阅读说明：本技术 瓷料组合物及瓷板的制备方法 (Porcelain composition and method for producing porcelain plate ) 是由 王辉 吴丽丹 徐景临 于 2021-09-15 设计创作，主要内容包括：本申请提供一种瓷料组合物及瓷板的制备方法,属于陶瓷建材领域。瓷料组合物的化学成分按质量百分比计包括：65～70％的SiO-(2)、17～19％的Al-(2)O-(3)、0～1.5％的Fe-(2)O-(3)、0～0.5％的TiO-(2)、1.0～3.0％的CaO、0.7～1.5％的MgO、3.0～4.0％的K-(2)O、1～1.8％的Na-(2)O以及3.5～5.5％的烧失IL。采用该瓷料组合物进行烧成处理制备瓷板,能有效降低成品瓷板吸水率并提高瓷板强度,同时能有效降低因施釉量降低带来的影响。(The application provides a porcelain composition and a preparation method of a porcelain plate, belonging to the field of ceramic building materials. The porcelain composition comprises the following chemical components in percentage by mass: 65-70% of SiO 2 17 to 19% of Al 2 O 3 0 to 1.5% of Fe 2 O 3 0 to 0.5% of TiO 2 1.0 to 3.0 percent of CaO, 0.7 to 1.5 percent of MgO, and 3.0 to 4.0 percent of K 2 O, 1-1.8% of Na 2 O and 3.5-5.5% of burn-out IL. The porcelain plate prepared by adopting the porcelain composition for sintering treatment can effectively reduce the water absorption of the finished porcelain plate and improve the strength of the porcelain plate, and can effectively reduce the influence caused by the reduction of the glazing amount.)

1. A porcelain composition is characterized by comprising the following chemical components in percentage by mass: 65-70% of SiO₂17 to 19% of Al₂O₃0 to 1.5% of Fe₂O₃0 to 0.5% of TiO₂1.0 to 3.0 percent of CaO, 0.7 to 1.5 percent of MgO, and 3.0 to 4.0 percent of K₂O, 1-1.8% of Na₂O and 3.5-5.5% of burn-out IL.

2. The porcelain composition according to claim 1, wherein the specific gravity is 1.68 to 1.70.

3. The porcelain composition according to claim 1, wherein the modulus of fineness is 1.0 to 2.0.

4. A porcelain composition according to any one of claims 1 to 3, wherein the porcelain composition comprises the following main materials in percentage by mass: 4-6% of black talc, 10-15% of white mud, 3-5% of diopside, 4-7% of bentonite, 45-55% of medium temperature sand, 15-20% of potash feldspar and 5-10% of ceramic waste.

5. The porcelain composition of claim 4, wherein the composition of the auxiliary materials further comprises: the dispergator comprises a dispergator body, wherein the mass of the dispergator body is 0.6-0.8% of that of the main material.

6. The porcelain composition of claim 4, wherein the composition of the auxiliary materials further comprises: the green body reinforcing agent accounts for 0.01-0.02% of the main material in mass.

7. A preparation method of a porcelain plate is characterized by comprising the following steps: the porcelain composition according to any one of claims 1 to 6 is fired.

8. The production method according to claim 7, wherein the firing treatment comprises bisque firing and glaze firing in this order; in the biscuit firing step, the firing temperature is 980-1020 ℃, and the firing time is 35-45 min; in the glaze firing step, the firing temperature is 1020-1040 ℃, and the firing time is 40-50 min.

9. The production method according to claim 7 or 8, wherein a pressing mold having a paste hardness of 97A or more and a paste thickness of 0.3mm or less is used in the pressing treatment before the firing treatment;

optionally, in the pressing treatment, the pressing pressure is above 33000 KN;

optionally, in the pressing treatment, the thickness of the pressed blank is 6.0-6.5 mm.

10. The method of claim 9, wherein the porcelain composition is granulated to have a 40 mesh oversize fraction of 25-35% prior to the pressing.

Technical Field

The application relates to the field of ceramic building materials, in particular to a porcelain composition and a preparation method of a porcelain plate.

Background

The problems of high water absorption, thick glaze layer and relatively low strength of the existing ceramic chip generally cause that the ceramic chip is easy to crack in the later period after being paved and pasted. In order to improve the problems, the prior porcelain plate is thinner than the conventional porcelain plate glaze, so that the risk of later cracking is greatly reduced. However, the base color of the blank after the base glaze is thinned is not easy to cover, and the later cracking phenomenon is still easily caused by the problems of high water absorption and relatively low strength of the material.

Disclosure of Invention

The application aims to provide a porcelain composition and a preparation method of a porcelain plate, which can effectively reduce the water absorption of a finished porcelain plate and improve the strength of the porcelain plate, and can effectively reduce the influence caused by the reduction of glazing amount.

The embodiment of the application is realized as follows:

in a first aspect, the embodiments of the present application provide a porcelain composition, which comprises the following chemical components by mass percent: 65-70% of SiO₂17 to 19% of Al₂O₃0 to 1.5% of Fe₂O₃0 to 0.5% of TiO₂1.0 to 3.0 percent of CaO, 0.7 to 1.5 percent of MgO, and 3.0 to 4.0 percent of K₂O, 1-1.8% of Na₂O and 3.5-5.5% of burn-out IL.

In a second aspect, an embodiment of the present application provides a method for preparing a porcelain plate, including: the porcelain composition as provided in the first aspect of the embodiment is used for firing treatment.

The porcelain composition and the preparation method of the porcelain plate provided by the embodiment of the application have the beneficial effects that:

in the porcelain composition, the iron, aluminum, potassium, sodium and magnesium elements have proper dosage proportion, so that on one hand, a blank obtained by sintering has better whiteness, and the ground penetration of the blank can be effectively reduced, thereby effectively reducing the influence that the ground color of the blank is not easily covered after the ground glaze is thinned. On the other hand, the water absorption of the finished product can be effectively reduced, the strength of the finished product can be improved, and the risk of later-stage cracking can be effectively reduced.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that "and/or" in the present application, such as "feature 1 and/or feature 2" refers to "feature 1" alone, "feature 2" alone, and "feature 1" plus "feature 2" alone.

In addition, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents both "unit of measure" of "numerical value a" and "numerical value b".

The porcelain composition and the method for producing the porcelain plate according to the examples of the present application will be described in detail below.

In a first aspect, the embodiments of the present application provide a porcelain composition, which comprises the following chemical components by mass percent:

65-70% of SiO₂SiO of the₂For example, but not limited to, any one of 65%, 66%, 67%, 68%, 69%, and 70%, or a range between any two.

17-19% of Al₂O₃Of the Al₂O₃For example, but not limited to, 16%, 17%, 17.5%, 18%, 18.5%, and 19%, or a range between any two.

0 to 1.5% Fe₂O₃Of the Fe₂O₃For example, but not limited to, any one of 0%, 0.5%, 1%, and 1.5%, or a range between any two.

0 to 0.5% of TiO₂The TiO being₂For example, but not limited to, 0%, 0.1%, 0.2%, 0.3%, 0.4%, and 0.5%, or a range between any two.

1.0-3.0% CaO, for example but not limited to, 1%, 1.5%, 2%, 2.5% and 3% CaO, or a range therebetween.

0.7 to 1.5% of MgO, wherein the mass percentage of MgO is, for example, but not limited to, any one of 0.7%, 0.9%, 1%, 1.1%, 1.3% and 1.5%, or a range between any two.

3.0 to 4.0% of K₂O, the K₂The mass percentage of O is, for example, but not limited to, any one of 3%, 3.2%, 3.5%, 3.7%, and 4%, or a range between any two.

1-1.8% of Na₂O, the Na₂The mass percentage of O is, for example, but not limited to, any one point value of 1%, 1.2%, 1.4%, 1.6%, and 1.8%, or a range value between any two.

3.5-5.5% of a loss on ignition IL, wherein the loss on ignition IL refers to a loss on ignition component, and the mass percentage thereof is, for example and without limitation, any one of 3.5%, 4%, 4.5%, 5% and 5.5% or a range value between any two.

Compared with the conventional ceramic chip, the porcelain composition provided by the application reduces the content of iron element, and simultaneously improves the content of aluminum, potassium, sodium and magnesium element, wherein the iron, aluminum, potassium, sodium and magnesium element has proper dosage proportion. On one hand, the blank obtained by sintering has better whiteness, and the bottom penetration of the blank can be effectively reduced, so that the influence that the ground color of the blank is not easily covered after the ground glaze is thinned is effectively reduced. On the other hand, the water absorption of the finished product can be effectively reduced, the strength of the finished product can be improved, and the risk of later-stage cracking can be effectively reduced.

The inventor researches and discovers that when the content of calcium oxide is too high, the loss on ignition is high, and further the water absorption of the finished product is high and pores on the glaze surface are large. The porcelain composition provided by the application reduces the content of calcium oxide, and can effectively avoid the influence caused by overhigh content of calcium oxide.

In the present application, the composition of the porcelain composition is not limited as long as the specific chemical component content is satisfied.

The conventional raw materials are adopted for mixing, so that the raw materials are easy to obtain, the mixing is convenient, and the control of the leather quality of the product is convenient. As an example, the porcelain composition comprises the following main materials in percentage by mass:

4-6% of black talc, wherein the mass percent of the black talc is, for example but not limited to, any one of 4%, 4.5%, 5% and 6% or a range between any two.

10-15% of white mud, wherein the mass percentage of the white mud is, for example and without limitation, 10%, 11%, 12%, 13%, 14% and 15% or any value or range between any two values.

3-5% of mixed mud, wherein the mass percentage of the mixed mud is any one of the values of 3%, 3.5%, 4%, 4.5% and 5% or the range value between any two.

4-7% of bentonite, wherein the mass percent of the bentonite is, for example and without limitation, any one of 4%, 5%, 6% and 7% or a range between any two.

45-55% of medium temperature sand, wherein the mass percentage of the medium temperature sand is, for example and without limitation, any one of 45%, 48%, 50%, 52% and 55% or a range value between any two.

15-20% of potash albite, wherein the mass percentage of the potash albite is, for example and without limitation, any one of 15%, 16%, 17%, 18%, 19% and 20% or a range value between any two.

5-10% of ceramic waste, wherein the mass percentage of the ceramic waste is, for example but not limited to, any one of 5%, 6%, 7%, 8%, 9% and 10% or a range value between any two.

It is understood that, in the present application, the raw material composition of the porcelain composition may be added with certain auxiliary materials according to the need.

As a first example, the auxiliary materials of the composition of the porcelain composition further include a debonder, the mass of the debonder is optionally 0.6-0.8% of the mass of the main material, such as but not limited to any one of 0.6%, 0.7% and 0.8%, or a range between any two.

As a second example, the auxiliary materials of the composition of the porcelain composition further include a green body reinforcing agent in mass percentage, and the mass of the green body reinforcing agent is optionally 0.01-0.02% of the mass of the main material, such as but not limited to any one of 0.01%, 0.015% and 0.02% or a range value between any two.

In the porcelain composition, the physical parameters such as specific gravity and fineness of the material also have certain influence on the preparation process and the performance of the final product. The parameters of the material such as specific gravity, fineness and the like are controlled within proper standards, so that the quality of the final product can be better controlled.

As a first example, the porcelain composition has a specific gravity of 1.68 to 1.70, such as, but not limited to, any one or a range of values between 1.68, 1.69, and 1.70.

As a second example, the porcelain composition has a modulus of fineness of 1.0 to 2.0, such as but not limited to any one of 1.0, 1.5, and 2.0 points or a range between any two.

In some exemplary embodiments, the present application provides ceramic panels having the following criteria for intermediate and finished products: the strength of the biscuit is more than or equal to 13MPa, the water absorption of the biscuit is more than or equal to 12%, the dry glaze speed is less than or equal to 50s, the strength of the finished product is more than or equal to 20, and the water absorption of the finished product is 5-10%.

In a second aspect, an embodiment of the present application provides a method for preparing a porcelain plate, including: the porcelain composition as provided in the first aspect of the embodiment is used for firing treatment.

The inventors have found that in the case of a reduced amount of glazing applied to the tile, a reduction in the overglaze results in a relatively large reduction in the flatness of the overglaze. When the porcelain composition provided by the application is used for firing treatment, the firing temperature in the bisque firing stage is properly reduced relative to the conventional bisque firing temperature, the water absorption rate of a bisque obtained after bisque firing can be improved, and the glaze can be ensured to be rapidly dried after overglaze construction, so that the improvement of the glaze flatness of a product is facilitated.

Based on the above findings, in order to effectively ensure the flatness of the glaze surface of the product with a reduced amount of glazing, in some exemplary embodiments, the firing treatment includes bisque firing and glaze firing performed in this order. Wherein: in the bisque firing step, the firing temperature is 980-1020 ℃, for example but not limited to, any one of 980 ℃, 990 ℃, 1000 ℃, 1010 ℃ and 1020 ℃ or a range value between any two; the firing time is 35-45 min, for example, but not limited to, 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min and 45min, or any value or range between any two values.

Further, in order to better match the biscuit firing step, in the glaze firing step, the firing temperature is 1020 to 1040 ℃, for example, but not limited to 1020 ℃, 1025 ℃, 1030 ℃, 1035 ℃ and 1040 ℃; the firing time is 40-50 min, such as but not limited to any value of 40min, 41min, 42min, 43min, 44min, 45min, 46min, 47min, 48min, 49min and 50min or a range value between any two.

The inventor also researches and discovers that in the preparation process of the porcelain plate, the glue layer of the currently used mould is thick and the hardness of the glue layer is insufficient, so that the requirement of a pressed blank can not be well met, and the flatness of the pressed blank can be influenced to a certain extent.

Based on the above findings, in order to well satisfy the green compact requirements in the green compact process, as an example, in the press treatment before the firing treatment, a press mold having a paste hardness of 97A or more and a paste thickness of 0.3mm or less is used.

Optionally, in order to provide a suitable pressing pressure, the pressing pressure is 33000KN or more in the pressing treatment, and the pressing pressure is 33000 to 35000KN, for example.

Optionally, in order to better meet the specification requirement of the product and enable the green body to be well fired and formed, in the pressing process, the thickness of the green body obtained by pressing is 6.0-6.5 mm, such as but not limited to any one value or a range value between any two of 6.0mm, 6.1mm, 6.2mm, 6.3mm, 6.4mm and 6.5 mm.

Further, in order to enable better press forming of the porcelain composition, the porcelain composition is granulated before the pressing process such that the grain ratio of the 40 mesh oversize is 25 to 35%, for example, but not limited to, any one of 25%, 30% and 35% or a range between any two. In the embodiment, the 40-mesh screen material grading particle is reduced from 45-55% to 25-35% conventionally, and under a specific forming condition, the uniformity and the evenness of a formed blank body are favorably ensured.

The features and properties of the present application are described in further detail below with reference to examples.

(I) preparation process

The preparation method of the porcelain plate comprises the following steps of:

s1, determining chemical components of the porcelain composition and determining a component formula.

And S2, feeding.

The forklift feeds according to the component formula, wherein the feeding error amount is not more than +/-10 Kg.

And S3, ball milling and pulping.

And (3) performing ball milling after the feeding is finished, performing pre-milling for 11h, detecting whether the fineness is qualified, directly discharging balls when the fineness is qualified, and performing additional milling until the fineness is detected according to a detection result when the fineness is unqualified. Then discharging the slurry to remove iron and sieving.

The standard for judging whether the fineness is qualified is within an error range of 2-3% of a preset standard.

And S4, granulating.

And S5, pressing the biscuit.

S6, biscuit firing.

And S7, storing the blank.

And S8, glaze pouring.

And S9, printing.

S10, putting the blank into a kiln for glaze firing.

S11, edging and sorting.

And S12, packaging and warehousing.

(II) examples and comparative examples

The porcelain plate was prepared according to the preparation process of the first section.

Example 1

The porcelain composition comprises the following chemical components in percentage by mass: 67.56% SiO₂17.48% of Al₂O₃0.97% of Fe₂O₃0.35% of TiO₂2.41 percent of CaO, 1.34 percent of MgO and 3.37 percent of K₂O, 1.65% of Na₂O and 4.8% loss on ignition IL.

The porcelain composition comprises the following main materials in percentage by mass: 5% of black talc, 10% of white mud, 5% of washing mud, 6% of bentonite, 50% of medium temperature sand, 15% of potash albite, 5% of ceramic waste and 4% of diopside. The auxiliary materials of the porcelain composition comprise the following components in percentage by mass relative to the main material: 0.8% of dispergator and 0.01% of green body reinforcing agent.

The porcelain composition had a specific gravity of 1.68 and a modulus of fineness of 1.87.

In the pressing treatment: the grain composition of the porcelain composition is that 40-mesh screen material accounts for about 25-35%, a pressing die with the hardness of 99A and the thickness of 0.15mm is used, the pressing pressure is 35000KN, and the thickness of a blank obtained by pressing is 6.0-6.5 mm.

In the firing treatment: the temperature of the biscuit firing is 990-1000 ℃, and the time of the biscuit firing is 38 min; the glaze firing temperature is 1020-1026 ℃, and the glaze firing time is 40 min.

It should be noted that, in the examples and comparative examples of the present application, since the porcelain composition has a structure obtained by testing through EDS or the like in terms of the chemical components by mass percentage, there may be inevitable errors in testing and value, and it is understood that the total amount thereof has a small error with respect to 100 wt%.

Example 2

Essentially the same as in example 1, with the following differences:

in the firing treatment: the temperature of the bisque firing is 1035-1045 ℃, and the time of the bisque firing is 36 min.

Example 3

Essentially the same as in example 1, with the following differences:

the temperature of the bisque firing is 988-.

Example 4

Essentially the same as in example 1, with the following differences:

the temperature of the biscuiting is 948-.

Example 5

Essentially the same as in example 1, with the following differences:

in the pressing treatment: a pressing die having a hardness of 93A and a thickness of 0.3mm was used.

It was found that the porcelain plate obtained in example 5 had a higher degree of flatness of the glaze surface than the porcelain plate obtained in example 1. Among them, the flatness of the porcelain plate obtained in example 1 was in class a, and the flatness of the porcelain plate obtained in example 5 was in class C.

Wherein, the flatness is A type, namely, the straight lamp tube is irradiated on the surface of the porcelain plate, and the image formed by the reflection of the straight lamp tube is straight; the flatness of C type means that the straight lamp tube irradiates the surface of the porcelain plate, and the image formed by the reflection of the straight lamp tube is wavy.

Comparative example 1

Essentially the same as in example 1, with the following differences:

the porcelain composition comprises the following chemical components in percentage by mass: 60.88% SiO₂15.3% of Al₂O₃2.39% of Fe₂O₃0.56% of TiO₂8.15 percent of CaO, 0.69 percent of MgO and 2.18 percent of K₂O, 0.43% of Na₂O and 9.36% loss on ignition IL.

The porcelain composition comprises the following main materials in percentage by mass: the porcelain composition comprises the following main materials in percentage by mass: 5% of black talc, 10% of white mud, 5% of washing mud, 6% of bentonite, 50% of medium temperature sand, 15% of potash albite, 5% of ceramic waste and 4% of diopside. The auxiliary materials of the porcelain composition comprise the following components in percentage by mass relative to the main material: 0.8% of dispergator and 0.01% of green body reinforcing agent.

In the firing treatment: the temperature of the bisque firing is 1035-1045 ℃, and the time of the bisque firing is 38 min.

Comparative example 2

Substantially the same as in comparative example 1, with the following differences:

in the firing treatment: the temperature of the bisque firing is 990-1000 ℃, and the time of the bisque firing is 40 min.

(III) test example

Each of the examples and comparative examples was subjected to a plurality of tests, and the green strength (modulus of rupture of green body obtained by firing), the green water absorption (water absorption of green body obtained by firing), the dry glaze speed, the finished product strength (modulus of rupture of finished product obtained by firing glaze) and the finished product water absorption (water absorption of finished product obtained by firing glaze) in the plurality of tests were measured.

The detection criteria for the relevant parameters are as follows:

biscuit strength detection standard: and (5) detecting by using an antiflex cracking instrument.

Biscuit water absorption detection standard: and (5) detecting by using a water absorption detector.

And (3) dry glaze speed detection standard: and (5) timing from the pouring glaze bell cover to the finish time of the complete drying of the overglaze.

And (3) the detection standard of the strength of the finished product is as follows: and (5) detecting by using an antiflex cracking instrument.

And (3) the detection standard of the water absorption of the finished product is as follows: and (5) detecting by using a water absorption detector.

The distribution of the relevant detection results is shown in table 1.

TABLE 1 distribution of Performance test results

Note: in performance testing, each test case usually acquires multiple sets of test data, so the test result is a range value of multiple sets of tests. The lower limit of the range is the minimum value among the plurality of measurements, and the upper limit of the range is the maximum value among the plurality of measurements.

As can be seen from table 1, the porcelain plate provided in the embodiment of the present application has both good strength and low water absorption of the finished product. In example 2, the biscuit firing temperature was higher than that in example 1, and the water absorption of the biscuit obtained after firing was reduced, so that the dry glaze rate was significantly reduced. In example 4, the bisque firing temperature was lower than that in example 1, and the water absorption of the finished product was increased to some extent.

Comparative example 1 provides a porcelain plate having a porcelain composition that is not formulated to the specific chemical requirements of the present application and has a relatively high bisque firing temperature; compared with example 1, the strength of the finished product is reduced to a certain degree, and the water absorption of the finished product is obviously increased. Comparative example 2 provides a porcelain plate having a porcelain composition that is not formulated in accordance with the specific chemical composition requirements of the present application; compared with example 1, the strength of the finished product is obviously reduced, and the water absorption of the finished product is obviously increased.

The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.