Cracked ceramic frit and preparation method thereof

Abstract

The invention provides a cracked ceramic frit and a preparation method thereof. The ceramic frit is prepared from the following raw materials: potassium feldspar, calcite, modified borax, sodium carbonate, lithium carbonate and strontium carbonate, the preparation raw materials in the cracked ceramic frit are controlled, so that the thermal expansion coefficient of the frit is controlled, and the cracking effect of the cracked ceramic frit is controlled.

Description

Technical Field

[0001] The present application relates to the field of ceramic technology, and in particular to a cracked ceramic frit and a preparation method thereof. Background Art

[0002] Crackle ceramic frit is often used to create ceramic products with unique textures and decorative effects. Crackle effect is achieved by adding specific ingredients to the glaze or frit to create cracks during the firing process, thus creating a unique visual effect.

[0003] The formation of the crack effect mainly depends on the difference in thermal expansion coefficients between the glaze and the body during firing. The cracking agent decomposes or reacts at high temperatures, causing stress in the glaze layer, thereby forming cracks. However, the cracking effect of the cracked ceramic frit in the related art is relatively poor. Summary of the invention

[0004] The present application is made in view of the above-mentioned problems, and its purpose is to provide a cracked ceramic frit, and the ceramic glaze made by using the frit has high strength.

[0005] Specifically, the first aspect of the present application provides a cracked ceramic frit, including the following preparation raw materials:

[0006] Potash feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate.

[0007] According to one of the technical solutions of the cracked ceramic frit technical solution of the present application, at least the following beneficial effects are achieved:

[0008] The cracked ceramic frit in the present application includes the following preparation raw materials: potassium feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate;

[0009] The functions of each preparation raw material are as follows:

[0010] Potassium feldspar is the main flux and glass phase former, providing potassium oxide (K 2 O), aluminum oxide (Al 2 O 3 ) and silicon dioxide (SiO 2 ), lowering the melting temperature and promoting the formation of glass phase; at the same time, potassium feldspar can also adjust the thermal expansion coefficient of the crack ceramic frit and adjust the formation of stress, thereby forming a crack effect;

[0011] Calcite decomposes into calcium oxide (CaO) and carbon dioxide (CO 2 ), providing calcium oxide, which plays a role in fluxing and adjusting the properties of the frit;

[0012] Borax is a strong flux, which can significantly reduce the melting temperature, promote the formation of glass phase, and improve the chemical stability of the frit; at the same time, by modifying the borax, the thermal expansion coefficient of the crack ceramic frit can be further adjusted, which is conducive to the production of crack effect.

[0013] Soda ash decomposes into sodium oxide (Na 2 O), is a strong flux, significantly reduces the melting temperature and promotes the formation of glass phase; at the same time, soda ash can also adjust the brittleness of the frit, making it easy to produce crack effects.

[0014] Lithium carbonate decomposes into lithium oxide (Li 2 O), is a strong flux, which significantly reduces the melting temperature and improves the fluidity and chemical stability of the frit; at the same time, the lithium ion radius is small, which can adjust the thermal expansion coefficient of the crack ceramic frit, which is conducive to the generation of crack effects.

[0015] Strontium carbonate decomposes into strontium oxide at high temperature, which plays a role in fluxing and adjusting the performance of the frit. At the same time, the strontium ion radius is large, which can adjust the thermal expansion coefficient of the crack ceramic frit, which is conducive to producing a crack effect.

[0016] The present application controls the raw materials prepared in the cracked ceramic frit, thereby controlling the thermal expansion coefficient of the frit, thereby controlling the crack effect of the cracked ceramic frit.

[0017] According to some embodiments of the present application, the cracked ceramic frit includes the following preparation raw materials in parts by weight:

[0018] 40 parts of potassium feldspar, 10 to 30 parts of calcite, 10 to 30 parts of modified borax, 10 to 30 parts of soda ash, 2 to 5 parts of lithium carbonate and 0.5 to 3 parts of strontium carbonate.

[0019] The present application controls the amount of each raw material used in the preparation, thereby controlling the thermal expansion coefficient of the cracked ceramic frit, thereby regulating the cracking effect.

[0020] According to some embodiments of the present application, the modified borax includes the following preparation raw materials:

[0021] 100 parts of borax, 10 to 20 parts of NHS-PEG-PBA and POSS-NH 2 3 to 5 servings.

[0022] In this application, the interaction between PEG and borax in NHS-PEG-PBA is used to modify the surface of borax; the NHS group is also used to interact with POSS-NH 2The amino groups of NHS-PEG-PBA and POSS-NH 2 The amino groups react to form an organic-inorganic cross-linking network, which allows the preparation raw materials to fully function and further improves the mechanical properties of the frit.

[0023] According to some embodiments of the present application, the method for preparing the modified borax comprises the following steps:

[0024] Borax, NHS-PEG-PBA, POSS-NH 2 reacting after mixing with a solvent;

[0025] According to some embodiments of the present application, the reaction temperature is 10°C to 30°C;

[0026] According to some embodiments of the present application, the reaction time is 1 h to 4 h.

[0027] According to some embodiments of the present application, the molecular weight of PEG in the NHS-PEG-PBA is 1000-3000.

[0028] According to some embodiments of the present application, the solvent is DMSO.

[0029] The second aspect of the present application discloses a method for preparing the above-mentioned cracked ceramic frit, comprising the following steps:

[0030] After pre-treating the potassium feldspar, pre-treated potassium feldspar is obtained;

[0031] Potassium feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate are mixed and fired, and then quenched and ground after firing.

[0032] According to some embodiments of the present application, the firing temperature is 1500°C to 1600°C.

[0033] According to some embodiments of the present application, the firing time is 20 hours to 30 hours.

[0034] According to some embodiments of the present application, the steps of pre-treating potassium feldspar are as follows:

[0035] S1, calcining potassium feldspar and then oxidizing it to obtain potassium feldspar oxide;

[0036] S2. Mix potassium oxide feldspar and borate.

[0037] According to some embodiments of the present application, the calcination temperature is 500°C to 600°C.

[0038] According to some embodiments of the present application, the calcination time is 6 h to 8 h.

[0039] According to some embodiments of the present application, the oxidation treatment uses hydrogen peroxide treatment.

[0040] According to some embodiments of the present application, the mass fraction of the hydrogen peroxide is 10% to 15%.

[0041] According to some embodiments of the present application, the mass volume ratio of potassium feldspar and hydrogen peroxide is 1g:10mL~20mL.

[0042] According to some embodiments of the present application, the temperature of the oxidation treatment is 20°C to 30°C.

[0043] According to some embodiments of the present application, the oxidation treatment time is 5 hours to 10 hours.

[0044] According to some embodiments of the present application, the borate ester is 2-aminoethylbiphenyl borate.

[0045] According to some embodiments of the present application, the mixing temperature is 70°C to 90°C.

[0046] According to some embodiments of the present application, the mixing time is 1 h to 3 h.

[0047] According to some embodiments of the present application, an ethanol aqueous solution is added during the mixing process.

[0048] According to some embodiments of the present application, the volume fraction of the ethanol aqueous solution is 90% to 99%.

[0049] According to some embodiments of the present application, the mass ratio of potassium oxide feldspar to borate ester is 10:1-3.

[0050] The present application modifies potassium feldspar by hydrogen peroxide, thereby introducing oxygen-containing groups on the surface of potassium feldspar; and introduces boron elements into potassium feldspar by mixing oxygen-containing groups with borate esters; and at the same time, it can also strengthen the interaction between potassium feldspar and modified borax to form an organic-inorganic composite structure, which is beneficial to further improve the performance of cracked ceramic frit. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] In order to more clearly illustrate the embodiments of the present drawings or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present drawings. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0052] Figure 1 This is the crack pattern effect formed by the cracked ceramic frit prepared in Example 1 of the present application.

[0053] The purpose, features and advantages of this figure will be further described in conjunction with the embodiments with reference to the accompanying drawings. DETAILED DESCRIPTION

[0054] In order to make the purpose, technical solutions and advantages of the present application clearer, the present application is described and illustrated below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not intended to limit the present application. Based on the embodiments provided in the present application, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present application.

[0055] Obviously, the following descriptions are only some examples or embodiments of the present application. For ordinary technicians in this field, the present application can also be applied to other similar scenarios without creative work. In addition, it can also be understood that although the efforts made in this development process may be complicated and lengthy, for ordinary technicians in the field related to the content disclosed in this application, some changes in design, manufacturing or production based on the technical content disclosed in this application are just conventional technical means, and should not be understood as insufficient content disclosed in this application.

[0056] If there is no special explanation, the "include" and "comprising" mentioned in this application are open-ended or closed-ended. For example, the "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0057] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0058] POSS-NH selected in the implementation mode of the present application 2 The CAS number is 150380-11-3.

[0059] Example 1

[0060] This embodiment is a cracked ceramic frit, which is composed of the following raw materials in parts by weight:

[0061] 40 parts of potassium feldspar, 20 parts of calcite, 20 parts of modified borax, 20 parts of soda ash, 4 parts of lithium carbonate and 2 parts of strontium carbonate.

[0062] The modified borax comprises the following raw materials in parts by weight:

[0063] Borax 100 parts, NHS-PEG2000-PBA 18 parts and POSS-NH 2 4 servings.

[0064] The preparation method of modified borax consists of the following steps:

[0065] Borax, NHS-PEG2000-PBA, POSS-NH 2 and a solvent (DMSO, dimethyl sulfoxide, the mass volume ratio of borax to the solvent is 1 g: 20 mL) and then reacted (stirring during the reaction), after the reaction is completed, the solvent is evaporated and the solid phase is collected;

[0066] The reaction temperature was 20°C and the reaction time was 3 h.

[0067] The method for preparing the cracked ceramic frit in this embodiment comprises the following steps:

[0068] After pre-treating the potassium feldspar, pre-treated potassium feldspar is obtained;

[0069] The pretreated potassium feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate are mixed and fired (1500°C, time is 25 hours), and after firing, they are quenched in water and ground (ground to a fineness of 300 meshes).

[0070] The steps of pretreatment of potassium feldspar in this embodiment are as follows:

[0071] S1, calcining potassium feldspar (550°C, time for 7 hours) and then oxidizing it to obtain potassium feldspar oxide;

[0072] The oxidation treatment was carried out with hydrogen peroxide (mass fraction 10%); the mass volume ratio of potassium feldspar and hydrogen peroxide was 1g:10mL;

[0073] The temperature of the oxidation treatment is 25°C; the time of the oxidation treatment is 10 hours.

[0074] S2, mixing potassium feldspar oxide and borate (2-aminoethyl biphenyl borate), collecting a solid phase after the mixing is completed, and drying the solid phase to obtain pretreated potassium feldspar;

[0075] The mixing temperature is 80°C; the mixing time is 3h;

[0076] During the mixing process, an ethanol aqueous solution (volume fraction of 95%, mass volume ratio of potassium oxide feldspar to ethanol solution of 1 g:10 mL) was added; the mass ratio of potassium oxide feldspar to borate was 10:1.2.

[0077] Example 2

[0078] This embodiment is a cracked ceramic frit, which is composed of the following raw materials in parts by weight:

[0079] 40 parts of potassium feldspar, 22 parts of calcite, 18 parts of modified borax, 12 parts of soda ash, 2 parts of lithium carbonate and 3 parts of strontium carbonate.

[0080] The modified borax comprises the following raw materials in parts by weight:

[0081] 100 parts of borax, 10 parts of NHS-PEG2000-PBA and 10 parts of POSS-NH 2 5 servings.

[0082] The preparation method of modified borax in this example is carried out with reference to Example 1.

[0083] The preparation method of the cracked ceramic frit in this embodiment is carried out with reference to that in Embodiment 1.

[0084] The steps of pretreatment of potassium feldspar in this embodiment differ from those in Embodiment 1 only in that:

[0085] The mass ratio of potassium oxide feldspar to borate is 10:3.

[0086] Example 3

[0087] This embodiment is a cracked ceramic frit, which is composed of the following raw materials in parts by weight:

[0088] 40 parts of potassium feldspar, 18 parts of calcite, 22 parts of modified borax, 18 parts of soda ash, 4 parts of lithium carbonate and 1 part of strontium carbonate.

[0089] The modified borax comprises the following raw materials in parts by weight:

[0090] Borax 100 parts, NHS-PEG2000-PBA 20 parts and POSS-NH 2 5 servings.

[0091] The preparation method of modified borax in this example is carried out with reference to Example 1.

[0092] The preparation method of the cracked ceramic frit in this embodiment is carried out with reference to that in Embodiment 1.

[0093] The steps of pretreatment of potassium feldspar in this embodiment differ from those in Embodiment 1 only in that:

[0094] The mass ratio of potassium oxide feldspar to borate is 10:1.8.

[0095] Example 4

[0096] This embodiment is a cracked ceramic frit, which is composed of the following raw materials in parts by weight:

[0097] 40 parts of potassium feldspar, 24 parts of calcite, 16 parts of modified borax, 22 parts of soda ash, 5 parts of lithium carbonate and 3 parts of strontium carbonate.

[0098] The modified borax comprises the following raw materials in parts by weight:

[0099] Borax 100 parts, NHS-PEG2000-PBA 20 parts and POSS-NH 2 5 servings.

[0100] The preparation method of modified borax in this example is carried out with reference to Example 1.

[0101] The preparation method of the cracked ceramic frit in this embodiment is carried out with reference to that in Embodiment 1.

[0102] The steps of pretreatment of potassium feldspar in this embodiment differ from those in Embodiment 1 only in that:

[0103] The mass ratio of potassium oxide feldspar to borate is 10:2.1.

[0104] Example 5

[0105] This embodiment is a cracked ceramic frit, which is composed of the following raw materials in parts by weight:

[0106] 40 parts of potassium feldspar, 24 parts of calcite, 20 parts of modified borax, 30 parts of soda ash, 2 parts of lithium carbonate and 0.5 parts of strontium carbonate.

[0107] The modified borax comprises the following raw materials in parts by weight:

[0108] 100 parts of borax, 10 parts of NHS-PEG2000-PBA and 10 parts of POSS-NH 2 3 servings.

[0109] The preparation method of modified borax in this example is carried out with reference to Example 1.

[0110] The preparation method of the cracked ceramic frit in this embodiment is carried out with reference to that in Embodiment 1.

[0111] The steps of pretreatment of potassium feldspar in this embodiment differ from those in Embodiment 1 only in that:

[0112] The mass ratio of potassium oxide feldspar to borate ester is 10:1.

[0113] Comparative Example 1

[0114] This comparative example is a cracked ceramic frit, which differs from Example 5 in that:

[0115] The modified borax comprises the following raw materials in parts by weight:

[0116] Borax 100 parts and POSS-NH 2 5 servings.

[0117] The preparation method of modified borax consists of the following steps:

[0118] Borax, POSS-NH 2 and a solvent (DMSO, dimethyl sulfoxide, the mass volume ratio of borax to the solvent is 1 g: 20 mL) and then reacted (stirring during the reaction), after the reaction is completed, the solvent is evaporated and the solid phase is collected;

[0119] The reaction temperature was 20°C and the reaction time was 3 h.

[0120] Comparative Example 2

[0121] This comparative example is a cracked ceramic frit, which differs from Example 5 in that:

[0122] The modified borax comprises the following raw materials in parts by weight:

[0123] 100 parts of borax and 10 parts of NHS-PEG2000-PBA.

[0124] The preparation method of modified borax consists of the following steps:

[0125] Borax, NHS-PEG2000-PBA and a solvent (DMSO, dimethyl sulfoxide, the mass volume ratio of borax to solvent is 1 g: 20 mL) are mixed and reacted (stirring during the reaction), and after the reaction is completed, the solvent is evaporated and the solid phase is collected;

[0126] The reaction temperature was 20°C and the reaction time was 3 h.

[0127] Comparative Example 3

[0128] This comparative example is a cracked ceramic frit, which differs from Example 5 in that:

[0129] Replace modified borax with borax.

[0130] Comparative Example 4

[0131] This comparative example is a cracked ceramic frit, which differs from comparative example 3 in that:

[0132] The steps of the pretreatment method of potassium feldspar are as follows:

[0133] The potassium feldspar is calcined (550°C, time is 7h) and then oxidized to obtain potassium feldspar oxide;

[0134] The oxidation treatment is carried out by using hydrogen peroxide (mass fraction is 10%); the mass volume ratio of potassium feldspar and hydrogen peroxide is 1g:10mL; after the oxidation is completed, the solid phase is collected, and the pretreated potassium feldspar is obtained after the solid phase is dried;

[0135] The temperature of the oxidation treatment is 25°C; the time of the oxidation treatment is 10 hours.

[0136] Comparative Example 5

[0137] This comparative example is a cracked ceramic frit, which differs from comparative example 3 in that:

[0138] Potash feldspar is not pretreated.

[0139] The cracked ceramic frit in the examples and comparative examples of the present application is used to prepare a glaze according to the following formula: 65 parts of cracked ceramic frit, 20 parts of potassium feldspar, 6 parts of Guizhou clay, 1 part of bentonite, 5 parts of calcite and 3 parts of colorant.

[0140] The above-mentioned formula materials were put into a ball mill, added with 45% water and ball-milled for 16 hours, passed through a 160-mesh sieve, and the glaze slurry concentration was controlled at a Baume concentration of 50° to obtain a glaze;

[0141] The glaze was applied on the body (thickness was 2 mm), and fired at 1200°C for 2 h to obtain the sample; and the Vickers hardness of the sample was tested (load 100 g, holding time 15 s). The test results are shown in Table 1.

[0142] Table 1

[0143] - Vickers hardness (Hv0.1) Example 1 1126 Example 2 1097 Example 3 1079 Example 4 1034 Example 5 1021 Comparative Example 1 923 Comparative Example 2 914 Comparative Example 3 871 Comparative Example 4 864 Comparative Example 5 853

[0144] In the embodiment of the present application, the crack ceramic frit includes the following raw materials: potassium feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate; potassium feldspar is the main flux and glass phase former, providing potassium oxide, aluminum oxide and silicon dioxide, reducing the melting temperature and promoting the formation of glass phase; at the same time, potassium feldspar can also adjust the thermal expansion coefficient of the crack ceramic frit, adjust the formation of stress, and thus form a crack effect; calcite decomposes into calcium oxide and carbon dioxide at high temperature, provides calcium oxide, plays a role in fluxing and adjusting the performance of the frit; borax is a strong flux, significantly reduces the melting temperature, promotes the formation of glass phase, and improves the chemical stability of the frit; at the same time, by modifying the borax, the thermal expansion coefficient of the crack ceramic frit is further adjusted, which is conducive to the generation of a crack effect. Soda ash decomposes into sodium oxide at high temperature, which is a strong flux, significantly reduces the melting temperature and promotes the formation of glass phase; at the same time, soda ash can also adjust the brittleness of the frit, and it is easy to produce a crack effect. Lithium carbonate decomposes into lithium oxide at high temperature, which is a strong flux, significantly reducing the melting temperature and improving the fluidity and chemical stability of the frit; at the same time, the lithium ion radius is small, which can adjust the thermal expansion coefficient of the cracked ceramic frit, which is beneficial to the production of a crack effect. Strontium carbonate decomposes into strontium oxide at high temperature, which plays a role in fluxing and adjusting the performance of the frit. At the same time, the strontium ion radius is large, which can adjust the thermal expansion coefficient of the cracked ceramic frit, which is beneficial to the production of a crack effect. The present application controls the thermal expansion coefficient of the frit by controlling the preparation of raw materials in the cracked ceramic frit, thereby controlling the crack effect of the cracked ceramic frit.

[0145] The present invention also utilizes the interaction between PEG and borax in NHS-PEG-PBA to modify the surface of borax; and utilizes the interaction between NHS group and POSS-NH 2 The amino groups of NHS-PEG-PBA and POSS-NH 2 The amino groups react to form an organic-inorganic cross-linking network, which allows the preparation raw materials to fully function and further improve the Vickers hardness of the frit.

[0146] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A cracked ceramic frit, characterized in that: The preparation includes the following raw materials: Potash feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate.

2. The cracked ceramic frit according to claim 1, characterized in that: The preparation comprises the following raw materials in parts by weight: 40 parts of potassium feldspar, 10 to 30 parts of calcite, 10 to 30 parts of modified borax, 10 to 30 parts of soda ash, 2 to 5 parts of lithium carbonate and 0.5 to 3 parts of strontium carbonate.

3. The cracked ceramic frit according to claim 1, characterized in that: The modified borax comprises the following preparation raw materials: 100 parts of borax, 10 to 20 parts of NHS-PEG-PBA and 3 to 5 parts of POSS-NH2.

4. The cracked ceramic frit according to claim 3, characterized in that: The preparation method of the modified borax comprises the following steps: Borax, NHS-PEG-PBA, POSS-NH2 and solvent are mixed and reacted; And / or, the reaction temperature is 10°C to 30°C; And / or, the reaction time is 1 h to 4 h.

5. The cracked ceramic frit according to claim 3, characterized in that: The molecular weight of PEG in the NHS-PEG-PBA is 1000-3000.

6. A method for preparing the cracked ceramic frit according to any one of claims 1 to 5, characterized in that: The following steps are involved: After pre-treating the potassium feldspar, pre-treated potassium feldspar is obtained; The pretreated potassium feldspar, calcite, modified borax, soda ash, lithium carbonate and strontium carbonate are mixed and fired, and then water quenched and ground after the firing is completed.

7. The method according to claim 6, characterized in that The firing temperature is 1500°C to 1600°C; And / or, the firing time is 20h to 30h.

8. The method according to claim 6, characterized in that The steps of the potassium feldspar pretreatment are as follows: S1, calcining potassium feldspar and then oxidizing it to obtain potassium feldspar oxide; S2. Mix potassium oxide feldspar and borate.

9. The method according to claim 8, characterized in that The calcination temperature is 500°C to 600°C; And / or, the calcination time is 6h to 8h; And / or, the oxidation treatment is carried out by hydrogen peroxide treatment; And / or, the mass fraction of the hydrogen peroxide is 10% to 15%; And / or, the mass volume ratio of potassium feldspar and hydrogen peroxide is 1g:10mL-20mL; And / or, the temperature of the oxidation treatment is 20°C to 30°C; And / or, the oxidation treatment time is 5h to 10h.

10. The method according to claim 8, characterized in that The borate ester is 2-aminoethylbiphenyl borate; And / or, the mixing temperature is 70°C to 90°C; And / or, the mixing time is 1h to 3h; and / or, adding ethanol aqueous solution during the mixing process; And / or, the volume fraction of the ethanol aqueous solution is 90% to 99%; And / or, the mass ratio of potassium oxide feldspar to borate ester is 10:1-3.

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