High-glaze-hardness bone china and manufacturing method thereof

Abstract

The invention discloses bone china with high glaze hardness and a preparation method thereof. The bone china comprises a synergistic modified basic glaze, functional small organic molecules, a silica structure regulating agent, an inorganic structure stabilizer, a melting behavior regulating agent, a dispersing agent, a flatting agent and a defoaming agent, wherein the synergistic modified basic glaze takes feldspar, quartz, bone ash and wollastonite as basic glaze minerals; gamma-aminopropyltriethoxysilane and boric acid are introduced to carry out synergistic structure regulation and control on a silicon-oxygen network, and the functional small organic molecule is adamantane-1, 3-dicarboxylic acid. The components are prepared into glazing slurry, the surface of a bone china green body is coated with the glazing slurry, and the bone china product with high glaze hardness is obtained through drying and high-temperature firing. According to the invention, on the premise of not obviously influencing the gloss and the appearance quality of the glaze surface, the densification of the glaze layer structure is realized, the wear resistance, the scratch resistance, the chemical corrosion resistance and the cold and heat cycle resistance of the glaze surface are obviously improved, and the practical value and the popularization prospect are good.

Description

Technical Field

[0001] This invention belongs to the field of daily-use ceramic materials technology, specifically relating to a high-glaze-hardness bone china and its preparation method. Background Technology

[0002] Bone china, with its high whiteness, good translucency, and fine texture, is widely used in high-end daily-use and decorative ceramics. However, with the continuous improvement of usage scenarios and quality requirements, existing bone china has gradually revealed problems such as insufficient glaze hardness and limited scratch resistance during long-term use. It is easily scratched during tableware washing, metal contact, or repeated friction, thus affecting its appearance quality and service life.

[0003] To improve the glaze hardness of bone china, existing technologies typically adjust the proportion of inorganic components such as quartz and feldspar in the base glaze, or introduce inorganic hard materials such as alumina and zirconium oxide as reinforcing phases. However, these methods often lead to decreased glaze transparency, reduced glaze gloss, and a narrower firing window, making it prone to process problems such as glaze opacity, pinholes, or cracking, which are detrimental to stable large-scale production.

[0004] In existing bone china glaze systems, the application of organic materials is mainly limited to forming aids or transient dispersants, which typically decompose or volatilize completely during firing, failing to play a substantial role in the glaze structure. Techniques for synergistic modification of the glaze structure, particularly through the participation of organic components in the regulation of the silicon-oxygen network structure to enhance glaze hardness, remain relatively rare in the current field of bone china.

[0005] Therefore, how to effectively modify the base glaze to achieve a denser glaze structure and improve the hardness and scratch resistance of the glaze without significantly affecting the transparency and gloss of the bone china glaze remains a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] To overcome the problems of insufficient glaze hardness, limited scratch resistance, and easy impact on glaze transparency and gloss in the aforementioned background art of bone china, the present invention aims to provide a high-glaze-hardness bone china and its preparation method. By synergistically modifying the base glaze and introducing functional organic small molecules, the glaze layer structure is densified and its hardness and wear resistance are significantly improved while ensuring the appearance quality of the bone china glaze. The present invention employs a bone china component system based on synergistically modified base glaze, combined with silicon-oxygen structure regulators, inorganic structure stabilizers, melt behavior modifiers, and functional organic small molecules, and combines this with appropriate glazing and firing processes to prepare high-glaze-hardness bone china. The present invention has the beneficial effects of a dense glaze layer structure, high glaze hardness, and excellent scratch resistance.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A high-glaze-hardness bone china, comprising the following raw materials in parts by weight: 85-95 parts of synergistically modified base glaze; 0.1-2.0 parts of functional organic small molecules; 0.5-3.0 parts of silicon-oxygen structure regulator; 0.3-2.0 parts of inorganic structure stabilizer; 0.1-1.0 parts of melt behavior regulator; 0.1-1.0 parts of dispersant; 0.05-0.5 parts of leveling agent; and 0.01-0.3 parts of defoamer. The synergistically modified base glaze is a modified glaze system formed by introducing feldspar, quartz, bone ash, and wollastonite as base glaze minerals, and synergistically regulating the silicon-oxygen network structure through the introduction of γ-aminopropyltriethoxysilane and boric acid during ball milling and firing. The functional organic small molecule is adamantane-1,3-dicarboxylic acid.

[0009] Optionally, the synergistically modified base glaze comprises the following raw materials in parts by weight: 35-55 parts potassium feldspar; 15-30 parts quartz; 10-25 parts bone ash; 5-15 parts wollastonite; 0.3-2.0 parts γ-aminopropyltriethoxysilane; and 0.2-1.5 parts boric acid.

[0010] Optionally, the preparation method of the synergistic modified base glaze includes the following steps: (1) Weigh potassium feldspar, quartz, bone ash and wollastonite according to the formula ratio, add them to the ball milling equipment, add deionized water for wet ball milling treatment, and obtain a uniformly dispersed base glaze slurry;

[0011] (2) Add γ-aminopropyltriethoxysilane and boric acid to the base glaze slurry, and continue ball milling or mixing and dispersing under stirring conditions to uniformly introduce the modified components into the base glaze system and obtain synergistic modified glaze slurry;

[0012] (3) The synergistic modified glaze slurry is dried, then crushed and sieved to obtain the synergistic modified base glaze.

[0013] Optionally, the reaction conditions in step (1) are a ball milling speed of 200-400 r / min, a ball milling time of 6-12 h, and a ball-to-material ratio of (1.5-3.0):1.

[0014] Optionally, the reaction conditions in step (2) are as follows: γ-aminopropyltriethoxysilane and boric acid are added at 20-40°C and mixed for 1-4 hours under continuous stirring.

[0015] Optionally, the reaction conditions in step (3) are drying at 80-120°C for 6-24 hours, followed by pulverization and passing through a 100-200 mesh sieve.

[0016] Optionally, the silicon-oxygen structure regulator is a mixture of tetraethoxysilane and γ-aminopropyltriethoxysilane in a mass ratio of (3-8):1; the inorganic structure stabilizer is a mixture of zirconium oxide and wollastonite in a mass ratio of (1-5):1; the melt behavior regulator is a mixture of boric acid and lithium carbonate in a mass ratio of (2-6):1; the dispersant is a mixture of sodium hexametaphosphate and sodium polyacrylate in a mass ratio of (1-4):1; the leveling agent is a mixture of polydimethylsiloxane and polyether-modified silicone oil in a mass ratio of (1-3):1; and the defoamer is a mixture of organosilicon defoamer and mineral oil in a mass ratio of (1-5):1.

[0017] Optionally, a method for preparing high-glaze-hardness bone china includes the following steps:

[0018] S1, the synergistic modified base glaze is mixed with silicon-oxygen structure regulator, inorganic structure stabilizer, melt behavior regulator, dispersant, leveling agent, defoamer and functional organic small molecules, and deionized water is added for stirring and dispersion to obtain a uniform glazing slurry.

[0019] S2, apply the glazing slurry to the surface of the bone china body, and dry it at low temperature to form a glaze layer;

[0020] S3 involves firing the bone china body at high temperature and then cooling it to obtain bone china products with high glaze hardness.

[0021] Optionally, the reaction conditions in step S1 are as follows: deionized water is added at room temperature and stirred and dispersed at a stirring speed of 300-800 r / min for 30-120 min, so that the components are evenly dispersed to form a glazing slurry.

[0022] Optionally, the reaction conditions for step S2 are drying at 20–60°C for 0.5–4 hours after glazing to ensure the glaze surface is dry and does not crack; the reaction conditions for step S3 are firing at 1150–1250°C for 30–120 minutes, followed by cooling to room temperature in the furnace.

[0023] The beneficial effects of this invention are:

[0024] This invention modifies the basic glaze system by introducing γ-aminopropyltriethoxysilane and boric acid in a synergistic manner. This allows the organosilicon component to participate in the reconstruction and connection of the silicon-oxygen network during ball milling and firing, breaking through the traditional technical path of relying solely on the adjustment of the inorganic mineral ratio to improve glaze performance. This achieves directional control of the glaze microstructure. Simultaneously, for the first time, adamantane-1,3-dicarboxylic acid is introduced as a functional organic small molecule into the bone china glaze system. Its rigid cage-like structure induces the densification of the glass phase and inhibits the formation of microcracks during high-temperature firing. Without significantly increasing the amount of inorganic hard fillers, it significantly improves the microhardness and scratch resistance of the glaze. Thus, while maintaining the high whiteness, high gloss, and good transparency of bone china, it achieves a simultaneous improvement in the mechanical properties of the glaze, demonstrating significant creativity and practical value. Attached Figure Description

[0025] The invention will now be further described with reference to the accompanying drawings.

[0026] Figure 1 This is a comparison of the infrared spectra of the base glaze and the synergistically modified base glaze;

[0027] Figure 2 This is a comparison chart of the performance test results of samples with different ratios. Detailed Implementation

[0028] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.

[0029] Example 1: This example aims to verify that, under the condition that the amount of each raw material and the process conditions are within the limited lower limit range, the glaze structure can still be effectively controlled by synergistic modification of the base glaze, and bone china products with high glaze hardness can be produced.

[0030] S1, Preparation of synergistically modified base glaze

[0031] The following raw materials were weighed according to the following weight proportions: 35 parts potassium feldspar, 15 parts quartz, 10 parts bone ash, 5 parts wollastonite, 0.3 parts γ-aminopropyltriethoxysilane, and 0.2 parts boric acid. Potassium feldspar, quartz, bone ash, and wollastonite were added to a ball mill, along with deionized water. Wet ball milling was performed at a speed of 200 r / min, a milling time of 6 h, and a ball-to-material ratio of 1.5:1 to obtain a uniformly dispersed basic glaze slurry. Subsequently, γ-aminopropyltriethoxysilane and boric acid were added to the basic glaze slurry at 20°C and mixed for 1 h under continuous stirring to obtain a synergistically modified glaze slurry. The obtained synergistically modified glaze slurry was dried at 80°C for 6 h, then pulverized and passed through a 200-mesh sieve to obtain the synergistically modified basic glaze.

[0032] S2, Glazing

[0033] The obtained synergistically modified base glaze is mixed with a silica-oxygen structure regulator, an inorganic structure stabilizer, a melt behavior modifier, a dispersant, a leveling agent, a defoamer, and functional organic small molecules in the specified ratio. Deionized water is added, and the mixture is stirred at 300 r / min for 30 min to obtain a glazing slurry. The glazing slurry is applied to the surface of the bone china body and dried at 20℃ for 0.5 h to form a glaze layer.

[0034] S3, firing

[0035] The glazed bone china body is fired at 1150℃ and held for 30 minutes, then cooled to room temperature in the kiln to obtain bone china products with high glaze hardness.

[0036] Example 2: This example aims to provide a preferred embodiment in which the proportions of each raw material and the process conditions are all within the median range, so as to obtain bone china products with stable glaze structure and balanced improvement in glaze hardness and scratch resistance.

[0037] S1, Preparation of synergistically modified base glaze

[0038] The following raw materials were weighed according to the following weight proportions: 45 parts potassium feldspar, 22 parts quartz, 18 parts bone ash, 10 parts wollastonite, 1.0 part γ-aminopropyltriethoxysilane, and 0.8 parts boric acid. Potassium feldspar, quartz, bone ash, and wollastonite were added to a ball mill, along with deionized water. Wet ball milling was performed at a speed of 300 r / min, a milling time of 9 h, and a ball-to-material ratio of 2.0:1 to obtain a basic glaze slurry. γ-aminopropyltriethoxysilane and boric acid were added at 30°C and mixed for 2 h under continuous stirring to obtain a synergistically modified glaze slurry. The obtained synergistically modified glaze slurry was dried at 100°C for 12 h, then pulverized and passed through a 150-mesh sieve to obtain the synergistically modified basic glaze. Figure 1 The infrared spectrum comparison shows that the base glaze before modification has a wavelength of 1100–1000 cm⁻¹. -1 The sample mainly exhibits typical Si–O–Si and Si–O–Al stretching vibration peaks, accompanied by characteristic phosphate absorption caused by bone ash; the modified sample, while maintaining the main peak position of the silicon-oxygen framework basically unchanged, shows peaks at 2950–2850 cm⁻¹. -1 A new C–H stretching vibration peak appears at 1400–1300 cm⁻¹. -1 The region exhibits characteristic absorptions related to the boron-oxygen structure, and the main peak intensity is enhanced and slightly shifted, indicating that γ-aminopropyltriethoxysilane and boric acid were successfully introduced and participated in the regulation of the silicon-oxygen network structure, making the glaze structure more compact and stable.

[0039] S2, Glazing

[0040] The synergistic modified base glaze, additives and functional organic small molecules were mixed in a median ratio, deionized water was added, and the mixture was stirred at 500 r / min for 60 min to obtain a glazing slurry. The glazing slurry was applied to the surface of the bone china body and dried at 40℃ for 2 h to form a glaze layer.

[0041] S3, firing

[0042] The glazed bone china body is fired at 1200℃ and held at that temperature for 60 minutes. It is then cooled to room temperature in the kiln to obtain bone china products with high glaze hardness.

[0043] Example 3: This example aims to verify the enhancing effect of synergistic modification of the base glaze on the densification of the glaze structure and the improvement of the glaze surface hardness under the condition that the amount of each raw material and the process conditions are within the upper limit range.

[0044] S1, Preparation of synergistically modified base glaze

[0045] The following raw materials were weighed according to the following weight proportions: 55 parts potassium feldspar, 30 parts quartz, 25 parts bone ash, 15 parts wollastonite, 2.0 parts γ-aminopropyltriethoxysilane, and 1.5 parts boric acid. Potassium feldspar, quartz, bone ash, and wollastonite were added to a ball mill, along with deionized water. Wet ball milling was performed at a speed of 400 r / min, a milling time of 12 h, and a ball-to-material ratio of 3.0:1 to obtain a highly refined basic glaze slurry. γ-aminopropyltriethoxysilane and boric acid were added at 40°C and mixed under continuous stirring for 4 h to obtain a synergistically modified glaze slurry. The obtained synergistically modified glaze slurry was dried at 120°C for 24 h, then pulverized and passed through a 100-mesh sieve to obtain the synergistically modified basic glaze.

[0046] S2, Glazing

[0047] The synergistic modified base glaze is mixed with various additives and functional organic small molecules in the upper limit ratio, deionized water is added, and the mixture is stirred at 800 r / min for 120 min to obtain the glazing slurry. The glazing slurry is applied to the surface of the bone china body and dried at 60℃ for 4 h to form a glaze layer.

[0048] S3, firing

[0049] The glazed bone china body is fired at 1250℃ and held for 120 minutes, then cooled to room temperature in the kiln to obtain bone china products with high glaze hardness.

[0050] Comparative Example 1: This comparative example aims to verify the effect of using only γ-aminopropyltriethoxysilane to modify the base glaze on the stability of the glaze structure, the hardness of the glaze surface, and the scratch resistance.

[0051] S1, Preparation of synergistically modified base glaze

[0052] The following raw materials were weighed according to the following weight proportions: 45 parts potassium feldspar, 22 parts quartz, 18 parts bone ash, 10 parts wollastonite, and 1.0 part γ-aminopropyltriethoxysilane. Potassium feldspar, quartz, bone ash, and wollastonite were added to a ball mill, along with deionized water. Wet ball milling was performed at a speed of 300 r / min, a milling time of 9 h, and a ball-to-material ratio of 2.0:1 to obtain a basic glaze slurry. γ-aminopropyltriethoxysilane was added at 30°C and mixed for 2 h under continuous stirring to obtain a single-modified glaze slurry. The obtained single-modified glaze slurry was dried at 100°C for 12 h, then pulverized and passed through a 150-mesh sieve to obtain a single-modified basic glaze.

[0053] S2, Glazing

[0054] 90 parts of the single modified base glaze were mixed with 1.05 parts of adamantane-1,3-dicarboxylic acid, 1.75 parts of silicon-oxygen structure regulator, 1.15 parts of inorganic structure stabilizer, 0.55 parts of melt behavior regulator, 0.55 parts of dispersant, 0.275 parts of leveling agent, and 0.155 parts of defoamer. Deionized water was added, and the mixture was stirred at 500 r / min for 60 min to obtain a glazing slurry. The glazing slurry was applied to the surface of the bone china body and dried at 40°C for 2 h to form a glaze layer.

[0055] S3, firing

[0056] The glazed bone china body is fired at 1200℃ and held at that temperature for 60 minutes. Then it is cooled to room temperature in the kiln to obtain bone china products.

[0057] Comparative Example 2: This comparative example aims to verify the effect of using only boric acid to modify the base glaze on the densification of the glaze layer, as well as the hardness and scratch resistance of the glaze surface.

[0058] S1, Preparation of synergistically modified base glaze

[0059] The following raw materials were weighed according to the following weight proportions: 45 parts potassium feldspar, 22 parts quartz, 18 parts bone ash, 10 parts wollastonite, and 0.8 parts boric acid. Potassium feldspar, quartz, bone ash, and wollastonite were added to a ball mill, along with deionized water. Wet ball milling was performed at a speed of 300 r / min, a milling time of 9 h, and a ball-to-material ratio of 2.0:1 to obtain a basic glaze slurry. Boric acid was added at 30°C and mixed for 2 h under continuous stirring to obtain a single-modified glaze slurry. The obtained single-modified glaze slurry was dried at 100°C for 12 h, then pulverized and passed through a 150-mesh sieve to obtain a single-modified basic glaze.

[0060] S2, Glazing

[0061] 90 parts of the single modified base glaze were mixed with 1.05 parts of adamantane-1,3-dicarboxylic acid, 1.75 parts of silicon-oxygen structure regulator, 1.15 parts of inorganic structure stabilizer, 0.55 parts of melt behavior regulator, 0.55 parts of dispersant, 0.275 parts of leveling agent, and 0.155 parts of defoamer. Deionized water was added, and the mixture was stirred at 500 r / min for 60 min to obtain a glazing slurry. The glazing slurry was applied to the surface of the bone china body and dried at 40°C for 2 h to form a glaze layer.

[0062] S3, firing

[0063] The glazed bone china body is fired at 1200℃ and held at that temperature for 60 minutes. Then it is cooled to room temperature in the kiln to obtain bone china products.

[0064] Comparative Example 3: This comparative example aims to verify the effect of removing functional organic small molecules on the stability of the glaze structure, the hardness of the glaze surface, and the scratch resistance under the condition of synergistic modification of the base glaze.

[0065] S1, Preparation of synergistically modified base glaze

[0066] The following raw materials were weighed according to the following weight proportions: 45 parts potassium feldspar, 22 parts quartz, 18 parts bone ash, 10 parts wollastonite, 1.0 part γ-aminopropyltriethoxysilane, and 0.8 parts boric acid. Potassium feldspar, quartz, bone ash, and wollastonite were added to a ball mill, along with deionized water. Wet ball milling was performed at a speed of 300 r / min, a milling time of 9 h, and a ball-to-material ratio of 2.0:1 to obtain a basic glaze slurry. γ-aminopropyltriethoxysilane and boric acid were added at 30°C and mixed under continuous stirring for 2 h to obtain a synergistically modified glaze slurry. The obtained synergistically modified glaze slurry was dried at 100°C for 12 h, then pulverized and passed through a 150-mesh sieve to obtain the synergistically modified basic glaze.

[0067] S2, Glazing

[0068] 90 parts of synergistically modified base glaze were mixed with 1.75 parts of silica-oxygen structure regulator, 1.15 parts of inorganic structure stabilizer, 0.55 parts of melt behavior modifier, 0.55 parts of dispersant, 0.275 parts of leveling agent, and 0.155 parts of defoamer. Deionized water was added, and the mixture was stirred at 500 r / min for 60 min to obtain a glazing slurry. The glazing slurry was applied to the surface of the bone china body and dried at 40℃ for 2 h to form a glaze layer.

[0069] S3, firing

[0070] The glazed bone china body is fired at 1200℃ and held at that temperature for 60 minutes. Then it is cooled to room temperature in the kiln to obtain bone china products.

[0071] Performance testing:

[0072] 1. Test method for abrasion resistance of glaze surface

[0073] The abrasion resistance of the glaze was tested on the bone china samples prepared in the examples and comparative examples. Before the test, the sample surface was cleaned and dried. Under the specified load conditions, the glaze was subjected to a reciprocating friction test using a standard abrasion medium, and the number of friction cycles and the stroke were kept consistent. After the test, the influence of different glaze systems on the abrasion resistance of the glaze was evaluated by comparing the degree of abrasion marks, changes in gloss, and visible wear differences of different samples.

[0074] 2. Test method for scratch resistance of glaze surface

[0075] The glaze scratch resistance test method was used to test the sample of the example and the comparative example. Under the same load conditions, the glaze surface was scratched unidirectionally using a metal needle or hard scratcher of specified hardness, and the appearance of continuous visible scratches or glaze layer damage was recorded. By comparing the scratch performance of different samples under the same test conditions, the influence of glaze composition and modification method on the scratch resistance of the glaze was evaluated.

[0076] 3. Test method for chemical corrosion resistance of glaze surface

[0077] Bone china samples prepared in the examples and comparative examples were respectively immersed in acidic and alkaline solutions of a certain concentration and kept at a constant temperature for a specified time. After immersion, the samples were taken out, washed with deionized water and dried. The stability of the glaze surface of different samples was compared by observing whether phenomena such as loss of gloss, discoloration, corrosion spots or surface roughness appeared. Thus, the influence of the glaze system on the chemical corrosion resistance of the glaze surface was evaluated.

[0078] 4. Test method for the resistance of glaze to thermal cycling

[0079] The bone china samples prepared in the examples and comparative examples were subjected to thermal cycling tests. The samples were subjected to multiple alternating cycles between high-temperature and low-temperature environments, with each cycle lasting the same amount of time. After the test, the stability and durability of different glaze systems under thermal stress were evaluated by observing whether cracks, peeling, loss of gloss, or other visible defects appeared on the glaze surface.

[0080] Table 1. Comparison of performance test results of bone china in the examples and comparative examples.

[0081] Sample number Glaze abrasion resistance (mg) Critical load for scratch resistance (N) Gloss retention rate after chemical corrosion resistance (%) Number of thermal cycles until failure (times) Example 1 6.8 18.5 91.2 42 Example 2 3.2 24.6 97.8 68 Example 3 5.4 20.1 93.5 55 Comparative Example 1 12.6 11.4 82.3 21 Comparative Example 2 14.1 9.8 79.6 18 Comparative Example 3 9.9 13.2 86.5 30

[0082] According to Table 1 and Figure 2 As shown, the bone china prepared in the examples and the comparative examples have significant differences in performance indicators such as glaze wear resistance, critical load for scratch resistance, gloss retention rate after chemical corrosion, and number of cold and hot cycles to failure. This indicates that different glaze compositions and modification methods have an important impact on the comprehensive performance of bone china glaze.

[0083] In terms of glaze wear resistance, the overall performance of the example samples was better than that of the comparative examples. The wear resistance of the glaze in Example 2 was only 3.2 mg, which was significantly lower than that of Example 1 (6.8 mg) and Example 3 (5.4 mg), and also significantly lower than that of Comparative Examples 1 (12.6 mg), 2 (14.1 mg), and 3 (9.9 mg), respectively. This indicates that under the median group ratio and process conditions, the synergistic effect of the synergistic modification of the base glaze and the functional organic small molecules can effectively reduce the degree of glaze wear.

[0084] Regarding the scratch resistance of the glaze, the critical scratch resistance load of Example 2 reached 24.6N, which is significantly higher than 18.5N of Example 1 and 20.1N of Example 3. It is also significantly higher than the highest test result of only 13.2N in the comparative sample, indicating that the glaze layer’s resistance to external mechanical scratches is significantly enhanced when synergistically modified base glaze and functional organic small molecules are present.

[0085] Regarding chemical corrosion resistance, the gloss retention rate of the glaze in Example 2 after being treated with chemical media reached 97.8%, which is higher than 91.2% in Example 1 and 93.5% in Example 3. In contrast, the gloss retention rate of the comparative sample was only 79.6% to 86.5%. This indicates that the synergistic modification system, while improving the hardness of the glaze, did not weaken the chemical stability of the glaze layer. On the contrary, it has a positive effect on maintaining the appearance of the glaze.

[0086] In terms of resistance to thermal cycling, all the sample examples showed good thermal stability. Among them, Example 2 could withstand 68 cycles in the thermal cycling test without failure, which was significantly higher than the 42 cycles of Example 1 and the 55 cycles of Example 3, and also significantly better than the 18-30 cycles of the comparative sample. This indicates that the synergistic modification of the glaze system helps to alleviate thermal stress concentration and improve the durability of the glaze layer.

[0087] In summary, a comprehensive analysis of the performance test results in Table 1 shows that bone china using synergistically modified base glaze and introducing functional organic small molecules exhibits significant advantages in terms of glaze wear resistance, scratch resistance, chemical corrosion resistance, and resistance to thermal cycling. Among them, Example 2 achieved the best level in all performance indicators, fully demonstrating that the component ratio and modification method adopted in this invention can achieve a synergistic improvement in glaze hardness and performance.

Claims

1. A type of bone china with high glaze hardness, characterized in that, The bone china comprises the following raw materials in parts by weight: 85-95 parts of synergistic modified base glaze; 0.1-2.0 parts of functional organic small molecules; 0.5-3.0 parts of silicon-oxygen structure regulator; 0.3-2.0 parts of inorganic structure stabilizer; 0.1-1.0 parts of melt behavior regulator; 0.1-1.0 parts of dispersant; 0.05-0.5 parts of leveling agent; and 0.01-0.3 parts of defoamer. The synergistic modified base glaze is a modified glaze system formed by introducing feldspar, quartz, bone ash, and wollastonite as base glaze minerals, and synergistically regulating the silicon-oxygen network structure through the introduction of γ-aminopropyltriethoxysilane and boric acid during ball milling and firing. The functional organic small molecule is adamantane-1,3-dicarboxylic acid.

2. The high-glaze-hardness bone china according to claim 1, characterized in that, The synergistically modified base glaze comprises the following raw materials in parts by weight: 35-55 parts potassium feldspar; 15-30 parts quartz; 10-25 parts bone ash; 5-15 parts wollastonite; 0.3-2.0 parts γ-aminopropyltriethoxysilane; and 0.2-1.5 parts boric acid.

3. A high-glaze-hardness bone china according to claim 1 or 2, characterized in that, The preparation method of the synergistic modified base glaze includes the following steps: (1) Weigh potassium feldspar, quartz, bone ash and wollastonite according to the formula ratio, add them to the ball milling equipment, add deionized water for wet ball milling treatment, and obtain a uniformly dispersed base glaze slurry. (2) Add γ-aminopropyltriethoxysilane and boric acid to the base glaze slurry, and continue ball milling or mixing and dispersing under stirring conditions to uniformly introduce the modified components into the base glaze system and obtain synergistic modified glaze slurry; (3) The synergistic modified glaze slurry is dried, then crushed and sieved to obtain the synergistic modified base glaze.

4. The high-glaze-hardness bone china according to claim 3, characterized in that, The reaction conditions for step (1) are: ball milling speed of 200-400 r / min, ball milling time of 6-12 h, and ball-to-material ratio of (1.5-3.0):

1.

5. A high-glaze-hardness bone china according to claim 3, characterized in that, The reaction conditions for step (2) are as follows: γ-aminopropyltriethoxysilane and boric acid are added at 20-40°C and mixed for 1-4 hours with continuous stirring.

6. A high-glaze-hardness bone china according to claim 3, characterized in that, The reaction conditions for step (3) are drying at 80-120℃ for 6-24 hours, followed by pulverization and passing through a 100-200 mesh sieve.

7. The high-glaze-hardness bone china according to claim 1, characterized in that, The silicon-oxygen structure regulator is a mixture of tetraethoxysilane and γ-aminopropyltriethoxysilane in a mass ratio of (3-8):1; the inorganic structure stabilizer is a mixture of zirconium oxide and wollastonite in a mass ratio of (1-5):1; the melt behavior regulator is a mixture of boric acid and lithium carbonate in a mass ratio of (2-6):1; the dispersant is a mixture of sodium hexametaphosphate and sodium polyacrylate in a mass ratio of (1-4):1; the leveling agent is a mixture of polydimethylsiloxane and polyether-modified silicone oil in a mass ratio of (1-3):1; and the defoamer is a mixture of organosilicon defoamer and mineral oil in a mass ratio of (1-5):

1.

8. A method for preparing high-glaze-hardness bone china, characterized in that, The preparation method includes the following steps: S1, the synergistic modified base glaze is mixed with silicon-oxygen structure regulator, inorganic structure stabilizer, melt behavior regulator, dispersant, leveling agent, defoamer and functional organic small molecules, and deionized water is added for stirring and dispersion to obtain a uniform glazing slurry. S2, apply the glazing slurry to the surface of the bone china body, and dry it at low temperature to form a glaze layer; S3 involves firing the bone china body at high temperature and then cooling it to obtain bone china products with high glaze hardness.

9. The method for preparing high-glaze-hardness bone china according to claim 8, characterized in that, The reaction conditions for step S1 are as follows: deionized water is added at room temperature and stirred and dispersed, with a stirring speed of 300-800 r / min and a stirring time of 30-120 min.

10. The method for preparing high-glaze-hardness bone china according to claim 8, characterized in that, The reaction conditions for step S2 are drying at 20-60℃ for 0.5-4 hours after glazing; the reaction conditions for step S3 are firing at 1150-1250℃ for 30-120 minutes, followed by cooling to room temperature in the furnace.

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