silicate, 1.5-2.5 parts of alumina, 5-7 parts of Suzhou soil, 2.5-3.5 parts of frit, 10-15 parts of modified pyrophyllite powder, 0.6-1.2 parts of montmorillonite, 0.5-0.8 part of sodium humate and 0.2-0.3 part of gelatin; the weight ratio of the montmorillonite to the sodium humate is (1.0-2.0): 1;
the preparation method of the modified pyrophyllite powder comprises the following steps:
a. crushing pyrophyllite, removing iron, adding water, ball-milling and drying to obtain pyrophyllite powder;
b. calcining the pyrophyllite powder obtained in the step a at the temperature of 500-700 ℃, and then putting the pyrophyllite powder into an acid washing tank for precipitation;
c. mixing the upper layer slurry obtained in the step b with magnesium stearate and nano hydrotalcite, and stirring at 75-85 ℃ to obtain a mixture; wherein the weight ratio of the pyrophyllite powder to the magnesium stearate to the nano hydrotalcite is (3-4) to 1 (0.8-1.2);
d. and c, carrying out suction filtration and drying on the mixture in the step c to obtain the modified pyrophyllite powder.
2. The high wear-resistant sanitary ceramic as claimed in claim 1, wherein: the particle size of the modified pyrophyllite powder obtained in the step d is 150-200 meshes.
3. The high wear-resistant sanitary ceramic as claimed in claim 1, wherein: the calcite is modified by adopting the following steps:
(1) preparation of powder slurry: calcite and titanate coupling agent are mixed according to the weight ratio of 1: (0.5-0.7%) to form a mixture, adding water to prepare slurry with the mass concentration of 70-75%, and grinding to form powder slurry;
(2) preparing titanium dioxide slurry: titanium dioxide, titanate coupling agent and silica sol are mixed according to the weight ratio of 1: (0.5-0.8%): (2-6%) and adding water and stirring to prepare titanium dioxide slurry with the mass concentration of 60-70%;
(3) and (2) mixing the powder slurry prepared in the step (1) and the titanium dioxide slurry prepared in the step (2) according to the weight ratio of (1.5-2.5): 1 to obtain a mixed slurry, stirring at the rotating speed of 1000-1500r/min, filtering and drying to obtain the modified calcite.
4. The high wear-resistant sanitary ceramic as claimed in claim 3, wherein: the specific conditions for drying in the step (3) are as follows: filtering the mixed slurry in the step (3), adding the filtered mixed slurry into water, performing ultrasonic dispersion for 8-10min, and performing freeze drying for 4-5h under the conditions that the temperature is minus 25 to minus 20 ℃ and the vacuum degree is 130 and 140 pa.
5. The high wear-resistant sanitary ceramic as claimed in claim 1, wherein: the pug of the sanitary ceramic blank comprises the following components in parts by weight: 10-14 parts of Zhangvillage soil, 5-7 parts of Zhangwu soil, 5-7 parts of Chengde soil, 10-14 parts of Tangshan mountain wood knot, 7-9 parts of Shanxi seed wood knot, 8-12 parts of Qinyang soil, 7-9 parts of Xuanhua soil, 6-8 parts of Funing china stone, 3-5 parts of ball soil, 3-5 parts of white mud, 4-6 parts of burnt lime, 1-3 parts of porcelain powder, 28390and 16-20 parts of county sandstone.
6. A method for preparing the high wear-resistant sanitary ceramic as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps:
s1: preparing a sanitary ceramic blank:
s11: mixing the pug of the sanitary ceramic blank, and then adding water accounting for 40-45wt% of the pug for ball milling to obtain slurry;
s12: standing and ageing the slurry in the step S11, grouting, demolding and drying to obtain a green body sample, and firing at 1100-1200 ℃ to obtain a sanitary ceramic blank;
s2: preparing glaze slip of the glaze layer:
s21: ball-milling the frit in advance, then mixing the rest raw materials in the glaze with the frit, and adding 40-50wt% of water into the glaze for ball-milling to obtain glaze slurry of a glaze layer;
s23: sieving the glaze layer glaze obtained in the step S21 through a 180-mesh and 200-mesh sieve, and removing iron;
s3: glazing: spraying the glaze slurry prepared in the step S23 on the sanitary ceramic blank obtained in the step S12 by adopting a glaze spraying method to prepare a glazed blank;
s4: and (4) carrying out glaze firing on the glazed blank body to obtain the high-wear-resistance sanitary ceramic.
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