CN115572150B - 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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- CN115572150B CN115572150B CN202211201004.7A CN202211201004A CN115572150B CN 115572150 B CN115572150 B CN 115572150B CN 202211201004 A CN202211201004 A CN 202211201004A CN 115572150 B CN115572150 B CN 115572150B
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Abstract
The invention discloses a barite radiation-proof ceramic plate and a preparation method thereof, wherein barite is used as a basic raw material, silicate and alumina are used as main sintering aids, zinc oxide and aluminum dihydrogen phosphate are used as structural reinforcing agents, and the radiation-proof ceramic plate is manufactured by sintering. The barite radiation-proof ceramic plate prepared by the invention is a novel functional plate, has excellent radiation resistance, simple, stable and reliable manufacturing process, easy quality control, low cost and environmental friendliness, and is a novel 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 using silicate and alumina as main sintering aids.
Background
Barite is an dominant mineral resource in China and is widely applied to the fields of petroleum, chemical industry, filling materials, medicines and the like.
Barite is prepared from barium sulfate (BaSO) 4 ) Nonmetallic mineral products, which are the main components, are white and glossy, and are also often gray, pale red, pale yellow, etc., due to the influence of impurities and mixtures, and are a mixture. The barium element has no radioactivity before the lead element in the periodic table, has larger relative atomic weight, has high probability of generating photoelectric effect with rays, and is very beneficial to preventing ionizing radiation. Barium ions have a high dielectric constant or magnetization and also have a good magnetic loss effect on non-ionizing radiation. Barite has stable chemical property and no toxicity, and the barite is increasingly valued in the aspect of radiation protection.
At present, the barite is mostly applied to concrete fillers 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, convenient implementation, and mainly has the problems that high compactness is not easy to realize when the barite is filled, and in microscopic view, large physical gaps exist among barite powder (particles), so that rays are easy to penetrate, the whole method is required to be thick and heavy to reach corresponding radiation protection standards, the occupied area is large, the standardization is poor, and the method is not attractive, so that the application range and the places of the method are limited.
Another type of barite radiation-proof plate is made up by using barite powder as main component (in which some fibre can be added to increase strength), then adding unsaturated polyester, epoxy resin and phenolic resin, etc. and pressing them into the plate. The method is characterized by high mechanical strength, good stain resistance, good corrosion resistance, good normalization and simple and convenient construction. However, the production of the plates has high requirements on equipment, complex production process and high cost, and a large number of bubbles can be generated in the interior and the surface of the plates due to the use of an organic solvent in the adhesive, so that the bubbles are difficult to completely eliminate, and the radiation resistance of the plates can be influenced.
The invention is a method for producing radiation-proof ceramic plate by using barite as basic raw material, on the basis of basically not damaging main structure and components of barite, through high-temperature sintering, sintering auxiliary agent and structure reinforcing agent and the surface of barite particles are formed into new compound, so as to form an adhesive tape with enough strength, and the barite particles are reformed into an integral body with high density and high strength, so that the radiation-proof ceramic plate is produced.
The invention prepares the radiation-proof ceramic plate by using the barite as a matrix, has the characteristics of meeting national standard related specifications, stable radiation resistance, high radiation resistance index, simple and quick installation, attractive appearance and the like, can be widely applied to the walls and the ground of places needing radiation resistance, such as radiology departments of medical institutions, laboratories, nuclear radiation research institutes (places), home fine decoration and the like, and is a new scheme for efficiently utilizing the barite.
Disclosure of Invention
The invention aims to provide a barite radiation-proof ceramic plate and a preparation method thereof, wherein barite is used as a basic raw material, sodium silicate and aluminum oxide are used as sintering aids, zinc oxide and aluminum dihydrogen phosphate are used as structural reinforcing agents, and the radiation-proof ceramic plate is manufactured by high-temperature sintering. The barite radiation-proof ceramic plate is a novel functional plate, is a novel way for utilizing barite, and has the advantages of simple preparation process, mild condition and environmental friendliness.
The technical scheme of the invention is as follows:
a barite radiation-proof ceramic plate takes barite as a basic raw material, and takes one or more of silicate, silicic acid or silicon dioxide and alumina as sintering auxiliary agents; the material is prepared by taking one or more of dihydrogen phosphate, monohydrogen phosphate and zinc oxide as a structure reinforcing agent.
The ceramic plate is prepared by taking barite as a basic raw material, silicate and alumina as sintering aids, and dihydrogen phosphate as a structural reinforcing agent and zinc oxide as a structural reinforcing agent.
Specifically, the barite radiation-proof ceramic plate is characterized in that 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 the grain diameter of 85-95% of barite reaches 20 μm, and obtaining a product A;
(2) Weighing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate, and dissolving in water to obtain product B;
(3) Adding the product A into the product B, fully stirring, uniformly mixing, drying, dehydrating to obtain a blocky product, crushing, and sieving with a 100-mesh sieve to obtain a product with the particle size of 0.150 mmC;
(4) Filling the C product into a die, pressing under 25MPa and maintaining the pressure for 2-10min to obtain a green block, placing the green block into a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at 900-1100 ℃ for 1.5-3h, and firing to obtain the radiation-proof ceramic plate.
In the step (1), the barite is crushed, and the grain size of 90% of the barite reaches 20 mu m, so that the product A is obtained.
In the step (2), weighing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate according to the proportion of 5-15:2-7:1-4:1-4, dissolving in water, wherein the addition amount of water is 3-5 times of the total weight of sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate, and obtaining the product B.
Specifically, in the step (2), sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate are weighed according to the proportion of 10:5:2.5:2.5 and dissolved in water, and the addition amount of water is 4 times of the total weight of the sodium silicate, the aluminum oxide, the zinc oxide and the aluminum dihydrogen phosphate, so that the product B is obtained.
In the step (3), the weight ratio of the product A to the product B is 75-80:20-25, and the drying temperature is 100 ℃.
Specifically, in the step (3), the weight ratio of the product A to the product B is 80:20.
In the step (4), filling the C product into a die, pressing under 25MPa and maintaining the pressure for 5min to obtain a green block, placing the green block into a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at a temperature of 1000 ℃, and preserving the heat for 2h, so as to fire 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 types of barite in different production areas, and can effectively sinter the barite into the radiation-proof ceramic plate.
2. The invention uses sodium silicate and alumina as main sintering aids, zinc oxide and aluminum dihydrogen phosphate as structural reinforcing agents to manufacture the radiation-proof ceramic plate, which is a novel functional plate. The sintering aid and the structure reinforcing agent mainly act to react on the surface of barium sulfate particles of barite to form 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, has easily controlled quality, low cost and environmental friendliness, is a new way for utilizing barite, and is expected to have good application prospect.
3. The invention can realize the production of the lead equivalent value plate required by protection applied to different places by controlling the pressure during the production of the plate green body. When the green body production pressure is 25When the thickness is 10mm, the lead equivalent value of the plate can reach about 1mmPb, the pressure of the plate green body during manufacturing is increased, and the radiation-proof effect with higher lead equivalent value can be obtained. The radiation-proof ceramic plate manufactured by the invention has excellent mechanical property, good compressive property and apparent density of 1470kg/m in terms of mechanical property 3 The compression resistance can reach 41.5MPa, meets the national standard of building material industry, has excellent protective and shielding effects on X rays, and has a lead equivalent value of 0.98mmPb in the aspect of radiation protection.
4. Sintering temperature and 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 ceramic plate obtained by sintering can not meet the requirement; too high sintering temperature can lead to high-temperature decomposition of barium sulfate in the barite, and can reduce radiation resistance of the barite ceramic plate. The heat preservation time is increased, the compressive strength of the sample tends to be increased and then reduced, and the mechanical property of the sample is reduced due to excessive heat preservation. According to the invention, the green body block is placed in a high-temperature furnace, the heating rate is 10 ℃/min, the sintering temperature is 1000 ℃, the heat preservation time is 2 hours, and the radiation-proof ceramic plate is prepared by firing, and 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 is 80:10:5:2.5:2.5);
fig. 2: is the barite XRD analysis pattern;
fig. 3: XRD analysis pattern of ceramic plate finished products;
fig. 4: is a 10 x 10cm barite radiation protection ceramic board sample.
Detailed Description
Example 1.
(1) Crushing barite, wherein the grain diameter of 90% of barite reaches 20 mu m, so as to obtain barite powder;
(2) 100g of sodium silicate, 50g of aluminum oxide, 25g of zinc oxide and 25g of aluminum dihydrogen phosphate are weighed and dissolved 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 into a mould, pressing under 25MPa and maintaining the pressure for 5min to obtain a green brick, placing the green brick in a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 1000 ℃, and preserving the heat for 2h, thus obtaining the radiation-proof ceramic plate.
Example 2.
(1) Crushing barite, wherein the grain diameter of 85% of barite reaches 20 mu m, so as to obtain barite powder;
(2) 100g of sodium silicate, 60g of alumina, 20g of zinc oxide and 20g of aluminum dihydrogen phosphate are weighed and dissolved 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 into a mould, pressing under 25MPa and maintaining the pressure for 2min to obtain a green brick, placing the green brick 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 diameter of 95% of barite reaches 20 mu m, so as to obtain barite powder;
(2) 80g of sodium silicate, 70g of alumina, 10g of zinc oxide and 40g of aluminum dihydrogen phosphate are weighed and dissolved 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 into a mould, pressing under 25MPa and maintaining the pressure for 10min to obtain a green brick, placing the green brick into a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 1100 ℃, and preserving heat for 1.5h, thus firing the green brick into the radiation-proof ceramic plate.
Example 4:
(1) Crushing barite, wherein the grain diameter of 90% of barite reaches 20 mu m, so as to obtain barite powder;
(2) 140g of sodium silicate, 50g of alumina, 30g of zinc oxide and 30g of aluminum dihydrogen phosphate are weighed and dissolved 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 blocky product, crushing, sieving with a 100-mesh sieve to obtain fine powder with the particle size of 0.150mm, filling into a mould, pressing under 25MPa and maintaining the pressure for 8min to obtain a green brick, placing the green brick into a high-temperature furnace, heating at the rate of 10 ℃/min, sintering at the temperature of 1050 ℃, and preserving heat for 1.8h, thus firing the green brick into the radiation-proof ceramic plate.
The applicant has conducted a great deal of experimental investigation on the present invention, in part as follows:
experimental example 1 barite feedstock preparation
The barite is crushed step by a plurality of crushers, and after the barite reaches the required granularity, the barite is used for standby:
1) Coarse cracking and medium cracking of the heavy crystal stone to obtain the heavy crystal stone with the particle size of: 0.05-0.5 mm barite.
2) Ball milling the barite with the grain diameter of 0.05-0.5 mm to obtain barite powder particles with the grain diameter of more than 90 percent and 20 mu m.
2 preparation of radiation-proof ceramic plate
Experimental example 2.
Preparing a radiation-proof ceramic plate by barite:
1) The proportion of the barite is 3.8, and the main components are as follows: 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) Mixing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate according to the weight ratio of 10:5:2.5:2.5, uniformly mixing, weighing 200g, dissolving in 800mL (800 g) of water to prepare a solution or suspension, adding 0.8kg of barite powder particles of experimental example 1, fully stirring, uniformly mixing, drying, dehydrating to obtain a block product, and crushing to obtain powder with the particle size of 0.150mm (100 meshes).
3) Filling the powder into a mould, pressing and forming under 25MPa, maintaining the pressure for 5min to obtain a green body, cooling the green body along with a hearth under the sintering temperature of 1000 ℃ and the heating rate of 10 ℃/min and the heat preservation time of 2h, and firing the green body into 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 compression resistance can reach 41.5MPa, which accords with the national standard.
5) The radiation protection performance test is carried out according to the national standard GBZ/T147-2002X of the attenuation performance of the radiation protection material, and the X-ray protection shielding detection is carried out by using (120 KV and additional filtration of 2.50 mmAl) standard X-rays, and the result is that: a sample of ceramic plate 10mm thick has a lead equivalent value of 0.96mmPb.
Experimental example 3.
Radiation-proof ceramic plate prepared from barite
1) The proportion of the barite is 4.2, and the main components are as follows: baO,58.608; SO (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) Mixing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate according to the weight ratio of 10:5:2.5:2.5, uniformly mixing, weighing 200g, dissolving in 800mL (800 g) of water to prepare a solution or suspension, adding 0.8kg of barite powder particles of experimental example 1, fully stirring, uniformly mixing, drying, dehydrating to obtain a block product, and crushing to obtain powder with the particle size of 0.150mm (100 meshes).
3) Filling the powder into a mould, pressing and forming under 25MPa, maintaining the pressure for 5min to obtain a green body, cooling the green body along with a hearth under the sintering temperature of 1000 ℃ and the heating rate of 10 ℃/min and the heat preservation time of 2h, and firing the green body into the radiation-proof ceramic plate.
4) The mechanical property of the heavy crystal plate is detected according to the national standard GB/T30018-2013 sintered decorative board, and the apparent density is 1467kg/m 3 The compression resistance can reach 37.9MPa, which accords with the national standard.
5) The radiation protection performance test is carried out according to the national standard GBZ/T147-2002X of the attenuation performance of the radiation protection material, and the X-ray protection shielding detection is carried out by using (120 KV and additional filtration of 2.50 mmAl) standard X-rays, and the result is that: a sample of ceramic plate 10mm thick has a lead equivalent value of 0.98mmPb.
Analysis of barite radiation-proof ceramic plate quality
Sintering temperature and 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 ceramic plate obtained by sintering can not meet the requirement; too high sintering temperature can lead to high-temperature decomposition of barium sulfate in the barite, and can reduce radiation resistance of the barite ceramic plate. The heat preservation time is increased, the compressive strength of the sample tends to be increased and then reduced, and the mechanical property of the sample is reduced due to excessive heat preservation.
XRD analysis of barite, a finished product sample (the radiation-proof ceramic plate prepared in Experimental example 2) and green brick thermal analysis revealed the physicochemical changes and sintering mechanism occurring during sintering. See fig. 1, 2 and 3.
The variation trend of the green embryo sample in the heating process is that the whole body is subjected to great weight loss and then slightly weighted and then a small amount of weight loss, the weight loss at 200 ℃ is mainly caused by free water evaporation in the sample and sodium silicate losing crystallization water, the weight loss at 200-600 ℃ is mainly caused by phosphate decomposition, the rapid weight loss at 600-700 ℃ is mainly caused by carbonate decomposition, the small weight gain at 700-1000 ℃ has an exothermic peak, and is presumed that the heavy stone contains a small amount of carbon, and BaS and Na generated after carbothermic reaction 2 SO 3 Begin to absorb O in air 2 Oxidation reaction occurs to cause weight gain, and the weight loss after 1000 ℃ is mainly BaSO 4 Is decomposed at high temperature. Sintering the barite added with sintering auxiliary agent at high temperatureAfter the junction, the peaks of silica and carbonate disappeared and there was BaSiO 3 Is generated by the peak of the (c).
From the sintering reaction mechanism, a small amount of soluble sulfate radical is 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 radical.
The leaching amount of soluble sulfate radical of the barite raw material is zero, the pressed barite blank is burnt under the condition of not adding a sintering aid, the soluble sulfate radical is basically not generated, the leaching amount is negligible, and meanwhile, the obtained sintered block has loose structure and almost no compressive strength, which indicates that the internal structure is not changed. However, after adding sintering auxiliary agents with certain components and proportions, the compressive strength of the pressed barite blank 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 of the sintered block and the equivalent value of the radiation-resistant lead reach the maximum value.
Summarizing:
the apparent density of the radiation-proof ceramic plate prepared by the invention in terms of mechanical property can reach 1470kg/m 3 The compression resistance can reach 41.5MPa, and the lead equivalent value reaches 0.98mmPb in the aspect of radiation protection. The composite material is a novel functional board, has simple, stable and reliable process, easy quality control, low cost and environmental protection, is a novel way for utilizing barite, and is expected to have good application prospect.
Claims (8)
1. The utility model provides a barite radiation protection ceramic plate which characterized in that: the ceramic plate is prepared by taking barite as a basic raw material, silicate and alumina as sintering aids and dihydrogen phosphate and zinc oxide as structural reinforcing agents;
the silicate is sodium silicate, and the dihydrogen phosphate is aluminum dihydrogen phosphate;
the ratio of the sodium silicate to the aluminum oxide to the zinc oxide to the aluminum dihydrogen phosphate is 5-15:2-7:1-4:1-4.
2. The method for preparing the barite radiation protection ceramic plate according to claim 1, wherein the method comprises the following steps: the preparation method of the ceramic plate comprises the following steps:
(1) Crushing barite, wherein the grain diameter of 85-95% of barite reaches 20 μm, and obtaining a product A;
(2) Weighing sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate, and dissolving in water to obtain product B;
(3) Adding the product A into the product B, fully stirring, uniformly mixing, drying, dehydrating to obtain a blocky product, crushing, and sieving with a 100-mesh sieve to obtain a product with the particle size of 0.150 mmC;
(4) Filling the C product into a die, pressing under 25MPa and maintaining the pressure for 2-10min to obtain a green block, placing the green block into a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at 900-1100 ℃ for 1.5-3h, and firing to obtain the radiation-proof ceramic plate.
3. The method for preparing the barite radiation protection ceramic plate according to claim 2, wherein the method comprises the following steps: in the step (1), the barite is crushed, and the grain diameter of 90 percent of the barite reaches 20 mu m, so that a product A is obtained.
4. The method for preparing the barite radiation protection ceramic plate according to claim 2, wherein the method comprises the following steps: in the step (2), sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate are weighed according to the proportion of 5-15:2-7:1-4:1-4 and dissolved in water, and the addition amount of water is 3-5 times of the total weight of the sodium silicate, the aluminum oxide, the zinc oxide and the aluminum dihydrogen phosphate, so that the product B is obtained.
5. The method for preparing the barite radiation protection ceramic plate according to claim 2, wherein the method comprises the following steps: in the step (2), sodium silicate, aluminum oxide, zinc oxide and aluminum dihydrogen phosphate are weighed according to the proportion of 10:5:2.5:2.5 and dissolved in water, and the addition amount of water is 4 times of the total weight of the sodium silicate, the aluminum oxide, the zinc oxide and the aluminum dihydrogen phosphate, so that a product B is obtained.
6. The method for preparing the barite radiation protection ceramic plate according to claim 2, wherein the method comprises the following steps: in the step (3), the weight ratio of the product A to the product B is 75-80:20-25, and the drying temperature is 100 ℃.
7. The method for preparing the barite radiation protection ceramic plate according to claim 6, wherein the method comprises the following steps: in the step (3), the weight ratio of the product A to the product B is 80:20.
8. The method for preparing the barite radiation protection ceramic plate according to claim 2, wherein the method comprises the following steps: in the step (4), filling the C product into a die, pressing under 25MPa and maintaining the pressure for 5min to obtain a green block, placing the green block into a high-temperature furnace, heating at a rate of 10 ℃/min, sintering at a temperature of 1000 ℃, and preserving the heat for 2h, so as to fire the radiation-proof ceramic plate.
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