CN114315341A - Manganese-containing high-purity tin ceramic, preparation method thereof, manganese-containing high-purity tin brick and application - Google Patents
Manganese-containing high-purity tin ceramic, preparation method thereof, manganese-containing high-purity tin brick and application Download PDFInfo
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 135
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011572 manganese Substances 0.000 title claims abstract description 134
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 134
- 239000000919 ceramic Substances 0.000 title claims abstract description 49
- 239000011449 brick Substances 0.000 title claims description 37
- 238000002360 preparation method Methods 0.000 title claims description 33
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 165
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000000498 ball milling Methods 0.000 claims abstract description 51
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000011810 insulating material Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 105
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 58
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000011541 reaction mixture Substances 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 41
- 239000002270 dispersing agent Substances 0.000 claims description 40
- 239000011812 mixed powder Substances 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 19
- 235000019353 potassium silicate Nutrition 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003801 milling Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011521 glass Substances 0.000 description 12
- 229910001887 tin oxide Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000011224 oxide ceramic Substances 0.000 description 9
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 5
- 229910001195 gallium oxide Inorganic materials 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 239000004677 Nylon Substances 0.000 description 2
- 229910002637 Pr6O11 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses manganese-containing high-purity tin ceramic, which comprises high-purity tin dioxide and a very small amount of manganese dioxide, and has the advantages of low porosity, high density, high resistance value and good insulating property at normal temperature. The manganese-containing high-purity tin ceramic can be prepared by controlling the diameter and high purity of the superfine grains of the raw materials, carrying out a sectional ball milling step and reasonably selecting the hardness and the diameter of a milling ball. The manganese-containing high-purity tin ceramic provided by the invention can be used for insulating materials.
Description
Technical Field
The invention relates to the field of high-purity tin ceramics, in particular to manganese-containing high-purity tin ceramics, a preparation method thereof, a manganese-containing high-purity tin brick and application thereof.
Background
The traditional tin oxide ceramic is mainly applied to the preparation of sensors, electrodes, crystal displays, detectors, rheostats and the like, mainly plays a role in auxiliary heating and electric conduction, and the electric conductivity of the traditional tin oxide ceramic is often further improved by doping. However, it is not always necessary that the tin oxide ceramic has good conductivity, for example, tin oxide ceramic is widely used in glass electric melting systems because it is not easily corroded by metal-containing glass, but the bottom and wall of the cell constituting the glass electric melting furnace must have insulation, otherwise short circuit is easily caused, and at this time, the conventional tin oxide ceramic is not suitable.
Patent document CN101439967A discloses a preparation method of high-density stannic oxide ceramic, which adopts SnO2Powder with MnO as sintering aid2Powder and CuO powder, and the dosage of the sintering aid is SnO20.5-5% of the powder mass, wherein MnO is2The powder and the CuO powder account for MnO in percentage by mass in the sintering aid25-95% of powder and 5-95% of CuO powder.
Patent document CN112723875A discloses a gallium oxide doped tin oxide ceramic target material, wherein the mass percentages of gallium oxide and tin oxide are 2-10% of gallium oxide and 90-98% of tin oxide respectively; the dispersing agent is ammonium polyacrylate, the binder is polyvinyl alcohol, the total mass of gallium oxide and tin oxide is taken as a reference, the adding amount of the dispersing agent and the binder is 0.5-2%, and the adding amount of water is 65-75%.
Patent document CN101830694A discloses a tin dioxide electrode ceramic material comprising 100 parts by weight of SnO2And 0.5 to 1.5 parts by weight of Sb as an additive2O30.1 to 1.5 parts by weight of ZnO and 0.1 to 1.5 parts by weight of Pr6O11In which Sb2O3ZnO and Pr6O11The total of the weight of (A) and (B) is 1 to 3 parts by weight, and 0.05 to 0.5 part by weight of sodium silicate.
In the above-mentioned disclosed technical solutions, the minimum addition amount of the metal oxide is 0.5% of the mass of the tin dioxide powder, and two or more sintering aids are required to be added.
Disclosure of Invention
The invention aims to provide manganese-containing high-purity tin ceramic which is high in compactness and good in insulativity.
The first aspect of the invention provides a manganese-containing high-purity tin ceramic, which comprises tin dioxide, manganese dioxide and a dispersant; the weight part of manganese dioxide is 0.1-0.3 in terms of 100 parts of tin dioxide; the weight part ratio of the total content of tin dioxide and manganese dioxide to the content of the dispersing agent is 100 (0.05-0.3);
the manganese-containing high-purity tin ceramic is prepared from raw materials including tin dioxide powder, manganese dioxide powder and the dispersing agent, wherein,
the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent;
the average grain diameter of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent.
In some embodiments of the invention, in the manganese-containing high-purity tin ceramic,
the average grain diameter of the tin dioxide powder is less than or equal to 0.6 mu m; and/or the presence of a catalyst in the reaction mixture,
the pH value of the tin dioxide powder is 4.9-6; and/or the presence of a catalyst in the reaction mixture,
the average grain diameter of the manganese dioxide powder is less than or equal to 3.86 mu m; and/or the presence of a catalyst in the reaction mixture,
the dispersing agent is water glass liquid, and the Baume degree of the water glass liquid is not less than 48.
In some embodiments of the invention, in the manganese-containing high-purity tin ceramic,
the tin dioxide powder is VS brand; and/or the presence of a catalyst in the reaction mixture,
the purity of the manganese dioxide powder is higher than analytical purity.
In some embodiments of the invention, in the manganese-containing high-purity tin ceramic,
the weight part of manganese dioxide is 0.1-0.15 in terms of 100 parts of tin dioxide; and/or the presence of a catalyst in the reaction mixture,
the weight part ratio of the total content of the tin dioxide and the manganese dioxide to the content of the dispersing agent is 100 (0.05-0.15).
The second aspect of the invention provides a preparation method of manganese-containing high-purity tin ceramic, which comprises the following steps:
mixing tin dioxide powder and manganese dioxide powder according to the weight part ratio of 100 (0.1-0.3), and performing first ball milling by using zirconia balls to prepare mixed powder I; wherein the diameter of the zirconia ball is 3 mm-4 mm; the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent; the average particle size of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent; the average grain diameter of the prepared mixed powder I is less than or equal to 0.6 mu m;
mixing zirconia balls, the mixed powder I, a dispersing agent and water according to the weight part ratio of (180-220): 100, (0.1-0.3): 25-35), and performing secondary ball milling to prepare manganese-containing high-purity tin slurry; wherein the diameter of the zirconia ball is 4 mm-6 mm;
drying the manganese-containing high-purity tin slurry at the temperature of 110-160 ℃ until the water content is less than or equal to 0.3%, and sieving to obtain manganese-containing high-purity tin powder;
pressing the manganese-containing high-purity tin powder under isostatic pressure, wherein the pressure is 180-230 MPa, and preparing a manganese-containing high-purity tin blank;
and heating the manganese-containing high-purity tin blank to 1430-1440 ℃ at the heating rate of 0.4-0.6 ℃/min, sintering for 10-12 h, and annealing to obtain the manganese-containing high-purity tin ceramic.
In some embodiments of the invention, in the method of making,
the average grain diameter of the tin dioxide powder is less than or equal to 0.6 mu m; and/or the presence of a catalyst in the reaction mixture,
the pH value of the tin dioxide powder is 4.9-6.0; and/or the presence of a catalyst in the reaction mixture,
the average grain diameter of the manganese dioxide powder is less than or equal to 3.86 mu m; and/or the presence of a catalyst in the reaction mixture,
the dispersing agent is water glass liquid, and the Baume degree of the water glass liquid is not less than 48.
In some embodiments of the invention, in the method of making,
when the first ball milling is carried out, the weight part ratio of the tin dioxide powder to the manganese dioxide powder is 100 (0.1-0.15); and/or the presence of a catalyst in the reaction mixture,
the time for performing the first ball milling is more than or equal to 6 hours; and/or the presence of a catalyst in the reaction mixture,
the average grain diameter of the prepared mixed powder I is less than or equal to 0.6 mu m; and/or the presence of a catalyst in the reaction mixture,
during the second ball milling, the weight part ratio of the zirconia balls to the mixed powder I to the dispersing agent to the water is 200:100 (0.05-0.15) to (25-35); and/or the presence of a catalyst in the reaction mixture,
drying the manganese-containing high-purity tin slurry at the temperature of between 130 and 150 ℃ for 6 to 8 hours; and/or the presence of a catalyst in the reaction mixture,
the mesh number of the sieved screen is less than or equal to 50 meshes; and/or the presence of a catalyst in the reaction mixture,
the particle size of the prepared manganese-containing high-purity tin powder is less than or equal to 0.5 mu m; and/or the presence of a catalyst in the reaction mixture,
before the manganese-containing high-purity tin powder is pressed under an isostatic pressure condition, the method also comprises a step of removing iron; and/or the presence of a catalyst in the reaction mixture,
the pressure maintaining time for pressing the manganese-containing high-purity tin powder under the isostatic pressure condition is 4-8 min; and/or the presence of a catalyst in the reaction mixture,
heating the manganese-containing high-purity tin blank to 1430-1440 ℃ at the heating rate of 0.5 ℃/min; and/or the presence of a catalyst in the reaction mixture,
the annealing mode is cooling to room temperature along with the furnace.
In some embodiments of the invention, in the method of making,
the rotating speed for carrying out the first ball milling is 60-70 r/min; and/or the presence of a catalyst in the reaction mixture,
the time for performing the first ball milling is 6-8 h; and/or the presence of a catalyst in the reaction mixture,
the rotation speed for performing the second ball milling is 70-80 r/min; and/or the presence of a catalyst in the reaction mixture,
the time for performing the second ball milling is 50-60 min; and/or the presence of a catalyst in the reaction mixture,
the mesh number of the sieved screen is less than or equal to 40 meshes.
The third aspect of the invention provides a manganese-containing high-purity tin brick which can be prepared by the preparation method provided by the second aspect of the invention, the porosity is less than 1%, and the volume density is more than 6.5g/cm3And the resistance value is more than or equal to 222M omega at the temperature of 30 ℃.
In a fourth aspect of the present invention, there is provided a manganese-containing high-purity tin ceramic provided in one aspect of the present invention, or a manganese-containing high-purity tin ceramic prepared by the preparation method provided in the second aspect of the present invention, or an application of a manganese-containing high-purity tin brick provided in the third aspect of the present invention as an insulating material.
The manganese-containing high-purity tin ceramic provided by the invention contains high-purity tin dioxide and a very small amount of manganese dioxide, and has the advantages of low porosity, high density, high resistance value and good insulating property. The manganese-containing high-purity tin ceramic can be prepared by reasonably matching the particle sizes of materials and grinding balls and cooperatively adjusting the ball-milling parameters through a sectional ball-milling step by controlling the superfine particle size and the high purity of the raw materials and reasonably selecting the hardness and the particle size of the grinding balls.
In order to achieve the compact effect, a certain amount of sintering aid is required to be added into the traditional tin oxide ceramic, and the purity is not high enough, so that the insulativity is poor, and the electric corrosion resistance is weak. According to the invention, tin dioxide with extremely low particle size is used as a raw material, the re-bonding force of the tin dioxide is strong, the tin dioxide can be sintered and molded without adding a large amount of sintering aids, the prepared ceramic has extremely high purity, high resistance value at normal temperature (for example, the resistance value at 30 ℃ is more than 220 MOmega), good insulating property and difficult electrochemical corrosion.
In the preparation method provided by the invention, the temperature can be raised in a constant-speed heating mode in the calcining process, and after sintering is finished, annealing can be carried out in a mode of cooling to room temperature along with a furnace, so that the manganese-containing high-purity tin brick with high density and small porosity can be prepared.
The manganese-containing high-purity tin ceramic and the manganese-containing high-purity tin brick provided by the invention can be used as an insulating material for a glass electric furnace system, such as environment-friendly glass, furnace wall bricks, parts of contact electrodes and the like.
Detailed Description
The present invention will be further illustrated by the following embodiments and examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Term(s) for
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or", "and/or" as used herein is intended to be inclusive of any one of two or more of the associated listed items and also to include any and all combinations of the associated listed items, including any two or any more of the associated listed items, or any and all combinations of the associated listed items. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or/and", "and/or", it should be understood that, in the present application, the technical solutions definitely include the technical solutions all connected by "logic and" and also the technical solutions all connected by "logic or". For example, "A and/or B" includes A, B and A + B. For example, the embodiments of "a, and/or, B, and/or, C, and/or, D" include any of A, B, C, D (i.e., all embodiments using "logical or" connection "), any and all combinations of A, B, C, D (i.e., any two or any three of A, B, C, D), and four combinations of A, B, C, D (i.e., all embodiments using" logical and "connection).
In the present invention, "preferred", "better", etc. are only used to describe better embodiments or examples, and it should be understood that the scope of the present invention is not limited by these terms.
In the present invention, "further", "still further", "specifically" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of the present invention.
In the present invention, the terms "first", "second", "third", "fourth", etc. in the terms of "first aspect", "second aspect", "third aspect", "fourth aspect", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying that importance or quantity indicating the technical feature being indicated. Also, "first," "second," "third," "fourth," etc. are used for non-exhaustive enumeration of description purposes only and should not be construed as a closed limitation to the number.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a variation within a certain temperature range. It will be appreciated that the described thermostatic process allows the temperature to fluctuate within the accuracy of the instrument control. Allowing fluctuations in a range of, for example,. + -. 0.5 ℃,. + -. 1 ℃,. + -. 2 ℃,. + -. 3 ℃,. + -. 4 ℃,. + -. 5 ℃.
In the present invention, "room temperature" means no temperature control operation, and mainly means 4 to 35 ℃, preferably 4 to 30 ℃, more preferably 20 ℃. + -. 5 ℃, 20 to 30 ℃ and the like. Examples of "room temperature" in the present invention include 4 ℃, 10 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 27 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃ and the like.
In the present invention, where a range of values (i.e., a numerical range) is recited, unless otherwise specified, alternative distributions of values within the range are considered to be continuous, and include both the numerical endpoints of the range (i.e., the minimum and maximum values), and each numerical value between the numerical endpoints. Unless otherwise specified, when a numerical range refers to integers only within the numerical range, both endpoints of the numerical range are inclusive of the integers and each integer between the endpoints is inclusive of the integer. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
In the present invention, the particle diameter refers to an average particle diameter unless otherwise specified. The term "diameter" means a diameter size unless otherwise specified, and further means an average diameter size unless otherwise specified.
In the present invention, the particle size of the substance A is X mesh, which means that the particle size of the substance A is controlled by the X mesh to control the particle diameter. For example, the particle size of the mixed powder, the particle size of the manganese-containing high-purity tin powder and the like are involved.
In a first aspect of the invention, there is provided a manganese-containing high purity tin ceramic comprising tin dioxide, manganese dioxide and a dispersant; the weight part of manganese dioxide is 0.1-0.3 in terms of 100 parts of tin dioxide; the weight part ratio of the total content of tin dioxide and manganese dioxide to the content of the dispersing agent is 100 (0.05-0.3); further, the air conditioner is provided with a fan,
the manganese-containing high-purity tin ceramic is prepared from raw materials including tin dioxide powder, manganese dioxide powder and the dispersing agent,
wherein,
the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent;
the average grain diameter of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent.
Usually, the raw material also includes water, and in this case, the raw material includes tin dioxide powder, manganese dioxide powder, the dispersant and water.
The particle size of the tin dioxide powder is generally 2-5 μm, a finer particle size (for example, not more than 0.6 μm) is difficult to obtain through ball milling, impurities are easy to introduce in the ball milling process, the form of the obtained powder is changed, the recombination capability is poor, more sintering aids are required to be added for sintering, and if the addition amount of the sintering aids is reduced for improving the purity, the fired ceramic has more pores and poor quality.
In some embodiments of the invention, tin dioxide powder with extremely fine particle size (such as 0.7 μm) is used as a raw material, the powder has strong recombination capability, is easy to sinter, and can be added with a small amount of sintering aid only, so that the original purity is ensured, and the pollution of impurities to glass products is reduced.
In some embodiments of the invention, the tin dioxide powder employed has a particle size of 0.7 μm or less, and further may be 0.6 μm or less, such as 0.7 μm, 0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm, 0.1 μm, and the like, for example.
In some embodiments of the invention, a tin dioxide powder having a particle size of 0.6 μm is used.
In some embodiments of the invention, the tin dioxide powder employed has a purity of 99.5% or more, such as 99.9%, 99.8%, 99.7%, 99.6%, 99.5%, etc., for example.
In some embodiments of the invention, the tin dioxide powder used has a purity of 99.5%.
In some embodiments of the present invention, the tin dioxide powder has a pH of 4 to 6, and further 4.9 to 6.0, for example, the tin dioxide powder has a pH of 4, 5, 6, etc.
In some embodiments of the present invention, the tin dioxide powder used may be VS brand.
In the traditional preparation of tin oxide ceramics, sintering aids with proper addition amount are beneficial to sintering, and common sintering aids comprise oxides of copper, manganese and zinc. The doping amount is generally 1 to 3 percent. For example, CN112723875A discloses a high purity tin ceramic containing 2% to 10% of gallium oxide and 90% to 98% of tin oxide.
In the invention, manganese dioxide with a proper particle size is used as a sintering aid and is cooperated with tin dioxide with a proper particle size, mixed powder (mixed powder I) with an average particle size of less than or equal to 0.6 mu m can be obtained by ball milling, and sintering can be carried out under the condition that the addition amount of manganese dioxide is extremely low. Manganese dioxide is cheap and easy to obtain, and glass is not easy to color. In some embodiments of the invention, manganese dioxide powder having an average particle size of 4 μm or less, and further 3.86 μm or less is used. Exemplary average particle diameters are, for example, 0.6. mu.m, 0.72. mu.m, 0.88. mu.m, 1.25. mu.m, 1.66. mu.m, 2.26. mu.m, 2.82. mu.m, 3.22. mu.m, 3.64. mu.m, 3.86. mu.m, etc.
In the present invention, the purity of the manganese dioxide powder is analytically pure or higher. In some embodiments, the purity of the manganese dioxide powder is greater than or equal to 85%, and further can be greater than or equal to 90%, such as 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.9%, and the like, for example. In some embodiments, the purity of the manganese dioxide powder is 85%.
In some embodiments of the invention, the amount of manganese dioxide added is such that: the weight portion of manganese dioxide is 0.1-0.3, calculated by 100 weight portions of tin dioxide. The prepared manganese-containing high-purity tin ceramic not only can ensure the purity, but also can obtain a ceramic body with better weight.
In some embodiments of the present invention, the manganese-containing high purity tin ceramic is prepared to contain 0.1 to 0.3 parts by weight of manganese dioxide, and further 0.1 to 0.15 parts by weight of tin dioxide. Exemplary parts by weight are 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, etc.
In the invention, water glass liquid is used as a dispersing agent. The main component of the water glass liquid is water solution of sodium silicate. The Baume degree (. degree. Be) of the water glass liquid represents the concentration of the solution, and the higher the Baume degree is, the higher the content of the water glass (sodium silicate) is, the higher the viscosity of the solution is, and the stronger the adhesive ability is. In the present invention, the Baume degree of the water glass liquid as the dispersant is not less than 48. In some embodiments of the present invention, water glass cullet is used as the dispersant, and the baume degree of the water glass cullet may be 48.
The dispersant with proper addition amount can increase the fluidity of the slurry to be fired, and is beneficial to sintering. If the dispersant is not added, the powder mixture does not have fluidity, and the powder mixture is not uniformly mixed, and thus the firing cannot be performed. The amount of the dispersant should not be too much, such as too much, to affect the purity, and should not be too little, such as too little, to achieve the bonding effect. In the invention, the addition amount of the dispersant satisfies the following conditions: the weight part ratio of the total content of the tin dioxide and the manganese dioxide to the content of the dispersant is 100 (0.05-0.3). The bonding effect is also better when guaranteeing purity. Further, the weight ratio of the total content of tin dioxide and manganese dioxide to the content of the dispersant may be 100 (0.1 to 0.15), such as 100:0.1, 100:0.11, 100:0.12, 100:0.13, 100:0.14, and 100: 0.15. In some embodiments, the weight portion ratio of the total content of tin dioxide and manganese dioxide to the content of dispersant is 100: 0.1. In some embodiments, the ratio of the total content of tin dioxide and manganese dioxide to the content of the dispersant is 100:0.1 parts by weight, and the dispersant is a 48 baume water glass liquid.
The second aspect of the present invention provides a method for preparing a manganese-containing high purity tin ceramic, which can prepare the manganese-containing high purity tin ceramic of the first aspect of the present invention. According to the preparation method, the manganese-containing high-purity tin ceramic with low porosity, large volume density and high resistance value and excellent comprehensive performance can be obtained under the condition that only a small amount of sintering aids are added by utilizing the matching among the particle sizes of the raw materials, the particle size of the raw materials and the particle size of the ball-milling medium, combining the gradient selection of the ball-milling type and proper ball-milling parameters, and the obtained manganese-containing high-purity tin ceramic is easy to obtain and low in price, and is not easy to color glass.
In a second aspect of the present invention, a method for preparing a manganese-containing high-purity tin ceramic is provided, which comprises the following steps:
s100: mixing tin dioxide powder and manganese dioxide powder according to the weight part ratio of 100 (0.1-0.3), and performing first ball milling by using zirconia balls to prepare mixed powder I; wherein the diameter of the zirconia ball is 3 mm-4 mm; the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent; the average grain diameter of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent; the average grain diameter of the prepared mixed powder I is less than or equal to 0.6 mu m;
s200: mixing zirconia balls, the mixed powder I, a dispersing agent and water according to the weight part ratio of (180-220): 100, (0.1-0.3): 25-35), and performing secondary ball milling to prepare manganese-containing high-purity tin slurry; wherein the diameter of the zirconia ball is 4 mm-6 mm;
s300: drying the manganese-containing high-purity tin slurry at the temperature of 110-160 ℃ until the water content is less than or equal to 0.3%, and sieving to obtain manganese-containing high-purity tin powder;
s400: pressing the manganese-containing high-purity tin powder under isostatic pressure, wherein the pressure is 180-230 MPa, and preparing a manganese-containing high-purity tin blank;
s500: and heating the manganese-containing high-purity tin blank to 1430-1440 ℃ at the heating rate of 0.4-0.6 ℃/min, sintering for 10h, and annealing to obtain the manganese-containing high-purity tin ceramic.
S100: preparation of the powder mixture I
In the invention, in step S100, tin dioxide powder and manganese dioxide powder are mixed, and zirconia balls are adopted for carrying out primary ball milling to prepare mixed powder I; wherein the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent; the average grain diameter of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent.
In some embodiments of the present invention, in step S100, the ratio of the weight parts of the tin dioxide powder and the manganese dioxide powder is 100 (0.1 to 0.3), and further may be 100 (0.1 to 0.15), for example, 100:0.1, 100:0.15, 100:0.2, 100:0.25, 100:0.3, and the like. In some embodiments, the ratio of tin dioxide powder to manganese dioxide powder in parts by weight is selected from 100:0.1, 100:0.15, 100: 0.3.
In some embodiments of the present invention, in step S100, the mixing and the ball milling may be performed simultaneously or sequentially. In some embodiments, the grinding stone subjected to the first ball milling is zirconia, which is not easily abraded. In some embodiments, the first ball milling is performed with a grindstone having a diameter of 3mm to 4 mm. In some embodiments, the first ball milling was performed with a grindstone diameter of 3 mm. In some embodiments, the first ball milling is performed at a rotation speed of 70 to 80 r/min. In some embodiments, the first ball milling is performed at a rotational speed of 70 r/min.
In some embodiments of the present invention, in step S100, the time for performing the first ball milling is not particularly limited, and it is preferable to obtain a powder mixture I with a suitable particle size (for example, an average particle size of 0.6 μm or less). In some embodiments, in step S100, the ball milling time is greater than or equal to 6h, and further may be greater than or equal to 8h, such as 6h, 7h, 8h, 9h, 10h, 24h, and the like. In some embodiments, in step S100, the time for ball milling is 6h to 8 h. In some embodiments, in step S100, the time for ball milling is 6 h. In some embodiments, after the first ball milling, the average particle size of the obtained powder mixture I is less than or equal to 0.6 μm, and further, the average particle size of the powder mixture I is less than or equal to 0.5 μm. In some examples, after the first ball milling, the resulting powder mixture I had an average particle size of 0.6. mu.m.
In some embodiments of the present invention, in step S100, tin dioxide powder and manganese dioxide powder are charged into a nylon ball mill pot, and ball milling is performed for 6 hours using zirconia balls having a diameter of 3mm to prepare mixed powder I having an average particle diameter of 0.6 μm.
S200: preparation of manganese-containing high-purity tin paste
In the present invention, in step S200, zirconia balls, the mixed powder I (prepared in step S100), a dispersant, and water are mixed and subjected to a second ball milling to prepare a manganese-containing high-purity tin paste.
In some embodiments of the present invention, in step S200, the weight ratio of the zirconia balls, the mixed powder I, the dispersant and the water is 200:100 (0.05-0.15): 25-35), and further 200:100 (0.05-0.15): 25-35. In some embodiments, the weight ratio of the zirconia balls, the mixed powder I, the dispersing agent and the water is 200:100:0.1: 30.
In some embodiments of the present invention, in step S200, the diameter of the zirconia balls may preferably be 4mm to 6mm, such as 4mm, 5mm, 6mm, and the like. In some embodiments, the zirconia balls in step S200 have a diameter of 5 mm. In some embodiments, the zirconia balls in step S200 have a diameter of 6 mm.
In some embodiments of the invention, in step S200, the rotation speed for performing the second ball milling is 70-80 r/min, such as 70r/min, 72r/min, 75r/min, 76r/min, 78r/min, 80r/min, and the like. In some embodiments, the second ball milling is performed at a rotational speed of 70r/min in step S200.
In some embodiments of the present invention, in step S200, the second ball milling is performed for 50min to 60min, such as 50min, 52min, 54min, 55min, 58min, 60min, etc., to fully grind the powder mixture i. In some embodiments, the second ball milling is performed for 60min in step S200.
In some embodiments of the invention, in step S200, the ratio is as follows 2: 1: 0.001: 0.3, mixing zirconia balls with the diameter of 5mm, the mixed powder I, the dispersant sodium silicate solution and water, and performing ball milling for 60min to prepare the manganese-containing high-purity tin slurry.
S300: preparation of manganese-containing high-purity tin powder
In step S300, the manganese-containing high-purity tin slurry (prepared in step S200) is dried until the moisture content is less than or equal to 0.3%, and is sieved to prepare the manganese-containing high-purity tin powder.
In some embodiments of the present invention, in step S300, the manganese-containing high purity tin powder prepared has a moisture content of 0.3% or less, such as 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.18%, 0.22%, 0.25%, 0.28%, 0.3%, etc., for example. In some embodiments, the manganese-containing high purity tin powder has a moisture content of 0.3%.
In the present invention, in step S300, the time and temperature for drying the manganese-containing high purity tin paste are not particularly limited, and the dried powder material may have a suitable moisture content (e.g., moisture content less than or equal to 0.3%). In some embodiments, the drying is carried out at a temperature of 130 ℃ or higher and for a time of 6 hours or longer. In some embodiments, the drying is performed at a temperature of 110 ℃ to 130 ℃ for a period of 6 hours.
In some embodiments of the present invention, the temperature for drying in step S300 is 110 to 160 ℃, and further may be selected from 140 to 160 ℃, 110 to 130 ℃, 130 to 160 ℃, 120 to 150 ℃, and the like. Exemplary drying temperatures are, for example, 140 ℃, 142 ℃, 143 ℃, 144 ℃, 145 ℃, 147 ℃, 150 ℃, 160 ℃, etc. In some embodiments, in step S300, the drying temperature is 110 ℃ to 130 ℃, and the drying time is not less than 6 hours, and further may be 6 hours to 12 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 12 hours, and the like. In some embodiments, in step S300, the drying temperature may be 130 ℃ to 160 ℃, further 130 ℃ to 150 ℃, and the drying time may be 6 hours to 8 hours. In some embodiments, the drying is performed at a temperature of 130 ℃ for a period of 6 hours. In some embodiments, the drying is carried out at a temperature of 150 ℃ for a period of 15 hours.
In some embodiments of the present invention, in step S300, after drying, pulverization is performed to facilitate subsequent sieving. Further, the crushing may be performed at 40 frequency using a 30B type stainless steel crusher.
In some embodiments of the present invention, in step S300, after drying and crushing, iron removal is performed, so that mechanical iron during crushing can be removed to ensure the purity of the raw material. Further, 6 layers of semi-automatic iron removal machines can be used for removing iron.
In some embodiments of the invention, the screening is performed in step S300 with no more than 50 mesh, further no more than 40 mesh, for example 20, 25, 28, 30, 35, 38, 40, 45, 48, 50, etc.
In some embodiments of the present invention, in step S300, the particle size of the prepared manganese-containing high-purity tin powder is less than or equal to 0.5 μm, and further may be 0.4 μm to 0.5 μm, such as 0.1 μm, 0.15 μm, 0.2 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.5 μm, and the like.
S400: preparation of manganese-containing high-purity tin green body
In the invention, in step S400, the manganese-containing high-purity tin powder is pressed under the isostatic pressure condition to prepare a manganese-containing high-purity tin blank.
In some embodiments, in step S400, the manganese-containing high-purity tin powder is pressed under an isostatic pressure of 180MPa to 230MPa, further 180MPa to 220MPa, such as 180MPa, 190MPa, 200MPa, 210MPa, 220MPa, 230MPa, and the like. In some embodiments, in step S400, the pressing is performed for 4-8 min, for example, 4min, 5min, 6min, 7min, 8min, and the like. In some embodiments, in step S400, the manganese-containing high-purity tin powder is pressed for 4min under an isostatic pressure of 180MPa to prepare a manganese-containing high-purity tin green body.
In some embodiments of the invention, in step S400, the size of the prepared manganese-containing high-purity tin blank is greater than 120mm × 120mm × 120mm, which facilitates the porosity test.
S500: preparation of manganese-containing high-purity tin ceramic
In step S500, the manganese-containing high-purity tin blank is heated to 1430-1440 ℃ at a heating rate of 0.4-0.6 ℃/min, sintered and annealed to obtain the manganese-containing high-purity tin ceramic.
In some embodiments of the present invention, in step S500, the manganese-containing high purity tin blank is heated to 1430-1440 ℃ at a constant speed. In some embodiments, the manganese-containing high-purity tin blank is heated at a heating rate of 0.4-0.6 ℃/min, such as 0.4 ℃/min, 0.5 ℃/min, 0.6 ℃/min, and the like.
In some embodiments of the present invention, a heat-preserving section is provided to remove water before the temperature is raised to 200 ℃ in step S500. In some embodiments, multiple holding sections are provided to remove water until the water content is less than 0.05% in step S500. In some embodiments, in step S500, after the temperature is raised to 60 ℃, a heat-preserving section is further provided to remove water. In some embodiments, in step S500, after the temperature is raised to 60 ℃, water is removed by keeping the temperature for 120min to 180min every 20 ℃ rise until the water content is less than 0.05%. In some embodiments, the moisture content of the manganese-containing high-purity tin green body is less than 0.05% when the temperature is raised to 200 ℃ in step S500.
In some embodiments of the invention, in step S500, the manganese-containing high-purity tin blank is heated to 1430-1440 ℃ and then is sintered for 10-12 h. In some embodiments, the manganese-containing high purity tin blank is sintered after being heated to 1440 ℃ for 10 h. In some embodiments, the annealing is furnace cooling to room temperature. In some embodiments, the manganese-containing high-purity tin blank is uniformly heated to 1440 ℃ at a heating rate of 0.5 ℃/min, is sintered after heat preservation for 10 hours, is cooled to room temperature along with the furnace, and is annealed to prepare the manganese-containing high-purity tin ceramic.
In some embodiments of the present invention, the manganese-containing high purity tin ceramic produced in step S500 is post-processed in a manner that may be disc refining. In some embodiments, the manganese containing high purity tin ceramic is post-processed with a M800 type disk mill having dimensions of 100mm by 100 mm.
The manganese-containing high-purity tin brick prepared by the preparation method provided by the second aspect of the invention has low porosity which can be lower than 1 percent, and large volume density which can be more than 6.5g/cm3The resistance value is high, and the resistance value is more than or equal to 222M omega at the temperature of 30 ℃. In some embodiments, the manganese content is highThe porosity of the pure tin brick is 0.4 to 0.9%, and further may be 0.4 to 0.7%. In some preferred embodiments, the porosity of the manganese-containing high purity tin brick may be as low as 0.4%. In some embodiments, the manganese-containing high purity tin brick has a bulk density greater than 6.5g/cm3And further may be more than 6.8g/cm3. In some preferred embodiments, the manganese-containing high-purity tin brick can have a bulk density of up to 6.84g/cm3。
The fourth aspect of the invention provides the application of the manganese-containing high-purity tin ceramic and the manganese-containing high-purity tin brick as insulating materials. The glass furnace can be used for glass furnace systems, such as the bottom and the wall of a glass furnace, and has strong insulating property. Short circuits are not easy to occur.
Some specific examples are as follows.
Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer.
The starting materials and reagents mentioned in the following specific examples can be commercially available or can be prepared by a person skilled in the art according to known means.
Raw materials:
tin dioxide powder with purity of 99.5% and average particle size of 0.7 μm;
manganese dioxide powder with the purity of 85 percent and the average grain diameter of 3.86 mu m;
water glass liquid with Baume degree of 48;
zirconia ball stone, diameter 6 mm.
Example 1
The manganese-containing high-purity tin brick is prepared by the following steps:
(1) 100 parts by weight of tin dioxide powder having an average particle diameter of 0.7 μm and a purity of 99.5% and 0.1 part by weight of manganese dioxide powder having an average particle diameter of 3.86 μm and a purity of 85% were mixed, and ball-milled for 6 hours in a nylon pot using zirconia having a diameter of 3mm to obtain mixed powder I having an average particle diameter of 0.6 μm.
(2) Weighing 100 parts by weight of the mixed powder I, adding 200 parts by weight of zirconia balls with the diameter of 6mm, 0.1 part by weight of water glass liquid dispersing agent and 30 parts by weight of water, adding into a ball milling tank, and carrying out ball milling for 60min at the rotating speed of 70r/min to obtain the manganese-containing high-purity tin slurry.
(3) And drying the prepared manganese-containing high-purity tin slurry at 130 ℃ for 6h to obtain a solid with the water content of 0.3%, crushing the solid in a 30B type stainless steel crusher at the frequency of 40, sieving the crushed solid by using a 40-mesh screen, and removing iron by using a 6-layer semi-automatic iron remover to obtain manganese-containing high-purity tin powder with the particle size of 0.5 mu m.
(4) And keeping the pressure of the manganese-containing high-purity tin powder for 4min under the isostatic pressure condition of 180MPa, and pressing to obtain a manganese-containing high-purity tin blank with the size of 120mm multiplied by 120 mm.
(5) And (3) loading the manganese-containing high-purity tin blank into a sintering furnace, heating to 1440 ℃ at the speed of 0.5 ℃/min in the atmosphere of air, sintering for 10h, and cooling along with the furnace to obtain the manganese-containing high-purity tin brick.
Example 2
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: the weight portion ratio of the tin dioxide powder to the manganese dioxide powder is 100: 0.15. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Example 3
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: the weight portion ratio of the tin dioxide powder to the manganese dioxide powder is 100: 0.3. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Example 4
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: the sintering temperature was 1430 ℃. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Example 5
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 6, except that: the sintering temperature was 1440 ℃. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 1
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: manganese dioxide powder is not added in the raw materials. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 2
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw materials, the weight part ratio of the tin dioxide powder to the manganese dioxide powder is 100: 0.05. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 3
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw materials, the weight portion ratio of tin dioxide powder to manganese dioxide powder is 100: 0.08. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 4
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw material, the particle size of the tin dioxide powder is 4 μm. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 5
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw materials, the weight portion ratio of the tin dioxide powder to the manganese dioxide powder is 100: 0.5. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 6
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw materials, the weight part ratio of the mixed powder I to the water glass liquid is 100: 0.05. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 7
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw materials, the weight portion ratio of the mixed powder I to the zirconia balls is 100: 160. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
Comparative example 8
A manganese-containing high-purity tin brick was produced in substantially the same manner as in example 1, except that: in the raw materials, the weight part ratio of the mixed powder I to the zirconia balls is 100: 100. The other parameters including the kinds of raw materials, the amounts of the raw materials, and the preparation method were the same as in example 1.
The formulations of the above examples and comparative examples can also be seen in table 1.
TABLE 1 comparison of formulations for examples 1-5 and comparative examples 1-8
Example 6 Performance testing
The porosity and bulk density were tested according to GB/T2997-. The normal temperature resistance value (30 ℃ resistance value) is measured by adopting a two-pole method, and the instrument is an insulation tester of type 1508. The test results are shown in Table 2.
Table 2 results of performance testing
| Item | Porosity (%) | Bulk Density (g/cm)3) | Resistance value at 30 ℃ (M omega) |
| Example 1 | 0.4 | 6.77 | ≥235 |
| Example 2 | 0.9 | 6.83 | ≥225 |
| Example 3 | 0.7 | 6.84 | ≥222 |
| Example 4 | 0.6 | 6.77 | ≥233 |
| Example 5 | 0.9 | 6.82 | ≥223 |
| Comparative example 1 | 35 | 4.48 | ≥321 |
| Comparative example 2 | 30.4 | 4.81 | ≥306 |
| Comparative example 3 | 12.9 | 5.94 | ≥283 |
| Comparative example 4 | 22 | 5.3 | ≥270 |
| Comparative example 5 | 18 | 5.6 | ≥332 |
| Comparative example 6 | 8 | 6.1 | ≥281 |
| Comparative example 7 | 5 | 6.3 | ≥266 |
| Comparative example 8 | 9 | 6.0 | ≥312 |
In table 2, the larger the values of porosity and bulk density are, the worse the sintering is, the worse the glass washing resistance is, and the shorter the service life is; the resistance value reflects the insulation performance of the material, and the larger the value corresponding to the resistance value, the stronger the insulation performance is.
As can be seen from the data in Table 2, the manganese-containing high-purity tin brick provided by the invention has compact brick body, the porosity of the whole brick body is lower than 1%, the volume density of the whole brick body is large and the whole brick body is higher than 6.5g/cm3While also realizing a largerThe surface resistance value of (2) is not less than 222M omega at 30 ℃. It can also be found that changing the particle size of the raw materials or the addition of each component in the formula (comparative examples 4-6), or changing the preparation parameters (comparative examples 7-8) can cause the brick body not to be sintered, thereby causing the porosity to be obviously increased and the performance of the brick body to be reduced.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. The citation referred to herein is incorporated by reference in its entirety for all purposes unless otherwise in conflict with the present disclosure's objectives and/or technical solutions. Where a citation is referred to herein, the definition of a reference in the document, including features, terms, nouns, phrases, etc., that is relevant, is also incorporated by reference. In the present invention, when the citation is referred to, the cited examples and preferred embodiments of the related art features are also incorporated by reference into the present application, but the present invention is not limited to the embodiments. It should be understood that where the citation conflicts with the description herein, the application will control or be adapted in accordance with the description herein.
The technical features of the embodiments and examples described above can be combined in any suitable manner, and for the sake of brevity, all possible combinations of the technical features of the embodiments and examples described above are not described, but should be considered within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above examples are only illustrative of several embodiments of the present invention, and should not be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above teachings of the present invention, and equivalents obtained thereby also fall within the scope of the present invention. It should also be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the patent of the invention is subject to the appended claims, and the description can be used for explaining the contents of the claims.
Claims (10)
1. The manganese-containing high-purity tin ceramic is characterized by comprising tin dioxide, manganese dioxide and a dispersing agent; the weight part of manganese dioxide is 0.1-0.3 in terms of 100 parts of tin dioxide; the weight part ratio of the total content of tin dioxide and manganese dioxide to the content of the dispersing agent is 100 (0.05-0.3);
the manganese-containing high-purity tin ceramic is prepared from raw materials including tin dioxide powder, manganese dioxide powder and the dispersing agent, wherein,
the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent;
the average grain diameter of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent.
2. The manganese-containing high-purity tin ceramic according to claim 1,
the average grain diameter of the tin dioxide powder is less than or equal to 0.6 mu m; and/or the presence of a catalyst in the reaction mixture,
the pH value of the tin dioxide powder is 4.9-6; and/or the presence of a catalyst in the reaction mixture,
the average grain diameter of the manganese dioxide powder is less than or equal to 3.86 mu m; and/or the presence of a catalyst in the reaction mixture,
the dispersing agent is water glass liquid, and the Baume degree of the water glass liquid is not less than 48.
3. The manganese-containing high-purity tin ceramic according to claim 1,
the tin dioxide powder is VS brand; and/or the presence of a catalyst in the reaction mixture,
the purity of the manganese dioxide powder is higher than analytical purity.
4. The manganese-containing high-purity tin ceramic according to any one of claims 1 to 3,
the weight part of manganese dioxide is 0.1-0.15 in terms of 100 parts of tin dioxide; and/or the presence of a catalyst in the reaction mixture,
the weight part ratio of the total content of the tin dioxide and the manganese dioxide to the content of the dispersing agent is 100 (0.05-0.15).
5. The preparation method of the manganese-containing high-purity tin ceramic is characterized by comprising the following steps of:
mixing tin dioxide powder and manganese dioxide powder according to the weight part ratio of 100 (0.1-0.3), and performing first ball milling by using zirconia balls to prepare mixed powder I; wherein the diameter of the zirconia ball is 3 mm-4 mm; the average grain diameter of the tin dioxide powder is less than or equal to 0.7 mu m, and the purity is more than or equal to 99.5 percent; the average particle size of the manganese dioxide powder is less than or equal to 4 mu m, and the purity is more than or equal to 85 percent; the average grain diameter of the prepared mixed powder I is less than or equal to 0.6 mu m;
mixing zirconia balls, the mixed powder I, a dispersing agent and water according to the weight part ratio of (180-220): 100, (0.1-0.3): 25-35), and performing secondary ball milling to prepare manganese-containing high-purity tin slurry; wherein the diameter of the zirconia ball is 4 mm-6 mm;
drying the manganese-containing high-purity tin slurry at the temperature of 110-160 ℃ until the water content is less than or equal to 0.3%, and sieving to obtain manganese-containing high-purity tin powder;
pressing the manganese-containing high-purity tin powder under isostatic pressure, wherein the pressure is 180-230 MPa, and preparing a manganese-containing high-purity tin blank;
and heating the manganese-containing high-purity tin blank to 1430-1440 ℃ at the heating rate of 0.4-0.6 ℃/min, sintering for 10-12 h, and annealing to obtain the manganese-containing high-purity tin ceramic.
6. The method according to claim 5,
the average grain diameter of the tin dioxide powder is less than or equal to 0.6 mu m; and/or the presence of a catalyst in the reaction mixture,
the pH value of the tin dioxide powder is 4.9-6; and/or the presence of a catalyst in the reaction mixture,
the average grain diameter of the manganese dioxide powder is less than or equal to 3.86 mu m; and/or the presence of a catalyst in the reaction mixture,
the dispersing agent is water glass liquid, and the Baume degree of the water glass liquid is not less than 48.
7. The method according to claim 5,
when the first ball milling is carried out, the weight part ratio of the tin dioxide powder to the manganese dioxide powder is 100 (0.1-0.15); and/or the presence of a catalyst in the reaction mixture,
the time for performing the first ball milling is more than or equal to 6 hours; and/or the presence of a catalyst in the reaction mixture,
the average grain diameter of the prepared mixed powder I is less than or equal to 0.6 mu m; and/or the presence of a catalyst in the reaction mixture,
during the second ball milling, the weight part ratio of the zirconia balls to the mixed powder I to the dispersing agent to the water is 200:100 (0.05-0.15) to (25-35); and/or the presence of a catalyst in the reaction mixture,
drying the manganese-containing high-purity tin slurry at the temperature of between 130 and 150 ℃ for 6 to 8 hours; and/or the presence of a catalyst in the reaction mixture,
the mesh number of the sieved screen is less than or equal to 50 meshes; and/or the presence of a catalyst in the reaction mixture,
the particle size of the prepared manganese-containing high-purity tin powder is less than or equal to 0.5 mu m; and/or the presence of a catalyst in the reaction mixture,
before the manganese-containing high-purity tin powder is pressed under an isostatic pressure condition, the method also comprises a step of removing iron; and/or the presence of a catalyst in the reaction mixture,
the pressure maintaining time for pressing the manganese-containing high-purity tin powder under the isostatic pressure condition is 4-8 min; and/or the presence of a catalyst in the reaction mixture,
heating the manganese-containing high-purity tin blank to 1430-1440 ℃ at the heating rate of 0.5 ℃/min; and/or the presence of a catalyst in the reaction mixture,
the annealing mode is cooling to room temperature along with the furnace.
8. The method according to any one of claims 5 to 7,
the rotating speed for carrying out the first ball milling is 60-70 r/min; and/or the presence of a catalyst in the reaction mixture,
the time for performing the first ball milling is 6-8 h; and/or the presence of a catalyst in the reaction mixture,
the rotation speed for performing the second ball milling is 70-80 r/min; and/or the presence of a catalyst in the reaction mixture,
the time for performing the second ball milling is 50-60 min; and/or the presence of a catalyst in the reaction mixture,
the mesh number of the sieved screen is less than or equal to 40 meshes.
9. The manganese-containing high-purity tin brick is characterized by being prepared by the preparation method of any one of claims 5 to 7, having a porosity of less than 1% and a volume density of more than 6.5g/cm3And the resistance value is more than or equal to 222M omega at the temperature of 30 ℃.
10. The use of the manganese-containing high-purity tin ceramic according to any one of claims 1 to 4, or the manganese-containing high-purity tin ceramic prepared by the preparation method according to any one of claims 5 to 8, or the manganese-containing high-purity tin brick according to claim 9 as an insulating material.
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