CN106478116A - A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of MgO refractory material - Google Patents

A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of MgO refractory material Download PDF

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Publication number
CN106478116A
CN106478116A CN201610862260.9A CN201610862260A CN106478116A CN 106478116 A CN106478116 A CN 106478116A CN 201610862260 A CN201610862260 A CN 201610862260A CN 106478116 A CN106478116 A CN 106478116A
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aluminate spinel
magnesium aluminate
magnesium
slurry
zro
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郭曙强
姜兰
张满
马帅
苏新
乔梦然
丁伟中
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/482—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Compositions Of Oxide Ceramics (AREA)
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Abstract

The invention discloses the thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of MgO refractory material.Its preparation process is as follows：In commercial oxidation magnesium oxide-stabilizing zirconia powder（MgO3.5%,ZrO296.5%）In, binding agent, deionized water, dispersant is proportionally added into, is made into the slurry of good fluidity；Its part by weight is 100：（7‑18）：（16‑35）:(0.2‑3)；During magnesium aluminate spinel is proportionally added into slurry；Its commercial oxidation magnesium oxide-stabilizing zirconia powder is 100 with magnesia-alumina spinel powder part by weight：（0.5‑1）；Mix 3 20h in ball mill, material ball ratio is 1：（0.8‑1.1）, obtain slurry；Slurry is poured into gypsum mold shaping；Sintering temperature is 1600 DEG C 1750 DEG C, obtain magnesium aluminate spinel doping with high-heat resistance shock resistant magnesia partial stabilized zirconia refractory products.The present invention makes magnesium aluminate spinel be pinned at the crystal boundary of commercial oxidation magnesium PSZ by magnesium aluminate spinel doping, it is suppressed that micro-crack spreads, hence it is evident that improve the thermal shock resistance of material.

Description

A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation of-MgO refractory material Method
Technical field
The present invention relates to a kind of ZrO of magnesium aluminate spinel doping2The preparation method of-MgO refractory material, particularly a kind of magnesium Aluminate is doped with the preparation method of the refractory material of high-heat resistance shock resistant magnesia partial stabilized zirconia.
Background technology
Vacuum induction melting is to produce one of main method of smelting of ultra-clean steel and alloy.But still suffer from high temperature alloy to melt Body is with crucible refractory material reaction contaminated melt and refractory material to the problems such as the oxygen supply of molten bath.Therefore suitable refractory material is selected Significant to lifting alloy mass.From thermodynamics, with traditional refractory material Al2O3Compare with MgO, titanium dioxide Zirconium has higher chemical stability.But zirconium oxide has polymorphous phase structure, respectively monoclinic phase (m-ZrO2), Tetragonal (t-ZrO2) and Emission in Cubic (c-ZrO2).Volume Changes are accompanied by transition process, often zircite product are produced broken Bad.As magnesium aluminate spinel is pinned at stabilized magnesium hydroxide zirconium oxide crystal boundary, suppression micro-crack diffusion, change phase amount distribution, drop The thermal coefficient of expansion of low material.Therefore, it can make which be pinned at stabilized magnesium hydroxide zirconium oxide crystal boundary by the magnesium aluminate spinel that adulterates, Suppression micro-crack extension, and then the thermal shock resistance of stabilized magnesium hydroxide zirconia ceramics material is improved, make the material can be in hot environment Used in.
Content of the invention
It is an object of the invention to provide the thermal shock resistance ZrO of magnesium aluminate spinel doping2- MgO (magnesia partial stabilized oxygen Change zirconium) refractory material preparation method, to solve the problems, such as magnesia partial stabilized zirconia ceramic thermal shock resistance.
To achieve the above object of the invention, the present invention is adopted the following technical scheme that.
A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of-MgO refractory material, it is characterised in that the party The concretely comprising the following steps of method：
A. per 100 parts of commercial oxidation magnesium oxide-stabilizing zirconia powder (MgO3.5%, ZrO296.5%), in, 7-18 part is added Binding agent, the deionized water of 16-35 part and 0.2-3 part dispersant；Uniform stirring is configured to slurry；Add 0.5-1 The magnesium aluminate spinel of part；Then ball milling is carried out, and wherein material is 1 with the ratio of ball：(0.8-1.1), last mechanical mixture 3-20h, Obtain the magnesium aluminate spinel doping magnesia partial stabilized zirconia ceramic slurry of full and uniform mixing；The binding agent is for I Uncle's natural gum；Above-mentioned dispersant is macromolecule dispersing agent acrylamide or triethanolamine；
B. step a gained slurry is poured into gypsum mold slip casting, the demoulding after slip casting time 6-25min, 0.5-1.5h, obtain The magnesia partial stabilized zirconia ceramic product element embryo of magnesium aluminate spinel doping；It is placed at sunshade and dries 2-4 days, finally repaiies Base；
C. step b gained biscuit is sintered, it is 1600 DEG C -1750 DEG C to burn temperature eventually, the described ZrO of final acquisition2- The magnesia partial stabilized zirconia refractory products of the refractory material of MgO, i.e. magnesium aluminate spinel doping.
The present invention has the advantages that process equipment is simple, low cost, be suitable for scale, adulterates in prepared magnesium aluminate spinel In stabilized magnesium hydroxide zirconium oxide product, magnesium aluminate spinel is pinned at commercial oxidation magnesium PSZ crystal boundary, it is suppressed that micro- Crackle spreads, and changes phase amount distribution, hence it is evident that improves the thermal shock resistance of material, makes the material can be used in hot environment.
Description of the drawings
Fig. 1 is the thermal dilatometry of the preferred embodiment of the present invention 1.
Fig. 2 is the magnesium aluminate spinel doping stabilized magnesium hydroxide zirconic SEM figure prepared by the preferred embodiment of the present invention 2.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
By commercial oxidation magnesium oxide-stabilizing zirconia powder (MgO3.5%, ZrO296.5%), deionized water, binding agent are Arabic Natural gum and dispersant triethanolamine are according to 100:30:16:The proportional arrangement of 0.8 (mass ratio) becomes slurry, and magnesium aluminate spinel is pressed During ratio is added to slurry；Wherein, stabilized magnesium hydroxide Zirconium powder is 100 with magnesia-alumina spinel powder mass ratio:1.Will slurry Material pour into and in ball grinder and add zirconia ball, slurry and zirconia ball ratio be 1：1.1, it is subsequently placed in cylinder and mixes Slurry 8h, is sufficiently mixed slurry.Slurry is poured in gypsum mold, the demoulding after slip casting time 15min, 1.5h, obtain product element embryo； It is placed at sunshade and dries 3 days, last repaired biscuit；The biscuit product of the drying of shaping is placed in high temperature furnace, in air atmosphere, eventually It is 1650 DEG C to burn temperature, and is incubated 6 hours, that is, obtain magnesium aluminate spinel doping stabilized magnesium hydroxide zirconium oxide product.
Embodiment 2
By commercial oxidation magnesium oxide-stabilizing zirconia powder (MgO3.5%, ZrO296.5%), deionized water, binding agent are Arabic Natural gum and dispersant triethanolamine are according to 100:22:15:The proportional arrangement of 1 (mass ratio) becomes slurry, by magnesium aluminate spinel press than During example is added to slurry；Wherein, stabilized magnesium hydroxide Zirconium powder is 100 with magnesium aluminate spinel mass ratio:0.5.Slurry is fallen Enter and in ball grinder and add zirconia ball, slurry and zirconia ball ratio be 1：0.8, it is subsequently placed in slurry in cylinder 5h, is sufficiently mixed slurry.Slurry is poured in gypsum mold, the demoulding after slip casting time 5min, 40min, obtain magnesium aluminate spinel Doping stabilized magnesium hydroxide zirconium oxide element embryo；It is placed at sunshade and dries 3 days, last repaired biscuit；The crucible biscuit that dries of shaping is placed in In high temperature furnace, in air atmosphere, it is 1690 DEG C to burn temperature eventually, and is incubated 4 hours, that is, obtain magnesium aluminate spinel doping magnesia Stabilizing zirconia product.Fig. 1 is the zirconic thermal dilatometry of magnesium aluminate spinel doping stabilized magnesium hydroxide, by the magnalium point that adulterates Spar, the thermal coefficient of expansion of stabilized magnesium hydroxide zirconia ceramics reduce.
Fig. 2 is the zirconic SEM figure of prepared magnesium aluminate spinel doping stabilized magnesium hydroxide, as seen from Figure 2：Aluminate is followed closely Prick in stabilized magnesium hydroxide zirconium oxide crystal boundary, suppress Crack Extension.

Claims (1)

1. the thermal shock resistance ZrO that a kind of magnesium aluminate spinel adulterates2The preparation method of-MgO refractory material, it is characterised in that the method Concretely comprise the following steps：
A. per 100 parts of commercial oxidation magnesium oxide-stabilizing zirconia powders（MgO3.5%,ZrO296.5%）In, add the bonding of 7-18 part The dispersant of agent, the deionized water of 16-35 part and 0.2-3 part；Uniform stirring is configured to slurry；Add the magnesium of 0.5-1 part Aluminate；Then ball milling is carried out, and wherein material is 1 with the ratio of ball：（0.8-1.1）, last mechanical mixture 3-20h, filled Divide mixed uniformly magnesium aluminate spinel doping magnesia partial stabilized zirconia ceramic slurry；The binding agent is Arabic tree Glue；Above-mentioned dispersant is macromolecule dispersing agent acrylamide or triethanolamine；
B. step a gained slurry is poured into gypsum mold slip casting, the demoulding after slip casting time 6-25min, 0.5-1.5h, obtain magnesium The magnesia partial stabilized zirconia refractory products element embryo of aluminate doping；It is placed at sunshade and dries 2-4 days, finally repaiies Base；
C. step b gained biscuit is sintered, it is 1600 DEG C -1750 DEG C to burn temperature eventually, the described ZrO of final acquisition2-MgO The magnesia partial stabilized zirconia refractory products of refractory material, i.e. magnesium aluminate spinel doping.
CN201610862260.9A 2016-09-29 2016-09-29 A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of MgO refractory material Pending CN106478116A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422537A (en) * 2017-08-22 2019-03-05 宝山钢铁股份有限公司 Continuous casting is with exempting to toast refractory material and preparation method thereof
CN110655399A (en) * 2019-09-06 2020-01-07 钟祥市中原电子有限责任公司 Breathable ceramic head for molten steel hydrogen determination probe and preparation method thereof
CN110903086A (en) * 2019-12-10 2020-03-24 中钢集团洛阳耐火材料研究院有限公司 High-performance magnesium-stabilized zirconia raw material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496990A (en) * 2013-09-13 2014-01-08 天津大学 High-temperature thermal-shock-resistant magnesia alumina spinel-zirconia complex-phase material and preparation method thereof
CN103601521A (en) * 2013-11-15 2014-02-26 瑞泰科技股份有限公司 Low-porosity periclase-magnesium aluminate spinel-zirconia sintered composite refractory material and production process thereof
CN103601506A (en) * 2013-10-09 2014-02-26 瑞泰科技股份有限公司 Low-porosity magnesium aluminate spinel-zirconia composite sintered refractory material and production technology thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496990A (en) * 2013-09-13 2014-01-08 天津大学 High-temperature thermal-shock-resistant magnesia alumina spinel-zirconia complex-phase material and preparation method thereof
CN103601506A (en) * 2013-10-09 2014-02-26 瑞泰科技股份有限公司 Low-porosity magnesium aluminate spinel-zirconia composite sintered refractory material and production technology thereof
CN103601521A (en) * 2013-11-15 2014-02-26 瑞泰科技股份有限公司 Low-porosity periclase-magnesium aluminate spinel-zirconia sintered composite refractory material and production process thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422537A (en) * 2017-08-22 2019-03-05 宝山钢铁股份有限公司 Continuous casting is with exempting to toast refractory material and preparation method thereof
CN109422537B (en) * 2017-08-22 2021-03-12 宝山钢铁股份有限公司 Baking-free refractory material for continuous casting and preparation method thereof
CN110655399A (en) * 2019-09-06 2020-01-07 钟祥市中原电子有限责任公司 Breathable ceramic head for molten steel hydrogen determination probe and preparation method thereof
CN110903086A (en) * 2019-12-10 2020-03-24 中钢集团洛阳耐火材料研究院有限公司 High-performance magnesium-stabilized zirconia raw material

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