An antique imitation unearthed ceramic glaze

Abstract

The present invention relates to the technical field of ceramic glazes, and specifically discloses an antique unearthed ceramic glaze, which comprises the following raw materials in parts by weight: 25-30 parts of kaolin, 20-30 parts of limestone, 10-20 parts of a modifier for modifying bentonite by compounding plant ash, and 2-5 parts of quartz powder; the method for making a ceramic product from the ceramic glaze is as follows: Step 1, raw material processing: accurately weigh the above raw materials according to the formula, and place them in a high-speed ball mill for wet grinding and processing; the ceramic glaze of the present invention uses kaolin in combination with limestone and quartz powder, and then the glaze prepared by coordinating with a modifier for modifying bentonite by compounding plant ash is applied to the green body. The ceramic product made by combining the glaze with the bisque-fired green body has excellent strength performance, and at the same time has strong easy-cleaning ability. The two performances can be coordinately improved, and the product has excellent performance stability under high temperature and acid corrosion conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glazes, and particularly relates to an antique unearthed ceramic glaze. Background Art

[0002] After the existing ceramic glazes are processed by technology, the easy-cleaning ability of the ceramic glazes is poor, they are not easy to clean, and the products are easily damaged during cleaning. At the same time, the strength performance of the products is poor and they are easily damaged, which limits the use efficiency of the products. It is very difficult for the products to achieve coordinated improvement in easy cleaning and strength performance. At the same time, under high-temperature and acid-corrosion conditions, the stability is poor, which further limits the use efficiency of the products. Summary of the Invention

[0003] Aiming at the defects of the prior art, the purpose of the present invention is to provide an antique unearthed ceramic glaze to solve the problems put forward in the above background art.

[0004] The present invention adopts the following technical solutions to solve the technical problems:

[0005] The present invention provides an antique unearthed ceramic glaze, which comprises the following raw materials in parts by weight:

[0006] 25-30 parts of kaolin, 20-30 parts of limestone, 10-20 parts of a modifier for modifying bentonite by compounding plant ash, and 2-5 parts of quartz powder;

[0007] The method for making the ceramic glaze into a ceramic product is as follows:

[0008] Step 1, raw material processing: accurately weigh the above raw materials according to the formula and place them in a high-speed ball mill for wet pulverization processing; the ratio of materials: balls: water in the ball mill is 1:(1.5-2):0.6; the ball milling time is 25 minutes, the fineness of the glaze is 0.3-0.5% of the residue on a 10,000-hole sieve, and the specific gravity is 1.55-1.65 g / cm 3 , and the glaze slurry is homogenized and aged for 3-5 days;

[0009] Step 2, glazing: after homogenization, the glaze slurry is passed through a 100-mesh sieve, with a specific gravity of 1.55-1.65 g / cm 3 , and the flow rate is 40 seconds;

[0010] Step 3, use a bisque body to remove ash and brush water to wash away the dust and make the water absorption rate of the body consistent; use dipping, pouring, and spraying glazing methods to evenly apply the glaze slurry in Step 2 to the body to obtain a glazed body; the glazed body is naturally dried with a water content of less than 1%;

[0011] Step 4, glaze firing: fire the glazed body in Step 3 in an electric kiln at a temperature of 1250-1270°C for 8-10 hours to obtain a ceramic product.

[0012] Preferably, the preparation method of the modifier for modifying bentonite by compounding plant ash is as follows:

[0013] S01: Add plant ash to an aqueous chitosan solution with a mass fraction of 5-7% at a weight ratio of 1:4, and then add sodium dodecyl sulfate accounting for 1-3% of the total amount of plant ash. Stir evenly first to obtain a plant ash-chitosan blending solution;

[0014] S02: Then add a pyrophyllite modifier doped with α-aluminum oxide accounting for 3-6% of the total amount of the plant ash-chitosan blending solution and a lanthanum sulfate solution accounting for 1-5% of the total amount of the plant ash-chitosan blending solution to the plant ash-chitosan blending solution, and stir well to obtain a modified plant ash blending solution;

[0015] S03: Add bentonite to a hydrochloric acid solution with a mass fraction of 5% at a weight ratio of 3:7, stir evenly, then wash with water and dry. Then heat-treat at 350-400 °C for 15-20 min. After the treatment, cool to room temperature at a rate of 2-4 °C / min to obtain a bentonite agent;

[0016] S04: Add the modified plant ash blending solution accounting for 15-20% of the total amount of the bentonite agent to the bentonite agent, and ball mill at a rotation speed of 1000-1500 r / min for 1-2 h. After the ball milling, wash with water and dry to obtain a modified regulator of plant ash-compounded bentonite.

[0017] Preferably, the mass fraction of the lanthanum sulfate solution is 4-8%.

[0018] Preferably, the preparation method of the pyrophyllite modifier doped with α-aluminum oxide is as follows:

[0019] Add pyrophyllite to a mixed acid solution at a weight ratio of 1:5, and ultrasonically disperse for 1-2 h first. The ultrasonic power is 350-400 W. After the ultrasonic treatment, wash with water and dry to obtain a modified pyrophyllite body;

[0020] Add 5-10 parts of the modified pyrophyllite body and 2-5 parts of α-aluminum oxide to 15-20 parts of a yttrium nitrate solution, then add 1-3 parts of isopropyltri(dioctylpyrophosphato)titanate and 1-2 parts of sodium lignosulfonate, and stir for reaction treatment. After the treatment, wash with water and dry to obtain a pyrophyllite modifier doped with α-aluminum oxide.

[0021] Preferably, the mixed acid solution is obtained by mixing citric acid, deionized water and hydrochloric acid at a weight ratio of 2:5:1; the mass fraction of the yttrium nitrate solution is 1-5%.

[0022] Preferably, the stirring temperature of the stirring reaction treatment is 42-44 °C, the rotation speed is 550-750 r / min, and the stirring time is 30-40 min.

[0023] Preferably, the preparation method of the green body is as follows:

[0024] Weigh the green body raw materials: Weigh 20 - 30 parts of albite, 5 - 10 parts of calcium carbonate, 5 - 10 parts of pyrophyllite, and 4 - 8 parts of whisker - blended magnesium oxide agent; then mix the green body raw materials evenly to obtain the green body material.

[0025] The green body material is mixed with water in a ratio of 1.5:1, ball - milled to form the green body mud, the green body mud is injection - molded and dried to obtain the initial green body, then it is subjected to conventional trimming, and finally it is subjected to biscuit firing at 950 - 1050 °C for 3 - 5 h to obtain the biscuit - fired green body.

[0026] Preferably, the preparation method of the whisker - blended magnesium oxide agent is as follows:

[0027] S101: First, pre - heat the silicon carbide whiskers at 115 - 125 °C for 10 - 20 min, then heat them at a rate of 3 - 5 °C / s to 160 - 170 °C, hold for 2 - 5 min, and then air - cool to room temperature.

[0028] S102: Then send them to be refrigerated at - 5 °C for 2 - 6 min, and then jointly perform proton irradiation treatment. After the irradiation ends, set aside for use.

[0029] S103: Then add cetyltrimethylammonium bromide accounting for 4 - 8% of the total amount of the S102 product, magnesium oxide accounting for 10 - 15% of the total amount of the S102 product, and dopamine solution accounting for 2 - 5% of the total amount of the S102 product to the product of S102, and then ball - mill at a rotation speed of 1000 - 1500 r / min for 1 - 2 h. After the ball - milling ends, wash with water and dry to obtain the whisker - blended magnesium oxide agent.

[0030] Preferably, the power of the proton irradiation in S102 is 300 - 350 W, and the irradiation time is 10 - 20 min.

[0031] Preferably, the mass fraction of the dopamine solution in S103 is 5 - 10%.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The ceramic glaze of the present invention uses kaolin in combination with limestone and quartz powder, and then the glaze prepared by coordinating and compounding with the modified regulator of potassium carbonate and bentonite is applied to the green body. The ceramic product made by combining the glaze with the biscuit - fired green body has excellent strength performance, and at the same time has strong easy - to - clean ability. The two performances can be coordinately improved, and the product has excellent performance stability under high - temperature and acid - corrosion conditions.

[0034] The biscuit body is made by mixing albite, calcium carbonate, pyrophyllite, whisker and magnesium oxide agent, and then through a series of processes. The whisker and magnesium oxide agent is preheated with silicon carbide whiskers at 115-125°C for 10-20 minutes, then heated at a rate of 3-5°C / s to 160-170°C, held for 2-5 minutes, and then air-cooled to room temperature; then it is sent to be refrigerated at -5°C for 2-6 minutes, and then combined with proton irradiation treatment. Through a specific heat treatment process combined with proton irradiation treatment, the whisker active body is optimized. At the same time, through coordination and ball milling between raw materials under a specific cetyltrimethylammonium bromide, magnesium oxide, and dopamine solution, the strength of the prepared biscuit body is significantly improved, and the overall performance of the product is optimized;

[0035] The ceramic glaze uses plant ash to compound and modify the bentonite modifier to prepare the raw materials. The plant ash compound and modified bentonite modifier is made by mixing plant ash with chitosan aqueous solution and sodium dodecyl sulfate to form a plant ash-chitosan compound solution, optimizing the interfacial activity between raw materials such as plant ash and bentonite agent, and improving the bonding degree between raw materials. Using a calcined talc modifier doped with α-aluminum oxide and lanthanum sulfate solution to compound and coordinate to improve the plant ash-chitosan compound solution. Thus, the prepared plant ash modified compound solution can better synergistically effect with the bentonite agent under ball milling conditions. The bentonite is activated and dispersed with hydrochloric acid solution, and then heat-treated at 350-400°C for 15-20 minutes. After the treatment, it is cooled to room temperature at a rate of 2-4°C / min to optimize its activity, and at the same time expand its lamellae and increase the lamellar spacing. The bentonite with improved spacing is interspersed in the system, which can provide a stable environment for the system, improve the acid corrosion resistance and temperature resistance of the product. At the same time, the calcined talc modifier doped with α-aluminum oxide coordinated by plant ash can better synergistically effect with the bentonite agent, improving the easy-cleaning performance and strength performance of the product. The calcined talc modifier doped with α-aluminum oxide is ultrasonically dispersed and activated with a mixed acid solution using calcined talc, and coordinated synergistically with α-aluminum oxide, yttrium nitrate solution, isopropyltri(dioctylpyrophosphato)titanate and sodium lignosulfonate to further enhance the easy-cleaning efficiency of the system, and at the same time optimize the temperature resistance and acid corrosion resistance stability of the system. Specific embodiments

[0036] The following combines specific embodiments to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of protection of the present invention.

[0037] The antique unearthed ceramic glaze proposed by the present invention includes the following raw materials in parts by weight:

[0038] 25 - 30 parts of kaolin, 20 - 30 parts of limestone, 10 - 20 parts of the compounded bentonite modifying regulator of plant ash, 2 - 5 parts of quartz powder;

[0039] The method for making a ceramic product from the said ceramic glaze is as follows:

[0040] Step 1, raw material processing: Weigh the above raw materials accurately according to the formula and place them in a high-speed ball mill for wet grinding; the ratio of materials: balls: water in the ball mill is 1:(1.5 - 2):0.6; the ball milling time is 25 minutes, the fineness of the glaze is 0.3 - 0.5% of the residue on the ten-thousand-hole sieve, and the specific gravity is 1.55 - 1.65 g / cm 3 , and the glaze slurry is homogenized and aged for 3 - 5 days;

[0041] Step 2, glazing: After homogenization, the glaze slurry is passed through a 100-mesh sieve, with a specific gravity of 1.55 - 1.65 g / cm 3 , and the flow rate is 40 seconds;

[0042] Step 3, use the biscuit body to remove ash and brush water, wash away the dust and make the water absorption rate of the body consistent; use dipping, pouring, and spraying glazing methods to evenly coat the glaze slurry in Step 2 onto the body to obtain a glazed body; the glazed body is naturally dried with a water content of less than 1%;

[0043] Step 4, glaze firing: Fire the glazed body in Step 3 in an electric kiln at a temperature of 1250 - 1270 °C for 8 - 10 hours to obtain the ceramic product.

[0044] The preparation method of the compounded bentonite modifying regulator of plant ash proposed by the present invention is as follows:

[0045] S01: Add plant ash to the chitosan aqueous solution with a mass fraction of 5 - 7% according to a weight ratio of 1:4, and then add sodium dodecyl sulfate accounting for 1 - 3% of the total amount of plant ash, and stir evenly first to obtain a plant ash - chitosan blending solution;

[0046] S02: Then add the calcined talc modifier doped with α - alumina accounting for 3 - 6% of the total amount of the plant ash - chitosan blending solution and the lanthanum sulfate solution accounting for 1 - 5% of the total amount of the plant ash - chitosan blending solution to the plant ash - chitosan blending solution, and stir well to obtain a plant ash modified blending solution;

[0047] S03: Add bentonite to the hydrochloric acid solution with a mass fraction of 5% according to a weight ratio of 3:7 and stir evenly, then wash with water and dry, and then heat - treat at 350 - 400 °C for 15 - 20 min. After the treatment is completed, cool to room temperature at a rate of 2 - 4 °C / min to obtain a bentonite agent;

[0048] S04: Add the plant ash modification solution which is 15 - 20% of the total amount of bentonite agent to the bentonite agent, ball mill for 1 - 2 h at a rotation speed of 1000 - 1500 r / min. After the ball milling is completed, wash with water and dry to obtain the plant ash re - adjusted bentonite modification regulator.

[0049] The mass fraction of the lanthanum sulfate solution in the present invention is 4 - 8%.

[0050] The preparation method of the doped α - alumina - modified pyrophyllite modifier in the present invention is as follows:

[0051] Add pyrophyllite to the mixed acid solution according to the weight ratio of 1:5, first perform ultrasonic dispersion for 1 - 2 h, the ultrasonic power is 350 - 400 W. After the ultrasonic dispersion is completed, wash with water and dry to obtain the pyrophyllite modification body;

[0052] Add 5 - 10 parts of the pyrophyllite modification body and 2 - 5 parts of α - alumina to 15 - 20 parts of yttrium nitrate solution, then add 1 - 3 parts of isopropyltri(dioctylpyrophosphato) titanate and 1 - 2 parts of sodium lignosulfonate, stir and react. After the reaction is completed, wash with water and dry to obtain the doped α - alumina - modified pyrophyllite modifier.

[0053] The mixed acid solution in the present invention is obtained by mixing citric acid, deionized water and hydrochloric acid according to the weight ratio of 2:5:1; the mass fraction of the yttrium nitrate solution is 1 - 5%.

[0054] The stirring temperature of the stirring reaction treatment in the present invention is 42 - 44 °C, the rotation speed is 550 - 750 r / min, and the stirring time is 30 - 40 min.

[0055] The preparation method of the biscuit body in the present invention is as follows:

[0056] Weigh the body raw materials: 20 - 30 parts of albite, 5 - 10 parts of calcium carbonate, 5 - 10 parts of pyrophyllite, 4 - 8 parts of whisker - blended magnesium oxide agent; then mix the body raw materials evenly to obtain the body material;

[0057] The body material is mixed with water according to the ratio of 1.5:1, ball milled to make the body mud, the body mud is injection - molded, dried to obtain the initial body, then perform conventional body trimming, and finally perform biscuit firing at 950 - 1050 °C for 3 - 5 h to obtain the biscuit body.

[0058] The preparation method of the whisker - blended magnesium oxide agent in the present invention is as follows:

[0059] S101: First pre - heat the silicon carbide whiskers at 115 - 125 °C for 10 - 20 min, then heat them at a rate of 3 - 5 °C / s to 160 - 170 °C, keep them warm for 2 - 5 min, and then air - cool to room temperature;

[0060] S102: Then it is sent to be refrigerated at -5°C for 2 - 6 minutes, and then combined with proton irradiation treatment. After the irradiation ends, it is reserved for use.

[0061] S103: Then add cetyltrimethylammonium bromide accounting for 4 - 8% of the total amount of the S102 product, magnesium oxide accounting for 10 - 15% of the total amount of the S102 product, and dopamine solution accounting for 2 - 5% of the total amount of the S102 product to the S102 product. Then ball mill at a rotation speed of 1000 - 1500 r / min for 1 - 2 hours. After the ball milling ends, wash with water and dry to obtain the whisker - blended magnesium oxide agent.

[0062] In this embodiment, the power of the proton irradiation in S102 is 300 - 350 W, and the irradiation time is 10 - 20 minutes.

[0063] In the present invention, the mass fraction of the dopamine solution in S103 is 5 - 10%.

[0064] Example 1.

[0065] The antique - style unearthed ceramic glaze in this embodiment includes the following raw materials in parts by weight:

[0066] Kaolin 25 parts, limestone 20 parts, compounded bentonite modified regulator with plant ash 10 parts, quartz powder 2 parts;

[0067] The method for making the ceramic glaze into a ceramic product is as follows:

[0068] Step 1, raw material processing: Weigh the above - mentioned raw materials accurately according to the formula and place them in a high - speed ball mill for wet pulverization processing; the ratio of material: ball: water in the ball mill is 1:1.5:0.6; the ball - milling time is 25 minutes, the fineness of the glaze is 0.3% residue on a ten - thousand - hole sieve, and the specific gravity is 1.55 g / cm 3 , and the glaze slurry is homogenized and aged for 3 days;

[0069] Step 2, glazing: After homogenization, the glaze slurry is passed through a 100 - mesh sieve, with a specific gravity of 1.55 g / cm 3 , and the flow rate is 40 seconds;

[0070] Step 3, use a biscuit body to remove ash and brush water to wash away the dust and make the water absorption rate of the biscuit body consistent; use dipping, pouring, and spraying glazing methods to evenly coat the glaze slurry in Step 2 onto the biscuit body to obtain a glazed biscuit; the glazed biscuit is naturally dried with a water content of less than 1%;

[0071] Step 4, glaze firing: Fire the glazed biscuit in an electric kiln at a temperature of 1250°C for 8 hours to obtain the ceramic product.

[0072] The preparation method of the compounded bentonite modified regulator with plant ash in this embodiment is as follows:

[0073] S01: Add plant ash to the chitosan aqueous solution with a mass fraction of 5% at a weight ratio of 1:4, and then add sodium dodecyl sulfate accounting for 1% of the total amount of plant ash. Stir evenly first to obtain a plant ash-chitosan blending solution;

[0074] S02: Then add a calcined talc modifier doped with α-aluminum oxide accounting for 3% of the total amount of the plant ash-chitosan blending solution and a lanthanum sulfate solution accounting for 1% of the total amount of the plant ash-chitosan blending solution to the plant ash-chitosan blending solution, and stir thoroughly to obtain a plant ash modified blending solution;

[0075] S03: Add bentonite to the hydrochloric acid solution with a mass fraction of 5% at a weight ratio of 3:7, stir evenly, then wash with water and dry, and then perform heat treatment at 350 °C for 15 min. After the treatment, cool to room temperature at a rate of 2 °C / min to obtain a bentonite agent;

[0076] S04: Add the plant ash modified blending solution accounting for 15% of the total amount of the bentonite agent to the bentonite agent, ball mill at a rotation speed of 1000 r / min for 1 h. After the ball milling, wash with water and dry to obtain a plant ash re-blended bentonite modified regulator.

[0077] In this embodiment, the mass fraction of the lanthanum sulfate solution is 4-8%.

[0078] The preparation method of the calcined talc modifier doped with α-aluminum oxide in this embodiment is as follows:

[0079] Add calcined talc to the mixed acid solution at a weight ratio of 1:5, first perform ultrasonic dispersion for 1 h, the ultrasonic power is 350 W. After the ultrasonic dispersion, wash with water and dry to obtain a calcined talc modified body;

[0080] Add 5 parts of the calcined talc modified body and 2 parts of α-aluminum oxide to 15 parts of yttrium nitrate solution, then add 1 part of isopropyl tri(dioctylpyrophosphato) titanate and 1 part of sodium lignosulfonate, and perform stirring reaction treatment. After the treatment, wash with water and dry again to obtain a calcined talc modifier doped with α-aluminum oxide.

[0081] The mixed acid solution in this embodiment is obtained by mixing citric acid, deionized water and hydrochloric acid at a weight ratio of 2:5:1; the mass fraction of the yttrium nitrate solution is 1%.

[0082] In this embodiment, the stirring temperature of the stirring reaction treatment is 42 °C, the rotation speed is 550 r / min, and the stirring time is 30 min.

[0083] The preparation method of the green body in this embodiment is as follows:

[0084] Weigh the body raw materials: weigh 20 parts of albite, 5 parts of calcium carbonate, 5 parts of pyrophyllite, and 4 parts of whisker-modified magnesium oxide agent; then mix the body raw materials evenly to obtain a body material;

[0085] The green body material is mixed with water in a ratio of 1.5:1, ball milled to form a green body mud material, the green body mud material is injection molded and dried to obtain a preliminary green body, then it is subjected to conventional green body trimming, and finally it is biscuit fired at 950 °C for 3 h to obtain a biscuit fired green body.

[0086] The preparation method of the whisker-modified magnesium oxide agent in this embodiment is as follows:

[0087] S101: First, preheat the silicon carbide whiskers at 115 °C for 10 min, then increase the temperature to 160 °C at a rate of 3 °C / s, hold for 2 min, and then air cool to room temperature;

[0088] S102: Then it is sent to be refrigerated at -5 °C for 2 min, and then combined with proton irradiation treatment. After the irradiation ends, it is reserved;

[0089] S103: Then add cetyltrimethylammonium bromide accounting for 4% of the total amount of the S102 product, magnesium oxide accounting for 10% of the total amount of the S102 product, and dopamine solution accounting for 2% of the total amount of the S102 product to the product of S102, and then ball mill at a rotation speed of 1000 r / min for 1 h. After the ball milling ends, wash with water and dry to obtain the whisker-modified magnesium oxide agent.

[0090] In this embodiment, the power of the proton irradiation in S102 is 300 W, and the irradiation time is 10 min.

[0091] In this embodiment, the mass fraction of the dopamine solution in S103 is 5%.

[0092] Example 2.

[0093] The antique unearthed ceramic glaze of this embodiment comprises the following raw materials in parts by weight:

[0094] 30 parts of kaolin, 30 parts of limestone, 20 parts of the compound modified regulator of plant ash and rectorite, 5 parts of quartz powder;

[0095] The method for making the ceramic glaze into a ceramic product is as follows:

[0096] Step 1, raw material processing: Weigh the above raw materials accurately according to the formula and place them in a high-speed ball mill for wet grinding; the ratio of material: ball: water in the ball mill = 1:2:0.6; the ball milling time is 25 minutes, the fineness of the glaze is 0.5% of the residue on the ten thousand-hole sieve, and the specific gravity is 1.65 g / cm 3 , and the glaze slurry is homogenized and aged for 5 days;

[0097] Step 2, glazing: After homogenization, the glaze slurry is sieved through a 100-mesh sieve, and the specific gravity is 1.65 g / cm 3 , and the flow rate is 40 s;

[0098] Step 3: Use the biscuit body to remove ash and brush water to wash away the dust and make the water absorption rate of the body uniform; use dipping, spraying, or glazing methods to evenly apply the glaze slurry from Step 2 to the body to obtain a glazed body; let the glazed body dry naturally until the water content is less than 1%.

[0099] Step 4: Glaze firing: Fire the glazed body from Step 3 in an electric kiln at a temperature of 1270 °C for 10 hours to obtain the ceramic product.

[0100] The preparation method of the wood ash compounded bentonite modifier in this example is as follows:

[0101] S01: Add wood ash to a 7% chitosan aqueous solution at a weight ratio of 1:4, then add 3% sodium dodecyl sulfate based on the total amount of wood ash, and stir evenly first to obtain a wood ash-chitosan blending solution.

[0102] S02: Then add 6% of the calcined talc modifier doped with α-aluminum oxide and 5% of the lanthanum sulfate solution based on the total amount of the wood ash-chitosan blending solution to the wood ash-chitosan blending solution, and stir well to obtain a wood ash modified blending solution.

[0103] S03: Add bentonite to a 5% hydrochloric acid solution at a weight ratio of 3:7 and stir evenly, then wash with water and dry, and then heat-treat at 400 °C for 20 min. After the treatment is completed, cool to room temperature at a rate of 4 °C / min to obtain a bentonite agent.

[0104] S04: Add 20% of the wood ash modified blending solution based on the total amount of the bentonite agent to the bentonite agent, and ball mill at a rotation speed of 1500 r / min for 2 h. After the ball milling is completed, wash with water and dry to obtain the wood ash compounded bentonite modifier.

[0105] The mass fraction of the lanthanum sulfate solution in this example is 8%.

[0106] The preparation method of the calcined talc modifier doped with α-aluminum oxide in this example is as follows:

[0107] Add calcined talc to a mixed acid solution at a weight ratio of 1:5 and ultrasonically disperse for 2 h. The ultrasonic power is 400 W. After the ultrasonic treatment is completed, wash with water and dry to obtain a calcined talc modified body.

[0108] Add 10 parts of the calcined talc modified body and 5 parts of α-aluminum oxide to 20 parts of yttrium nitrate solution, then add 3 parts of isopropyltri(dioctylpyrophosphato)titanate and 2 parts of sodium lignosulfonate, and stir and react. After the treatment is completed, wash with water and dry to obtain the calcined talc modifier doped with α-aluminum oxide.

[0109] The mixed acid solution in this embodiment is obtained by mixing citric acid, deionized water and hydrochloric acid in a weight ratio of 2:5:1; the mass fraction of the yttrium nitrate solution is 5%.

[0110] In this embodiment, the stirring temperature of the stirring reaction treatment is 44 °C, the rotation speed is 750 r / min, and the stirring time is 40 min.

[0111] The preparation method of the biscuit body in this embodiment is as follows:

[0112] Weigh the body raw materials: weigh 30 parts of albite, 10 parts of calcium carbonate, 10 parts of pyrophyllite, and 8 parts of whisker-modified magnesium oxide agent; then mix the body raw materials evenly to obtain the body material.

[0113] The body material is mixed with water in a ratio of 1.5:1, ball-milled to form a body mud, the body mud is injection-molded, dried to obtain a preliminary body, then subjected to conventional body trimming, and finally biscuit-fired at 1050 °C for 5 h to obtain the biscuit body.

[0114] The preparation method of the whisker-modified magnesium oxide agent in this embodiment is as follows:

[0115] S101: First preheat the silicon carbide whiskers at 125 °C for 20 min, then heat them up to 170 °C at a rate of 5 °C / s, hold for 5 min, and then air-cool to room temperature.

[0116] S102: Then send them to be refrigerated at -5 °C for 6 min, and then jointly perform proton irradiation treatment. After the irradiation is completed, set aside for use.

[0117] S103: Then add 8% of cetyltrimethylammonium bromide, 15% of magnesium oxide, and 5% of dopamine solution based on the total amount of the S102 product to the S102 product, and then ball-mill at a rotation speed of 1500 r / min for 2 h. After the ball-milling is completed, wash with water and dry to obtain the whisker-modified magnesium oxide agent.

[0118] In this embodiment, the power of the proton irradiation in S102 is 350 W, and the irradiation time is 20 min.

[0119] In this embodiment, the mass fraction of the dopamine solution in S103 is 10%.

[0120] Example 3.

[0121] The antique unearthed ceramic glaze in this embodiment comprises the following raw materials in parts by weight:

[0122] 27.5 parts of kaolin, 25 parts of limestone, 15 parts of plant ash complex-modified bentonite modifier, and 3.5 parts of quartz powder.

[0123] The method for making a ceramic product from the said ceramic glaze is as follows:

[0124] Step 1, raw material processing: Weigh the above raw materials accurately according to the formula and place them in a high-speed ball mill for wet grinding; the ratio of materials: balls: water in the ball mill is 1:1.75:0.6; the ball milling time is 25 minutes, the sieve residue of the glaze through a ten-thousand-hole sieve is 0.4%, and the specific gravity is 1.60 g / cm 3 , and the glaze slurry is homogenized and aged for 4 days;

[0125] Step 2, glazing: After homogenization, the glaze slurry is passed through a 100-mesh sieve, with a specific gravity of 1.60 g / cm 3 , and the flow rate is 40 seconds;

[0126] Step 3, remove ash and brush water on the biscuit body, wash away the dust and make the water absorption rate of the biscuit body consistent; use dipping, pouring, and spraying glazing methods to evenly coat the glaze slurry in Step 2 onto the biscuit body to obtain a glazed biscuit; the glazed biscuit is naturally dried with a water content of less than 1%;

[0127] Step 4, glaze firing: Fire the glazed biscuit in Step 3 in an electric kiln at a temperature of 1260 °C for 9 hours to obtain the ceramic product.

[0128] The preparation method of the wood ash compounded bentonite modifier in this embodiment is as follows:

[0129] S01: Add wood ash to the chitosan aqueous solution with a mass fraction of 6% according to a weight ratio of 1:4, and then add sodium dodecyl sulfate accounting for 2% of the total amount of wood ash, and stir evenly first to obtain a wood ash-chitosan blending liquid;

[0130] S02: Then add a calcined talc modifier doped with α-aluminum oxide accounting for 4.5% of the total amount of the wood ash-chitosan blending liquid and a lanthanum sulfate solution accounting for 3% of the total amount of the wood ash-chitosan blending liquid to the wood ash-chitosan blending liquid, and stir well to obtain a wood ash modified blending liquid;

[0131] S03: Add bentonite to the hydrochloric acid solution with a mass fraction of 5% according to a weight ratio of 3:7 and stir evenly, then wash with water and dry, and then heat-treat at 375 °C for 17 minutes. After the treatment is completed, cool to room temperature at a rate of 3 °C / min to obtain a bentonite agent;

[0132] S04: Add the wood ash modified blending liquid accounting for 17.5% of the total amount of the bentonite agent to the bentonite agent, ball mill at a rotation speed of 1250 r / min for 1.5 h, after the ball milling is completed, wash with water and dry to obtain the wood ash compounded bentonite modifier.

[0133] The mass fraction of the lanthanum sulfate solution in this embodiment is 6%.

[0134] The preparation method of the calcined talc modifier doped with α-aluminum oxide in this embodiment is as follows:

[0135] Add calcined talc to the mixed acid solution at a weight ratio of 1:5, ultrasonically disperse for 1.5 h, with an ultrasonic power of 370 W. After the ultrasonic treatment, wash with water and dry to obtain the modified calcined talc;

[0136] Add 7.5 parts of the modified calcined talc and 3.5 parts of α-aluminum oxide to 17.5 parts of yttrium nitrate solution, then add 2 parts of isopropyltri(dioctylpyrophosphato) titanate and 1.5 parts of sodium lignosulfonate, stir and react. After the reaction, wash with water and dry to obtain the modified calcined talc doped with α-aluminum oxide.

[0137] The mixed acid solution in this example is obtained by mixing citric acid, deionized water, and hydrochloric acid at a weight ratio of 2:5:1; the mass fraction of the yttrium nitrate solution is 2%.

[0138] In this example, the stirring temperature for the stirring reaction treatment is 43 °C, the rotation speed is 600 r / min, and the stirring time is 35 min.

[0139] The preparation method of the green body in this example is as follows:

[0140] Weigh the green body raw materials: 25 parts of albite, 7.5 parts of calcium carbonate, 7.5 parts of pyrophyllite, and 6 parts of whisker-blended magnesium oxide agent; then mix the green body raw materials evenly to obtain the green body material;

[0141] The green body material is mixed with water at a ratio of 1.5:1, ball-milled to form the green body mud, the green body mud is injection-molded, dried to obtain the initial green body, then subjected to conventional green body trimming, and finally sintered at 1000 °C for 4 h to obtain the green body.

[0142] The preparation method of the whisker-blended magnesium oxide agent in this example is as follows:

[0143] S101: Preheat the silicon carbide whiskers at 120 °C for 15 min, then heat at a rate of 4 °C / s to 165 °C, hold for 3 min, and then air-cool to room temperature;

[0144] S102: Then send it to be refrigerated at -5 °C for 4 min, and then jointly perform proton irradiation treatment. After the irradiation, set it aside for use;

[0145] S103: Then add 6% of cetyltrimethylammonium bromide, 12% of magnesium oxide, and 3.5% of dopamine solution based on the total amount of the S102 product to the S102 product, and then ball-mill at a rotation speed of 1250 r / min for 1.5 h. After the ball-milling, wash with water and dry to obtain the whisker-blended magnesium oxide agent.

[0146] In this example, the power of the proton irradiation in S102 is 325 W, and the irradiation time is 15 min.

[0147] In S103 of this embodiment, the mass fraction of the dopamine solution is 7.5%.

[0148] Comparative Example 1.

[0149] Different from Example 3, the plant ash compounded bentonite modifier is not added.

[0150] Comparative Example 2.

[0151] Different from Example 3, bentonite is used instead of bentonite agent in the preparation of the plant ash compounded bentonite modifier.

[0152] Comparative Example 3.

[0153] Different from Example 3, plant ash is not added to the plant ash modified and blended liquid in the preparation of the plant ash compounded bentonite modifier.

[0154] Comparative Example 4.

[0155] Different from Example 3, lanthanum sulfate solution is not added in the preparation of the plant ash compounded bentonite modifier.

[0156] Comparative Example 5.

[0157] Different from Example 3, the modified talc modified with doped α-aluminum oxide is not added in the preparation of the plant ash compounded bentonite modifier.

[0158] Comparative Example 6.

[0159] Different from Example 3, the whisker blended magnesium oxide agent is not added in the preparation of the green body.

[0160] Comparative Example 7.

[0161] Different from Example 3, the treatment of Step S102 is not adopted in the preparation of the whisker blended magnesium oxide agent.

[0162] Comparative Example 8.

[0163] Different from Example 3, the silicon carbide whiskers are preheated at 120 °C for 15 min and then air-cooled to room temperature in the preparation of the whisker blended magnesium oxide agent.

[0164] Comparative Example 9.

[0165] Different from Example 3, magnesium oxide is not added in the preparation of the whisker blended magnesium oxide agent.

[0166] Comparative Example 10.

[0167] Different from Example 3, dopamine solution is not added in the preparation of the whisker blended magnesium oxide agent.

[0168] Apply the contaminated material with a weight ratio of oil stain to dust of 3:1 onto the product, then place it at 35°C for 5 hours, wipe it, and test the wiping force to wipe the contaminated material clean;

[0169] Conduct performance tests on the products of Examples 1 to 3 and Comparative Examples 1 to 10. At the same time, place the products under the condition of 2% hydrochloric acid mist for 12 hours, and place the products at 65°C for 12 hours, and test the acid corrosion resistance and temperature resistance of the products respectively. The test results are as follows

[0170]

[0171]

[0172] It can be seen from Comparative Examples 1-10 and Examples 1-3;

[0173] The product of Example 3 has excellent easy-cleaning ability, and at the same time has excellent flexural strength performance. The two can be coordinately improved. In addition, the product has excellent performance stability under acid corrosion conditions and high temperature resistance;

[0174] It can be seen from Comparative Example 1, Comparative Example 6 and Example 3 that in the present invention, the compounded bentonite modified regulator of plant ash is not added, and the whisker and magnesium oxide agent are not added in the preparation of the biscuit body. The wiping force and flexural strength of the product both show an obvious downward trend. Without adding the compounded bentonite modified regulator of plant ash, the easy self-cleaning ability of the product becomes significantly worse. Without adding the whisker and magnesium oxide agent in the preparation of the biscuit body, the flexural strength performance becomes significantly worse. By using the compounded bentonite modified regulator of plant ash and not adding the whisker and magnesium oxide agent in the preparation of the biscuit body, the performance of the product can be coordinately improved;

[0175] It can be seen from Comparative Examples 1-5 and Example 3 that in the preparation of the compounded bentonite modified regulator of plant ash, bentonite is used instead of bentonite agent, plant ash is not added in the plant ash modified and blended liquid, lanthanum sulfate solution is not added in the preparation of the compounded bentonite modified regulator of plant ash, and the modified agent of calcined talc doped with α-aluminum oxide is not added in the preparation of the compounded bentonite modified regulator of plant ash. The performance of the product all shows a downward trend. Only by using the compounded bentonite modified regulator of plant ash prepared by the method of the present invention, the performance effect of the product is the most significant; at the same time, not adding the modified agent of calcined talc doped with α-aluminum oxide has the greatest influence on the performance in the preparation of the compounded bentonite modified regulator of plant ash. Only by using the compounded bentonite modified regulator of plant ash prepared by the modified agent of calcined talc doped with α-aluminum oxide, the performance effect of the product is the most obvious;

[0176] It can be seen from Comparative Examples 6-10 and Example 3 that in the preparation of the whisker-modified magnesium oxide agent, the S102 step was not adopted; in the preparation of the whisker-modified magnesium oxide agent, the silicon carbide whiskers were preheated at 120°C for 15 minutes and then air-cooled to room temperature; in the preparation of the whisker-modified magnesium oxide agent, magnesium oxide was not added; in the preparation of the whisker-modified magnesium oxide agent, dopamine solution was not added, and the performance of the products all showed a deteriorating trend. Only when the whisker-modified magnesium oxide agent prepared by the method of the present invention is combined with the plant ash complex-modified bentonite modifier prepared by the method of the present invention, the performance effect of the product is the most obvious.

[0177] The present invention further explores the product performance by preparing a calcined talc modifier doped with α-aluminum oxide;

[0178] Experimental Example 1.

[0179] The only difference from Example 3 is that α-aluminum oxide was not added in the preparation of the calcined talc modifier doped with α-aluminum oxide.

[0180] Experimental Example 2.

[0181] The only difference from Example 3 is that the calcined talc modifier in the preparation of the calcined talc modifier doped with α-aluminum oxide was replaced with calcined talc.

[0182] Experimental Example 3.

[0183] The only difference from Example 3 is that the yttrium nitrate solution in the preparation of the calcined talc modifier doped with α-aluminum oxide was replaced with deionized water.

[0184] Experimental Example 4.

[0185] The only difference from Example 3 is that sodium lignosulfonate was not added in the preparation of the calcined talc modifier doped with α-aluminum oxide.

[0186] Experimental Example 5.

[0187] The only difference from Example 3 is that the calcined talc in the preparation of the calcined talc modifier doped with α-aluminum oxide was replaced with graphene.

[0188]

[0189] As can be seen from Experimental Examples 1-5, in the preparation of the talc modifier doped with α-aluminum oxide, when α-aluminum oxide was not added and graphene was used instead of talc, the performance of the product was most affected by the factors in the preparation of the talc modifier doped with α-aluminum oxide. The selection of α-aluminum oxide and talc in the preparation of the talc modifier doped with α-aluminum oxide was proprietary. Replacing them with other raw materials was not as effective as the present invention. When the talc modifier was replaced with talc, the yttrium nitrate solution was replaced with deionized water, and sodium lignosulfonate was not added in the preparation of the talc modifier doped with α-aluminum oxide, the performance of the product showed a deteriorating trend. Only by using the process ingredients and process conditions of the present invention, the performance effect of the product was the most significant. The talc modifier doped with α-aluminum oxide prepared by other methods was not as effective as the present invention.

[0190] Through experimental studies on the chemical composition, color development, and firing temperature of unearthed ceramics, the present invention obtained a glaze formula and fired ceramic products, filling the archaeological gap in the historical production of physical ceramic products using local ceramic raw materials.

[0191] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0192] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An antique imitation unearthed ceramic glaze, characterized in that, It includes the following raw materials in parts by weight: 25-30 parts of kaolin, 20-30 parts of limestone, 10-20 parts of wood ash compounded bentonite modification regulator, and 2-5 parts of quartz powder; The method for preparing ceramic products from the ceramic glaze is as follows: Step 1, raw material processing: Weigh the above raw materials accurately according to the formula and place them in a high-speed ball mill for wet grinding; the ratio of materials: balls: water in the ball mill is 1: (1.5 - 2): 0.6; the ball milling time is 25 minutes, the fineness of the glaze is 0.3 - 0.5% of the residue on a 10,000-hole sieve, and the specific gravity is 1.55 - 1.65 g / cm 3 , and the glaze slurry is homogenized and aged for 3 - 5 days; Step 2, glazing: After homogenization, the glaze slurry is passed through a 100-mesh sieve, with a specific gravity of 1.55 - 1.65 g / cm 3 , and the flow rate is 40 seconds; Step 3: Use the unglazed body to remove dust and brush water to clean the dust so that the water absorption rate of the body is uniform; use the dipping, pouring or spraying method to evenly apply the glaze slurry of step 2 to the body to obtain a glaze body; the glaze body is naturally dried to a water content of less than 1%; Step 4: Glaze firing: The glaze blank prepared in step 3 is fired in an electric kiln at 1250-1270°C for 8-10 hours to obtain a ceramic product. The preparation method of the plant ash compounded bentonite modified regulator is as follows: S01: Add wood ash to a chitosan aqueous solution with a mass fraction of 5-7% in a weight ratio of 1:4, then add sodium lauryl sulfate at a mass fraction of 1-3% of the total amount of wood ash, and stir evenly to obtain a wood ash-chitosan mixture; S02: Then, adding 3-6% of the total amount of the plant ash-chitosan formulation of the plant ash-chitosan formulation of α-alumina-doped talc modifier and 1-5% of the total amount of the plant ash-chitosan formulation of the plant ash-chitosan formulation of the lanthanum sulfate solution to the plant ash-chitosan formulation, stirring thoroughly to obtain a plant ash-modified formulation; S03: adding bentonite to a 5% hydrochloric acid solution in a weight ratio of 3:7 and stirring evenly, then washing with water, drying, and heat treating at 350-400°C for 15-20 minutes. After the treatment, cooling to room temperature at a rate of 2-4°C / min to obtain a bentonite agent; S04: adding 15-20% of the total amount of bentonite to the plant ash modified blending liquid into the bentonite agent, ball milling at a speed of 1000-1500 r / min for 1-2 hours, washing with water, and drying to obtain the plant ash composite bentonite modified conditioning agent; The preparation method of the calcined talc modifier doped with α-alumina is as follows: Add calcined talc to the mixed acid solution at a weight ratio of 1:5 and perform ultrasonic dispersion for 1-2 hours at an ultrasonic power of 350-400W. After the ultrasonic dispersion is completed, wash with water and dry to obtain a modified calcined talc. 5 to 10 parts of calcined talc modifier and 2 to 5 parts of α-alumina are added to 15 to 20 parts of yttrium nitrate solution, and then 1 to 3 parts of isopropyl tri(dioctyl pyrophosphate) titanate and 1 to 2 parts of sodium lignin sulfonate are added. The mixture is stirred for reaction. After the reaction is completed, the mixture is washed with water and dried to obtain a calcined talc modifier doped with α-alumina.

2. An imitated ancient unearthed ceramic glaze according to claim 1, characterized in that, The mass fraction of the lanthanum sulfate solution is 4-8%.

3. An antique imitation unearthed ceramic glaze according to claim 1, characterized in that, The mixed acid solution is obtained by mixing citric acid, deionized water and hydrochloric acid in a weight ratio of 2:5:1; the mass fraction of the yttrium nitrate solution is 1-5%.

4. An imitated ancient unearthed ceramic glaze according to claim 1, characterized in that, The stirring temperature of the stirring reaction treatment is 42-44° C., the rotation speed is 550-750 r / min, and the stirring time is 30-40 min.

5. An antique imitation unearthed ceramic glaze according to claim 1, characterized in that, The preparation method of the bisque-fired green body is as follows: Weigh the following raw materials for the green body: 20-30 parts of albite, 5-10 parts of calcium carbonate, 5-10 parts of pyrophyllite, and 4-8 parts of whisker-blended magnesium oxide; Then, the above green body raw materials are mixed evenly to obtain green body material; The green body material is mixed with water in a ratio of 1.5:1, ball milled to form a green body mud material, the green body mud material is injection molded and dried to obtain a preliminary green body, then conventional green body trimming is carried out, and finally it is biscuit fired at 950 - 1050 °C for 3 - 5 h to obtain a biscuit fired green body; The preparation method of the whisker - blended magnesium oxide agent is as follows: S101: First, pre - heat the silicon carbide whiskers at 115 - 125 °C for 10 - 20 min, then heat them at a rate of 3 - 5 °C / s to 160 - 170 °C, keep warm for 2 - 5 min, and then air - cool to room temperature; S102: Then send them to be refrigerated at - 5 °C for 2 - 6 min, and then jointly carry out proton irradiation treatment. After the irradiation ends, set aside for use; S103: Then add cetyltrimethylammonium bromide accounting for 4 - 8% of the total amount of the S102 product, magnesium oxide accounting for 10 - 15% of the total amount of the S102 product, and dopamine solution accounting for 2 - 5% of the total amount of the S102 product to the product of S102, and then ball mill at a rotation speed of 1000 - 1500 r / min for 1 - 2 h. After the ball milling ends, wash with water and dry to obtain the whisker - blended magnesium oxide agent.

6. An antique unearthed ceramic glaze according to claim 5, characterized in that, The power of the proton irradiation in S102 is 300 - 350 W, and the irradiation time is 10 - 20 min.

7. An antique imitation unearthed ceramic glaze according to claim 5, characterized in that, The mass fraction of the dopamine solution in S103 is 5 - 10%.

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