Antibacterial ceramic product and manufacturing method thereof

Abstract

The invention discloses an antibacterial ceramic product and a manufacturing method, and belongs to the technical field of ceramics. A green body of the antibacterial ceramic product comprises the following components: kaolin, potassium feldspar, albite, quartz and titanium oxide. The antibacterial ceramic product comprises a ceramic body and a ceramic glaze layer from inside to outside, and the glaze layer comprises the following components: kaolin, quartz, potassium feldspar, calcined talcum powder, zinc phosphate, silver phosphate, cerium oxide and frit. The prepared antibacterial product has more excellent glaze strength, antibacterial rate and glossiness.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramics, and in particular relates to an antibacterial ceramic product and a manufacturing method thereof. Background Art

[0002] With the vigorous development of society, people's lives are changing with each passing day, and people are paying more and more attention to hygiene issues. Hygiene issues are not only limited to washing hands frequently, but also need to pay attention to the cleanliness of objects.

[0003] Ceramic products have many uses in life, especially in tableware, tea sets, water cups and other catering related products.

[0004] The Chinese public patent application document with application number 202310651494.9 discloses an antibacterial sanitary ceramic, which requires the preparation of modified titanium dioxide and antibacterial agents first. The preparation processes of both are complicated and time-consuming. Although the products produced have antibacterial effects, for enterprises, the overall production process is relatively cumbersome and time-consuming, which is not conducive to large-scale and efficient production.

[0005] Therefore, it is necessary to develop a method for producing antibacterial ceramic products with a convenient and efficient production process. Summary of the invention

[0006] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for producing an antibacterial ceramic product with a convenient production process and high efficiency.

[0007] The present invention adopts the following technical solution: An antibacterial ceramic product, comprising a ceramic body and a ceramic glaze layer from the inside to the outside, wherein the ceramic glaze layer covers the surface of the ceramic body; The glaze layer comprises the following components by weight: 20-30 parts of kaolin, 10-15 parts of quartz, 9-11 parts of potassium feldspar, 10-12 parts of calcined talc, 8-12 parts of zinc phosphate, 12-15 parts of silver phosphate, 13-17 parts of cerium oxide, and 12-16 parts of frit; The frit includes the following components by mass: 11-17 parts of kaolin, 3-4 parts of zirconium oxide, 8-11 parts of boric acid, 12-15 parts of titanium oxide, and 5-9 parts of silver nitrate.

[0008] Furthermore, the ceramic body includes the following components in parts by mass: 70-80 parts of kaolin, 15-20 parts of potassium feldspar, 20-30 parts of quartz, 8-11 parts of spodumene, 12-17 parts of calcined talc, 13-15 parts of alumina, and 9-11 parts of calcite.

[0009] Furthermore, the method for preparing the ceramic body comprises the following steps: S1. Mixing According to the mass fractions, all the components are mixed and crushed to obtain a crushed material; S2, calcination and ball milling The crushed material obtained in S1 is calcined, and the calcined material is ball-milled to obtain a ball-milled material; S3, clay preparation, aging and molding The ball mill obtained from S2 is subjected to mud kneading, aging and molding to obtain a ceramic body.

[0010] Furthermore, the calcination temperature is 110-130° C., and the calcination time is 60-70 min; the aging temperature is 55-65° C., and the aging time is 2-3 d.

[0011] Furthermore, the ball milling process adopts a mass ratio of ball: material: water = 1: 0.8~0.9: 0.7~0.8, the rotation speed of the ball mill is 500~550r / min, and passes through a 200~250 mesh sieve.

[0012] A method for preparing an antibacterial ceramic product comprises the following steps: Step 1: Prepare glaze S11, according to the mass fractions, the kaolin, quartz, potassium feldspar, calcined talc, zinc phosphate, silver phosphate, cerium oxide and frit are mixed, crushed and calcined to obtain a calcined material; S22, ball-milling the calcined material obtained in S11 to obtain a ball-milled material; S33, drying the ball mill material obtained in S22 to obtain a dried material; S44, adding 16-21 parts of zeolite powder, 15-18 parts of hydroxypropyl methylcellulose and 9-11 parts of cetyltrimethylammonium bromide to the dried material obtained in S33, and pounding and mixing them uniformly to obtain a mixed material; S55, add water to the mixture obtained in S44 to obtain glaze water Step 2: Glaze and Firing The glaze obtained in step 1 is coated on the surface of the ceramic body, and the antibacterial ceramic product is obtained after firing and cooling.

[0013] Furthermore, the calcination temperature in S11 is 120-130° C., and the calcination time is 60-120 min; the drying temperature in S33 is 80-90° C., and the drying time is 60-80 min.

[0014] Furthermore, during the ball milling in S22, a mass ratio of ball: material: water = 1: 0.8~0.9: 0.7~0.8 is adopted for ball milling, a rotation speed of the ball mill is 500~550r / min, and the ball mill passes through a 200~250 mesh sieve.

[0015] Further, the firing process in step 2 is as follows: First, heat from room temperature to 180-220°C at a heating rate of 0.8-0.9°C / min and keep the temperature constant for 10-20 minutes; Next, the temperature was raised to 800-900°C at a heating rate of 1.1-1.2°C / min and kept at this temperature for 2-3 hours; Then, the temperature was raised to 1250~1280°C at a heating rate of 0.9~1.1°C / min, kept at a constant temperature for 2~3h, and finally cooled naturally.

[0016] Compared with the prior art, the present invention has the following beneficial effects: First, the antibacterial ceramic product of the present invention has silver phosphate with antibacterial properties added to the glaze material, and at the same time, Enteromorpha and silver nitrate with antibacterial properties are also added to the frit.

[0017] Second, in addition to making the product antibacterial, the performance of the ceramic body is also crucial. Therefore, the glaze layer uses kaolin and quartz as the main framework structure to improve the strength of the glaze layer. At the same time, the mixture of potassium feldspar, zinc phosphate and cerium oxide has the effect of a clarifier, which effectively improves the gloss of the glaze layer, and the addition of frit further improves the strength of the glaze layer.

[0018] Third, in order to achieve good adhesion between the various components of the glaze layer, when preparing the glaze water, the zeolite powder, sticky hydroxypropyl methylcellulose and cetyltrimethylammonium bromide as a surfactant are mixed with the glaze layer components and then hammered to mix evenly. Combined with the staged firing process, the glaze layer pores can be better reduced and the glaze surface strength can be improved. DETAILED DESCRIPTION

[0019] The raw materials used in the present invention are all commercially available products.

[0020] Hydroxypropyl methylcellulose was purchased from Hebei Haoshuo Chemical Co., Ltd.

[0021] Example 1 An antibacterial ceramic product, comprising a ceramic body and a ceramic glaze layer from the inside to the outside, wherein the ceramic glaze layer covers the surface of the ceramic body; The glaze layer comprises the following components by weight: 20 parts of kaolin, 10 parts of quartz, 9 parts of potassium feldspar, 10 parts of calcined talc, 8 parts of zinc phosphate, 12 parts of silver phosphate, 13 parts of cerium oxide, and 12 parts of frit; The frit includes the following components by mass: 11 parts of kaolin, 3 parts of zirconium oxide, 8 parts of boric acid, 12 parts of titanium oxide, and 5 parts of silver nitrate.

[0022] The ceramic body comprises the following components by mass: 70 parts of kaolin, 15 parts of potassium feldspar, 20 parts of quartz, 8 parts of spodumene, 12 parts of calcined talc, 13 parts of alumina and 9 parts of calcite.

[0023] The preparation method of the ceramic body comprises the following steps: S1. Mixing According to the mass fractions, all the components are mixed and crushed to obtain a crushed material; S2, calcination and ball milling The crushed material obtained in S1 was calcined at a temperature of 110° C. for 60 min, and the calcined material was ball-milled at a mass ratio of ball: material: water = 1:0.8:0.7, with a rotation speed of 500 r / min, and passed through a 200-mesh sieve to obtain a ball-milled material; S3, clay preparation, aging and molding The ball mill obtained in S2 is kneaded, aged and formed. The aging temperature is 55° C., the aging time is 2 days, and during the forming, rolling is used to obtain a ceramic green body.

[0024] A method for preparing an antibacterial ceramic product comprises the following steps: Step 1: Prepare glaze S11, according to the mass fractions, the kaolin, quartz, potassium feldspar, calcined talc, zinc phosphate, silver phosphate, cerium oxide and frit are mixed and crushed, and then calcined at a temperature of 120° C. and a calcination time of 60 min to obtain a calcined material; S22, ball-milling the calcined material obtained in S11, wherein the mass ratio of ball:material:water=1:0.8:0.7~ is adopted for ball-milling, the rotation speed of the ball mill is 500r / min, and the ball mill is passed through a 200-mesh sieve to obtain a ball-milled material; S33, drying the ball mill obtained in S22, wherein the drying temperature is 80° C. and the drying time is 60 min to obtain a dried material; S44, adding 16 parts of zeolite powder, 15 parts of hydroxypropyl methylcellulose and 9 parts of cetyltrimethylammonium bromide to the dried material obtained in S33, and pounding and mixing them uniformly to obtain a mixed material; S55, add water to the mixture obtained in S44 to obtain glaze water Step 2: Glaze and Firing The glaze obtained in step 1 is applied to the surface of the ceramic body and fired. The firing process is as follows: First, the temperature was raised from room temperature to 180°C at a rate of 0.8°C / min and kept constant for 10 min; Then, the temperature was raised to 800 °C at a heating rate of 1.1 °C / min and kept at this temperature for 2 h; Then, the temperature was raised to 1250°C at a heating rate of 0.9°C / min, kept constant for 2 hours, and finally cooled naturally to obtain an antibacterial ceramic product.

[0025] Example 2 An antibacterial ceramic product, comprising a ceramic body and a ceramic glaze layer from the inside to the outside, wherein the ceramic glaze layer covers the surface of the ceramic body; The glaze layer comprises the following components by weight: 30 parts of kaolin, 15 parts of quartz, 11 parts of potassium feldspar, 12 parts of calcined talc, 12 parts of zinc phosphate, 15 parts of silver phosphate, 17 parts of cerium oxide, and 16 parts of frit; The frit includes the following components by mass: 17 parts of kaolin, 4 parts of zirconium oxide, 11 parts of boric acid, 15 parts of titanium oxide, and 9 parts of silver nitrate.

[0026] The ceramic body comprises the following components by mass: 80 parts of kaolin, 20 parts of potassium feldspar, 30 parts of quartz, 11 parts of spodumene, 17 parts of calcined talc, 15 parts of alumina and 11 parts of calcite.

[0027] The preparation method of the ceramic body comprises the following steps: S1. Mixing According to the mass fractions, all the components are mixed and crushed to obtain a crushed material; S2, calcination and ball milling The crushed material obtained in S1 was calcined at a temperature of 130° C. for 70 min, and the calcined material was ball-milled at a mass ratio of ball: material: water = 1:0.9:0.8, with a rotation speed of 550 r / min, and passed through a 250-mesh sieve to obtain a ball-milled material; S3, clay preparation, aging and molding The ball mill obtained in S2 is kneaded, aged and formed. The aging temperature is 65° C., the aging time is 3 days, and during the forming, rolling is adopted to obtain a ceramic green body.

[0028] A method for preparing an antibacterial ceramic product comprises the following steps: Step 1: Prepare glaze S11, according to the mass fractions, the kaolin, quartz, potassium feldspar, calcined talc, zinc phosphate, silver phosphate, cerium oxide and frit are mixed and crushed, and then calcined at a temperature of 130° C. and a calcination time of 120 min to obtain a calcined material; S22, ball-milling the calcined material obtained in S11, wherein the mass ratio of ball:material:water=1:0.9:0.8 is adopted for ball milling, the rotation speed of the ball mill is 550r / min, and the ball mill is passed through a 250-mesh sieve to obtain a ball-milled material; S33, drying the ball mill obtained in S22, wherein the drying temperature is 90° C. and the drying time is 80 min to obtain a dried material; S44, adding 21 parts of zeolite powder, 18 parts of hydroxypropyl methylcellulose and 11 parts of cetyltrimethylammonium bromide to the dried material obtained in S33, and pounding and mixing them uniformly to obtain a mixed material; S55, add water to the mixture obtained in S44 to obtain glaze water Step 2: Glaze and Firing The glaze obtained in step 1 is applied to the surface of the ceramic body and fired. The firing process is as follows: First, the temperature was raised from room temperature to 220°C at a heating rate of 0.9°C / min and kept constant for 20 min; Then, the temperature was raised to 900 °C at a heating rate of 1.2 °C / min and kept at this temperature for 3 h; Then, the temperature was raised to 1280°C at a heating rate of 1.1°C / min, kept at a constant temperature for 3 hours, and finally cooled naturally to obtain an antibacterial ceramic product.

[0029] Example 3 An antibacterial ceramic product, comprising a ceramic body and a ceramic glaze layer from the inside to the outside, wherein the ceramic glaze layer covers the surface of the ceramic body; The glaze layer includes the following components by weight: 25 parts of kaolin, 13 parts of quartz, 10 parts of potassium feldspar, 11 parts of calcined talc, 11 parts of zinc phosphate, 14 parts of silver phosphate, 15 parts of cerium oxide, and 14 parts of frit; The frit includes the following components by mass: 15 parts of kaolin, 3 parts of zirconium oxide, 9 parts of boric acid, 13 parts of titanium oxide, and 7 parts of silver nitrate.

[0030] The ceramic body comprises the following components by mass: 75 parts of kaolin, 18 parts of potassium feldspar, 25 parts of quartz, 10 parts of spodumene, 15 parts of calcined talc, 14 parts of alumina and 10 parts of calcite.

[0031] The preparation method of the ceramic body comprises the following steps: S1. Mixing According to the mass fractions, all the components are mixed and crushed to obtain a crushed material; S2, calcination and ball milling The crushed material obtained in S1 was calcined at a temperature of 120° C. for 65 min, and the calcined material was ball-milled at a mass ratio of ball: material: water = 1:0.9:0.7, with a rotation speed of 520 r / min, and passed through a 200-mesh sieve to obtain a ball-milled material; S3, clay preparation, aging and molding The ball mill obtained in S2 is kneaded, aged and formed, the aging temperature is 60°C, the aging time is 2 days, and during the forming, rolling is adopted to obtain a ceramic green body.

[0032] A method for preparing an antibacterial ceramic product, used to implement the antibacterial ceramic product according to claim 1, comprising the following steps: Step 1: Prepare glaze S11, according to the mass fractions, the kaolin, quartz, potassium feldspar, calcined talc, zinc phosphate, silver phosphate, cerium oxide and frit are mixed and crushed, and then calcined at a temperature of 125° C. and a calcination time of 90 min to obtain a calcined material; S22, ball-milling the calcined material obtained in S11, wherein the mass ratio of ball:material:water=1:0.9:0.7 is adopted for ball milling, the rotation speed of the ball mill is 520r / min, and the ball mill is passed through a 200-mesh sieve to obtain a ball-milled material; S33, drying the ball mill obtained in S22, wherein the drying temperature is 85° C. and the drying time is 70 min to obtain a dried material; S44, adding 18 parts of zeolite powder, 16 parts of hydroxypropyl methylcellulose and 10 parts of cetyltrimethylammonium bromide to the dried material obtained in S33, and pounding and mixing them uniformly to obtain a mixed material; S55, add water to the mixture obtained in S44 to obtain glaze water Step 2: Glaze and Firing The glaze obtained in step 1 is applied to the surface of the ceramic body and fired. The firing process is as follows: First, the temperature was raised from room temperature to 200°C at a heating rate of 0.8°C / min and kept at this temperature for 15 min; Then, the temperature was raised to 850°C at a heating rate of 1.1°C / min and kept at this temperature for 2.5 h; Then, the temperature was raised to 1270°C at a heating rate of 1.0°C / min, kept at a constant temperature for 2.5h, and finally cooled naturally to obtain an antibacterial ceramic product.

[0033] Comparison Example An antibacterial ceramic product, comprising a ceramic body and a ceramic glaze layer from the inside to the outside, wherein the ceramic glaze layer covers the surface of the ceramic body; The glaze layer comprises the following components by weight: 25 parts of kaolin, 13 parts of quartz, 10 parts of potassium feldspar, 11 parts of calcined talc, 11 parts of zinc phosphate, 14 parts of silver phosphate, and 14 parts of frit;

[0034] The ceramic body comprises the following components by mass: 75 parts of kaolin, 18 parts of potassium feldspar, 25 parts of quartz, 10 parts of spodumene, 15 parts of calcined talc, 14 parts of alumina and 10 parts of calcite.

[0035] The preparation method of the ceramic body comprises the following steps: S1. Mixing According to the mass fractions, all the components are mixed and crushed to obtain a crushed material; S2, calcination and ball milling The crushed material obtained in S1 was calcined at a temperature of 120° C. for 65 min, and the calcined material was ball-milled at a mass ratio of ball: material: water = 1:0.9:0.7, with a rotation speed of 520 r / min, and passed through a 200-mesh sieve to obtain a ball-milled material; S3, clay preparation, aging and molding The ball mill obtained in S2 is kneaded, aged and formed, the aging temperature is 60°C, the aging time is 2 days, and during the forming, rolling is adopted to obtain a ceramic green body.

[0036] A method for preparing an antibacterial ceramic product, used to implement the antibacterial ceramic product according to claim 1, comprising the following steps: Step 1: Prepare glaze S11, according to the mass fractions, the kaolin, quartz, potassium feldspar, calcined talc, zinc phosphate, silver phosphate, cerium oxide and frit are mixed and crushed, and then calcined at a temperature of 125° C. and a calcination time of 90 min to obtain a calcined material; S22, ball-milling the calcined material obtained in S11, wherein the mass ratio of ball:material:water=1:0.9:0.7 is adopted for ball milling, the rotation speed of the ball mill is 520r / min, and the ball mill is passed through a 200-mesh sieve to obtain a ball-milled material; S33, drying the ball mill obtained in S22, wherein the drying temperature is 85° C. and the drying time is 70 min to obtain a dried material; S44, add water to the mixture obtained in S33 to obtain glaze water Step 2: Glaze and Firing The glaze obtained in step 1 is applied to the surface of the ceramic body and fired. The firing process is as follows: First, the temperature was raised from room temperature to 200°C at a heating rate of 0.8°C / min and kept at this temperature for 15 min; Then, the temperature was raised to 850°C at a heating rate of 1.1°C / min and kept at this temperature for 2.5 h; Then, the temperature was raised to 1270°C at a heating rate of 1.0°C / min, kept at a constant temperature for 2.5h, and finally cooled naturally to obtain an antibacterial ceramic product.

[0037] The antibacterial ceramic products prepared in the above three embodiments and the control example were tested, wherein: the lead dissolution amount was <0.1 mg / L, the chromium dissolution amount was <0.01 mg / L, and in the thermal shock resistance test, they could achieve a heat exchange from 180°C to 20°C without cracking.

[0038] However, in the tests of the antibacterial rates of Escherichia coli and Staphylococcus aureus, the antibacterial rates of Examples 1 to 3 all reached above 98%, while the antibacterial rates of the control example were above 96%.

[0039] In the glossiness test, Examples 1 to 3 all reached above 93, while the control example was 89.

[0040] From the test results of the antibacterial ceramic products prepared in Examples 1 to 3 of the present invention and the control example, it can be seen that the antibacterial products prepared in Examples 1 to 3 have more excellent glaze strength, antibacterial rate and glossiness.

[0041] The above is a preferred embodiment of the present invention, and it should be noted that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications are also considered as the protection scope of the present invention.

Claims

1. An antibacterial ceramic product, characterized in that: From the inside to the outside, it includes a ceramic body and a ceramic glaze layer, wherein the ceramic glaze layer covers the surface of the ceramic body; The glaze layer comprises the following components by weight: 20-30 parts of kaolin, 10-15 parts of quartz, 9-11 parts of potassium feldspar, 10-12 parts of calcined talc, 8-12 parts of zinc phosphate, 12-15 parts of silver phosphate, 13-17 parts of cerium oxide, and 12-16 parts of frit; The frit includes the following components by mass: 11-17 parts of kaolin, 3-4 parts of zirconium oxide, 8-11 parts of boric acid, 12-15 parts of titanium oxide, and 5-9 parts of silver nitrate.

2. The antibacterial ceramic product according to claim 1, characterized in that: The ceramic body comprises the following components by weight: 70-80 parts of kaolin, 15-20 parts of potassium feldspar, 20-30 parts of quartz, 8-11 parts of spodumene, 12-17 parts of calcined talc, 13-15 parts of alumina, and 9-11 parts of calcite.

3. The antibacterial ceramic product according to claim 2, characterized in that: The preparation method of the ceramic body comprises the following steps: S1. Mixing According to the mass fractions, all the components are mixed and crushed to obtain a crushed material; S2, calcination and ball milling The crushed material obtained in S1 is calcined, and the calcined material is ball-milled to obtain a ball-milled material; S3, clay preparation, aging and molding The ball mill obtained from S2 is subjected to mud kneading, aging and molding to obtain a ceramic body.

4. The antibacterial ceramic product according to claim 3, characterized in that: The calcination temperature is 110-130° C., and the calcination time is 60-70 minutes; the aging temperature is 55-65° C., and the aging time is 2-3 days.

5. The antibacterial ceramic product according to claim 3, characterized in that: The ball milling process adopts a mass ratio of ball: material: water = 1: 0.8-0.9: 0.7-0.8 for ball milling, the rotation speed of the ball mill is 500-550r / min, and the ball mill passes through a 200-250 mesh screen.

6. A method for preparing an antibacterial ceramic product, used to implement the antibacterial ceramic product according to claim 1, characterized in that: The steps include: Step 1: Prepare glaze S11, according to the mass fractions, the kaolin, quartz, potassium feldspar, calcined talc, zinc phosphate, silver phosphate, cerium oxide and frit are mixed, crushed and calcined to obtain a calcined material; S22, ball-milling the calcined material obtained in S11 to obtain a ball-milled material; S33, drying the ball mill material obtained in S22 to obtain a dried material; S44, adding 16-21 parts of zeolite powder, 15-18 parts of hydroxypropyl methylcellulose and 9-11 parts of cetyltrimethylammonium bromide to the dried material obtained in S33, and pounding and mixing them uniformly to obtain a mixed material; S55, add water to the mixture obtained in S44 to obtain glaze water Step 2: Glaze and Firing The glaze obtained in step 1 is coated on the surface of the ceramic body, and the antibacterial ceramic product is obtained after firing and cooling.

7. The method for preparing the antibacterial ceramic product according to claim 6, characterized in that: The calcination temperature in S11 is 120-130° C., and the calcination time is 60-120 min; the drying temperature in S33 is 80-90° C., and the drying time is 60-80 min.

8. The method for preparing the antibacterial ceramic product according to claim 6, characterized in that: During the ball milling in S22, the mass ratio of ball: material: water = 1: 0.8~0.9: 0.7~0.8 is adopted for ball milling, the rotation speed of the ball mill is 500~550r / min, and the material is passed through a 200~250 mesh sieve.

9. The method for preparing the antibacterial ceramic product according to claim 6, characterized in that: The firing process described in step 2 is as follows: First, heat from room temperature to 180-220°C at a heating rate of 0.8-0.9°C / min and keep the temperature constant for 10-20 minutes; Next, the temperature was raised to 800-900°C at a heating rate of 1.1-1.2°C / min and kept at this temperature for 2-3 hours; Then, the temperature was raised to 1250~1280°C at a heating rate of 0.9~1.1°C / min, kept at a constant temperature for 2~3h, and finally cooled naturally.