CN115572150A - Barite radiation-proof ceramic plate and preparation method thereof - Google Patents
Barite radiation-proof ceramic plate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a barite radiation-proof ceramic plate and a preparation method thereof. The barite radiation-proof ceramic plate prepared by the invention is a novel functional plate, has excellent radiation resistance, is simple, stable and reliable in manufacturing process, easy to control quality, low in cost and environment-friendly, and is a new way for utilizing barite.
Description
Technical Field
The invention relates to a ceramic plate and a preparation method thereof, in particular to a preparation method of a barite radiation-proof ceramic plate prepared by taking silicate and alumina as main sintering aids.
Background
The barite is a dominant mineral resource in China and is widely applied to the fields of petroleum, chemical engineering, fillers, medicines and the like.
The barite is barium sulfate (BaSO) 4 ) The nonmetallic mineral product as the main component is white and glossy, and is also gray, light red, light yellow and the like due to the influence of impurities and mixed substances, and is a mixture. Barium is more front than lead in the periodic table of elements, has no radioactivity, has a relatively large atomic weight, has a high probability of generating a photoelectric effect with rays, and is very beneficial to preventing ionizing radiation. Barium ion has a lower valence thanHigh dielectric constant or magnetization, and good magnetic loss effect on non-ionizing radiation. The barite has stable chemical property and no toxicity, and the application of the barite in the radiation protection aspect is increasingly emphasized.
At present, the barite is mostly applied to concrete filler as a radiation-proof material, and the radiation-proof effect is achieved by filling barite powder (particles) in an interlayer of a concrete wall. The method has the advantages of simple construction and technology and convenient implementation, and mainly has the problems that high compactness is not easy to realize when the barite is filled, and in a microscopic view, large physical gaps exist among barite powder (particles), so that rays are easy to penetrate, the whole body needs to be thick and heavy, the occupied area is large, the standardization is poor, and the method is not attractive so as to limit the application range and places of the method.
The other kind of barite radiation-proof plate is made up by using barite powder as main component (in which a portion of fibre can be added to raise strength), then adding unsaturated polyester, epoxy resin and phenolic resin, and pressing them into plate material. Its advantages are high mechanical strength, high dirt resistance, corrosion resistance, normalization and simple construction. However, the production of the board has high requirements on equipment, relatively complex production process and high cost, and because the organic solvent is used in the adhesive, a large amount of bubbles are generated inside and on the surface of the board, so that the bubbles are difficult to completely eliminate, and the radiation resistance of the board is influenced.
The invention relates to a method for manufacturing a radiation-proof ceramic plate by taking barite as a basic raw material, which is characterized in that on the basis of basically not damaging the main structure and components of the barite, a sintering aid, a structure reinforcing agent and new compounds are generated on the surfaces of barite particles through high-temperature sintering to form an adhesive tape with enough strength, so that the barite particles form a whole with high density and high strength again to manufacture the radiation-proof ceramic plate.
The invention utilizes barite as a matrix to prepare the radiation-proof ceramic plate, has the characteristics of meeting the relevant national standard, stable radiation resistance, high radiation resistance index, simple and quick installation, attractive appearance and the like, can be widely applied to walls and grounds of radiation-resistant places such as radiology departments, laboratories, nuclear radiation research institutes (houses), home fine decorations and the like of medical institutions, and is a new scheme for efficiently utilizing barite.
Disclosure of Invention
The invention aims to provide a barite radiation-proof ceramic plate and a preparation method thereof. The barite radiation-proof ceramic plate is a novel functional plate, is a new way for utilizing barite, and is simple in preparation process, mild in condition and environment-friendly.
The technical scheme of the invention is as follows:
a barite radiation protection ceramic plate is characterized in that barite is used as a basic raw material, and silicate, silicic acid or silicon dioxide, which are the same or a plurality of the same or different, and aluminum oxide are used as sintering aids; the zinc oxide-zinc complex is prepared by using the same or a plurality of dihydric phosphate, monohydrogen phosphate and zinc oxide as a structural reinforcing agent.
The ceramic plate is prepared by using barite as a basic raw material, using silicate and aluminum oxide as sintering aids, and using dihydrogen phosphate and zinc oxide as structural reinforcing agents.
Specifically, in the barite radiation-proof ceramic plate, the silicate is sodium silicate, and the dihydrogen phosphate is aluminum dihydrogen phosphate.
The preparation method of the barite radiation-proof ceramic plate comprises the following steps:
(1) Crushing barite, wherein 85-95% of the barite has a particle size of 20 μm to obtain product A;
(2) Weighing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate, and dissolving in water to obtain product B;
(3) Adding product A into product B, stirring, oven drying, dewatering to obtain block product, crushing, and sieving with 100 mesh sieve to obtain product with particle size of 0.150 mmC;
(4) Filling the product C into a mold, pressing under 25MPa and maintaining the pressure for 2-10min to obtain a green billet, placing the green billet in a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at a temperature of 900-1100 ℃, and keeping the temperature for 1.5-3h, and sintering to obtain the radiation-proof ceramic plate.
In the step (1), the barite is crushed, and 90% of the barite has a particle size of 20 μm, so that the product A is obtained.
In the step (2), sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate are weighed according to the proportion of 5-15 to 1-7.
Specifically, in the step (2), sodium silicate, alumina, zinc oxide and aluminum dihydrogen phosphate are weighed according to a ratio of 10.
In the step (3), the weight ratio of the product A to the product B is 75-80.
Specifically, in the step (3), the weight ratio of the product A to the product B is 80.
And (5) in the step (4), filling the product C into a mold, pressing under 25MPa and maintaining the pressure for 5min to obtain a green compact, placing the green compact in a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at a temperature of 1000 ℃, and keeping the temperature for 2h to obtain the radiation-proof ceramic plate.
Compared with the prior art, the invention has the following beneficial effects:
1. the sintering aid used in the invention can be widely applied to various barites in different producing areas, and can effectively sinter the barite into the radiation-proof ceramic plate.
2. The invention relates to a novel functional plate which is made of anti-radiation ceramic plates by using sodium silicate and aluminum oxide as main sintering aids and zinc oxide and aluminum dihydrogen phosphate as structural reinforcing agents. The sintering aid and the structure reinforcing agent mainly have the functions of reacting on the surfaces of barium sulfate particles of the barite to generate barium silicate and form a barium silicate adhesive tape, so that the barium sulfate particles are connected into a whole. The process is simple, stable and reliable, the quality is easy to control, the cost is low, the method is environment-friendly, the method is a new way for utilizing the barite, and the method is expected to have good application prospects.
3. The invention can realize the manufacture of the lead equivalent value plate required by protection in different places by controlling the pressure of the plate blank during manufacture. When the green body manufacturing pressure is 25MPa, the thickness of the plate is 10mm, the lead equivalent value of the plate can reach about 1mmPb, the pressure during the plate green body manufacturing is increased, and the radiation protection effect with higher lead equivalent value can be obtained. The anti-radiation ceramic plate manufactured by the invention has excellent mechanical property, good compression resistance and apparent density of 1470kg/m in the aspect of mechanical property 3 The pressure resistance can reach 41.5MPa, the building material meets the national standard of the building material industry, the X-ray shielding material has excellent X-ray shielding effect, and the lead equivalent value reaches 0.98mmPb in the radiation protection aspect.
4. The sintering temperature and the heat preservation time are two key factors in the manufacturing process of the barite ceramic plate. The sintering temperature is too low, the chemical reaction of the internal components of the material is insufficient, and the mechanical strength of the sintered ceramic plate cannot meet the requirement; the barium sulfate in the barite is decomposed at high temperature due to the over-high sintering temperature, and the radiation resistance of the barite ceramic plate is reduced. The heat preservation time is increased, the compressive strength of the sample tends to increase and then decrease, and the mechanical property of the sample is reduced due to excessive heat preservation. According to the invention, the green block is placed in a high-temperature furnace, the heating rate is 10 ℃/min, the sintering temperature is 1000 ℃, the heat preservation time is 2h, the radiation-proof ceramic plate is fired, the production process is simple, the product quality is stable, the compression resistance is good, and the radiation-proof performance is excellent.
Drawings
FIG. 1: is a TG-DSC-DTG thermogram of a plate green body (barite: sodium silicate: alumina: zinc oxide: aluminum dihydrogen phosphate weight ratio of 80;
FIG. 2: is barite XRD analysis spectrum;
FIG. 3: XRD analysis spectrum of the ceramic plate finished product;
FIG. 4 is a schematic view of: is a 10 x 10cm sample of barite radiation protective ceramic slab.
Detailed Description
Example 1.
(1) Crushing barite, wherein the grain size of 90% of barite reaches 20 mu m, so as to obtain barite powder;
(2) Weighing 100g of sodium silicate, 50g of alumina, 25g of zinc oxide and 25g of aluminum dihydrogen phosphate, and dissolving in 800mL (800 g) of water to obtain a sintering aid solution;
(3) Dissolving 800g of barite powder in a sintering aid solution, fully stirring and uniformly mixing, drying and dehydrating at 100 ℃ to obtain a blocky product, crushing, sieving with a 100-mesh sieve to obtain fine powder with the particle size of 0.150mm, filling the fine powder into a mold, pressing under 25MPa and maintaining the pressure for 5min to obtain a green billet, placing the green billet in a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 1000 ℃, keeping the temperature for 2h, and firing to obtain the radiation-proof ceramic plate.
Example 2.
(1) Crushing barite, wherein 85% of the barite has a particle size of 20 μm, so as to obtain barite powder;
(2) Weighing 100g of sodium silicate, 60g of alumina, 20g of zinc oxide and 20g of aluminum dihydrogen phosphate, and dissolving in 800mL (800 g) of water to obtain a sintering aid solution;
(3) Adding 750g of barite powder into the sintering aid solution, fully stirring and uniformly mixing, drying and dehydrating at 100 ℃ to obtain a blocky product, crushing, sieving with a 100-mesh sieve to obtain fine powder with the particle size of 0.150mm, filling the fine powder into a mold, pressing at 25MPa and maintaining the pressure for 2min to obtain a green billet, placing the green billet into a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 950 ℃ for 2.5h, and firing to obtain the radiation-proof ceramic plate.
Example 3:
(1) Crushing barite, wherein the grain size of 95% of barite reaches 20 mu m, so as to obtain barite powder;
(2) Weighing 80g of sodium silicate, 70g of alumina, 10g of zinc oxide and 40g of aluminum dihydrogen phosphate, and dissolving in 1000mL (1000 g) of water to obtain a sintering aid solution;
(3) Adding 750g of barite powder into the sintering aid solution, fully stirring and uniformly mixing, drying and dehydrating at 100 ℃ to obtain a blocky product, crushing, sieving with a 100-mesh sieve to obtain fine powder with the particle size of 0.150mm, filling the fine powder into a mold, pressing under 25MPa and maintaining the pressure for 10min to obtain a green billet, placing the green billet into a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 1100 ℃, keeping the temperature for 1.5h, and firing to obtain the radiation-proof ceramic plate.
Example 4:
(1) Crushing barite, wherein the grain size of 90% of the barite reaches 20 mu m, so as to obtain barite powder;
(2) Weighing 140g of sodium silicate, 50g of alumina, 30g of zinc oxide and 30g of aluminum dihydrogen phosphate, and dissolving in 1200mL (1200 g) of water to obtain a sintering aid solution;
(3) Adding 800g of barite powder into the sintering aid solution, fully stirring and uniformly mixing, drying and dehydrating at 100 ℃ to obtain a block product, crushing, sieving with a 100-mesh sieve to obtain fine powder with the particle size of 0.150mm, filling the fine powder into a mold, pressing at 25MPa and maintaining the pressure for 8min to obtain a green billet, placing the green billet in a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 1050 ℃, keeping the temperature for 1.8h, and firing to obtain the radiation-proof ceramic plate.
The applicant has carried out a number of experimental studies on the present invention, partly as follows:
experimental example 1 preparation of barite raw material
The barite is crushed step by step through various crushers, and after the barite reaches the required granularity, the barite is used for later use:
1) Coarse crushing and intermediate crushing of the barite to obtain the barite with the grain diameter: 0.05-0.5 mm barite.
2) The barite with the particle size of more than 90 percent and the particle size of more than 20 mu m is obtained by ball milling the barite with the particle size of 0.05-0.5 mm.
2. Preparation of radiation-proof ceramic plate
Experimental example 2.
Preparing an anti-radiation ceramic plate from barite:
1) The barite used has a specific gravity of 3.8 and comprises the following main components: baO,52.305; SO (SO) 3 ，21.306；SiO 2 ，9.669；CaO，6.262； MgO，1.287；Al 2 O 3 ，1.125；P 2 O 5 ，1.001；Fe 2 O 3 ，0.921；Na 2 O，0.605；K 2 O，0.352；SrO，0.153；Cr 2 O 3 ，0.111；ZnO，0.091；NiO，0.037；MnO，0.035；CO 2 ,4.740. BaSO in barite 4 The mass fraction is 73.611%.
2) The preparation method comprises the following steps of mixing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate according to a weight ratio of 2.5.
3) And filling the powder into a mold, performing compression molding under 25MPa, maintaining the pressure for 5min to obtain a green body, cooling the green body along with a hearth under the conditions of a sintering temperature of 1000 ℃, a heating rate of 10 ℃/min and a heat preservation time of 2h, and firing to obtain the radiation-proof ceramic plate.
4) The mechanical property of the plate is detected according to the national standard GB/T30018-2013 sintered decorative plate, and the apparent density is 1470kg/m 3 The compressive resistance can reach 41.5MPa, and the national standard is met.
5) The radiation protection performance test is carried out according to the national standard GBZ/T147-2002X-ray protection material attenuation performance measurement, the standard X-ray (120 KV, additional filtration of 2.50 mmAl) is used for carrying out X-ray protection shielding detection, and the result is as follows: a ceramic plate sample having a thickness of 10mm had a lead equivalent value of 0.96mmPb.
Experimental example 3.
Anti-radiation ceramic plate prepared from barite
1) The barite used has a specific gravity of 4.2 and comprises the following main components: baO,58.608; SO 3 ，27.340；SiO 2 ，4.908；CaO，1.458；MgO，0.996；SrO，0.856；Na 2 O，0.685；Fe 2 O 3 ，0.592；P 2 O 5 ，0.584；Al 2 O 3 ，0.213；ZnO，0.042；K 2 O，0.035；CO 2 ,3.683. BaSO in barite 4 The mass fraction is 85.948%.
2) The preparation method comprises the following steps of mixing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate according to a weight ratio of 10.
3) And filling the powder into a mold, performing compression molding under 25MPa, maintaining the pressure for 5min to obtain a green body, cooling the green body along with a hearth at the sintering temperature of 1000 ℃, the heating rate of 10 ℃/min and the heat preservation time of 2h, and firing to obtain the radiation-proof ceramic plate.
4) The mechanical property of the barite plate is detected according to the national standard GB/T30018-2013 sintered decorative plate, and the apparent density is 1467kg/m 3 The compression resistance can reach 37.9MPa, and the national standard is met.
5) The radiation protection performance test is carried out according to the national standard GBZ/T147-2002X-ray protection material attenuation performance measurement, the standard X-ray (120 KV, additional filtration of 2.50 mmAl) is used for carrying out X-ray protection shielding detection, and the result is as follows: a sample of a ceramic plate having a thickness of 10mm had a lead equivalent value of 0.98mmPb.
Analysis of quality of barite radiation-proof ceramic plate
The sintering temperature and the heat preservation time are two key factors in the manufacturing process of the barite ceramic plate. The sintering temperature is too low, the chemical reaction of the internal components of the material is insufficient, and the mechanical strength of the sintered ceramic plate cannot meet the requirement; the barium sulfate in the barite is decomposed at high temperature due to the over-high sintering temperature, and the radiation resistance of the barite ceramic plate is reduced. The heat preservation time is increased, the compressive strength of the sample tends to increase firstly and then decrease, and the mechanical property of the sample is reduced due to excessive heat preservation.
XRD analysis and thermal analysis of the green body of barite, a finished sample (the radiation-proof ceramic plate prepared in experimental example 2) revealed the physicochemical changes and sintering mechanism that occurred during sintering. See fig. 1, 2, 3.
The change trend of the green sample in the heating process is that the whole sample is subjected to large-scale weight loss firstly and then slightly increased in weight and then slightly lost in weight, the weight loss at 200 ℃ is mainly caused by evaporation of free water in the sample and loss of crystallization water of sodium silicate, the weight loss at 200-600 ℃ is mainly caused by decomposition of phosphate, the rapid weight loss at 600-700 ℃ is mainly caused by decomposition of carbonate, and the slight weight gain at 700-1000 DEG isAnd an exothermic peak, which is presumed that the barite contains a small amount of carbon, baS and Na generated after carbothermic reduction reaction 2 SO 3 Start to absorb O in air 2 Oxidation reaction occurs to cause weight gain, and weight loss after 1000 ℃ is mainly BaSO 4 Pyrolysis of (2). After barite is added with sintering aid and sintered at high temperature, the peaks of silicon dioxide and carbonate disappear, and BaSiO exists 3 The peak of (2) is generated.
According to the sintering reaction mechanism, a small amount of soluble sulfate radicals are generated in the sintering process, and the change condition of the internal structure after sintering can be mastered by testing the amount of the sulfate radicals.
The leaching amount of soluble sulfate radicals of the barite raw material is zero, the barite embryo blocks pressed by burning are basically free of the soluble sulfate radicals without adding a sintering aid, the leaching amount can be ignored, and meanwhile, the obtained sintering blocks are loose in structure and almost free of any compressive strength, which indicates that the internal structure is not changed. But after the sintering aid with certain components and proportion is added, the compression strength of the barite embryo block which is burned and pressed is continuously enhanced along with the increase of the leaching amount of the soluble sulfate radical until the leaching amount reaches the maximum value after a certain temperature, and meanwhile, the strength and the equivalent value of the radiation-resistant lead of the sintering block also reach the maximum value.
To summarize:
the apparent density of the radiation-proof ceramic plate prepared by the invention can reach 1470kg/m in the aspect of mechanical property 3 The pressure resistance can reach 41.5MPa, and the lead equivalent value reaches 0.98mmPb in the radiation protection aspect. The method is a novel functional plate, has simple, stable and reliable process, easily-controlled quality, low cost and environmental friendliness, is a new way for utilizing barite, and is expected to have good application prospect.
Claims (10)
1. A barite radiation protection ceramic plate is characterized in that: the ceramic plate is prepared by taking barite as a basic raw material, using silicate, silicic acid or silicon dioxide as well as or in a plurality of types, and taking alumina as a sintering aid; the compound is prepared by using the same or a plurality of dihydric phosphate, monohydrogen phosphate and zinc oxide as a structural reinforcing agent.
2. The barite radiation protective ceramic plate of claim 1, wherein: the ceramic plate is prepared by taking barite as a basic raw material, taking silicate and aluminum oxide as sintering aids, and taking dihydrogen phosphate and zinc oxide as structural reinforcing agents.
3. The barite radiation protective ceramic plate of claim 2, wherein: the silicate is sodium silicate, and the dihydrogen phosphate is aluminum dihydrogen phosphate.
4. The method for preparing the barite radiation protective ceramic plate as claimed in any one of claims 1 to 3, wherein: the preparation method of the ceramic plate comprises the following steps:
(1) Crushing barite, wherein 85-95% of the barite has a particle size of 20 μm to obtain product A;
(2) Weighing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate, and dissolving in water to obtain product B;
(3) Adding product A into product B, stirring, oven drying, dewatering to obtain block product, crushing, and sieving with 100 mesh sieve to obtain product with particle size of 0.150 mmC;
(4) Filling the product C into a mold, pressing under 25MPa and maintaining the pressure for 2-10min to obtain a green billet, placing the green billet in a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at a temperature of 900-1100 ℃, and keeping the temperature for 1.5-3h, and sintering to obtain the radiation-proof ceramic plate.
5. The method for preparing the barite radiation-proof ceramic plate as claimed in claim 4, wherein the method comprises the following steps: in the step (1), the barite is crushed, and 90% of the barite has a particle size of 20 μm, so that a product A is obtained.
6. The method for preparing the barite radiation-proof ceramic plate as claimed in claim 4, wherein the method comprises the following steps: in the step (2), sodium silicate, alumina, zinc oxide and aluminum dihydrogen phosphate are weighed according to the proportion of 5-15 to 1-7.
7. The method for preparing the barite radiation-proof ceramic plate as claimed in claim 4, wherein the method comprises the following steps: in the step (2), sodium silicate, alumina, zinc oxide and aluminum dihydrogen phosphate are weighed according to the proportion of 10.
8. The method for preparing the barite radiation-proof ceramic plate as claimed in claim 4, wherein the method comprises the following steps: in the step (3), the weight ratio of the product A to the product B is 75-80.
9. The method for preparing the barite radiation protection ceramic plate as claimed in claim 8, wherein the method comprises the following steps: in the step (3), the weight ratio of the product A to the product B is 80.
10. The method for preparing the barite radiation-proof ceramic plate as claimed in claim 4, wherein the method comprises the following steps: and (4) filling the product C into a mold, pressing under 25MPa and maintaining the pressure for 5min to obtain a green compact, placing the green compact in a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at 1000 ℃, and keeping the temperature for 2h, and firing to obtain the radiation-proof ceramic plate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813332A (en) * | 2023-05-06 | 2023-09-29 | 河北领标科技发展有限公司 | Radiation-proof ceramic rock plate and processing method thereof |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU478533B2 (en) * | 1973-04-26 | 1974-10-31 | RALPH ASHWORTH and KATHLEEN MARY PLUCK DEREK | Improvements in or relating tothe processing ofa ceramic body |
| GB8425807D0 (en) * | 1983-10-13 | 1984-11-21 | Didier Werke Ag | Manufacturing refractory bodies |
| US4762811A (en) * | 1987-01-21 | 1988-08-09 | Dresser Industries, Inc. | Castable refractory |
| JPH02307866A (en) * | 1989-05-22 | 1990-12-21 | Murata Mfg Co Ltd | Production of barium titanate-based dielectric ceramic material and dielectric ceramic |
| CN1052649A (en) * | 1989-12-18 | 1991-07-03 | 高洪生 | The barium aluminate salt concrete and the tapestry brick thereof that are used for the worn-out protection of radioactive rays screen |
| JPH09132450A (en) * | 1995-11-10 | 1997-05-20 | Sharp Corp | Ceramic molded body and its production |
| JP2006182576A (en) * | 2004-12-27 | 2006-07-13 | Toshiba Ceramics Co Ltd | Castable refractories |
| US20070102672A1 (en) * | 2004-12-06 | 2007-05-10 | Hamilton Judd D | Ceramic radiation shielding material and method of preparation |
| WO2008080282A1 (en) * | 2006-12-28 | 2008-07-10 | Shandong Wanjie High-Tech Co., Ltd | A protective concrete for weakening the intensity of proton radiation |
| JP2009256176A (en) * | 2008-03-28 | 2009-11-05 | Nichias Corp | Composition for refractory, refractory shaped article, and refractory fired substance |
| CN101642928A (en) * | 2009-08-20 | 2010-02-10 | 冷文魁 | Manufacturing method of anti-radiation marble wood-based panel |
| JP2012041222A (en) * | 2010-08-17 | 2012-03-01 | Nippon Carbide Ind Co Inc | Compound sintered compact |
| CN103739275A (en) * | 2013-02-07 | 2014-04-23 | 贵州省建筑材料科学研究设计院 | Flotation barite mine tailing sintered wall material and preparation method thereof |
| US20150174644A1 (en) * | 2012-06-06 | 2015-06-25 | Ask Chemicals Gmbh | Molding material mixtures containing barium sulfate |
| CN106316435A (en) * | 2016-08-05 | 2017-01-11 | 佛山市凯撒大道陶瓷有限公司 | Anti-static tile and production method thereof |
| CN107098670A (en) * | 2017-06-03 | 2017-08-29 | 合肥慧林建材有限公司 | A kind of ceramic water permeable pavior brick and preparation method thereof |
| CN107572976A (en) * | 2017-08-15 | 2018-01-12 | 河北卓达建材研究院有限公司 | A kind of radiation proof function plate and preparation method thereof |
| BR102020014600A2 (en) * | 2020-07-17 | 2021-01-05 | Universidade Federal Do Parana | composite formed with a mixture of lead powder and barite powder to coat ceramic pieces in order to attenuate radiation x |
| CN114349412A (en) * | 2021-12-30 | 2022-04-15 | 佛山欧神诺陶瓷有限公司 | Radiation-proof green brick, radiation-proof brick and preparation method thereof |
| CN114956631A (en) * | 2022-06-30 | 2022-08-30 | 安徽建工建材科技集团有限公司 | Radiation-proof functional aggregate and preparation method thereof |
-
2022
- 2022-09-29 CN CN202211201004.7A patent/CN115572150B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU478533B2 (en) * | 1973-04-26 | 1974-10-31 | RALPH ASHWORTH and KATHLEEN MARY PLUCK DEREK | Improvements in or relating tothe processing ofa ceramic body |
| GB8425807D0 (en) * | 1983-10-13 | 1984-11-21 | Didier Werke Ag | Manufacturing refractory bodies |
| US4762811A (en) * | 1987-01-21 | 1988-08-09 | Dresser Industries, Inc. | Castable refractory |
| JPH02307866A (en) * | 1989-05-22 | 1990-12-21 | Murata Mfg Co Ltd | Production of barium titanate-based dielectric ceramic material and dielectric ceramic |
| CN1052649A (en) * | 1989-12-18 | 1991-07-03 | 高洪生 | The barium aluminate salt concrete and the tapestry brick thereof that are used for the worn-out protection of radioactive rays screen |
| JPH09132450A (en) * | 1995-11-10 | 1997-05-20 | Sharp Corp | Ceramic molded body and its production |
| US20070102672A1 (en) * | 2004-12-06 | 2007-05-10 | Hamilton Judd D | Ceramic radiation shielding material and method of preparation |
| JP2006182576A (en) * | 2004-12-27 | 2006-07-13 | Toshiba Ceramics Co Ltd | Castable refractories |
| WO2008080282A1 (en) * | 2006-12-28 | 2008-07-10 | Shandong Wanjie High-Tech Co., Ltd | A protective concrete for weakening the intensity of proton radiation |
| JP2009256176A (en) * | 2008-03-28 | 2009-11-05 | Nichias Corp | Composition for refractory, refractory shaped article, and refractory fired substance |
| CN101642928A (en) * | 2009-08-20 | 2010-02-10 | 冷文魁 | Manufacturing method of anti-radiation marble wood-based panel |
| JP2012041222A (en) * | 2010-08-17 | 2012-03-01 | Nippon Carbide Ind Co Inc | Compound sintered compact |
| US20150174644A1 (en) * | 2012-06-06 | 2015-06-25 | Ask Chemicals Gmbh | Molding material mixtures containing barium sulfate |
| CN103739275A (en) * | 2013-02-07 | 2014-04-23 | 贵州省建筑材料科学研究设计院 | Flotation barite mine tailing sintered wall material and preparation method thereof |
| CN106316435A (en) * | 2016-08-05 | 2017-01-11 | 佛山市凯撒大道陶瓷有限公司 | Anti-static tile and production method thereof |
| CN107098670A (en) * | 2017-06-03 | 2017-08-29 | 合肥慧林建材有限公司 | A kind of ceramic water permeable pavior brick and preparation method thereof |
| CN107572976A (en) * | 2017-08-15 | 2018-01-12 | 河北卓达建材研究院有限公司 | A kind of radiation proof function plate and preparation method thereof |
| BR102020014600A2 (en) * | 2020-07-17 | 2021-01-05 | Universidade Federal Do Parana | composite formed with a mixture of lead powder and barite powder to coat ceramic pieces in order to attenuate radiation x |
| CN114349412A (en) * | 2021-12-30 | 2022-04-15 | 佛山欧神诺陶瓷有限公司 | Radiation-proof green brick, radiation-proof brick and preparation method thereof |
| CN114956631A (en) * | 2022-06-30 | 2022-08-30 | 安徽建工建材科技集团有限公司 | Radiation-proof functional aggregate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张煜;聂登攀;王艳书;陈琨;廖裕辉;: "重晶石熟料水浸过程热力学及动力学分析", 非金属矿, no. 03 * |
| 董伟霞: "ZnO-CaO-MgO-SiO2 助烧剂对氧化铝陶瓷性能的影响", vol. 30, no. 30, pages 195 - 199 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813332A (en) * | 2023-05-06 | 2023-09-29 | 河北领标科技发展有限公司 | Radiation-proof ceramic rock plate and processing method thereof |
| CN116813332B (en) * | 2023-05-06 | 2024-04-30 | 河北领标科技发展有限公司 | Radiation-proof ceramic rock plate and processing method thereof |
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