A ceramic composite material formulation, preparation method and application

Abstract

This application provides a ceramic composite material formulation, preparation method, and application. The ceramic composite material formulation includes a body formulation and a glaze formulation. The body formulation includes the following components by weight: 35-50 parts modified phosphate rock slag, 15-35 parts waste glass fiber short fibers, 7-25 parts blast furnace slag, 2-10 parts kaolin, and 0-10 parts clay. The modified phosphate rock slag contains ≥40 wt% calcium oxide, and the blast furnace slag contains ≤0.15 wt% iron oxide. The glaze formulation includes the following components by weight: 20-50 parts aluminum dihydrogen phosphate, 20-40 parts waste glass fiber microparticles, 10-20 parts kaolin, 8-15 parts apatite, 3-10 parts zinc oxide, and 1-4 parts whitening agent. By using three types of industrial waste residues—phosphate slag, waste glass fiber, and blast furnace slag—and making full use of the calcium, phosphorus, and silicon they contain, a calcium-aluminum-silicon ceramic composite material with appearance characteristics similar to bone china is prepared. This process not only eliminates solid waste but also achieves energy conservation, aligning with the development trend of low-cost and environmentally friendly new ceramic composite materials.

Description

Technical Field

[0001] This application relates to the field of daily-use ceramics technology, and in particular to a ceramic composite material formulation, preparation method and application. Background Technology

[0002] The formulation systems for daily-use ceramics are divided into potassium-aluminum-silicon systems, magnesium-aluminum-silicon systems, and calcium-aluminum-silicon systems, among others. Bone china is a representative example of the calcium-aluminum-silicon system. One of the key raw materials for bone china is animal bone ash, which serves as the source of calcium in the formulation. In some bone china formulations, animal bone ash accounts for as much as 55% of the total. This high proportion of animal bone ash is because components such as calcium phosphate in the ash interact with other components in the ceramic body during firing, giving bone china a unique milky white or ivory-white appearance. This adds a unique texture and depth to the finished porcelain, making it highly popular with consumers.

[0003] However, animal cremated remains are susceptible to factors such as animal breeding and slaughter, resulting in a limited and unstable supply of raw materials that cannot meet the needs of large-scale production. Furthermore, the burning of cremated remains consumes fuel resources and pollutes the environment, which is detrimental to environmental protection. On the other hand, the quality of animal cremated remains from different batches and sources is also easily affected by the animal raw materials, making it difficult to meet the quality control requirements of large-scale production.

[0004] Meanwhile, the inventors of this application discovered during the implementation process that the waste residue generated in many industrial scenarios contains elements such as calcium, phosphorus, silicon, and aluminum. Therefore, in combination with the development trend of low-cost and environmentally friendly ceramics production in the daily ceramics industry, there is an urgent need for a formula and preparation method of a calcium-aluminum-silicon system ceramic composite material that can utilize industrial waste residue and does not rely on animal bone ash raw materials. Summary of the Invention

[0005] Based on this, the present application provides a ceramic composite material formulation that utilizes three industrial wastes: phosphate slag, waste glass fiber, and blast furnace slag. It fully utilizes elements such as calcium, phosphorus, and silicon in the industrial wastes to achieve the preparation of a calcium-aluminum-silicon ceramic composite material without relying on animal bone ash raw materials.

[0006] The specific embodiments of this application are as follows:

[0007] In a first aspect, embodiments of this application provide a ceramic composite material formulation, including a raw material formulation and a glaze formulation. The raw material formulation comprises the following components by weight: 35-50 parts modified phosphate rock slag, 15-35 parts waste glass fiber short fibers, 7-25 parts blast furnace slag, 2-10 parts kaolin, and 0-10 parts clay. The modified phosphate rock slag contains ≥40 wt% calcium oxide, and the blast furnace slag contains ≤0.15 wt% iron oxide. The glaze formulation comprises the following components by weight: 20-50 parts aluminum dihydrogen phosphate, 20-40 parts waste glass fiber microparticles, 10-20 parts kaolin, 8-15 parts apatite, 3-10 parts zinc oxide, and 1-4 parts whitening agent.

[0008] In some optional embodiments, the modified phosphate slag is obtained by defluorinating and dephosphorizing phosphate slag raw materials, and the dephosphorization of the phosphate slag raw materials produces phosphorus-containing waste liquid, and the aluminum dihydrogen phosphate is obtained by mixing the phosphorus-containing waste liquid with kaolin.

[0009] In some optional embodiments, the apatite is prepared by mixing the phosphorus-containing waste liquid with the acidic leachate of the blast furnace slag, and the apatite has a grain size of <200nm.

[0010] In some optional embodiments, the length of the waste glass fiber short fiber is 0.5-1 mm. A portion of the blast furnace slag is mixed and melted with the waste glass fiber short fiber at a mass ratio of (6-8):3 to form glass microspheres. The particle size of the glass microspheres is D50≤15 μm, while the remaining portion is mechanically activated to generate hydrated calcium silicate gel.

[0011] In some optional embodiments, the particle size D50 of the waste glass fiber microparticles is 5 μm.

[0012] In some optional embodiments, the whitening agent is one or more of cerium oxide, vanadium pentoxide, and zinc sulfide.

[0013] In some optional embodiments, the glaze formulation further includes 1-4 parts of a light-transmitting agent and 1-3 parts of a defoamer, wherein the light-transmitting agent is lithium carbonate or spodumene and the particle size of the light-transmitting agent is <5μm, and the defoamer is one or more of ammonium nitrate, magnesium oxide and barium carbonate and the particle size D50 of the defoamer is 3-5μm.

[0014] Secondly, this application provides a method for preparing a ceramic composite material, which is used to prepare the ceramic composite material according to the formulation of any of the preceding claims, including the following steps: S11: Take phosphate slag raw material, defluorinate and dephosphorize to obtain the modified phosphate slag, ball mill the modified phosphate slag to D50 of 3-5μm, and use a cutting machine to cut waste glass fiber into the waste glass fiber short fibers; S12: Weigh 15-35 parts of the waste glass fiber short fibers, add the blast furnace slag according to the mass ratio of the waste glass fiber short fibers to the blast furnace slag (6-8):3, melt at 1350℃ and water quench to form glass microspheres, add 10% NaOH solution to the remaining blast furnace slag, and wet ball mill for 1 hour to obtain hydrated calcium silicate gel; S13: Feed 35-50 parts of the modified phosphate slag, 0-10 parts of the clay, and 2-10 parts of the kaolin into a mixer in sequence, and dry mix for 5 minutes; S14: Add the glass microspheres into the mixer in three batches, with an interval of at least 2 minutes between each batch; S15: Slowly add the hydrated calcium silicate gel into the mixer; S16: Add water into the mixer until the viscosity of the prepared blank is 25-30 Pa·s; S17: Shape the blank to obtain a green body and preheat it at 150°C for 20 minutes.

[0015] In some optional implementation methods, the method further includes the following steps: S21: Immersing the phosphate slag raw material in a 0.5wt% concentration of citric acid, acetic acid, or oxalic acid solution, filtering to obtain phosphorus-containing waste liquid; immersing the blast furnace slag in a 10wt% concentration of acetic acid or oxalic acid solution, filtering to obtain a calcium-containing solution; mixing the calcium-containing solution and the phosphorus-containing waste liquid in a molar ratio of Ca:P=1.67; reacting at 180℃ for 2 hours under alkaline conditions; centrifuging and drying to obtain the apatite; mixing the phosphorus-containing waste liquid and the kaolin in a molar ratio of P:Al=1:2; reacting at 85℃ for 1.5 hours under acidic conditions; filtering to obtain the aluminum dihydrogen phosphate. S22: Add 23-55 parts of deionized water, 20-50 parts of the aluminum dihydrogen phosphate, 20-40 parts of the waste glass fiber microparticles, 10-20 parts of the kaolin, 8-15 parts of the apatite, 3-10 parts of the zinc oxide, and 1-4 parts of the whitening agent to a ball mill jar, and ball mill for 2 hours to obtain a glaze; S23: Coat the surface of the blank with the glaze, controlling the glaze thickness to be 0.1-0.2 mm; S24: The green body is fed into the kiln, and the stepped firing curve is controlled as follows: the heating rate from room temperature to 300℃ is 2℃ / min, the heating rate from 300℃ to 900℃ is 5℃ / min, the heating rate from 900℃ to 1080℃ is 8℃ / min, the temperature is held at 1080℃ for 60-120min, the temperature is then lowered to 800℃ at a cooling rate of 50℃ / min, the temperature is then lowered to 300℃ at a cooling rate of 10℃ / min, and finally the temperature is naturally cooled to room temperature to obtain the ceramic composite material. In the three stages of heating, the atmosphere in the furnace corresponds to an oxidizing atmosphere, a weak reducing atmosphere of 3% CO, and a nitrogen atmosphere, respectively. During the holding period, the atmosphere in the furnace is a wet nitrogen atmosphere containing 15% water vapor.

[0016] Thirdly, embodiments of this application provide an application of a ceramic composite material, wherein the ceramic composite material is prepared from the formulation of any of the preceding ceramic composite materials, and the ceramic composite material is applied to antibacterial tableware, outdoor cookware, heat-resistant teaware, or handicrafts.

[0017] Compared with the prior art, this application has the following advantages:

[0018] (1) In this embodiment, by using three industrial wastes, namely phosphate slag, waste glass fiber and blast furnace slag, the calcium, phosphorus and silicon contained therein are fully utilized to prepare a calcium-aluminum-silicon ceramic composite material with appearance characteristics similar to bone china. The addition of apatite in the glaze formula also increases the antibacterial properties of the ceramic composite material. The addition of waste glass fiber can help melt at low temperature, reduce the firing temperature of the ceramic composite material, and further reduce firing energy consumption. While consolidating solid waste, it can also save energy, which is in line with the development trend of low cost and high environmental protection of new ceramic composite materials.

[0019] Specifically, the phosphate slag raw material needs to be defluorinated and dephosphorized to become modified phosphate slag, achieving a calcium oxide content of ≥40wt%. The phosphorus-containing waste liquid obtained from dephosphorization can also be used as one of the raw materials for the synthesis of apatite, an antibacterial active ingredient, and aluminum dihydrogen phosphate, a fluxing ingredient, in the glaze formula. While solidifying the waste, the waste liquid generated from the solid waste can also be reused, achieving a utilization rate of more than 95% for the phosphate slag raw material.

[0020] (2) In this embodiment, waste glass fibers are processed into different sizes and applied to the blank formulation and glaze formulation respectively. The size of the waste glass fibers is adjusted according to different material systems to improve the adaptability of waste glass fibers in the material system. On the one hand, waste glass fibers can play a low-temperature fluxing role in both blanks and glazes. On the other hand, short-fiber waste glass fibers can also play a bridging role in blanks, enhance the strength of the blank skeleton, and improve the impact resistance of ceramic composite materials. Meanwhile, microparticle waste glass fibers can optically control the appearance of the glaze and improve the gloss of the ceramic composite materials.

[0021] (3) In this application embodiment, by controlling the iron oxide content in blast furnace slag, the influence of iron elements on the color may be reduced. In addition, a whitening agent is used to correct the color of the colored metal impurities that may be brought by blast furnace slag, phosphate slag, etc., thereby improving the color consistency of daily porcelain, achieving a color appearance close to that of bone china, and enhancing the aesthetics.

[0022] (4) In the embodiments of this application, aluminum dihydrogen phosphate is added to the glaze, and the aluminum dihydrogen phosphate reacts with CaO in the blank to generate CaAl2P3O. 12 This enhances the bonding force between the glaze layer and the body, and improves the thermal shock resistance of ceramic composite materials.

[0023] (5) This application also provides a method for preparing ceramic composite materials. Through simple chemical or physical treatment of phosphate slag raw materials and waste glass fiber, the preparation of blanks and glazes can be achieved by simple feeding. In the subsequent firing process, the firing temperature is lower than that of traditional ceramic processes, thus realizing a low-cost and environmentally friendly ceramic manufacturing process.

[0024] (6) This application also provides an application of ceramic composite material. Under the premise that the formulation of ceramic composite material has the aforementioned performance characteristics, the antibacterial biological properties of apatite in the ceramic composite material make it applicable to antibacterial tableware, the high-strength skeleton properties make it applicable to outdoor cookware, the good thermal shock resistance makes it applicable to heat-resistant teaware, and the aesthetic appeal similar to bone china makes it applicable to handicrafts. Attached Figure Description

[0025] To more clearly illustrate the technical solution of this application, the accompanying drawings used in the description of this application will be briefly introduced below.

[0026] Figure 1 The X-ray diffraction pattern is that of the modified phosphate slag used in Example 1. Detailed Implementation

[0027] The embodiments of this implementation are described in detail below. These embodiments are only used to explain this implementation and should not be construed as limiting this implementation.

[0028] In the description of the embodiments of this application, it should be noted that all scopes disclosed in this application are to be understood to encompass any and all subscopes included therein. For example, the stated scope "35-50 parts" should be considered to include any and all subscopes that begin with a minimum of 35 parts or greater and end with a maximum of 50 parts or less, such as 35 to 37 parts, or 40-45 parts, or 43 to 49 parts. Furthermore, all scopes disclosed in this application are also considered to include the endpoints of the scope, unless otherwise expressly stated. For example, the scope "between 15 and 35," "15 to 35," or "15-35" should generally be considered to include the endpoints 15 and 35.

[0029] Unless otherwise specified, in this article, ratio refers to mass ratio and percentage refers to mass percentage.

[0030] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0031] The phosphate slag mentioned in this application refers to the waste residue generated during the production of phosphorus-containing products such as phosphoric acid and ammonium phosphate from phosphate rock. Its main chemical components are: fluorapatite, calcium oxide, silicon dioxide, and phosphorus pentoxide. The blast furnace slag refers to the waste residue generated during the blast furnace smelting of pig iron. Its main chemical components are: calcium oxide, aluminum oxide, silicon dioxide, and iron oxide. The waste glass fiber refers to glass fiber materials that are discarded or unusable during use. Its main chemical components are: silicon dioxide, sodium oxide, potassium oxide, and calcium oxide. It is understood that, in order to reduce the introduction of impurity elements, the kaolin used in this application is high-quality kaolin with an iron oxide content of less than 0.1 wt%.

[0032] In summary, the inventors of this application have innovatively provided a ceramic composite material formulation. By using three industrial wastes—phosphate slag, waste glass fiber, and blast furnace slag—and fully utilizing the calcium, phosphorus, and silicon elements contained within them, a calcium-aluminum-silicon system ceramic composite material with appearance characteristics similar to bone china is prepared. The addition of apatite in the glaze further enhances the antibacterial properties of the ceramic composite material. The addition of waste glass fiber enables low-temperature melting, reducing the firing temperature of the ceramic composite material and further reducing firing energy consumption. This approach achieves energy conservation while conserving solid waste, aligning with the development trend of low-cost, environmentally friendly new ceramic composite materials.

[0033] The first aspect of this application provides a ceramic composite material formulation, including a body formulation and a glaze formulation. The body formulation comprises the following components in parts by weight: 35-50 parts modified phosphate rock slag, 15-35 parts waste glass fiber short fibers, 7-25 parts blast furnace slag, 2-10 parts kaolin, and 0-10 parts clay. The modified phosphate rock slag contains ≥40 wt% calcium oxide, and the blast furnace slag contains ≤0.15 wt% iron oxide. The glaze formulation comprises the following components in parts by weight: 20-50 parts aluminum dihydrogen phosphate, 20-40 parts waste glass fiber microparticles, 10-20 parts kaolin, 8-15 parts apatite, 3-10 parts zinc oxide, and 1-4 parts whitening agent.

[0034] Specifically, the modified phosphate slag originates from phosphate slag raw materials. These raw materials undergo defluorination and dephosphorization to obtain the modified phosphate slag. In practice, defluorination can be achieved by calcining the phosphate slag raw materials at 850°C for 2 hours. The defluorinated phosphate slag is then immersed in a 5wt% solution of citric acid, acetic acid, or oxalic acid, with a liquid-to-solid ratio of 3:1, which removes 80% of soluble phosphorus, such as phosphorus pentoxide. Simultaneously, the resulting modified phosphate slag has a calcium oxide content ≥40wt%. The X-ray diffraction pattern of the modified phosphate slag is shown below. Figure 1 As shown, characteristic diffraction peaks of the CaO(200) crystal plane appear at 2θ≈30°.

[0035] Furthermore, the iron oxide content of the blast furnace slag is ≤0.15wt%, which can be achieved by magnetic separation combined with acid leaching. Specifically, the blast furnace slag is first ground to D90=45μm, and then a 1.2T neodymium iron boron magnetic separator is used to remove more than 85% of the magnetic material. The magnetically separated blast furnace slag is then reduced and roasted, and then immersed in oxalic acid solution. After filtration, blast furnace slag with an iron oxide content of ≤0.15wt% is obtained.

[0036] In some optional embodiments, the modified phosphate slag is obtained by defluorinating and dephosphorizing phosphate slag raw materials. The dephosphorization of the phosphate slag raw materials produces phosphorus-containing wastewater, and the aluminum dihydrogen phosphate is obtained by mixing the phosphorus-containing wastewater with kaolin. Aluminum dihydrogen phosphate can act as a flux to form an AlPO4-Al2O3 eutectic, thereby lowering the firing temperature. It also acts as a stabilizer to ensure that the glaze settling rate is <3%, while simultaneously enhancing the hardness of the glaze layer and the bonding strength between the glaze layer and the body.

[0037] In some optional embodiments, the apatite is prepared by mixing the phosphorus-containing waste liquid with the acidic leachate of the blast furnace slag, and the apatite grain size is <200nm. The waste liquid generated from the secondary utilization of solid waste achieves a utilization rate of over 95% for the phosphate slag raw material. In specific implementation, during the dephosphorization process of the phosphate slag, over 80% of soluble phosphorus can be removed, while the residual phosphorus in the modified phosphate slag can still react with calcium oxide in the green body to generate apatite, fully utilizing phosphorus to achieve an antibacterial effect. Specifically, PO4... 3- The functional groups can disrupt bacterial cell membranes through electrostatic adsorption, while simultaneously releasing Ca2+. 2+ It binds to bacterial enzymes, causing them to become inactive. Apatite in the body can also enhance the fracture toughness of ceramic composites and improve the translucency of finished porcelain. Specifically, apatite grains dispersed in the body can significantly improve the fracture toughness of ceramics by hindering crack propagation paths; apatite grains <200nm enhance PO4 through high specific surface area. 3- Ion leaching disrupts bacterial cell membranes, while nanoscale crystals can penetrate bacterial walls, physically inactivating microorganisms. Apatite forms a chemically bonded interface, Ca-O-Si, with the silicate glass phase, enhancing grain boundary bonding and reducing grain boundary slip at high temperatures. Furthermore, Ca²⁺ vacancies in the apatite lattice can adsorb heavy metals (such as Pb). 2+ Cd 2+ It solidifies toxic elements through ion exchange and inhibits the leaching of heavy metals.

[0038] In some alternative embodiments, the length of the waste glass fiber short fibers is 0.5-1 mm. A portion of the blast furnace slag is mixed and melted with the waste glass fiber short fibers at a mass ratio of (6-8):3 to form glass microspheres. The particle size of the glass microspheres is D50≤15 μm, while the remaining portion is mechanically activated to generate hydrated calcium silicate gel.

[0039] In some alternative embodiments, the particle size D50 of the waste glass fiber microparticles is 5 μm.

[0040] By reprocessing waste glass fibers into different sizes and applying them to both the raw material and the glaze, the size of the waste glass fibers can be adjusted according to different material systems to improve their adaptability. On the one hand, the waste glass fibers can exert low-temperature fluxing properties in both the raw material and the glaze. On the other hand, the short-fiber waste glass fibers in the raw material can also act as a bridge, enhancing the strength of the raw material skeleton and improving the impact resistance of the ceramic composite material. Meanwhile, the microparticle-shaped waste glass fibers in the glaze can optically control the appearance of the glaze and improve the gloss of the ceramic composite material.

[0041] In addition, a portion of the blast furnace slag is mixed and melted with the waste glass fiber short fibers at a mass ratio of (6-8):3 to form glass microspheres. The mixing and melting of the waste glass fiber short fibers and the blast furnace slag synergistically reduces the melting temperature of the billet, and on the other hand, the Ca in the blast furnace slag... 2+ It can cut the Si-O-Si network of waste glass fibers, reduce viscosity, and improve the mixing uniformity of the billet. The remaining blast furnace slag is mechanically activated to generate hydrated calcium silicate gel, releasing active CSH nanogels and improving the strength of the billet.

[0042] In some alternative embodiments, the brightener is one or more of cerium oxide, vanadium pentoxide, and zinc sulfide. In specific implementations, cerium oxide can decompose Fe... 3+ Ti 4+ The isochromic complex, wherein vanadium pentoxide serves as a physical color adjuster to counteract Fe. 2+ The yellow hue is achieved by using a dual mechanism of optical scattering and chemical bleaching to mask impurities such as iron and titanium.

[0043] In some optional embodiments, the glaze further includes 1-4 parts of a light-transmitting agent and 1-3 parts of a defoamer. The light-transmitting agent is lithium carbonate or spodumene, and its particle size is <5 μm. The defoamer is one or more of ammonium nitrate, magnesium oxide, and barium carbonate, and its particle size D50 is 3-5 μm. By adding the light-transmitting agent and defoamer to the glaze and precisely controlling the particle size, the light transmittance of the ceramic composite material and the zero-defect effect of the glaze surface can be synergistically achieved.

[0044] Secondly, this application provides a method for preparing a ceramic composite material, which is used to prepare the ceramic composite material according to the formulation of any of the preceding claims, including the following steps: S11: Take phosphate slag raw material, defluorinate and dephosphorize to obtain the modified phosphate slag, ball mill the modified phosphate slag to D50 of 3-5μm, and use a cutting machine to cut waste glass fiber into the waste glass fiber short fibers; S12: Weigh 15-35 parts of the waste glass fiber short fibers, add the blast furnace slag according to the mass ratio of the waste glass fiber short fibers to the blast furnace slag (6-8):3, melt at 1350℃ and water quench to form glass microspheres, add 10% NaOH solution to the remaining blast furnace slag, and wet ball mill for 1 hour to obtain hydrated calcium silicate gel; S13: Feed 35-50 parts of the modified phosphate slag, 0-10 parts of the clay, and 2-10 parts of the kaolin into a mixer in sequence, and dry mix for 5 minutes; S14: Add the glass microspheres into the mixer in three batches, with an interval of at least 2 minutes between each batch; S15: Slowly add hydrated calcium silicate gel to the mixer; S16: Add water to the mixer until the viscosity of the prepared blank is 25-30 Pa·s; S17: Shape the blank to obtain a green body and preheat it at 150°C for 20 minutes.

[0045] Understandably, during the feeding process, the mixer maintains a stirring action at a speed of 60 rpm, and the total mixing time is controlled within 20 minutes. The billet prepared by mixing also needs to pass through a 100-mesh sieve, and the sieve residue is controlled to be <0.1%.

[0046] In some alternative implementations, the method further includes the following steps: S21: The phosphate slag raw material is immersed in a 0.5wt% solution of citric acid, acetic acid, or oxalic acid, and filtered to obtain a phosphorus-containing waste liquid. The blast furnace slag is immersed in a 10wt% solution of acetic acid or oxalic acid, and filtered to obtain a calcium-containing solution. The calcium-containing solution and the phosphorus-containing waste liquid are mixed at a molar ratio of Ca:P=1.67 and reacted at 180℃ for 2 hours under alkaline conditions. After centrifugation and drying, the apatite is obtained. The phosphorus-containing waste liquid is mixed with kaolin at a molar ratio of P:Al=1:2 and reacted at 85℃ for 1.5 hours under acidic conditions. The mixture is then filtered to obtain aluminum dihydrogen phosphate. S22: 23-55 parts of deionized water, 20-50 parts of aluminum dihydrogen phosphate, 20-40 parts of waste glass fiber microparticles, 10-20 parts of kaolin, 8-15 parts of apatite, 3-10 parts of zinc oxide, and 1-4 parts of whitening agent are added to a ball mill jar and ball milled for 2 hours to obtain a glaze. S23: Coat the surface of the green body with the glaze, controlling the glaze thickness to be 0.1-0.2 mm; S24: Send the green body into the kiln and control the step firing curve: the heating rate from room temperature to 300℃ is 2℃ / min, the heating rate from 300℃ to 900℃ is 5℃ / min, the heating rate from 900℃ to 1080℃ is 8℃ / min, hold at 1080℃ for 60-120 min, then lower the furnace temperature to 800℃ at a cooling rate of 50℃ / min, then lower the furnace temperature to 300℃ at a cooling rate of 10℃ / min, and finally cool naturally to room temperature to obtain the ceramic composite material. In the three stages of heating, the furnace atmosphere corresponds to an oxidizing atmosphere, a weakly reducing atmosphere of 3% CO, and a nitrogen atmosphere, respectively. During the holding period, the furnace atmosphere is a wet nitrogen atmosphere containing 15% water vapor.

[0047] In the specific implementation process, the purpose of the room temperature to 300℃ stage is to remove the bound water from the glaze surface of the body; the purpose of controlling the furnace atmosphere to be a weakly reducing atmosphere in the 300℃ to 900℃ stage is to remove Fe 3+ Reduced to colorless Fe 2+ To control the color development of iron, the furnace atmosphere is controlled as follows: from 900℃ to 1080℃, the atmosphere is controlled as a nitrogen inert protective atmosphere to protect the glass phase melting of the body and glaze, and at the same time protect the crystallization of apatite; during the 1080℃ holding stage, wet nitrogen with 15% H2O is used to promote the reaction: Ca3(PO4)2 + H2O → Ca5(PO4)3OH, which generates hydroxyapatite and enhances antibacterial properties; after the holding stage, the furnace temperature is reduced to 800℃ at a cooling rate of 50℃ / min. The rapid cooling helps to freeze the glass phase structure; and during the 800℃ to 300℃ stage, the cooling rate is reduced to 10℃ / min to prevent the quartz crystal transformation from causing cracking of the ceramic body.

[0048] Thirdly, embodiments of this application provide an application of a ceramic composite material, wherein the ceramic composite material is a ceramic composite material prepared from the formulation of any of the preceding ceramic composite materials, and the ceramic composite material is applied to antibacterial tableware, outdoor cookware, heat-resistant teaware, or handicrafts.

[0049] Given that the ceramic composite material formulation possesses the aforementioned performance characteristics, the antibacterial and biological properties of apatite in the ceramic composite material enable its application in antibacterial tableware, its high-strength skeletal properties enable its application in outdoor cookware, its good thermal shock resistance enables its application in heat-resistant teaware, and its aesthetic appeal, similar to bone china, enables its application in handicrafts.

[0050] The following examples will further illustrate this application.

[0051] Example 1

[0052] Example 1 provides a ceramic composite material formulation. The raw material formulation includes the following components by weight: 40 parts deionized water, 40 parts modified phosphate slag, 25 parts waste glass fiber short fibers, 20 parts blast furnace slag, and 10 parts kaolin. The glaze formulation includes the following components by weight: 35 parts aluminum dihydrogen phosphate, 30 parts waste glass fiber microparticles, 15 parts kaolin, 10 parts apatite, 5 parts zinc oxide, and 2 parts cerium oxide.

[0053] Example 2:

[0054] Example 2 provides a ceramic composite material formulation. The difference between Example 2 and Example 1 is that the glaze formulation further contains 3 parts of magnesium oxide.

[0055] Example 3:

[0056] Example 3 provides a ceramic composite material formulation. The difference between Example 3 and Example 1 is that the glaze formulation further contains 3 parts of lithium carbonate.

[0057] Example 4

[0058] Example 4 provides a formulation for a ceramic composite material. The difference between Example 4 and Example 1 is that 15 parts of the waste glass fiber short fibers are used.

[0059] Example 5

[0060] Example 5 provides a ceramic composite material formulation. The difference between Example 5 and Example 1 is that the apatite content in the glaze formulation is 5 parts.

[0061] Example 6

[0062] Example 6 provides a ceramic composite material formulation. The difference between Example 6 and Example 1 is that the aluminum dihydrogen phosphate in the glaze formulation is 20 parts.

[0063]

[0064] Experimental method for color difference: 1. Sample preparation: Take a flat glazed surface with an area ≥10×10mm and clean the surface; 2. Calibration: Calibrate the spectrophotometer using a standard white plate (L*=95±0.2); 3. Light source settings: D65 standard light source, viewing angle: 10°;

[0065] 4. Select at least 5 points for measurement and calculate ΔE, ΔE = √(ΔL) 2 +(Δa) 2 +(Δ b ) 2 5. Take the average value of the measured ΔE and calculate the color difference of the sample.

[0066] Experimental method for point defects: 1. Sampling: Take a 50×50mm sample area from the glaze surface; 2. Scanning: 600dpi high-definition imaging; 3. Software automatically identifies defects >50μm in size; 4. Calculate density (points / cm³). 2 ).

[0067] Transmittance Test: 1. Sample Preparation: Take a thin film polished to a thickness of 1.0 ± 0.05 mm; 2. Reference Calibration: Air transmittance is set to 100%; 3. Measurement: Wavelength: 550 nm; 4. Integrating sphere collects the fully transmitted light; 5. Calculation: T = I sample / I air ×100% is the light transmittance.

[0068] Antibacterial rate test 1. Inoculation: Apply Escherichia coli suspension (10) to the surface 5 1. CFU / mL); 2. Incubation: Incubate at 37℃ and 90%RH for 24 h; 3. Elution: Elute residual bacteria with PBS buffer; 4. Counting: Count bacteria on nutrient agar plates; 5. Calculation: Antibacterial rate = (1 - sample colonies / blank colonies) × 100%,

[0069] Bending strength test: 1. Sample preparation: Cut the ceramic composite material into 50×10×4mm strips and polish the edges; 2. Clamping: Use a three-point bending fixture with a span of 40mm; 3. Loading: Speed: 0.5mm / min, record the fracture load F; 4. Calculation: σ f =3FL / 2bd 2 L = span, b = width, d = thickness.

[0070] Impact strength test: 1. Fix the sample: hold it horizontally; 2. Impact: a steel ball (Φ25.4mm, 68g) is dropped freely from a height of 0.5m; 3. Judgment: the height is increased successively until the sample breaks, and the energy E=mgh is calculated.

[0071] Thermal shock resistance test: 1. Preheating: Place the sample in an oven at 220±5℃ for 30 min; 2. Rapid cooling: Quickly immerse the sample in water at 25±1℃; 3. Inspection: Visually inspect for cracks using a combination of visual and ultrasonic testing; 4. Cycling: Repeat until cracks appear and record the number of cycles.

[0072] In conjunction with Examples 1 and 2, the addition of magnesium oxide can reduce the point defects on the glaze of the ceramic composite material, but it will affect the light transmittance of the glaze. This may be because the high refractive index of magnesium aluminum spinel causes slight turbidity. At the same time, the formation of magnesium aluminum spinel enhances the bending strength and thermal shock resistance. In conjunction with Examples 1 and 3, the addition of lithium carbonate can comprehensively improve the optical properties of the glaze. In conjunction with Examples 1 and 4, reducing the proportion of short waste glass fibers will cause the optical and mechanical properties of the ceramic composite material to deteriorate. This may be because the waste glass fibers do not provide sufficient flux to the body, leaving impurities in the finished porcelain. In conjunction with Examples 1 and 5, reducing the proportion of apatite will directly affect the antibacterial effect of the finished porcelain. In conjunction with Examples 1 and 6, reducing the content of aluminum dihydrogen phosphate will cause a significant performance degradation in both the optical and mechanical properties of the ceramic composite material. This may be because aluminum dihydrogen phosphate participates in the vitrification of the glaze, affects the bonding force between the glaze and the body, and also has the antibacterial properties of phosphate, thus having a significant impact on the performance of the ceramic composite material.

[0073] In summary, within the scope of the ceramic composite material formulations provided in this application, the amount of specific components added can be adjusted according to different performance focuses. For example, in the application scenario of decorative handicrafts where the optical properties of finished ceramic composite porcelain are more important, a formulation system similar to Example 3 is preferred; while in the scenario of outdoor cookware where mechanical properties are more important, a formulation system similar to Example 2 is preferred.

[0074] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A formulation for a ceramic composite material, characterized in that, The product includes a raw material formula and a glaze formula. The raw material formula comprises the following components by weight: 35-50 parts modified phosphate rock slag, 15-35 parts waste glass fiber short fibers, 7-25 parts blast furnace slag, 2-10 parts kaolin, and 0-10 parts clay. The modified phosphate rock slag contains ≥40 wt% calcium oxide, and the blast furnace slag contains ≤0.15 wt% iron oxide. The glaze formula comprises the following components by weight: 20-50 parts aluminum dihydrogen phosphate, 20-40 parts waste glass fiber microparticles, 10-20 parts kaolin, 8-15 parts apatite, 3-10 parts zinc oxide, and 1-4 parts whitening agent. The modified phosphate slag is obtained by defluorinating and dephosphorizing phosphate slag raw materials. Specifically, the phosphate slag raw materials are calcined at high temperature to achieve defluorination, and the defluorinated phosphate slag is immersed in citric acid, acetic acid or oxalic acid solution to remove soluble phosphorus.

2. The formulation of the ceramic composite material according to claim 1, characterized in that, The phosphorus-containing waste liquid is generated from the dephosphorization of the phosphorus slag raw material, and the aluminum dihydrogen phosphate is prepared by mixing the phosphorus-containing waste liquid with kaolin.

3. The formulation of the ceramic composite material according to claim 2, characterized in that, The apatite is prepared by mixing the phosphorus-containing waste liquid with the acidic leachate of the blast furnace slag, and the apatite has a grain size of <200nm.

4. The formulation of the ceramic composite material according to claim 1, characterized in that, The length of the waste glass fiber short fiber is 0.5-1mm. A portion of the blast furnace slag is mixed and melted with the waste glass fiber short fiber at a mass ratio of (6-8):3 to form glass microspheres. The particle size of the glass microspheres is D50≤15μm, while the remaining portion is mechanically activated to generate hydrated calcium silicate gel.

5. The formulation of the ceramic composite material according to claim 1, characterized in that, The particle size D50 of the waste glass fiber microparticles is 5 μm.

6. The formulation of the ceramic composite material according to claim 1, characterized in that, The whitening agent is one or more of cerium oxide, vanadium pentoxide, and zinc sulfide.

7. The formulation of the ceramic composite material according to claim 1, characterized in that, The glaze formulation also includes 1-4 parts of a light-transmitting agent and 1-3 parts of a defoamer. The light-transmitting agent is lithium carbonate or spodumene, and the particle size of the light-transmitting agent is <5μm. The defoamer is one or more of ammonium nitrate, magnesium oxide, and barium carbonate, and the particle size D50 of the defoamer is 3-5μm.

8. A method for preparing a ceramic composite material, characterized in that, The ceramic composite material is prepared using a formulation according to any one of claims 1 to 7, comprising the following steps: S11: The modified phosphate slag is obtained by defluorinating and dephosphorizing the phosphate slag raw material. The modified phosphate slag is ball-milled until the D50 is 3-5μm. The waste glass fiber is cut into the waste glass fiber short fiber using a cutting machine. S12: Weigh 15-35 parts of the waste glass fiber short fibers, add the waste glass fiber short fibers to the blast furnace slag in a mass ratio of (6-8):3, melt at 1350℃ and quench in water to form glass microspheres, add 10% NaOH solution to the remaining blast furnace slag, and wet ball mill for 1 hour to obtain hydrated calcium silicate gel. S13: Feed 35-50 parts of the modified phosphate slag, 0-10 parts of the clay, and 2-10 parts of the kaolin into the mixer in sequence, and dry mix for 5 minutes. S14: Add the glass microspheres into the mixer in three separate batches, with at least a 2-minute interval between each batch; S15: Slowly add the hydrated calcium silicate gel into the mixer; S16: Add water to the mixer until the viscosity of the prepared billet is 25-30 Pa·s; S17: Shape the billet to obtain a blank, and preheat it at 150°C for 20 minutes.

9. The method for preparing the ceramic composite material according to claim 8, characterized in that, The method further includes the following steps: S21: The phosphate slag raw material is immersed in a 0.5wt% solution of citric acid, acetic acid or oxalic acid, and filtered to obtain a phosphorus-containing waste liquid. The blast furnace slag is immersed in a 10wt% solution of acetic acid or oxalic acid, and filtered to obtain a calcium-containing solution. The calcium-containing solution and the phosphorus-containing waste liquid are mixed in a molar ratio of Ca:P=1.67 and reacted at 180℃ for 2 hours under alkaline conditions. After centrifugation and drying, the apatite is obtained. The phosphorus-containing waste liquid and the kaolin are mixed in a molar ratio of P:Al=1:2 and reacted at 85℃ for 1.5 hours under acidic conditions. After filtration, the aluminum dihydrogen phosphate is obtained. S22: Add 23-55 parts of deionized water, 20-50 parts of the aluminum dihydrogen phosphate, 20-40 parts of the waste glass fiber microparticles, 10-20 parts of the kaolin, 8-15 parts of the apatite, 3-10 parts of the zinc oxide, and 1-4 parts of the whitening agent to a ball milling jar, and ball mill for 2 hours to obtain the glaze. S23: Coat the surface of the blank with the glaze, controlling the glaze thickness to be 0.1-0.2 mm; S24: The green body is fed into the kiln, and the stepped firing curve is controlled as follows: the heating rate from room temperature to 300℃ is 2℃ / min, the heating rate from 300℃ to 900℃ is 5℃ / min, the heating rate from 900℃ to 1080℃ is 8℃ / min, the temperature is held at 1080℃ for 60-120min, the temperature is then lowered to 800℃ at a cooling rate of 50℃ / min, the temperature is then lowered to 300℃ at a cooling rate of 10℃ / min, and finally the temperature is naturally cooled to room temperature to obtain the ceramic composite material. In the three stages of heating, the atmosphere in the furnace corresponds to an oxidizing atmosphere, a weak reducing atmosphere of 3% CO, and a nitrogen atmosphere, respectively. During the holding period, the atmosphere in the furnace is a wet nitrogen atmosphere containing 15% water vapor.

10. An application of a ceramic composite material, characterized in that, The ceramic composite material is a ceramic composite material prepared according to the formulation of the ceramic composite material according to any one of claims 1 to 7, and the ceramic composite material is used in antibacterial tableware, outdoor cookware or heat-resistant teaware.

Images