CN112341218B - Method for preparing high-performance magnesium-zirconium composite ceramic tile by spark plasma sintering - Google Patents
Method for preparing high-performance magnesium-zirconium composite ceramic tile by spark plasma sintering Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002490 spark plasma sintering Methods 0.000 title claims abstract description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000843 powder Substances 0.000 claims abstract description 86
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 55
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 43
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 37
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 37
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 37
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 37
- 239000011812 mixed powder Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 23
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 15
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 235000010755 mineral Nutrition 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 abstract description 13
- 230000035939 shock Effects 0.000 abstract description 11
- 230000003628 erosive effect Effects 0.000 abstract description 8
- 239000011449 brick Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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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
- C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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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
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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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
- 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
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
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- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a method for preparing a high-performance magnesium-zirconium composite ceramic tile by adopting a spark plasma sintering technology, which adopts natural magnesite and zircon ore as raw materials, the magnesite and the zircon are respectively crushed and ground, then the magnesite powder is calcined into light-burned magnesia powder, the light-burned magnesia powder and the zircon powder are fully mixed by adding water, slurry is dried, and finally the dried mixed powder is placed in a spark plasma sintering device for high-temperature sintering, so that the high-performance magnesium-zirconium composite ceramic tile is prepared. The high-performance magnesium-zirconium composite ceramic tile prepared by the invention has the advantages of refined grains, high density and strength, and remarkable thermal shock resistance and erosion resistance. The method is simple to operate, green and environment-friendly, and can be used for preparing the high-performance magnesium-zirconium composite ceramic tiles in batches on the premise of greatly saving the cost.
Description
Technical Field
The invention relates to the field of refractory materials, in particular to a method for preparing a high-performance magnesium-zirconium composite ceramic tile by using a spark plasma sintering technology.
Background
Magnesite is a special natural mineral resource, is an important raw material for producing magnesia refractory materials, can be used for preparing various pure magnesium and magnesia composite materials, and can be widely applied to the fields of metallurgy, chemical industry, building and the like.
The high-purity magnesia brick directly prepared from magnesite has poor thermal shock resistance and erosion resistance, so that the high-purity magnesia brick is not suitable for being used in extreme and complex environments, such as lining materials of a refining furnace and a glass kiln, and a magnesia product is easy to crack due to cyclic thermal shock, thereby influencing the production process. The volume density of the magnesium-zirconium composite ceramic prepared by the prior art is generally 3.45 g-cm-3The room-temperature compressive strength is 70 to 150 MPa. Therefore, in order to improve the performance of the magnesium material, high-purity magnesium oxide and other oxides are combined in production to prepare high-performance magnesium composite refractory materials, such as a magnesium chromium material and a magnesium aluminate spinel material. However, the magnesium-chromium material is very easy to cause chromium pollution in the using process, thereby harming the health of production personnel. For the magnesium-aluminum spinel material, although the thermal shock resistance and the erosion resistance are better, aluminum element is easy to enter products to form inclusions, so that the quality of metal products such as steel, iron and the like is reduced. Therefore, the market at present puts higher demands on high-quality and environment-friendly magnesium composite refractory materials.
The zircon is also a natural mineral, and can be added into the magnesia brick to be fired into the magnesia-zirconia composite brick with high performance. However, due to the limitation of the technological level, the production method of the magnesium-zirconium brick mainly uses high-price fused magnesium and high-purity zircon as raw materials, and the magnesium-zirconium brick is formed by high-pressure forming and then calcined in a rotary kiln or a vertical kiln at the temperature of over 1800 ℃. The production cost is high, the production process is complex, and the rotary kiln or the shaft kiln can consume a large amount of resources in the production process and cause environmental pollution in peripheral areas, so that the rotary kiln or the shaft kiln is not suitable for large-scale industrial production and does not accord with the green and environment-friendly production policy.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing a high-performance magnesium-zirconium composite ceramic tile by using a spark plasma sintering technology. The method takes natural magnesite and zircon ore as raw materials and adopts spark plasma high-temperature pressurizing sintering for the high-performance magnesium-zirconium composite ceramic tile. The invention has simple production process, low energy consumption and no environmental pollution.
The technical scheme of the preparation method of the spark plasma sintering high-performance magnesium-zirconium composite ceramic tile is characterized by comprising the following preparation steps:
1) crushing and grinding raw materials, namely crushing and grinding the magnesite and the zircon ore to below 200 meshes in a crusher and a grinder respectively to obtain magnesite powder and zircon powder;
2) performing light burning on mineral powder, and calcining the obtained magnesite powder in a heating furnace at the calcining temperature of 750-850 ℃ for 1-2 hours to prepare light-burned magnesia powder;
3) uniformly mixing and drying the mineral powder, putting the prepared light-burned magnesia powder and the obtained zircon powder into a mixing machine, adding sufficient water, fully and uniformly mixing to obtain slurry, and drying the slurry in drying equipment after uniformly mixing to obtain mixed powder of magnesium hydroxide and zircon; wherein,
the mixing ratio of the light-burned magnesia powder to the zircon powder is 20: 1-10: 1, the adding amount of water and the powder are in a ratio of 3: 1-5: 1, uniformly mixing for 2-8 hours, drying for 12-24 hours at the drying temperature of 90-120 ℃;
4) performing spark plasma sintering, namely placing the mixed powder of the magnesium hydroxide and the zirconite in a spark plasma sintering furnace for molding and high-temperature pressure sintering; cooling after sintering to obtain the magnesium-zirconium composite ceramic tile;
wherein the high-temperature sintering temperature is 1450-1650 ℃, the heating rate is 100 ℃/min, the sintering heat preservation time is 15-35 minutes, and the applied pressure is 50-150 MPa.
The contribution of the invention is that when the spark plasma high-temperature pressure sintering is carried out, the mixed powder is rapidly decomposed into magnesium oxide and forms a certain amount of micro pores, the micro pores enable zirconium oxide grains in the mixed powder to rapidly grow and fill the micro pores along with the rise of the temperature, and meanwhile, the growth of the magnesium oxide grains is inhibited, the magnesium oxide grains are refined, and the density and the strength of the magnesium-zirconium composite ceramic tile are enhanced. The volume density of the high-performance magnesium-zirconium composite ceramic tile can reach 3.50-3.82 g-cm-3And the normal-temperature compressive strength reaches 437-625 MPa.
Further, the mixing ratio of the light-burned magnesia powder and the zircon powder can be 16: 1-14: 1, and the ratio of the addition amount of water to the powder can be 4:1, the mixing time can be 4-6 hours, the drying time can be 16-20 hours, and the drying temperature can be 100-115 ℃. The high-temperature sintering temperature can be 1550-1650 ℃, the heating rate can be 100 ℃/min, the sintering heat preservation time can be 20-35 minutes, and the applied pressure can be 50-150 MPa.
The heating furnace is a muffle furnace heating device. The forming of the mixed powder of the magnesium hydroxide and the zircon is carried out in a graphite mould of a plasma sintering furnace. The discharge plasma high-temperature pressure sintering adopts a direct-current pulse power supply electrifying sintering technology, and compared with the consumption of coal or petroleum and other energy sources, the consumption of the energy sources is greatly reduced.
The invention has the following advantages and beneficial effects:
(1) the method for preparing the high-performance magnesium-zirconium composite ceramic tile by using the spark plasma sintering technology is simple and easy to operate, has a short production period, and can greatly reduce the production cost.
(2) The raw materials adopted by the invention are natural minerals, so that harmful gas or other toxic substances cannot be generated in the production process, and the environment cannot be polluted.
(3) The discharge plasma sintering technology utilized by the invention is a direct-current pulse power supply electrifying sintering technology, and energy sources such as coal, petroleum and the like can not be consumed, so that the energy source loss is greatly reduced.
(4) The discharge plasma high-temperature pressure sintering technology adopted by the invention is used for high-temperature pressure sintering, the temperature rise time is short, and the growth of oxide crystal grains is facilitated under the action of pressure. During the pressure sintering process, the magnesium hydroxide in the mixed powder is rapidly decomposed into magnesium oxide, so that micro pores are formed in situ, and the micro pores provide space for the growth of zirconium oxide grains. Along with the rise of the temperature, the zirconium oxide crystal grains rapidly grow and fill the tiny pores, and meanwhile, the growth of the magnesium oxide crystal grains is inhibited, and the function of refining the magnesium oxide crystal grains is achieved. Therefore, the invention greatly improves the density and the strength of the magnesium-zirconium composite ceramic tile and greatly improves the comprehensive performance of the magnesium-zirconium composite ceramic tile.
Drawings
FIG. 1 is a process flow diagram of the manufacturing process of the present invention;
FIG. 2 is a scanning electron microscope image of a magnesium zirconium ceramic composite brick prepared in example 1;
FIG. 3 is a scanning electron microscope image of a magnesium zirconium ceramic composite brick prepared in example 2.
Detailed Description
The invention is explained in detail below with reference to the figures and exemplary embodiments. Preferred embodiments are shown in the following figures. The extent of certain regions in the drawings have been exaggerated or exaggerated in order to provide a clear description of the present invention, or some graphical structures have not been shown in the context of a clear description of the text. The size of the preferred embodiments and the pattern configurations are not limiting of the invention.
Referring to fig. 1, the preparation steps and design concept of the present invention are explained in detail as follows:
The invention verifies in the course of many times of experiments that the original raw materials in step 1, such as magnesite or zircon, have the best decomposition effect when the granularity is below 200 meshes. If the particle size is too large, the magnesite cannot be completely decomposed at the calcining temperature and the heat preservation time in the step 2, so that a longer heat preservation time is needed to obtain the completely decomposed light-burned magnesia powder. The hydration reaction rate of the light-burned magnesium oxide is also greatly related to the particle size, and the hydration rate can be slowed down when the particle size is too large. And the excessive granularity of the zircon powder influences the sintering process in the step 4, and directly reduces the growth and migration rate of zirconia grains in the sintering process. However, if the particle size is too small, the final effect is improved, but the loss and cost caused by crushing and ball milling are also greatly increased. Therefore, after a plurality of tests and verifications, the inventor selects magnesite powder and zircon powder with the optimal proportion of less than 200 meshes.
As the initial decomposition temperature of magnesite is about 550 ℃, the magnesite powder with the granularity of less than 200 meshes is subjected to decomposition experiments by the inventor to obtain the result that the magnesite powder can be completely decomposed after heat preservation for 1-2 hours at the temperature of 750-850 ℃. When the calcining temperature is lower than 750 ℃ or the holding time is less than 1 hour, the decomposition of the magnesite powder is incomplete. When the calcination temperature exceeds 850 ℃ or the holding time exceeds 2 hours, the activity of the lightly calcined magnesia is seriously affected although the lightly calcined magnesia is completely decomposed. It is well known to those skilled in the art that the reduction of the activity of the light-burned magnesia severely inhibits the hydration rate and sintering performance, thus reducing the mixing and drying efficiency of the ore powder in step 3 and affecting the final sintering result in step 4.
In step 3, mixing can be performed in various ways, such as mechanical dry mixing, organic solvent mixing. The invention not only aims at adding water for mixing and uniformly mixing, but also completely converts the light-burned magnesium oxide powder into the magnesium hydroxide powder. In the experimental process, the inventors have uniformly mixed the light-burned magnesia powder and the zircon powder by dry mixing and carried out the experiment of the step 4, but the experimental result is not ideal. The purpose of adding water to prepare the magnesium hydroxide is to skillfully utilize the phenomenon that pores are generated during pyrolysis so as to achieve the purpose of promoting the growth of zirconium oxide grains. The ratio of the addition amount of water to the powder is 3: 1-5: 1 was experimentally verified, and below this amount it is possible to cause incomplete hydration of the magnesia into magnesium hydroxide and also directly affect the final result of step 4, i.e. the performance of the magnesium zirconium composite ceramic tile.
The discharge plasma high-temperature pressure sintering in the step 4 of the invention is a necessary step for preparing the magnesium-zirconium composite ceramic tile. The blank formed under high temperature and pressure can reach an obviously compact and high-strength structural state. However, when the conventional technology utilizes a sample press for molding and a rotary kiln or a shaft kiln for high-temperature sintering, the process flow is long, the cost is high, the strength and the density of the produced magnesium-zirconium ceramic composite brick are low, and the erosion resistance and the thermal shock resistance of the produced magnesium-zirconium ceramic composite brick are poor.
When the spark plasma high-temperature pressure sintering is carried out, the mixed powder is rapidly decomposed into magnesium oxide and forms a certain amount of micro pores, the micro pores enable zirconium oxide grains in the mixed powder to rapidly grow and fill the micro pores along with the rise of the temperature, and meanwhile, the growth of the magnesium oxide grains is inhibited, so that the effect of refining the magnesium oxide grains is achieved. As the zirconia grains are filled at the periphery of the magnesia grains, the density and the strength of the magnesium-zirconium composite ceramic tile are improved and strengthened.
The volume density of the high-performance magnesium-zirconium composite ceramic tile prepared by the invention is 3.50-3.82 g-cm-3And the normal-temperature compressive strength is 437-625 MPa. The volume density of the magnesium-zirconium composite ceramic prepared by the conventional method is generally 3.45 g-cm-3The room-temperature compressive strength is 70 to 150 MPa. Therefore, the volume density and compressive strength of the magnesium-zirconium composite ceramic tile prepared by the method are both obviously improved. Even if the high-temperature-resistant cable is applied to a more severe high-temperature environment, the service life of the high-temperature-resistant cable is correspondingly prolonged.
The spark plasma sintering adopted by the invention has the characteristic of sintering in the pressurizing process, and the plasma generated by the pulse current of the adopted direct current pulse power supply and the pressurizing in the sintering process are beneficial to reducing the sintering temperature of the powder. Meanwhile, the powder can be rapidly sintered and compacted due to the characteristics of low voltage and high current. Therefore, compared with the traditional pressure sintering mode such as hot-pressing sintering and hot isostatic pressing sintering, the spark plasma sintering method has the advantages of high heating speed, short sintering time, remarkable inhibition of grain coarsening and the like. In the actual production, the production rate and the comprehensive performance of the product can be greatly improved.
The forming of the mixed powder of magnesium hydroxide and zircon is carried out in a graphite mould of a plasma sintering furnace. In the prior art, for the forming of the magnesium-zirconium ceramic tile, dry pressing forming or cold isostatic pressing forming is used, and usually, mixed powder is placed in a steel mould and formed under a hydraulic press. Due to the technical limitations of the hydraulic machine, such as the highest pressure, the uniformity of force transmission in the pressing process and the like, the two forming modes can cause the phenomenon of uneven density of different parts of the blank. Meanwhile, the two technologies are formed and then sintered. The size and the shape of the graphite die can be designed according to actual needs by spark plasma sintering, so that the molding and sintering processes of a part with a complex structural shape can be completed simultaneously, the time is short, and the loss is small. Because the green body becomes hard and compact after sintering, the phenomenon of green body fracture in the demoulding process is avoided, and the production efficiency is greatly improved.
The following will explain the implementation of the present manufacturing method in detail by specific examples with reference to fig. 1 to 3.
In the following examples, natural magnesite and zircon ore were used as raw materials, and the main components thereof are shown in tables 1 and 2.
Table 1: chemical composition of magnesite (wt/%)
| Composition (I) | MgO | SiO2 | Al2O3 | Fe2O3 | CaO | I.L. |
| Mass fraction | 47.03 | 0.26 | 0.06 | 0.27 | 0.66 | 51.72 |
TABLE 2 chemical composition of zircon ore (wt/%)
| Composition (I) | ZrO2 | SiO2 | Al2O3 | TiO2 | Fe2O3 | CaO | MgO |
| Mass fraction | 66.62 | 32.24 | 0.52 | 0.35 | 0.07 | 0.1 | 0.1 |
Example 1
In the embodiment, a spark plasma sintering technology is adopted, and a high-performance magnesium-zirconium composite ceramic tile is prepared through high temperature and pressurization, wherein the process is as shown in fig. 1 and comprises the following steps:
1) crushing and grinding natural raw materials, respectively putting magnesite and zircon ore with mass percentages shown in tables 1 and 2 into crushing and grinding equipment for crushing and grinding, and finally obtaining magnesite powder and zircon powder with the particle size of less than 200 meshes;
2) carrying out light burning on magnesite powder, placing the magnesite powder in a muffle furnace at 800 ℃ for calcining, and keeping the temperature for 1 hour to prepare light-burned magnesia powder;
3) the light-burned magnesia powder and the zircon powder are uniformly mixed according to a proportion and dried, 400g of the light-burned magnesia powder and 20g of the zircon powder are placed in a mixer, water with the amount being 3 times of the mixed powder is added for uniform mixing for 2 hours, and then the uniformly mixed slurry is taken out and dried for 20 hours in a drying oven at the temperature of 90 ℃ to obtain dry mixed powder.
The light-burned magnesia powder can be completely reacted into magnesium hydroxide after being mixed for 2 hours by 3 times of water amount, and the full mixing of 420g of powder can be ensured after the reaction, so that the powder cannot be completely mixed because the powder becomes viscous due to too little water.
4) And (2) performing pressurized high-temperature sintering on the mixed powder by adopting discharge plasma, placing the dried mixed powder in a graphite mould in a discharge plasma sintering furnace, applying a pressure of 50MPa, heating up at a rate of 100 ℃/min, and preserving heat for 20 minutes at a sintering temperature of 1550 ℃, so that the crystal grains of the magnesium-zirconium composite ceramic tile are refined in the molding process, and the density and the strength are increased, thereby obtaining the high-performance magnesium-zirconium composite ceramic tile.
The volume density of the magnesium-zirconium composite ceramic tile prepared by the embodiment is 3.50 g-cm detected by the GB/T2999-2002 national standard method-3The above; the bulk density of the prior art is 3.45g cm-3The following. Meanwhile, the detection of the GB/T5072-2008 national standard method shows that the normal-temperature compressive strength of the magnesium-zirconium composite ceramic tile is 437MPa, and the rapid cooling and rapid heating thermal shock cycle is carried out at 1100 DEG CCracks only occur after more than 20 cycles. And the normal temperature compressive strength of the prior art is about 70-150MPa, so that cracks can quickly appear under the rapid cooling and rapid heating thermal shock cycle at the same temperature. Thus, the performance of this embodiment is far superior to the prior art. Meanwhile, as can be seen from the scanning electron microscope image of the magnesium-zirconium ceramic composite brick shown in fig. 1, the tiny pores formed by the magnesium oxide are filled with the grown zirconium oxide grains, so that the growth of the magnesium oxide grains is inhibited, and the effect of refining the magnesium oxide grains is achieved. When the magnesium-zirconium composite ceramic brick is used as a lining material of a refining furnace, the magnesium-zirconium composite ceramic brick shows remarkable thermal shock resistance and erosion resistance under strong thermal cycle impact, the thermal cracking phenomenon does not occur even if the magnesium-zirconium composite ceramic brick is subjected to thermal cycle impact for more than 30 times, the service time is more than 2 times that of the existing high-purity magnesium brick, the service life is long, and therefore the production efficiency is greatly improved.
Example 2
The present example is as in example 1, and the process is shown in fig. 1, and a high performance magnesium zirconium composite ceramic tile is prepared by high temperature and pressurization using spark plasma sintering technology.
1) According to the mass percentages of magnesite and zircon ore shown in tables 1 and 2, the magnesite and the zircon ore are respectively placed in crushing and grinding equipment for crushing and grinding, and magnesite powder and zircon powder with the particle size of less than 200 meshes are finally obtained.
2) Putting the magnesite powder into a muffle furnace at 850 ℃ for calcination and light burning, and keeping the temperature for 2 hours to prepare light-burned magnesia powder.
3) The light-burned magnesia powder and the zircon powder are uniformly mixed according to a proportion and dried, 400g of the light-burned magnesia powder and 40g of the zircon powder are placed in a mixer, water with the amount being 5 times of the mixed powder is added for uniform mixing for 4 hours, and then the uniformly mixed slurry is taken out and dried for 16 hours in a drying oven at 100 ℃ to obtain dry mixed powder.
4) And placing the dried mixed powder into a graphite mould in a spark plasma sintering furnace, applying 100MPa of pressure, sintering temperature 1650 ℃, heating rate of 100 ℃/min, and keeping the temperature for 35 minutes, so that the crystal grains of the magnesium-zirconium composite ceramic tile are more refined in the molding process, and the density and the strength are greatly improved, thereby obtaining the high-performance magnesium-zirconium composite ceramic tile.
The volume density of the magnesium-zirconium composite ceramic tile is measured to be 3.82 g-cm by the detection of a national standard method-3(ii) a The measured normal temperature compressive strength of the magnesium-zirconium composite ceramic tile is 625MPa, and the performance of the magnesium-zirconium composite ceramic tile is far superior to that of the ceramic tile in the prior art. It can be seen from the scanning electron microscope image of fig. 2 that the micro-pores formed by the magnesium oxide are filled with the grown zirconium oxide grains, thereby inhibiting the growth of the magnesium oxide grains and refining the magnesium oxide grains. When the magnesium-zirconium composite ceramic brick is used as a lining material of a glass kiln, the magnesium-zirconium composite ceramic brick of the embodiment also shows excellent thermal shock resistance and erosion resistance under strong thermal cycle impact, the service life of the magnesium-zirconium composite ceramic brick is about 3 times of that of the existing high-purity magnesium brick, the maintenance period of equipment is prolonged, and the production efficiency is remarkably improved.
Example 3
This example is as in examples 1 and 2, and the process is shown in fig. 1, and a high performance magnesium zirconium composite ceramic tile is prepared by high temperature and pressure using spark plasma sintering technology.
1) Magnesite and zircon ores with mass percentages shown in tables 1 and 2 are respectively put into crushing and grinding equipment for crushing and grinding to obtain magnesite powder and zircon powder with the particle size of less than 200 meshes.
2) Putting the magnesite powder into a muffle furnace at 830 ℃ for light burning, and keeping the temperature for 1.5 hours to prepare light-burned magnesia powder.
3) 400g of light-burned magnesia powder and 26g of zircon powder are placed in a mixer, water with the amount 4 times that of the mixed powder is added for uniform mixing for 3 hours, and then the uniformly mixed slurry is taken out and dried for 12 hours in a drying oven at 110 ℃ to obtain dry mixed powder.
4) And (3) placing the dried mixed powder into a graphite mould in a spark plasma sintering furnace, and preserving heat for 30 minutes at the pressure of 130MPa, the sintering temperature of 1600 ℃, the heating rate of 100 ℃/min to prepare the high-performance magnesium-zirconium composite ceramic tile with more refined crystal grains and higher density and strength.
Through detection, the magnesium is compounded with the zirconiumThe volume density of the ceramic tile is 3.65 g-cm-3(ii) a The normal temperature compressive strength is 512MPa, and the material shows good thermal shock resistance and erosion resistance under strong thermal cycle impact when being used as a lining material of a refining furnace. And the heat cracking phenomenon does not occur even if the brick is impacted for more than 30 times through heat cycle, and the service life of the brick is more than 2 times of that of the existing high-purity magnesite brick. The effect of the organization structure is similar to the result in the scanning electron microscope images of fig. 2 and fig. 3.
The preparation method is simple and easy to implement, short in production period, energy-saving and capable of greatly reducing the production cost. The magnesium-zirconium composite ceramic tile sintered by the discharging plasma high-temperature pressurization is adopted, the crystal grains are refined, the density and the strength are greatly improved, the thermal shock resistance and the erosion resistance are obvious, the service life is long, the maintenance period of equipment is prolonged, and the production efficiency is obviously improved.
The above are only preferred embodiments of the present invention. Various modifications may be made by those skilled in the art without departing from the principles of the invention and are intended to be within the scope of the invention.
Claims (8)
1. A method for preparing a spark plasma sintering high-performance magnesium-zirconium composite ceramic tile is characterized in that natural magnesite and zircon ore are selected as raw materials, the spark plasma high-temperature pressure sintering magnesium-zirconium composite ceramic tile is adopted, and the preparation steps are as follows:
1) crushing and grinding raw materials, namely crushing and grinding the magnesite and the zircon ore to below 200 meshes in a crusher and a grinder respectively to obtain magnesite powder and zircon powder;
2) performing light burning on mineral powder, and calcining the obtained magnesite powder in a heating furnace at the calcining temperature of 750-850 ℃ for 1-2 hours to prepare light-burned magnesia powder;
3) uniformly mixing and drying the mineral powder, putting the prepared light-burned magnesia powder and the obtained zircon powder into a mixing machine, adding sufficient water, fully and uniformly mixing to obtain slurry, and drying the slurry in drying equipment after uniformly mixing to obtain mixed powder of magnesium hydroxide and zircon; wherein,
the mixing ratio of the light-burned magnesia powder to the zircon powder is 20: 1-10: 1, the adding amount of water and the powder are in a ratio of 3: 1-5: 1, uniformly mixing for 2-8 hours, drying for 12-24 hours at the drying temperature of 90-120 ℃;
4) performing spark plasma sintering, namely placing the mixed powder of the magnesium hydroxide and the zirconite in a spark plasma sintering furnace for molding and high-temperature pressure sintering; cooling after sintering to obtain the magnesium-zirconium composite ceramic tile;
wherein the high-temperature sintering temperature is 1450-1650 ℃, the heating rate is 100 ℃/min, the sintering heat preservation time is 15-35 minutes, and the applied pressure is 30-150 MPa.
2. The preparation method of claim 1, wherein when the mixed powder is subjected to spark plasma high-temperature pressure sintering, the mixed powder is rapidly decomposed into magnesium oxide and forms a certain amount of micro pores, and the micro pores enable zirconium oxide grains therein to rapidly grow and fill the micro pores along with the increase of temperature, and simultaneously inhibit the growth of the magnesium oxide grains, refine the magnesium oxide grains and strengthen the density and strength of the magnesium-zirconium composite ceramic tile.
3. The preparation method of claim 1 or 2, wherein the bulk density of the magnesium-zirconium composite ceramic tile is 3.50-3.82 g-cm-3And the normal-temperature compressive strength is 437-625 MPa.
4. The preparation method according to claim 1, wherein the high-temperature sintering temperature is 1550-1650 ℃, the heating rate is 100 ℃/min, the sintering heat preservation time is 25-35 minutes, and the applied pressure is 100-150 MPa.
5. The preparation method according to claim 1, wherein the mixing ratio of the light-burned magnesia powder to the zircon powder is 16: 1-14: 1, and the ratio of the addition amount of water to the powder is 4:1, uniformly mixing for 3-6 hours, drying for 16-20 hours, and drying at 90-100 ℃.
6. The production method according to claim 1, wherein the heating furnace is a muffle furnace heating apparatus.
7. The method according to claim 1, wherein the mixed powder is molded in a graphite mold of a plasma sintering furnace.
8. The method according to claim 1, wherein the spark plasma sintering is performed by applying a DC pulse power.
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