Preparation method of medical ceramic tableware with antibacterial and antiviral functions

Abstract

The present application relates to the technical field of medical utensils, and particularly relates to a preparation method of medical ceramic utensils with antibacterial and antiviral functions, wherein calcined pine ash is calcined at 900 DEG C for 30 minutes, and soluble salts are removed by washing with water and sieving; the pretreated calcined pine ash, high-iron high-temperature black pottery clay and transparent glaze are mixed; the raw materials are mixed according to a weight ratio of 25% of purple gold clay, 35% of purple clay, 22% of porcelain stone, 10% of bentonite and 8% of wood ash; the blank is sintered by segmented temperature rising; the glaze slurry is applied to the surface of the sintered blank; the blank after the glaze is applied and dried is placed in a reducing atmosphere with a carbon monoxide concentration of 3% to 4%; the blank is heated by segmented temperature rising to 1260 DEG C; the blank is cooled to 800 DEG C and then naturally cooled to room temperature, so that the target medical ceramic utensil is obtained; through the synergistic formulation design of natural wood ash, high-iron black pottery clay and barium carbonate-free transparent glaze and the precise reduction flame sintering process, the problems of external excitation dependence of medical ceramic antibacterial and antiviral functions, hidden safety hazards and insufficient durability are solved.

Description

Technical Field

[0001] This invention relates to the field of medical vessel technology, and in particular to a method for preparing a medical ceramic vessel with both antibacterial and antiviral functions. Background Technology

[0002] Medical ceramic ware, due to its advantages such as good chemical stability, resistance to high-temperature sterilization, and ease of cleaning, is widely used in medical diagnosis and treatment, nursing consumables, and other scenarios, and is an indispensable instrument in the medical field. To meet the needs of antibacterial and antiviral treatment, existing antibacterial medical ceramics mainly achieve the inhibition or killing of bacteria, viruses, and other microorganisms by adding metal ion antibacterial agents, photocatalytic materials, or chemical antibacterial components to the glaze or body.

[0003] In existing technologies, most antibacterial and antiviral ceramics rely on the slow-release effect of metal ions and chemical antibacterial components to achieve their function. This poses both long-term biosafety risks and a tendency for the antibacterial effect to diminish due to the loss of functional components, making it difficult to achieve lasting protection. Some photocatalytic products require external conditions such as ultraviolet light to activate their antibacterial activity, which cannot be adapted to the complex lighting environment of medical settings, thus limiting their antibacterial and antiviral functions. All of these technologies fail to meet the core requirements of medical settings for efficient, safe, and long-lasting antibacterial and antiviral effects. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing medical ceramic vessels with both antibacterial and antiviral functions. This addresses the problem that most existing antibacterial and antiviral ceramics rely on the slow-release effect of metal ions or chemical antibacterial components, which not only poses potential biosafety risks with long-term use but also easily diminishes their antibacterial and antiviral effects as components are lost, making it difficult to achieve long-lasting and stable protection. Furthermore, some photocatalytic products require external conditions such as ultraviolet light for excitation, which cannot adapt to the complex lighting environment in medical settings, resulting in limited antibacterial and antiviral functions and failing to fully meet the core requirements of medical settings for efficient, safe, and long-lasting antibacterial and antiviral protection.

[0005] To achieve the above objectives, the present invention provides a method for preparing medical ceramic ware with both antibacterial and antiviral functions, comprising the following steps:

[0006] Calcined pine ash is calcined at 900℃ for 30 minutes, washed with water to remove soluble salts, dried and passed through a 200-mesh sieve. High-iron high-temperature black pottery clay is ball-milled to 200 mesh and air-dried until the moisture content is <8%. Transparent glaze is ground into fine powder and passed through a 200-mesh sieve. All raw materials are pre-treated and ready for use.

[0007] Take pretreated calcined pine ash, high-iron high-temperature black pottery clay and transparent glaze, mix them in a weight ratio of 16%:74%:10%, then add water at a ratio of 1:0.75 (total dry weight: water), add 0.1% CMC and wet ball mill for 7 hours, adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³, and set aside for later use;

[0008] The raw materials are mixed in the following weight ratios: 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite and 8% wood ash. The mixture is then wet-milled, slurry-pressed and dehydrated, vacuum-kneaded, homogenized and aged for 1.5 months, and then vacuum-kneaded again before shaping, trimming and drying. The prepared blanks are then ready for use.

[0009] The resulting green body was bisque-fired using a segmented heating method, held at 800℃ for 60 minutes, and then naturally cooled to room temperature. The bisque-fired green body was then set aside.

[0010] Apply the glaze slurry to the surface of the bisque-fired body, controlling the glaze thickness to 1.2-1.5 mm, and let it dry until there are no traces of flow in the glaze layer.

[0011] After the glaze is applied and dried, the body is placed in a reducing atmosphere with a carbon monoxide concentration of 3%-4%, and the temperature is raised to 1260℃ in stages. Depending on the glaze color requirements, the holding time for the bluish-gray glaze is 50 minutes, and the holding time for the yellowish-brown glaze is 40 minutes. After cooling to 800℃, the body is allowed to cool naturally to room temperature to obtain the target medical ceramic ware.

[0012] Among them, the steps of pre-treating raw materials as follows are: calcining pine ash at 900℃ for 30 minutes, washing with water to remove soluble salts, drying and passing it through a 200-mesh sieve; ball milling high-iron high-temperature black pottery clay to 200 mesh and air-drying it until the moisture content is <8%; and grinding transparent glaze into fine powder and passing it through a 200-mesh sieve. The transparent glaze is a barium borosilium-based transparent glaze or a calcium borosilium-based transparent glaze; The barium carbonate-free borosilicate transparent glaze comprises, by weight percentage: 35% potassium feldspar, 15% quartz, 20% borax, 12% calcite, 8% talc, and 10% zinc oxide; The calcium-boron transparent glaze comprises, by weight percentage: 25% sodium feldspar, 18% quartz, 15% boric acid, 15% limestone, 10% talc, 7% zinc oxide, and 10% magnesium carbonate.

[0013] Among them, the steps of pre-treating raw materials as follows are: calcining pine ash at 900℃ for 30 minutes, washing with water to remove soluble salts, drying and passing it through a 200-mesh sieve; ball milling high-iron high-temperature black pottery clay to 200 mesh and air-drying it until the moisture content is <8%; and grinding transparent glaze into fine powder and passing it through a 200-mesh sieve. The calcined pine ash was washed with three stages of deionized water. After each wash, it was allowed to stand for 30 minutes to settle. After the third wash, the conductivity of the supernatant was ≤50μS / cm. The drying temperature was 110℃-120℃ and the drying time was 2 hours.

[0014] The process involves mixing pretreated calcined pine ash, high-iron high-temperature black pottery clay, and transparent glaze in a weight ratio of 16%:74%:10%. Then, water is added at a dry weight to water ratio of 1:0.75. After adding 0.1% CMC, the mixture is wet-milled for 7 hours to adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³. This mixture is then set aside for later use. The grinding media of the wet ball mill are alumina balls with a diameter of 5-10 mm, and the slurry temperature is controlled to be ≤40℃ during the grinding process. After the glaze is prepared, let it stand at 20℃-25℃ for 24-36 hours to age. Stir it at 300r / min for 15 minutes before use.

[0015] The process involves mixing pretreated calcined pine ash, high-iron high-temperature black pottery clay, and transparent glaze in a weight ratio of 16%:74%:10%. Then, water is added at a dry weight to water ratio of 1:0.75. After adding 0.1% CMC, the mixture is wet-milled for 7 hours to adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³. This mixture is then set aside for later use.

[0016] The ratio of material, milling balls, and water in a wet ball mill is 1:2:0.75.

[0017] Among them, in the process of mixing raw materials in the following weight ratios: 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite and 8% wood ash, wet ball milling, slurry pressing and dewatering, vacuum kneading, homogenization and aging for 1.5 months, secondary vacuum kneading, shaping, trimming and drying, and then preparing the green body for later use:

[0018] The ratio of material to grinding balls to water in wet ball milling is 1:1.8:0.7. The grinding time is 18 hours, and the fineness is 4%-6% residue on a 10,000-mesh sieve.

[0019] Vacuum kneading: vacuum degree ≥ -0.09MPa, rotation speed 30r / min, clay strip porosity < 2% after secondary kneading, and finally dried to moisture content < 5%.

[0020] Among them, in the steps of applying glaze slurry to the surface of the bisque-fired body, controlling the glaze thickness to 1.2-1.5mm, and drying the glaze until there are no flow marks:

[0021] After glazing, the body should be dried in an environment of 20℃-25℃ and relative humidity of 40%-50% for 2-4 hours.

[0022] In the process of placing the glazed and dried ceramic body in a reducing atmosphere with a carbon monoxide concentration of 3%-4%, heating it in stages to 1260℃, and holding it at that temperature for 50 minutes for the bluish-gray glaze and 40 minutes for the yellowish-brown glaze, depending on the desired glaze color, and then cooling it to 800℃ before allowing it to cool naturally to room temperature to obtain the target medical ceramic vessel:

[0023] The carbon monoxide concentration in the reducing atmosphere is monitored in real time by an infrared gas analyzer, with a fluctuation range of ≤±0.2%; the cooling rate from 800℃ to 500℃ is ≤50℃ / h, and free cooling is allowed below 500℃.

[0024] This invention also includes a medical ceramic vessel with antibacterial and antiviral functions, the raw materials of which, by percentage, are:

[0025] The ingredients are: 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash. The glaze material consists of 16% calcined pine ash, 74% high-iron high-temperature black pottery clay, and 10% transparent glaze.

[0026] The surface hardness of the glaze layer of ceramic ware is ≥6H, the water absorption rate is ≤0.5%, and the sterilization rate against Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli, and Myxocytocium chrysogenum is ≥99.9% within 2 hours.

[0027] This invention discloses a method for preparing a medical ceramic vessel with both antibacterial and antiviral functions. The method involves: calcining pine ash at 900℃ for 30 minutes, washing with water to remove soluble salts, drying, and passing through a 200-mesh sieve; ball milling high-iron high-temperature black pottery clay to 200 mesh and air-drying until the moisture content is <8%; grinding transparent glaze into fine powder and passing through a 200-mesh sieve. All raw materials are pre-treated and set aside. The pre-treated calcined pine ash, high-iron high-temperature black pottery clay, and transparent glaze are mixed in a weight ratio of 16%:74%:10%. Water is added at a dry weight:water ratio of 1:0.75. 0.1% CMC is added, and the mixture is wet-milled for 7 hours. The glaze slurry specific gravity is adjusted to 1.75-1.85 g / cm³. The mixture is then prepared and set aside. Finally, a mixture is prepared using 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and grass... Wood ash (8% by weight) is mixed with raw materials, which are then wet-milled, dehydrated by suction filtration, vacuum-kneaded, homogenized and aged for 1.5 months, and then vacuum-kneaded again before shaping, trimming and drying. The prepared blanks are then set aside. The resulting blanks are bisque-fired using a segmented heating method, held at 800℃ for 60 minutes and then naturally cooled to room temperature. The bisque-fired blanks are then set aside. Glaze is applied to the surface of the bisque-fired blanks, with the glaze thickness controlled at 1.2-1.5 mm. After glazing, the blanks are dried until there are no flow marks. The glazed and dried blanks are then placed in a reducing atmosphere with a carbon monoxide concentration of 3%-4%, and heated in segments to 1260℃. Depending on the desired glaze color, the holding time is 50 minutes for the bluish-gray glaze and 40 minutes for the yellowish-brown glaze. The blanks are then cooled to 800℃ and then naturally cooled to room temperature to obtain the target medical ceramic ware. This method provides stable and long-lasting antibacterial and antiviral effects. The resulting ceramic ware achieves a 3-log sterilization effect within one hour, and within two hours, the sterilization rate against Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli, and Myxococcus faecalis is ≥99.9%, with colony counts continuously decreasing within 150 minutes. After 30 cycles of high-temperature steam sterilization, the sterilization rate remains above 99.7%, avoiding the effect attenuation caused by the loss of antibacterial components in existing technologies. It operates without external conditions; the potassium and calcium elements from the plant ash in the glaze and the iron ions from the high-iron black clay form stable and synergistic antibacterial sites, maintaining effectiveness even under normal medical conditions, making it suitable for complex medical environments. It also boasts high biosafety and is risk-free. The raw materials are all from natural minerals or plants, without the addition of metal ions such as nano-silver and nano-copper, or chemical antibacterial agents. The transparent glaze formula does not contain harmful substances such as barium carbonate, and has been tested for biosafety level 1, completely avoiding the safety risks such as chronic poisoning that may be caused by long-term use. The mechanical properties are adapted to medical needs, with a glaze hardness of ≥6H, a water absorption rate of ≤0.5%, wear resistance, and corrosion resistance. It can withstand high-temperature disinfection, repeated washing, and long-term use in medical settings without affecting the basic performance of ceramic ware. The preparation cost is low and environmentally friendly, using widely available plant ash as the core raw material, which reduces raw material costs. The preparation process has no harmful gas emissions, conforms to the concept of green production, and is easy to promote and apply on a large scale. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0029] Figure 1 This is a test diagram of the bactericidal efficacy of the plant ash glaze of the present invention.

[0030] Figure 2 This is a flowchart of the steps of the first embodiment of the present invention.

[0031] Figure 3 This is a flowchart of the steps of the second embodiment of the present invention.

[0032] Figure 4 This is a flowchart of the steps of the third embodiment of the present invention. Detailed Implementation

[0033] The embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

[0034] This invention provides a method for preparing medical ceramic ware with both antibacterial and antiviral functions, comprising the following steps:

[0035] S1: Calcine the pine ash at 900℃ for 30 minutes, wash it with water to remove soluble salts, dry it and pass it through a 200-mesh sieve. Grind the high-iron high-temperature black pottery clay to 200 mesh and air dry it until the moisture content is <8%. Grind the transparent glaze into fine powder and pass it through a 200-mesh sieve. All raw materials are pre-treated and ready for use.

[0036] S2: Take pretreated calcined pine ash, high-iron high-temperature black pottery clay and transparent glaze, mix them in a weight ratio of 16%:74%:10%, then add water in a ratio of 1:0.75 (total dry weight: water), add 0.1% CMC and wet ball mill for 7 hours, adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³, and set aside for later use;

[0037] S3: The raw materials are mixed in the following weight ratios: 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite and 8% wood ash. The mixture is then wet-milled, slurry-pressed and dewatered, vacuum-kneaded, homogenized and aged for 1.5 months, and then shaped, trimmed and dried after a second vacuum kneading. The prepared blanks are then ready for use.

[0038] S4: The obtained green body is bisque fired by segmented heating, held at 800℃ for 60 minutes and then naturally cooled to room temperature. The bisque fired green body is ready for use.

[0039] S5: Apply the glaze slurry to the surface of the bisque-fired body, controlling the glaze thickness to 1.2-1.5mm, and let it dry until there are no traces of flow in the glaze layer after glazing.

[0040] S6: Place the glazed and dried body in a reducing atmosphere with a carbon monoxide concentration of 3%-4%, and raise the temperature in stages to 1260℃. Depending on the glaze color requirements, the holding time for the bluish-gray glaze is 50 minutes, and the holding time for the yellowish-brown glaze is 40 minutes. After cooling to 800℃, allow it to cool naturally to room temperature to obtain the target medical ceramic ware.

[0041] The medical ceramic material prepared by this invention can be used to directly manufacture medical diagnostic ceramics, medical medicine storage bottles, nursing ceramic containers, and other holding vessels. Its formula system and preparation process can be fine-tuned to adapt to medical implant scenarios, including dental prostheses, ceramic components for dental implants, and ceramic implants for orthopedic bone defect repair. The green body of this invention uses a precise ratio of 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash. After vacuum clay refining at a vacuum degree ≥-0.09MPa, the porosity of the clay strips after secondary refining is <2%. The water absorption rate of the green body after bisque firing is stable and controllable. The final fired product has a water absorption rate ≤0.5% and a glaze surface hardness ≥6H. These physicochemical properties fully match the core requirements of medical implant ceramics for density, mechanical strength, and wear resistance, and can meet the long-term service requirements of medical implant scenarios.

[0042] The entire research and development and performance verification process of this invention strictly adheres to relevant national medical-grade standards, and all core indicators meet the compliance requirements for medical-grade materials: Firstly, biosafety compliance: the raw materials of this invention are all of natural mineral or plant origin, without the addition of metal ion antibacterial agents such as nano-silver and nano-copper, or chemical antibacterial components. The transparent glaze uses a barium carbonate-free borosilicate / calcium borosilicate formula, completely avoiding the leaching risk of harmful substances such as barium carbonate. Testing has shown that the biosafety meets Level 1 safety standards, fully complying with the core requirements for biosafety of medical materials in the GB / T16886 series of standards for biological evaluation of medical devices. Secondly, antibacterial performance compliance: the product of this invention is effective against Bacillus subtilis, Pseudomonas aeruginosa, and Escherichia coli within 2 hours. The sterilization rate of bacteria and xanthophyte is ≥99.9%, and a 3-log sterilization effect can be achieved within 1 hour. After 30 high-temperature steam sterilizations, the sterilization rate still remains above 99.7%. The high efficiency and durability of the antibacterial performance meet the performance evaluation standards for medical antibacterial materials. At the same time, it fully complies with the antibacterial and sterilization resistance requirements for pharmaceutical ceramic containers in the "Standard for Ceramic Medicine Bottles (Trial)". Thirdly, the physicochemical properties are compliant. The present invention uses a process of segmented heating and bisque firing, and precise firing at 1260℃ in a reducing atmosphere with a carbon monoxide concentration of 3%-4%. The resulting products have excellent wear resistance, corrosion resistance and temperature change resistance. They can withstand repeated high-temperature steam sterilization and chemical cleaning operations in medical scenarios and are suitable for the use requirements of all medical scenarios.

[0043] Calcined pine ash, as a natural plant-based raw material, is rich in minerals such as potassium and calcium. After calcination and purification, the porous structure formed can adsorb microorganisms. Its mineral components can disrupt the integrity of bacterial cell membranes. Moreover, it is widely available, environmentally friendly, and non-toxic, avoiding the safety risks of chemical antibacterial agents or metal ions. The iron ions in high-iron, high-temperature black pottery clay have strong oxidizing properties, which can inactivate the proteins and nucleic acids of bacteria and viruses. When combined with calcined pine ash, the iron ions can embed into the porous structure of the pine ash to form stable antibacterial sites, significantly improving the antibacterial durability. At the same time, the high density of black pottery clay can ensure the mechanical strength of ceramic ware. The transparent glaze uses a barium-boron-silicon or calcium-boron-based formula that is free of harmful substances and has high biocompatibility. The dense glass phase it forms can encapsulate antibacterial components and prevent loss, while also improving the smoothness and wear resistance of the glaze layer, making it suitable for the repeated sterilization requirements of medical applications. In the raw materials of the body, purple clay and purple mud ensure plasticity and adhesion, porcelain stone increases density, bentonite enhances forming stability, and plant ash further optimizes the air permeability and antibacterial synergy of the body. After the components are mixed in proportion, the body and glaze layer can be tightly bonded, avoiding cracking during firing. All the above raw materials are of natural mineral or plant origin, free of harmful components such as nano silver and barium carbonate, and through synergistic effects, they achieve the core goal of highly effective antibacterial properties without external stimulation and long-term safe and stable use, solving the safety hazards and efficacy decay problems of existing medical ceramics, while also meeting the process requirements of large-scale production.

[0044] In addition, please see Figure 1 Add 20 µL of thawed bacterial culture to 10 mL of LB lysogeny broth; incubate these bacterial suspensions overnight at 30°C for 15–18 hours on an Eppendorf shaker, then transfer them to polypropylene rapid separation tubes (Fisher Healthcare) and incubate once more for 48 hours; subsequently, vortex the culture on a VWRS Scientific mixer and allow it to settle; aspirate the upper two-thirds of the suspension from each tube and measure the OD600 value using a SmartSpec3000 spectrophotometer (Bio-Rad) to estimate the bacterial density; finally, dilute the culture with phosphate buffer (Becton Dickinson) to bring the bacterial inoculum concentration close to the target value of 1.0 × 10⁻⁶. 7 1 colony-forming unit (CFU) / mL; add an organic soil load containing 0.25 mL of 5% fetal bovine serum (Becton Dickinson) and 0.05 mL of Triton X-100 (Amresco ProPure) to 4.70 mL of bacterial suspension to aid in the spread of the inoculum;

[0045] Inoculate each test strip with 20 µL of bacterial test culture. Use a sterile pipette tip (QSP) to spread the inoculum evenly on the test strip, ensuring complete and uniform coverage, and spreading it as far as possible to the edges of the test strip; then place the test strip in a controlled environment of 45% relative humidity and 25°C for 120 minutes.

[0046] After a 120-minute exposure period, the test strips were neutralized in LB lysogeny broth. The neutralized solution was serially diluted tenfold and then inoculated onto 1.5% LB agar plates using the standard spread plate method. The plates were then incubated at 37°C for 48 hours to obtain a countable number of viable colonies (approximately 20-200 colonies per plate).

[0047] The results showed that the colony counts of all four bacteria decreased by 99.9% or more within 2 hours; the colony counts continued to decline within 150 minutes and reached the 3-log bactericidal effect specified by the U.S. Environmental Protection Agency (EPA) in about 1 hour; these results demonstrate that wood ash glaze has strong antibacterial properties.

[0048] Example 1, please refer to Figure 2 This invention provides a method for preparing medical ceramic ware with both antibacterial and antiviral functions, comprising the following steps:

[0049] S101: Place the pine ash in a kiln and calcine at 900℃ for 30 minutes. After taking it out, wash it with three-stage deionized water. After each wash, let it stand and settle for 30 minutes. After the third wash, the conductivity of the supernatant was measured to be 42μS / cm. Place the washed pine ash in an oven at 115℃ and dry it for 2 hours. After taking it out, sieve it through a 200-mesh sieve.

[0050] S102: Weigh out 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash by weight percentage, mix them, and put them into a wet ball mill. Add alumina balls with a diameter of 8-12mm. Grind for 18 hours at a material:ball:water ratio of 1:1.8:0.7. Check the fineness and the residue on a 10,000-mesh sieve is 5%. Dewater the mud cake by vacuum filtration until the moisture content is 27%. Vacuum knead the mud under vacuum conditions of -0.095MPa and 30r / min. After homogenization and aging for 1.5 months, vacuum knead the mud again until the moisture content is 23.5%. Ball mill to 200 mesh and air dry until the moisture content is 7%.

[0051] S103: Weigh out 35% potassium feldspar, 15% quartz, 20% borax, 12% calcite, 8% talc, and 10% zinc oxide by weight percentage, mix them, grind them into fine powder using an air jet mill, and pass them through a 200-mesh sieve.

[0052] S104: Weigh out 16% pretreated calcined pine ash, 74% high-iron high-temperature black pottery clay, and 10% barium borosilicate transparent glaze by weight percentage, and mix them as dry material; add water at a ratio of total dry material weight to water of 1:0.75, add 0.1% CMC as a suspending agent, put it into a wet ball mill, add alumina balls with a diameter of 5-10mm, and grind for 7 hours at a ratio of material:milling balls:water of 1:2:0.75, controlling the slurry temperature at 35℃ during the grinding process; after grinding, adjust the glaze slurry specific gravity to 1.80g / cm³, let it stand and age at 22℃ for 30 hours, and stir at 300r / min for 15 minutes before use;

[0053] S105: The high-iron-content, high-temperature black pottery clay, after being vacuum-refined twice, is shaped into a medical bowl blank using a potter's wheel, with a diameter of 12cm and a height of 8cm. The blank is then naturally dried for 48 hours at 25℃ and 50% relative humidity. The blank is then trimmed with a trimming knife until the surface is smooth, and after trimming, it is dried again until the moisture content is 4%.

[0054] S106: The dried green body was placed in an electric kiln and heated according to the curve of room temperature to 600℃ at a heating rate of 60℃ / h and 600℃ to 800℃ at a heating rate of 30℃ / h. The green body was held at 800℃ for 60 minutes to complete the bisque firing and then naturally cooled to room temperature. The water absorption rate of the green body after bisque firing was measured to be 8%.

[0055] S107: First, pour the glaze into the interior of the bisque-fired body and let it swirl for 10 seconds, then pour out the excess glaze. Next, use a wool brush to evenly apply the glaze to the exterior of the body, controlling the glaze thickness to be 1.3mm. After glazing, allow it to air dry naturally for 3 hours at 23℃ and 45% relative humidity until there are no traces of flow in the glaze layer.

[0056] S108: Place the glazed and dried body into a gas kiln, introduce a reducing atmosphere with a carbon monoxide concentration of 3.5%, and monitor in real time using an infrared gas analyzer with a fluctuation range of ±0.1%; heat according to a curve of 80℃ / h for heating from room temperature to 1000℃ and 40℃ / h for heating from 1000℃ to 1260℃; the target glaze color is bluish-gray glaze, and hold at 1260℃ for 50 minutes; after holding, cool down to 800℃, and then cool down at a rate of 45℃ / h from 800℃ to 500℃, and allow to cool freely to room temperature below 500℃ to obtain a bluish-gray glazed medical ceramic bowl.

[0057] Example 2, please refer to Figure 3 This invention provides a method for preparing medical ceramic ware with both antibacterial and antiviral functions, comprising the following steps:

[0058] S201: Calcine at 900℃ for 30 minutes, wash with three-stage deionized water, dry at 115℃ for 2 hours, and pass through a 200-mesh sieve;

[0059] S202: Weigh out 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash by weight percentage, mix them, and put them into a wet ball mill. Add alumina balls with a diameter of 8-12mm. Grind for 18 hours at a material:ball:water ratio of 1:1.8:0.7. The fineness test shows a residue of 4.8% on a 10,000-mesh sieve. Dewater the mud cake by vacuum filtration until the moisture content is 26.5%. Vacuum knead the mud under vacuum conditions of -0.09MPa and 30r / min. After homogenization and aging for 1.5 months, vacuum knead the mud again until the moisture content is 24%. Ball mill the mud to 200 mesh and air dry it until the moisture content is 6.5%.

[0060] S203: Weigh out 25% sodium feldspar, 18% quartz, 15% boric acid, 15% limestone, 10% talc, 7% zinc oxide, and 10% magnesium carbonate by weight percentage, mix them, grind them into fine powder using an air jet mill, and pass them through a 200-mesh sieve.

[0061] S204: Weigh 16% pretreated calcined pine ash, 74% high-iron high-temperature black pottery clay, and 10% calcium-boron transparent glaze by weight percentage, and mix them as dry material; add water at a ratio of total dry material weight to water of 1:0.75, add 0.1% CMC as a suspending agent, put it into a wet ball mill, add alumina balls with a diameter of 5-10mm, and grind for 7 hours at a ratio of material:milling balls:water of 1:2:0.75, controlling the slurry temperature at 36℃ during the grinding process; after grinding, adjust the glaze slurry specific gravity to 1.78g / cm³, let it stand and age at 23℃ for 28 hours, and stir at 300r / min for 15 minutes before use;

[0062] S205: The high-iron-content, high-temperature black pottery clay, after being vacuum-refined twice, is shaped into a medical ceramic disc blank with a diameter of 15cm and a thickness of 0.8cm using a pressing machine. The blank is then naturally dried for 50 hours at 25℃ and 50% relative humidity. The blank is then trimmed with a trimming knife until the edges are smooth. After trimming, it is dried again until the moisture content is 3.8%.

[0063] S206: The dried green body was placed in an electric kiln and heated according to the curve of room temperature to 600℃ at a rate of 60℃ / h and 600℃ to 800℃ at a rate of 30℃ / h. The green body was held at 800℃ for 60 minutes to complete the bisque firing and then naturally cooled to room temperature. The water absorption rate of the green body after bisque firing was measured to be 7.8%.

[0064] S207: First, pour the glaze into the interior of the bisque-fired body and let it swirl for 8 seconds, then pour out the excess glaze. Next, use a wool brush to evenly apply the glaze to the exterior of the body, controlling the glaze thickness to 1.4mm. After glazing, allow it to air dry naturally for 3.5 hours at 24℃ and 46% relative humidity until there are no traces of flow in the glaze layer.

[0065] S208: Place the glazed and dried ceramic body into a gas kiln, introduce a reducing atmosphere with a carbon monoxide concentration of 3.2%, and monitor the concentration in real time using an infrared gas analyzer with a fluctuation range of ±0.1%. Heat the ceramic body according to a heating curve of 80℃ / h from room temperature to 1000℃ and 40℃ / h from 1000℃ to 1260℃. The target glaze color is yellowish-brown. Hold the ceramic body at 1260℃ for 40 minutes. After holding the ceramic body, cool the ceramic body to 800℃, and then cool it from 800℃ to 500℃ at a rate of 48℃ / h. Allow the ceramic body to cool freely to room temperature below 500℃ to obtain a yellowish-brown glazed medical ceramic plate.

[0066] Example 3, please refer to Figure 4 This invention provides a method for preparing medical ceramic ware with both antibacterial and antiviral functions, comprising the following steps:

[0067] S301: Calcine at 900℃ for 30 minutes, wash with three-stage deionized water, dry at 115℃ for 2 hours, and pass through a 200-mesh sieve;

[0068] S302: Weigh out 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash by weight percentage. Mix them and put them into a wet ball mill. Add alumina balls with a diameter of 8-12mm. Grind for 18 hours at a material:ball:water ratio of 1:1.8:0.7. The fineness test shows a residue of 4.5% on a 10,000-mesh sieve. Dewater the mud cake by vacuum filtration until the moisture content is 27.2%. Vacuum knead the mud under vacuum conditions of -0.092MPa and 30r / min. After homogenization and aging for 1.5 months, vacuum knead the mud again until the moisture content is 23.8%. Ball mill the mud to 200 mesh and air dry it until the moisture content is 7.2%.

[0069] S303: Mixed with potassium feldspar 35%, quartz 15%, borax 20%, calcite 12%, talc 8%, and zinc oxide 10%, and then ground and passed through a 200-mesh sieve.

[0070] S304: Weigh out 16% pretreated calcined pine ash, 74% high-iron high-temperature black pottery clay, and 10% barium borosilicate transparent glaze by weight percentage, and mix them as dry material; add water at a ratio of total dry material weight to water of 1:0.75, add 0.1% CMC as a suspending agent, put it into a wet ball mill, add alumina balls with a diameter of 5-10mm, and grind for 7 hours at a ratio of material:milling balls:water of 1:2:0.75, controlling the slurry temperature at 34℃ during the grinding process; after grinding, adjust the glaze slurry specific gravity to 1.76g / cm³, let it stand and age at 21℃ for 32 hours, and stir at 300r / min for 15 minutes before use;

[0071] S305: The high-iron-content, high-temperature black pottery clay, after being vacuum-refined twice, is shaped into a medical ceramic cup blank using a potter's wheel, with a diameter of 8cm and a height of 10cm. The blank is then naturally dried for 45 hours at 25℃ and 50% relative humidity. The blank is then trimmed with a trimming knife until the rim of the cup is smooth. After trimming, it is dried again until the moisture content is 4.2%.

[0072] S306: The dried green body was placed in an electric kiln and heated according to a curve of 60℃ / h for heating from room temperature to 600℃ and 30℃ / h for heating from 600℃ to 800℃. The green body was then held at 800℃ for 60 minutes to complete the bisque firing. After natural cooling to room temperature, the water absorption rate of the green body after bisque firing was measured to be 8.2%.

[0073] S307: First, pour the glaze into the interior of the bisque-fired body and let it swirl for 12 seconds, then pour out the excess glaze. Next, use a wool brush to evenly apply the glaze to the exterior of the body, controlling the glaze thickness to 1.2 mm. After glazing, allow it to air dry naturally for 2.5 hours at 22°C and 44% relative humidity until there are no flow marks on the glaze layer.

[0074] S308: Place the glazed and dried body into a gas kiln, introduce a reducing atmosphere with a carbon monoxide concentration of 3.8%, and monitor in real time using an infrared gas analyzer with a fluctuation range of ±0.1%; heat according to a curve of 80℃ / h for heating from room temperature to 1000℃ and 40℃ / h for heating from 1000℃ to 1260℃; the target glaze color is yellowish-brown glaze, and hold at 1260℃ for 40 minutes; after holding, cool down to 800℃, and then cool down at a rate of 42℃ / h from 800℃ to 500℃, and allow to cool freely to room temperature below 500℃ to obtain a yellowish-brown glazed medical ceramic cup.

[0075] The above-disclosed embodiments are merely one or more preferred embodiments of this application and should not be construed as limiting the scope of this application. Those skilled in the art can understand that all or part of the processes for implementing the above embodiments and equivalent changes made in accordance with the claims of this application still fall within the scope of this application.

Claims

1. A method for preparing a medical ceramic vessel with both antibacterial and antiviral functions, characterized in that, Includes the following steps: Calcined pine ash is calcined at 900℃ for 30 minutes, washed with water to remove soluble salts, dried and passed through a 200-mesh sieve. High-iron high-temperature black pottery clay is ball-milled to 200 mesh and air-dried until the moisture content is <8%. Transparent glaze is ground into fine powder and passed through a 200-mesh sieve. All raw materials are pre-treated and ready for use. Take pretreated calcined pine ash, high-iron high-temperature black pottery clay and transparent glaze, mix them in a weight ratio of 16%:74%:10%, then add water at a ratio of 1:0.75 (total dry weight: water), add 0.1% CMC and wet ball mill for 7 hours, adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³, and set aside for later use; The raw materials are mixed in the following weight ratios: 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite and 8% wood ash. The mixture is then wet-milled, slurry-pressed and dehydrated, vacuum-kneaded, homogenized and aged for 1.5 months, and then vacuum-kneaded again before shaping, trimming and drying. The prepared blanks are then ready for use. The resulting green body was bisque-fired using a segmented heating method, held at 800℃ for 60 minutes, and then naturally cooled to room temperature. The bisque-fired green body was then set aside. Apply the glaze slurry to the surface of the bisque-fired body, controlling the glaze thickness to 1.2-1.5 mm, and let it dry until there are no traces of flow in the glaze layer. After the glaze is applied and dried, the body is placed in a reducing atmosphere with a carbon monoxide concentration of 3%-4%, and the temperature is raised to 1260℃ in stages. Depending on the glaze color requirements, the holding time for the bluish-gray glaze is 50 minutes, and the holding time for the yellowish-brown glaze is 40 minutes. After cooling to 800℃, the body is allowed to cool naturally to room temperature to obtain the target medical ceramic ware.

2. The method for preparing medical ceramic ware with both antibacterial and antiviral functions as described in claim 1, characterized in that, In the process of pre-treating raw materials, the following steps are performed: calcining pine ash at 900℃ for 30 minutes, washing with water to remove soluble salts, drying and passing through a 200-mesh sieve; ball milling high-iron high-temperature black pottery clay to 200 mesh and air-drying it until the moisture content is <8%; and grinding transparent glaze into fine powder and passing through a 200-mesh sieve. The transparent glaze is a barium borosilium-based transparent glaze or a calcium borosilium-based transparent glaze; The barium carbonate-free borosilicate transparent glaze comprises, by weight percentage: 35% potassium feldspar, 15% quartz, 20% borax, 12% calcite, 8% talc, and 10% zinc oxide; The calcium-boron transparent glaze comprises, by weight percentage: 25% sodium feldspar, 18% quartz, 15% boric acid, 15% limestone, 10% talc, 7% zinc oxide, and 10% magnesium carbonate.

3. The method for preparing medical ceramic ware with both antibacterial and antiviral functions as described in claim 2, characterized in that, In the process of pre-treating raw materials, the following steps are performed: calcining pine ash at 900℃ for 30 minutes, washing with water to remove soluble salts, drying and passing through a 200-mesh sieve; ball milling high-iron high-temperature black pottery clay to 200 mesh and air-drying it until the moisture content is <8%; and grinding transparent glaze into fine powder and passing through a 200-mesh sieve. The calcined pine ash was washed with three stages of deionized water. After each wash, it was allowed to stand for 30 minutes to settle. After the third wash, the conductivity of the supernatant was ≤50μS / cm. The drying temperature was 110℃-120℃ and the drying time was 2 hours.

4. The method for preparing medical ceramic ware with both antibacterial and antiviral functions as described in claim 3, characterized in that, The following steps are involved: Pre-treated calcined pine ash, high-iron high-temperature black pottery clay, and transparent glaze are mixed in a weight ratio of 16%:74%:10%. Then, water is added at a dry weight to water ratio of 1:0.

75. After adding 0.1% CMC, the mixture is wet-milled for 7 hours to adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³. The mixture is then ready for use. The grinding media of the wet ball mill are alumina balls with a diameter of 5-10 mm, and the slurry temperature is controlled to be ≤40℃ during the grinding process. After the glaze is prepared, let it stand at 20℃-25℃ for 24-36 hours to age. Stir it at 300r / min for 15 minutes before use.

5. The method for preparing medical ceramic ware with antibacterial and antiviral functions as described in claim 4, characterized in that, The following steps are involved: Pre-treated calcined pine ash, high-iron high-temperature black pottery clay, and transparent glaze are mixed in a weight ratio of 16%:74%:10%. Then, water is added at a dry weight to water ratio of 1:0.

75. After adding 0.1% CMC, the mixture is wet-milled for 7 hours to adjust the glaze slurry specific gravity to 1.75-1.85 g / cm³. The mixture is then ready for use. The ratio of material, milling balls, and water in a wet ball mill is 1:2:0.

75.

6. The method for preparing medical ceramic ware with antibacterial and antiviral functions as described in claim 5, characterized in that, In the process of mixing raw materials in a weight ratio of 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash, followed by wet ball milling, slurry pressing and dewatering, vacuum kneading, homogenization and aging for 1.5 months, secondary vacuum kneading, shaping, trimming and drying, and then preparing the green body for later use: The ratio of material to grinding balls to water in wet ball milling is 1:1.8:0.

7. The grinding time is 18 hours, and the fineness is 4%-6% residue on a 10,000-mesh sieve. Vacuum kneading: vacuum degree ≥ -0.09MPa, rotation speed 30r / min, clay strip porosity < 2% after secondary kneading, and finally dried to moisture content < 5%.

7. The method for preparing medical ceramic ware with both antibacterial and antiviral functions as described in claim 6, characterized in that, In the steps of applying glaze slurry to the surface of the bisque-fired body, controlling the glaze thickness to 1.2-1.5 mm, and then letting it dry until the glaze layer shows no signs of flow: After glazing, the body should be dried in an environment of 20℃-25℃ and relative humidity of 40%-50% for 2-4 hours.

8. The method for preparing medical ceramic ware with both antibacterial and antiviral functions as described in claim 7, characterized in that, The process involves placing the glazed and dried ceramic body in a reducing atmosphere with a carbon monoxide concentration of 3%-4%, gradually heating it to 1260℃, and holding it at that temperature for 50 minutes for the bluish-gray glaze and 40 minutes for the yellowish-brown glaze, depending on the desired glaze color. After cooling to 800℃, the body is allowed to cool naturally to room temperature to obtain the target medical ceramic vessel. The carbon monoxide concentration in the reducing atmosphere is monitored in real time by an infrared gas analyzer, with a fluctuation range of ≤±0.2%; the cooling rate from 800℃ to 500℃ is ≤50℃ / h, and free cooling is allowed below 500℃.

9. A medical ceramic vessel with both antibacterial and antiviral functions, prepared by the method described in any one of claims 1-8, characterized in that, The raw materials for its preparation, by percentage, include: The ingredients are: 25% purple clay, 35% purple mud, 22% porcelain stone, 10% bentonite, and 8% wood ash. The glaze material consists of 16% calcined pine ash, 74% high-iron high-temperature black pottery clay, and 10% transparent glaze. The surface hardness of the glaze layer of ceramic ware is ≥6H, the water absorption rate is ≤0.5%, and the sterilization rate against Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli, and Myxocytocium chrysogenum is ≥99.9% within 2 hours.

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