WO2012008352A1 - Matériau réfractaire isolant thermique et son procédé de production - Google Patents

Matériau réfractaire isolant thermique et son procédé de production Download PDF

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WO2012008352A1
WO2012008352A1 PCT/JP2011/065567 JP2011065567W WO2012008352A1 WO 2012008352 A1 WO2012008352 A1 WO 2012008352A1 JP 2011065567 W JP2011065567 W JP 2011065567W WO 2012008352 A1 WO2012008352 A1 WO 2012008352A1
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heat
insulating refractory
particles
refractory
pore
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PCT/JP2011/065567
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English (en)
Japanese (ja)
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辰己 津山
謙一郎 古賀
打田 龍彦
渡邊 浩二
光宣 村島
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三井金属鉱業株式会社
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Priority to CN2011800149415A priority Critical patent/CN102811973A/zh
Priority to KR1020127024461A priority patent/KR20130097059A/ko
Publication of WO2012008352A1 publication Critical patent/WO2012008352A1/fr

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Definitions

  • the present invention relates to a heat insulating refractory and a method for manufacturing the same.
  • a heat insulating refractory having a purity of about 70 to 99% of alumina is often used as a heat insulating member for a furnace wall or ceiling of a kiln furnace for firing a workpiece containing a large amount of alkali components.
  • the purity of alumina in the heat-insulating refractory is low, it may be necessary to apply a high-purity alumina coat to the surface of the refractory in order to suppress deterioration of the refractory due to the alkali component. It takes time to perform such alumina coating. Further, even when a refractory having a high alumina purity is used, a reaction with an alkali component is unavoidable, and it cannot be said to be sufficient for suppressing deterioration of the refractory.
  • heat insulation refractories are required to be lighter.
  • a high-alumina, high-alumina heat-insulating refractory having a bulk specific gravity after firing of 1.35 to 1.60 and an alumina content ratio of 97% by weight or more has been proposed (see Patent Document 1).
  • This refractory is fired using a raw material powder containing 35 to 60% by weight of high-purity hollow alumina and containing 2.0 to 7.0% by weight of particles having an outer diameter of 3.360 mm or more. It is a thing.
  • this refractory contains a relatively large amount of silica, and it cannot be said that the purity of alumina is sufficiently high. As a result, the reaction between the silica and the alkali component derived from the workpiece tends to proceed, and the refractory tends to deteriorate. Moreover, since it cannot be said that the porosity is high, it will become heavy. Moreover, it becomes disadvantageous also in terms of heat capacity. In other words, energy efficiency is poor. Furthermore, since heat conductivity is high, it is inferior to heat insulation.
  • An object of the present invention is to provide a heat-insulating refractory that can eliminate various drawbacks of the above-described conventional technology.
  • the present invention is made of alumina ceramics or zirconia ceramics, does not contain silica, or even if it contains 1% by weight or less, has a porosity of 65 to 85%, and has a compressive strength of 2 MPa or more. It provides the heat insulation refractory characterized by these.
  • this invention is as a suitable manufacturing method of the said heat insulation refractory, A kneaded product obtained by kneading alumina particles or zirconia particles, a water-soluble polymer material, a polysaccharide, pore-forming particles that can be lost by firing, and a liquid medium is press-molded at a pressure at which the pore-forming particles are not destroyed. A molded product is obtained, and then the molded product is fired under conditions where the pore-forming particles disappear.
  • a heat-insulating refractory having sufficient strength for actual use is provided while the reaction with the alkali component is suppressed and further weight reduction is achieved.
  • FIG. 1 (a) thru
  • FIG. 2 is a schematic diagram showing a stacked structure of the heat insulating refractories shown in FIG. 3 (a) to 3 (c) are diagrams showing another embodiment of the heat-insulating refractory according to the present invention.
  • FIG. 4 is a schematic diagram showing a stacked structure of the heat insulating refractories shown in FIG.
  • the heat-insulating refractory of the present invention is mainly composed of high-purity alumina ceramics or zirconia ceramics.
  • the heat-insulating refractory of the present invention mainly composed of these ceramics has excellent alkali resistance.
  • the ratio of alumina or zirconia in the heat insulating refractory is required to be 99% by weight or more, preferably 99.5% by weight or more from the viewpoint of suppressing the reaction with the alkali component. That is, the heat-insulating refractory of the present invention is of high purity alumina or high purity zirconia.
  • alumina or a zirconia there is no restriction
  • high-purity artificial alumina or artificial zirconia may be used as a raw material for the heat insulating refractory.
  • alumina or the like derived from natural raw materials such as clay there is a possibility that impurities are mixed.
  • the ratio of alumina or zirconia in the heat-insulating refractory can be measured, for example, by photoelectric photometric emission spectrometry.
  • the zirconia ceramics include stabilized zirconia ceramics.
  • Stabilized zirconia ceramics contain, for example, CaO, Y 2 O 3 , MgO or the like as a stabilizer. In the present invention, these stabilizers are also considered as a part of zirconia ceramics and are excluded from impurities.
  • the heat-insulating refractory according to the present invention is preferably made of high-purity alumina or high-purity zirconia. That is, it is preferable that impurities are not included as much as possible.
  • the amount of the heat-insulating refractory according to the present invention is very small even if it does not contain or contains silica. This is because silica easily reacts with an alkali component, thereby easily producing a low-melting-point substance that causes deterioration.
  • the ratio of silica in the heat insulating refractory is required to be 1% by weight or less, and preferably 0.5% by weight or less.
  • oxides of alkali metals such as sodium and potassium are substances that affect the deterioration of heat-insulating refractories.
  • Alkali metal oxides promote the vitrification of heat-insulating refractories and cause the creep performance of heat-insulating refractories to deteriorate.
  • the heat insulating refractory of the present invention does not contain an alkali metal oxide. Even if the heat-insulating refractory contains an alkali metal oxide, it is advantageous that the amount is as small as possible. Specifically, it is preferable to suppress the ratio of the alkali metal oxide (the ratio of the total amount of Na 2 O and K 2 O) in the heat insulating refractory to 0.3% by weight or less, particularly 0.2% by weight or less.
  • iron oxide is a substance that affects the deterioration of heat insulating refractories.
  • the heat-insulating refractory of the present invention does not contain iron oxide. Even if the heat-insulating refractory contains iron oxide, the amount is advantageously as small as possible. Specifically, it is preferable to keep the ratio of iron oxide in the heat insulating refractory (the ratio of the total amount of various iron oxides) to 0.5% by weight or less, particularly 0.2% by weight or less.
  • the ratio of the total of silica, alkali metal oxide and iron oxide in the heat-insulating refractory of the present invention is 1.3% by weight or less, particularly 0.7% by weight or less. It is preferable to suppress.
  • the ratio of silica, alkali metal oxide and iron oxide contained in the heat insulating refractory can be measured by, for example, photoelectric photometric emission spectroscopic analysis.
  • the adiabatic refractory of the present invention is characterized by a high porosity.
  • the heat-insulating refractory according to the present invention has a very high porosity of 65 to 85%, preferably 70 to 80%.
  • the upper limit value of the porosity of the heat-insulating refractory is determined in consideration of the weight reduction of the refractory and the balance between heat insulation and strength. From this viewpoint, in the present invention, the upper limit value of the porosity of the heat insulating refractory is set to 85%.
  • the porosity of the heat-insulating refractory can be calculated from, for example, a formula of (1 ⁇ bulk specific gravity / apparent specific gravity) ⁇ 100.
  • the bulk specific gravity in the above formula is calculated by measuring the weight of the heat insulating refractory and dividing by the volume obtained from the measurement of the dimensions of the heat insulating refractory.
  • the apparent specific gravity is a value obtained by dividing the mass of the heat insulating refractory by the mass of water at 4 ° C. having the same volume as the apparent volume (JIS R2001), and is measured by the Archimedes method.
  • pore-forming particles that can be lost by firing may be used as raw materials, or hollow particles may be used.
  • the porosity can be within the above-described range without using hollow particles (that is, even when solid particles are used).
  • the heat-insulating refractory of the present invention is also characterized by having sufficient strength for actual use despite its high porosity.
  • the compressive strength of the heat insulating refractory measured in accordance with JIS R2615 is 2 MPa or more, preferably 3 MPa or more. That is, the heat-insulating refractory of the present invention satisfies the contradictory requirements of high porosity and high compressive strength at the same time. If the compressive strength of the heat-insulating refractory is 2 MPa or more, when the heat-insulating refractory is stacked to form a stacked structure to be described later, it is possible to effectively prevent inconvenience such as crushing in each cut-off refractory. Can do.
  • the heat insulating refractory according to the present invention has a bending strength of the heat insulating refractory measured according to JIS R2619 of 0.5 MPa or more, particularly preferably 1 MPa or more. If the bending strength of the heat insulating refractories is 0.5 MPa or more, it is possible to effectively prevent inconveniences such as breakage of the respective heat insulating refractories in the stacked structure.
  • a method described later may be employed to manufacture the heat-insulating refractory.
  • the heat insulating refractory of the present invention generally has a predetermined three-dimensional shape.
  • the heat-insulating refractory of the present invention is used for the lining or backing of various furnaces, it is preferable to assemble a plurality of the refractories having a predetermined three-dimensional shape.
  • polyhedron shapes such as standard shape, standard horizontal edge shape, standard vertical edge shape, standard edge shape, etc., which are standard brick shapes defined in JIS R2101 shall be adopted. Can do.
  • the irregular shape used for a joint can also be employ
  • the shape for an arch structure can also be employ
  • a shape for example, a horizontal hull, a vertical hull, a drum shape (fan shape), a longitudinal hug, a forehead hug, a body hug, and the like can be mentioned. Details of the various shapes described above are described in, for example, “Kiln Furnace Engineering” (first edition, issued in April 1983) issued by the Refractory Technology Association.
  • the heat-insulating refractory 10 has a rectangular parallelepiped (cuboid) shape, and faces opposite to other heat-insulating refractories adjacent in the assembled state, for example, the upper surface 11 and the lower surface 12 in the assembled state.
  • One or two or more recessed portions 21 and 22 can be formed on the surface corresponding to.
  • This heat-insulating refractory 10 has an upper surface 11 and a lower surface 12 having a longitudinal direction X and a width direction Y orthogonal thereto, and the length in the longitudinal direction X is approximately twice the length in the width direction Y. .
  • Each recess 21 and 22 does not penetrate to the surface opposite to the surface on which it is formed.
  • the depth of each recessed part 21, 22 is less than 1 ⁇ 2 of the thickness T of the heat insulating refractory 10.
  • Each of the recessed portions 21 and 22 has the same shape and has a cylindrical shape. However, the recessed portions 21 and 22 do not need to have the same shape, and various different shapes may be employed depending on the specific use of the heat-insulating refractory and the assembly position in the furnace.
  • the recessed portion 21 formed on the upper surface 11 and the recessed portion 22 formed on the lower surface 12 are arranged so that the positions of the recessed portions 21 and 22 do not overlap in the plan view of the heat-insulating refractory 10. Yes. That is, the upper surface 11 corresponding to the position where the recessed portion 22 is formed on the lower surface 12 and the recessed portion 22 is not formed at the position of the lower surface 12 corresponding to the position where the recessed portion 21 is formed on the upper surface 11. No recess is formed at the position of.
  • the specific formation positions of the recessed portions 21 and 22 on the upper surface 11 and the lower surface 12 of the heat insulating refractory 10 are as follows. That is, as shown in FIG. 1, the upper surface 11 (lower surface 12) is virtually divided into left and right by a center line L that bisects the upper surface 11 (lower surface 12) of the heat insulating refractory 10 in the width direction Y. Considering the left half quadrangle 11a and the right half quadrangle 11b formed by equally dividing, the center of the recess 21 is located on one diagonal line (not shown) of each quadrangle 11a, 11b. The center of the recessed portion 22 is located on another diagonal line (not shown).
  • the sum of the volumes of the recessed portions 21 and 22 formed in the heat insulating refractory 10 is 10 to 40% of the apparent volume of the heat insulating refractory 10. In particular, it is preferably 20 to 30%. Further, from the same viewpoint, the volume of each of the recessed portions 21 and 22 is preferably 2 to 40%, particularly 5 to 40%, of the apparent volume of the heat insulating refractory 10.
  • a stacked structure as shown in FIG. 2 can be adopted. That is, the heat insulating refractories 10 are arranged in a row along the longitudinal direction X to form the first stage 31, and the second stage 32 is formed thereon in the same manner. In this case, the second stage 32 is arranged such that the arrangement of the heat insulating refractory 10 is shifted by 1/2 pitch with respect to the first stage 31.
  • the recessed portions 21 and 22 in each heat insulating refractory 10 are not opposed to the recessed portions 21 and 22 in the heat insulating refractory 10 adjacent in the vertical direction.
  • FIG. 3 shows another form of the heat insulating refractory 10.
  • the recessed portion 21 formed on the upper surface 11 and the recessed portion 22 formed on the lower surface 12 are arranged so that the positions of the recessed portions 21 and 22 do not overlap in the plan view of the heat-insulating refractory 10. Yes.
  • a concave portion 21 is formed on the upper surface 11 corresponding to the quadrangle 11a, and a concave portion 22 is formed on the lower surface 12 corresponding to the right half quadrilateral 11b.
  • the centers of the two recesses 21 (22) are positioned on each of the two diagonals, and one more recess at the intersection of the two diagonals.
  • the center of 21 (22) is located. That is, a total of five recessed portions 21 (22) are formed in each half quadrilateral 11a (11b).
  • FIG. 3 is stacked, for example, a stacked structure as shown in FIG. 4 can be employed.
  • This stacked structure is the same as the stacked structure shown in FIG. 2 described above.
  • the arrangement of the heat insulating refractory 10 is shifted by 1/2 pitch in the second stage 32 with respect to the first stage 31. Therefore, the recessed portions 21 and 22 in each heat insulating refractory 10 are not opposed to the recessed portions 21 and 22 in the heat insulating refractory 10 adjacent in the vertical direction.
  • This production method is roughly divided into (i) a step of obtaining a molded body using a kneaded product containing alumina particles or zirconia particles, and (b) a step of firing the molded body to obtain a target refractory.
  • a step of obtaining a molded body using a kneaded product containing alumina particles or zirconia particles and (b) a step of firing the molded body to obtain a target refractory.
  • alumina particles or zirconia particles, a water-soluble polymer material, a polysaccharide, pore-forming particles that can be lost by firing, and a liquid medium are kneaded to obtain a kneaded product.
  • high-purity alumina particles or zirconia particles as components constituting the kneaded product.
  • the purity of the zirconia particles is the total value of the zirconia particles and the stabilizer. Specifically, it is preferable to use those having a purity of 98.5% by weight or more, particularly 99.0% by weight or more.
  • Such high purity alumina particles or zirconia particles are readily available commercially.
  • alumina particles or zirconia particles it is preferable to use a particle having a relatively large particle size as an aggregate material and a particle having a relatively small particle size as a bond.
  • Alumina particles or zirconia particles as an aggregate raw material preferably have a particle size of 30 to 500 ⁇ m, particularly 45 to 300 ⁇ m from the viewpoint of maintaining porosity and strength.
  • the alumina particles or zirconia particles as a bond preferably have a particle size of 0.1 to 30 ⁇ m, particularly 1 to 25 ⁇ m.
  • the particle size of the alumina particles or zirconia particles is measured by a microtrack or a laser type particle size distribution analyzer.
  • the ratio between the aggregate raw material and the bond in the kneaded product is 50 to 90% by weight of the aggregate / 50 to 10% by weight of the bond, particularly the aggregate 60 from the viewpoint of increasing the porosity and maintaining the strength of the heat-insulating refractory. It is preferable to set it to ⁇ 80 wt% / bond 40 to 20 wt%.
  • the shape of the alumina particles or zirconia particles is not particularly critical in the present production method, and various commercially available shapes can be used.
  • the pore-forming particles that can be eliminated by firing are used to increase the porosity of the intended heat-insulating refractory.
  • the pore-forming particles can be lost by heating in air.
  • a material that starts at least disappearing at a heating temperature of 150 ° C. or higher are composed of organic polymer compounds such as acrylic acid ester, polyimide, polystyrene, polyethylene, polypropylene, and ethylene vinyl acetate.
  • disappearance as used herein means that the residue is decomposed by oxidation by heating, and no residue remains.
  • the particle size of the pore-forming particles affects the porosity and strength of the intended heat-insulating refractory.
  • the pore-forming particles preferably have a particle size of 0.5 to 5 mm, particularly 1 to 4 mm.
  • the particle diameter of the pore-forming particles is measured by the same method as the method for measuring the particle diameter of the alumina particles or zirconia particles described above.
  • the shape of the pore-forming particles also affects the bulk specific gravity and porosity of the intended heat-insulating refractory. From this viewpoint, it is preferable to use pore-forming particles whose shape is closer to a true sphere.
  • the ratio of the pore-forming particles contained in the kneaded product is 100 to 300 cm 3, particularly 150 to 250 cm 3 with respect to 100 g of alumina particles or zirconia particles, from the viewpoint of the balance between the porosity and strength of the intended heat-insulating refractory. It is preferable.
  • the water-soluble polymer material and polysaccharide contained in the kneaded product are used to enhance the shape retention of a molded product formed from the kneaded product.
  • the ratio of the pore-forming particles is increased, the shape retention in the case of molding a molded body from the kneaded product is lowered, and it is difficult to obtain a molded body having a desired shape. Further, even when the press pressure is lowered, the shape retention of the molded body is lowered and it is difficult to obtain the desired molded body.
  • the molded body can be produced even if the ratio of the pore-forming particles contained in the kneaded product is increased. It can be molded successfully, and the molded body can be molded successfully even when the press pressure is low. Furthermore, the firing step (b) described later can be carried out successfully.
  • a water-soluble polymer material that exhibits a high binding force even when used in a small amount.
  • polyvinyl alcohol, cellulose, agar, gelatin or the like can be used.
  • a suitable material is selected from the same viewpoint as the water-soluble polymer material.
  • starch, glycogen, etc. can be used.
  • the water-soluble polymer material exhibits a necessary and sufficient binding force with a minimal amount of use.
  • the proportion of the water-soluble polymer material contained in the kneaded product is preferably 5 to 15% by weight, particularly 8 to 12% by weight.
  • the ratio of the polysaccharide contained in the kneaded product is preferably 0.1 to 3% by weight, particularly 0.5 to 2% by weight.
  • water As the liquid medium contained in the kneaded product, water is basically used.
  • the above-described components are uniformly mixed to obtain a desired kneaded product.
  • the method similar to the method used in the said technical field can be used.
  • a molded body having a predetermined shape is obtained.
  • press molding in which a kneaded product is filled in a mold having a predetermined shape and the kneaded product is pressed at a predetermined pressure can be used.
  • the press molding is preferably performed at a pressure with an upper limit that the pore-forming particles contained in the kneaded product are not destroyed. This pressure depends on the type and particle size of the pore-forming particles. As a general range, 50 to 500 kg / cm 2 is preferably employed.
  • the molded body thus obtained is taken out of the mold or from the mold and subjected to a drying process.
  • the liquid medium is removed by means such as heating or infrared irradiation. Drying is performed until the ratio of the liquid medium contained in the molded body is preferably 1% by weight, more preferably 0.5% by weight or less.
  • the dried compact is subjected to the firing step (b).
  • Firing can be performed in air. Firing is performed under conditions where pore-forming particles contained in the molded body disappear.
  • the firing conditions depend on the type and particle size of the pore-forming particles, but as a general condition, the pore-forming particles disappear by holding the temperature of 1400 to 1800 ° C. for 1 to 10 hours, and the alumina particles Alternatively, the zirconia particles are sufficiently sintered.
  • This refractory has a high purity of alumina or zirconia and has a low content of impurities such as silica and alkali metal oxides that cause deterioration of the refractory. It is particularly preferably used as an adiabatic refractory. For example, it is suitably used in a kiln for firing alkaline ion battery materials. In addition to this application, it is also suitably used in electronic component firing furnaces and the like.
  • Example 1 (1) Preparation of kneaded material As an aggregate raw material, 70 parts of solid alumina particles (purity 99.7%) having an average particle diameter of 100 ⁇ m were used. Further, 30 parts of solid alumina particles (purity 99.8%) having an average particle diameter of 5 ⁇ m were used as bonds. One part of polyvinyl alcohol was used as the water-soluble polymer material. Two parts of starch was used as the polysaccharide. Styrene beads having an average particle size of 3mm as the pore-forming particles were used 150 cm 3 with respect to the alumina particles 100 g. These were uniformly mixed with 10 parts of water to obtain a kneaded product.
  • Example 2 A heat-insulating refractory having the shape shown in FIG. 1 was obtained in the same manner as in Example 1 using the conditions shown in Table 1 below.
  • Example 3 60 parts of solid CaO-stabilized zirconia particles (purity: ZrO 2 95.6%, CaO 3.7%) as an aggregate raw material with an average particle diameter of 150 ⁇ m, and CaO-stabilized zirconia with a solid average particle diameter of 2 ⁇ m as a bond particles (purity: ZrO 2 95.6%, CaO3.7% ) 100cm 3 using 40 parts, 2 parts starch as polysaccharide, a styrene bead particles having an average particle size of 3mm as the pore-forming particles with respect to the zirconia particles 100g
  • a heat-insulating refractory having the shape shown in FIG. 1 was obtained in the same manner as in Example 1 except that press molding was performed at a pressure of 80 kg / cm 2 .
  • Comparative Example 3 Alumina refractory heat insulating brick LBK-28 (trade name) manufactured by Isolite Industry Co., Ltd. was used as Comparative Example 3.
  • Lithium carbonate Li 2 CO 3
  • Li 2 CO 3 Lithium carbonate
  • the crucible was heated at 1000 ° C. for 10 hours. Then, it cooled to room temperature and removed the heat insulation refractory from the crucible. The state of the surface of the heat-insulating refractory removed from the surface facing the lithium carbonate was observed, and the alkali resistance of the heat-insulating refractory was evaluated.
  • the evaluation criteria are as follows.
  • the heat-insulating refractories of each Example have a higher porosity than the heat-insulating refractories of Comparative Examples 1 and 2.
  • the heat-insulating refractory of each example shows a lower value than the heat-insulating refractories of Comparative Examples 1 and 2, but has strength that does not interfere with actual use.
  • the heat-insulated refractory of Comparative Example 3 has a relatively high porosity and a large compressive strength and bending strength, but the purity of alumina is low and the amount of impurities such as silica is large. Compared with the heat insulation refractory material 3, the alkali resistance was inferior.

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Abstract

La présente invention concerne un matériau réfractaire isolant thermique caractérisé en ce qu'il est formé à partir d'une céramique d'alumine ou de zircone, ne contenant pas de silice ou une teneur inférieure ou égale à 1 % en poids de silice, et ayant une porosité dans la plage allant de 65 à 85 % et une résistance à la compression de 2 MPa. Ce matériau réfractaire isolant thermique est de préférence produit en : obtenant un corps moulé par moulage à la presse d'un matériau malaxé, qui est obtenu en malaxant des particules d'alumine ou des particules de zircone, un matériau polymère soluble dans l'eau, un polysaccharide, des particules formant des pores qui peuvent être éliminées par cuisson et un milieu liquide, sous une pression à laquelle les particules formant des pores ne sont pas cassées ; et en cuisant ensuite le corps moulé dans des conditions telles que les particules formant des pores soient éliminées.
PCT/JP2011/065567 2010-07-13 2011-07-07 Matériau réfractaire isolant thermique et son procédé de production WO2012008352A1 (fr)

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JP6207423B2 (ja) * 2014-02-24 2017-10-04 イソライト工業株式会社 軽量耐アルカリ耐火断熱れんが及びその製造方法
EP3670477B1 (fr) * 2017-08-14 2021-05-19 Nissan Motor Co., Ltd. Composant d'écran thermique et son procédé de fabrication
CN107540355B (zh) * 2017-09-16 2020-07-24 长沙恒安工程技术有限公司 一种轻质耐火材料的制备方法
US11874679B2 (en) 2019-01-09 2024-01-16 Mitsubishi Electric Corporation Using an imaging device to correct positioning errors
CN115947597B (zh) * 2022-09-30 2023-08-04 武汉科技大学 一种微闭孔轻量氧化锆耐火材料及其制备方法

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