阅读说明：本技术 一种具有装饰效果的调湿陶瓷砖及其制备方法 (Humidity-adjusting ceramic tile with decorative effect and preparation method thereof ) 是由 刘一军 程科木 王贤超 杨元东 汪陇军 于 2020-11-20 设计创作，主要内容包括：本发明公开一种具有装饰效果的调湿陶瓷砖及其制备方法。所述调湿陶瓷砖的砖面具有腐蚀釉面产生的凹坑以及在凹坑中填充的包含调湿材料的蜡水。现有调湿砖多数通过含有调湿材料的纳米多孔坯体层实现调湿功能,然而为了保证纳米多孔坯体层的高孔隙率,该类调湿砖的烧成温度低于1000℃,此时调湿砖未完全瓷化,导致调湿砖的吸水率高于20%,且该调湿砖的强度近似于泡沫瓷质砖,仅能达到10-20MPa左右。本发明在高温烧成实现调湿砖完全瓷化的基础上,通过釉面腐蚀的办法增加调湿材料在釉面表层凹坑中的填充量,解决现有调湿砖表面装饰单一、强度低的问题,实现调湿砖装饰功能、良好调湿和较高强度的统一。(The invention discloses a humidity-adjusting ceramic tile with a decorative effect and a preparation method thereof. The brick surface of the humidity-regulating ceramic brick is provided with pits generated by corroding glaze surfaces and wax water containing humidity-regulating materials and filled in the pits. The existing humidity-regulating brick mostly realizes the humidity-regulating function through a nano-porous green body layer containing humidity-regulating materials, however, in order to ensure the high porosity of the nano-porous green body layer, the sintering temperature of the humidity-regulating brick is lower than 1000 ℃, at the moment, the humidity-regulating brick is not completely vitrified, so that the water absorption rate of the humidity-regulating brick is higher than 20 percent, and the strength of the humidity-regulating brick is similar to that of a foamed ceramic brick and can only reach about 10-20 MPa. On the basis of realizing the complete vitrification of the humidity-regulating brick by high-temperature sintering, the filling amount of the humidity-regulating material in the pit of the surface layer of the glaze is increased by a glaze corrosion method, the problems of single surface decoration and low strength of the existing humidity-regulating brick are solved, and the unification of the decoration function, good humidity regulation and higher strength of the humidity-regulating brick is realized.)

1. The humidity-regulating ceramic tile with the decoration effect is characterized in that a tile surface of the humidity-regulating ceramic tile is provided with pits generated by corroding a glaze surface and wax water containing humidity-regulating materials filled in the pits.

2. The humidity-conditioning ceramic tile as claimed in claim 1, wherein the area of the pits accounts for 30-50% of the tile surface, and the diameter of the pits is less than or equal to 50 μm.

3. The conditioning ceramic tile according to claim 1 or 2, wherein the polished glaze is etched with an acid solution; the mass fraction of acid in the acid liquid is 20-40%, and the acid liquid is at least one of oxalic acid, hydrochloric acid and hydrofluoric acid.

4. The humidity-conditioning ceramic tile according to any one of claims 1 to 3, wherein the wax water containing the humidity-conditioning material comprises the humidity-conditioning material and ultra-clean wax water, wherein the weight percentage of the humidity-conditioning material is 10-30%.

5. The humidity conditioning ceramic tile of any one of claims 1 to 4, wherein the humidity conditioning material comprises a combination of one or more of diatomaceous earth, zeolite, sepiolite.

6. The humidity conditioned ceramic tile according to any one of claims 3 to 5, wherein the acid liquor has a pH of 2-4.

7. The method for preparing conditioning ceramic tiles with decorative effect according to any one of claims 1 to 6, characterized in that it comprises the following steps:

drying and sintering the blank body after the protective glaze is applied;

polishing the sintered ceramic tile;

corroding the polished glaze surface by using acid liquor;

and filling wax water containing a humidity adjusting material into pits generated after the glaze surface is corroded by polishing.

8. The method as claimed in claim 7, wherein the maximum firing temperature is 1160-1180 ℃ and the firing period is 60-100 min.

9. The method according to claim 7 or 8, characterized in that the chemical composition of the protective glaze comprises: in mass percent, SiO₂：45-50%、Al₂O₃: 18-22%, alkaline earth metal oxide: 14-19%, ZnO: 2-4%, alkali metal oxide: 5 to 9 percent.

10. The production method according to any one of claims 7 to 9, characterized in that, before applying the protective glaze on the surface of the body, a cover glaze is applied on the surface of the body and a pattern is ink-jet printed; preferably, the chemical composition of the overglaze comprises: by mass percent, SiO₂：61-65%、Al₂O₃: 19-23%, alkali metal oxide: 6-8% of ZrO₂：3-10%。

Technical Field

The invention relates to a humidity-adjusting ceramic tile with a decorative effect and a preparation method thereof, belonging to the technical field of ceramic tile production and manufacturing.

Background

The humidity of the air in the room affects the health of people to a large extent. If the air humidity is too low, the mucus in the upper respiratory tract may become dry, resulting in chronic inflammation of the mucous membrane, accompanied by a feeling of dryness in the nose and throat, and possibly a reduction in immunity to bacteria and viruses. If the humidity of the air is too high, people feel that the air breathes difficultly, and food and other objects are affected with damp, so that the mold grows. Currently, two modes of active humidity conditioning and passive humidity conditioning are adopted for indoor humidity conditioning, wherein the active humidity conditioning mostly adopts household appliances with humidity conditioning functions such as air conditioners and the like, so that not only is energy consumed, but also health problems such as 'air conditioning diseases' and the like can be caused; the passive mode adopts moisture absorption and release functional materials to realize the adjustment of the indoor humidity of the building, is an ecological control and adjustment method, does not generate pollution in the using process, and has an important effect on maintaining the ecological sustainable development of the environment. The current commercially available humidity control material is mainly prepared by pressing powder and then directly firing in a kiln, has no surface decoration effect and has lower breaking strength.

Disclosure of Invention

In a first aspect, the present invention provides a humidity conditioning ceramic tile having a decorative effect. The brick surface of the humidity-regulating ceramic brick is provided with pits generated by corroding glaze surfaces and wax water containing humidity-regulating materials and filled in the pits.

The existing humidity-regulating brick mostly realizes the humidity-regulating function through a nano-porous green body layer containing humidity-regulating materials, however, in order to ensure the high porosity of the nano-porous green body layer, the sintering temperature of the humidity-regulating brick is lower than 1000 ℃, at the moment, the humidity-regulating brick is not completely vitrified, so that the water absorption rate of the humidity-regulating brick is higher than 20 percent, and the strength of the humidity-regulating brick is similar to that of a foamed ceramic brick and can only reach about 10-20 MPa. On the basis of realizing the complete vitrification of the humidity-regulating brick by high-temperature sintering, the filling amount of the humidity-regulating material in the pit of the surface layer of the glaze is increased by a glaze corrosion method, the problems of single surface decoration and low strength of the existing humidity-regulating brick are solved, and the unification of the decoration function, good humidity regulation and higher strength of the humidity-regulating brick is realized.

Preferably, the area of the pit accounts for 30-50% of the brick surface, and the diameter of the pit is less than or equal to 50 μm. The 'pit area accounts for 30-50% of the brick surface' means that the ratio of the pit area to the brick surface area (glaze surface area) is 30-50%.

Preferably, the polished glaze surface is corroded by acid liquor; the mass fraction of acid in the acid liquid is 20-40%, and the acid liquid is at least one of oxalic acid, hydrochloric acid and hydrofluoric acid.

Preferably, the wax water containing the humidity adjusting material comprises the humidity adjusting material and ultra-clean wax water, wherein the mass percentage of the humidity adjusting material is 10-30%.

Preferably, the humidity controlling material comprises one or more of diatomite, zeolite and sepiolite.

Preferably, the pH of the acid solution is 2-4.

In a second aspect, the present invention provides a method for producing a humidity-controlling ceramic tile having a decorative effect as described above. The preparation method comprises the following steps:

drying and sintering the blank body after the protective glaze is applied;

polishing the sintered ceramic tile;

corroding the polished glaze surface by using acid liquor;

and filling wax water containing a humidity adjusting material into pits generated after the glaze surface is corroded by polishing.

The preparation method of the invention mixes the humidity-controlling material into the wax water to be filled in the glaze surface, thus repairing the air holes and micro cracks on the polished surface, forming a continuous and compact smooth surface, reducing the roughness of the brick surface, effectively preventing various dirt from entering the brick body through the air holes and micro cracks, endowing the product with good humidity-controlling performance and higher breaking strength.

Preferably, the maximum firing temperature is 1160-1180 ℃, and the firing period is 60-100 min.

Preferably, the chemical composition of the protective glaze comprises: in mass percent, SiO₂：45-50％、Al₂O₃: 18-22%, alkaline earth metal oxide: 14-19%, ZnO: 2-4%, alkali metal oxide: 5 to 9 percent.

Preferably, before applying the protective glaze on the surface of the blank, applying a cover glaze on the surface of the blank and carrying out ink-jet printing on a pattern; preferably, the chemical composition of the overglaze comprises: by mass percent, SiO₂：61-65％、Al₂O₃: 19-23%, alkali metal oxide: 6-8% of ZrO₂：3-10％。

Drawings

FIG. 1 is a flow chart illustrating the preparation of a humidity-controlling ceramic tile with decorative effect according to an embodiment of the present invention;

FIG. 2 is a graph showing the effect of the surface of the humidity-controlling ceramic tile according to comparative example 2 on the appearance of white spots.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.

The following describes an exemplary method for preparing the humidity-controlling ceramic tile with decorative effect with reference to fig. 1.

And pressing and molding the blank powder to obtain the blank. The green body can be formed by dry pressing using a press. The chemical composition of the green body powder is not limited, and the conventional ceramic tile green body powder in the field can be adopted.

And drying the green body. The drying time can be 20-60min, and the drying temperature can be 200-250 ℃.

And applying surface glaze on the surface of the dried blank. The invention has no special limitation on the chemical composition of the overglaze, and can cover the bottom color flaw and make the pattern color better.

In some embodiments, the chemistry of the overglazeThe composition comprises: by mass percent, SiO₂：61-65％、Al₂O₃: 19-23%, alkali metal oxide: 6-8% of ZrO₂：3-10％。

As an example, the chemical composition of the overglaze comprises: by mass percent, SiO₂：61.9-64.15％、Al₂O₃：19.7-22.1％、Fe₂O₃：0.2-0.4％、TiO₂：0.15-0.25％、CaO：0.2-0.4％、MgO：0.1-0.2％、K₂O：3-4％、Na₂O：3.1-3.8％、ZrO₂: 3.2-9.6%, loss on ignition: 1.5-2 percent.

The overglaze can be applied by spraying glaze, pouring glaze and the like. In some embodiments, the overglaze is applied by spraying. The specific gravity of the overglaze can be 1.3-1.5g/cm³The application amount is 500-600g/m²。

And (4) ink-jet printing a pattern on the surface of the blank after the overglaze is applied. The texture and color of the ink jet printed pattern can be adapted to the specific layout requirements. The printing can be carried out by a digital ink-jet printer. The ceramic ink mainly has blue, brown, orange, lemon yellow, black, red, etc.

And applying protective glaze on the surface of the blank after the pattern is printed by ink jet. The protective glaze is applied to improve the quality of the brick surface and ensure the basic performances of the brick surface such as antifouling performance, flatness, hardness and the like.

In some embodiments, the chemical composition of the protective glaze comprises: in mass percent, SiO₂：45-50％、Al₂O₃: 18-22%, alkaline earth metal oxide: 14-19%, ZnO: 2-4%, alkali metal oxide: 5 to 9 percent.

As an example, the chemical composition of the protective glaze includes: in mass percent, SiO₂：45-50％、Al₂O₃：18-22％、Fe₂O₃：0.08-0.15％、TiO₂：0.1-0.2％、CaO：0.1-0.3％、MgO：4-6％、BaO：10-13％、ZnO：2-4％、K₂O：4-5％、Na₂O: 1-2%, loss on ignition: 4 to 6 percent。

The protective glaze can be applied by spraying glaze. In some embodiments, the specific gravity of the protective glaze can be 1.3 to 1.6g/cm³The application amount is 400-500g/m²。

And drying and sintering the green body applied with the protective glaze. The drying temperature can be 200-250 ℃, and the water content after drying is controlled within 0.3-0.7 wt%. The maximum firing temperature is 1160-1180 ℃, and the firing period is 60-100 min.

And polishing the sintered ceramic tile. The protective glaze layer after polishing contains uniformly distributed bubbles with a diameter of 15 μm or less. The bubbles have small diameter, do not influence the transparency of the glaze layer, and form a small number of hemispherical pits after polishing. Because the diameter of the pits is less than 15 mu m and the number of the pits is relatively small (the ratio of the area of the pits to the area of the brick surface is 10-25%), the filling amount of the humidity-adjusting material on the surface of the protective glaze is limited, and the humidity absorbing and releasing effect of the humidity-adjusting ceramic brick is not ideal.

In some embodiments, the polished glaze is etched using an acid solution. The acid solution contains 20-40 wt% of acid. For example, the acid solution may be at least one of oxalic acid, hydrochloric acid, and hydrofluoric acid. The mass fraction of the acid liquor is in the range, so that the condition that the glaze surface is seriously corroded by excessive acid liquor easily, and the brick surface has uneven texture can be avoided. Preferably, the pH of the acid solution is 2 to 4.

The glaze layer is preferably etched with an acid solution until the number and diameter of the pits fall within the following ranges. For example, the proportion of the pit area to the total area of the brick face is 30 to 50%. In the actual test process, the calculation is carried out by counting the area of the brick pit per square centimeter. The diameter of the pits is preferably 50 μm or less. Thus, the filling amount of the humidity control material in the pits can be increased to a large extent, and the filling effect can be optimized. When the diameter of the pit is more than 50 μm, the glaze filled with the humidity-controlling material has obvious white spots because the humidity-controlling material and the ultra-clean wax liquid used in the invention are white, and the decorative effect of the glaze is influenced.

In the actual production process, the glaze corrosion can be carried out through a rotating roller. For example, the roller makes the roller surface coating go up acidizing fluid in rotatory process, and then rotatory roller and glaze contact for the glaze is corroded by acidizing fluid. The corrosion time and the corrosion degree can be controlled by adjusting the rotating speed of the roller. Preferably, the roller speed is from 1 to 10 revolutions per minute, preferably 3 revolutions per minute. In addition, glue and the like can be added into the acid liquor to adjust the fluidity of the acid liquor to be 30-50 seconds (the inner diameter of a mouth hole is about 4mm measured by using a Turkey cup), and the fluidity of the acid liquor is moderate, so that the uneven surface corrosion caused by the quick fluidity of the acid liquor can be avoided.

A wax water containing a humidity conditioning material is prepared. The wax water comprises a humidity adjusting material and ultra-clean wax water, wherein the mass percent of the humidity adjusting material is 10-30%, and the mass percent of the ultra-clean wax water is 70-90%. When the mass percentage of the humidity control material is higher than 30%, the humidity control material has poor dispersibility in wax water and is likely to settle, thereby affecting the filling effect of the humidity control material in the pits.

The humidity conditioning material includes, but is not limited to, one or more combinations of diatomaceous earth, zeolite, sepiolite. The particle size of the humidity controlling material is on the order of nanometers, and may be, for example, 10 to 500 nm. The diatomite, the zeolite and the sepiolite have porous structures, and the pore size of the diatomite is 2-50 nm.

The ultra-clean and bright wax water is prepared by adopting a formula commonly used in the field, and can be obtained in a commercially available mode or prepared by self. The ultra-clean wax water used in the examples was purchased from Shatoucaihua chemical Co., Ltd, south sea area, Foshan City. Ultra-clear wax water containing organic silane and organic solvent as main ingredients can also be used.

And filling wax water containing a humidity adjusting material into pits generated by the corrosion glaze layer by using a grinding mode. The wax water containing the humidity control material can be uniformly coated by an ultra-clean polisher. The amount of the wax water containing the humidity control material can be 20-50 g/m². For example, in the specific actual operation process, the first grinding wheel and the second grinding wheel are adopted for surface cleaning in sequence, and no wax water is dripped on the brick surface (glaze surface); the third through eighth grinding wheels were then used to grind the wax water containing the moisture conditioning material on the brick face.

Most of the existing humidity-regulating ceramic tiles realize the humidity regulating function by preparing a nano porous green body layer containing humidity regulating materials. However, the preparation method has the defect that when the glaze decoration is carried out on the humidity-controlling brick, the glaze layer is easy to block pores of the green body layer, so that the humidity-controlling material in the green body is difficult to contact with air to achieve the ideal humidity-controlling effect. In addition, the proportion of materials such as diatomite, zeolite, sepiolite and the like in the formula of the nano porous blank body is higher and can reach 30-60%, so that on one hand, the porosity of the blank body is higher, the strength of the humidity-adjusting brick is equivalent to that of a foamed ceramic brick, and the humidity-adjusting brick is far lower than that of the humidity-adjusting ceramic brick; on the other hand, in order to ensure high porosity of the green body and promote contact between the moisture-absorbing material in the green body and air, a lower firing temperature and a narrow firing interval are generally adopted to avoid complete vitrification of the humidity-controlling brick. According to the invention, the formula composition of the green body is not required to be specially regulated, the glaze surface is corroded by using acid liquor to reach the pit number of a specific proportion and the pit diameter of a specific size, and the humidity-regulating material is attached to the pits in a higher content, so that the strength of the humidity-regulating ceramic tile is improved and the firing interval of the humidity-regulating ceramic tile is expanded while an excellent humidity-regulating effect is obtained. In some embodiments, the strength of the humidity-conditioned ceramic tiles of the present invention is from 35 to 60 MPa.

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.

Example 1

1. And pressing and molding the blank powder by a press to obtain a blank. And drying the green body.

2. And spraying overglaze on the surface of the dried blank. The overglaze comprises the following chemical components: by mass percent, SiO₂：61.9-64.15％、Al₂O₃：19.78-22.08％、Fe₂O₃：0.22-0.4％、TiO₂：0.15-0.25％、CaO：0.2-0.4％、MgO：0.1-0.2％、K₂O：3-4％、Na₂O：3.15-3.77％、ZrO₂: 3.2-9.6%, loss on ignition: 1.5-2 percent. The specific gravity of the overglaze is 1.3-1.5g/cm³The glazing amount is 500-²。

3. And (4) carrying out ink-jet printing on the surface of the blank after the surface glaze is sprayed with the design pattern.

4. And spraying protective glaze on the surface of the blank after the design pattern is printed by ink jet. The chemical composition of the protective glaze comprises: in mass percent, SiO₂：45-50％、Al₂O₃：18-22％、Fe₂O₃：0.08-0.15％、TiO₂：0.1-0.2％、CaO：0.1-0.3％、MgO：4-6％、BaO：10-13％、ZnO：2-4％、K₂O：4-5％、Na₂O: 1-2%, loss on ignition: 4-6 percent. The specific gravity of the protective glaze is 1.3-1.6g/cm³The glazing amount is 400-²。

5. Drying and sintering the blank body sprayed with the protective glaze. The sintering time is 60-100min, and the maximum sintering temperature is 1160-1180 ℃.

6. Adopt the polishing of elasticity abrasive brick, the abrasive brick is arranged: 240 mesh 5 group, 300 mesh 8 group, 400 mesh 3 group; 600 mesh 8 group, 800 mesh 5 group, 1000 mesh 3 group; 1500 mesh 4 group, 2000 mesh 4 group, 3000 mesh 8 group.

7. And corroding the polished glaze. And turning over the polished glaze surface to enable the glazed surface to face downwards. The roller makes the roller surface coating go up acidizing fluid at rotatory in-process, and then rotatory roller makes the glaze corroded by acidizing fluid with the glaze contact. The roller speed was 3 revolutions per minute.

8. A wax water containing a humidity conditioning material is prepared. The wax water comprises a humidity adjusting material and ultra-clean wax water, wherein the mass percent of the humidity adjusting material is 20%, and the mass percent of the ultra-clean wax water is 80%. Super clean and bright wax water was purchased from Shatoucaihua chemical Co., Ltd, south sea area, Foshan City.

9. And (6) waxing. And waxing the glaze until the wax water is coated on the pits of the whole glaze. And (4) waxing by adopting an ultra-clean and bright polisher. The glaze surface is cleaned by the first grinding wheel and the second grinding wheel, and no wax water is dripped on the brick surface (glaze surface); and the third grinding wheel to the eighth grinding wheel drop wax water containing the humidity adjusting material on the brick surface for grinding.

The humidity conditioning performance of the ceramic tile is tested: placing the ceramic tile to be tested in a constant temperature and humidity box, setting the environmental temperature to be 25 ℃, controlling the moisture absorption humidity to be 75% in the first 24h and the moisture desorption humidity to be 33% in the second 24h, and testing the moisture absorption capacity and the moisture desorption capacity of the ceramic tile sample respectively. The moisture absorption of the conditioned ceramic tile product of example 1 was tested to be 90g/m²Moisture releasing amount 70g/m²。

The strength of the ceramic tiles was tested according to the standard "ceramic plate" (GB/T23266-2009). The flexural strength of the tested ceramic tile product is 55 MPa.

Comparative example 1

Essentially the same as example 1, except that: step 7 is omitted, namely the polished glaze is directly waxed. The test shows that the adsorption capacity of the humidity-conditioning ceramic tile product of the comparative example 1 is 60g/m²Moisture content of 50g/m². The reason is that the pits of the humidity adjusting surface are small in diameter and small in distribution quantity, so that the filling amount of the humidity adjusting material in the pits is small, and the humidity absorbing and releasing effect is influenced.

Comparative example 2

Essentially the same as example 1, except that: and 7, corroding to ensure that the diameter of a pit of the glaze surface is more than 50 micrometers, and the proportion of the area of the pit in the area of the brick surface is more than 50%.

In the comparative example, the glaze of the humidity-regulating ceramic tile has obvious white spots, because the pore diameter of the pits of the glaze is too large after corrosion, white substances in wax water fill the pits to form white spots, and the glaze of the ceramic tile is extremely unfavorable for decoration (see figure 2).