CN108530094B - Basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter and preparation method thereof - Google Patents
Basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter and preparation method thereof Download PDFInfo
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- CN108530094B CN108530094B CN201810306500.6A CN201810306500A CN108530094B CN 108530094 B CN108530094 B CN 108530094B CN 201810306500 A CN201810306500 A CN 201810306500A CN 108530094 B CN108530094 B CN 108530094B
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- magnesium sulfate
- magnesium
- ceramic
- magnesia
- aluminate spinel
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 188
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 152
- 239000000919 ceramic Substances 0.000 title claims abstract description 141
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 124
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 76
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 74
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 59
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000011029 spinel Substances 0.000 title claims abstract description 55
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011777 magnesium Substances 0.000 title claims description 88
- 229910052749 magnesium Inorganic materials 0.000 title claims description 86
- -1 magnesium aluminate Chemical class 0.000 title claims description 50
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 122
- 238000005245 sintering Methods 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 41
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- 238000000034 method Methods 0.000 claims description 30
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
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- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 6
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- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
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- 229910026161 MgAl2O4 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
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- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 2
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- C04B35/803—
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
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- C04B38/0645—Burnable, meltable, sublimable materials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- 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
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Abstract
The invention discloses a basic magnesium sulfate whisker in-situ synthesized magnesia-alumina spinel reinforced magnesia-based foamed ceramic filter which can be sintered at low temperature and has excellent chemical stability and thermal shock resistance and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing 15-25% of nano alumina sol, 0.8-1.5% of rheological agent and the balance of magnesium oxide ceramic powder containing alkali magnesium sulfate whiskers according to the mass percentage, adding absolute ethyl alcohol, and performing ball milling and mixing uniformly to prepare ceramic slurry with the solid content of 60-70%; (2) immersing a polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove redundant immersion slurry to prepare a biscuit, and then removing an ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit; (3) and (3) putting the dried biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesia-based foamed ceramic filter.
Description
Technical Field
The invention relates to a magnesium oxide based foamed ceramic filter and a preparation method thereof, in particular to a magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter synthesized in situ by basic magnesium sulfate whiskers and a preparation method thereof, belonging to the field of metal materials and metallurgy. The filter prepared by the invention is particularly suitable for filtering and purifying magnesium and magnesium alloy melts, and can also be used for filtering and purifying aluminum and aluminum alloy melts.
Background
Magnesium is active in chemical properties, and is very easy to react with oxygen, nitrogen and water vapor in the casting and processing processes, and the generated product remains in magnesium, thereby affecting the internal quality of products and deteriorating the performance of the products. According to the type and property of inclusions in magnesium alloy, the inclusions are generally divided into two main types of metal inclusions and non-metal inclusions: (1) metal inclusionsMagnesium alloy will inevitably introduce some metal simple substance or metal compound impurities in the course of original magnesium production and later processing, they remain on the magnesium alloy matrix or grain boundary in the form of particle, cluster, etc., mainly including metal simple substance α -Fe particle, manganese-iron metal compound such as (Fe, Mn)3Si，(Fe,Mn)5Si3Etc.; (2) non-metallic inclusions: the non-metallic inclusions in the magnesium alloy are mainly based on magnesium oxynitrides, such as MgO, Mg3N2Etc.; the magnesium alloy is added with chloride (KCl, NaCl, MgCl) in the smelting process2Etc.) as the main refining agent, the flux can not be completely removed in the refining process, and a small amount of flux remains in the magnesium melt, causing the inclusion of magnesium metal flux. The suspended oxide inclusions are pushed to the grain boundary from the crystal front during crystallization, and the inclusions generally remain in the form of a film, particles, or clusters at the grain boundary of the magnesium alloy. Statistical data show that MgO accounts for more than 80% of all inclusions in the magnesium alloy, and the distribution form is film, particle and cluster. The inclusion produced in the process of casting the magnesium alloy not only seriously deteriorates the mechanical property and the corrosion resistance of the alloy, but also reduces the surface quality of the alloy after machining and anodic oxidation treatment. For die-cast magnesium alloy, the content of film-like and particle-like oxides in the alloy needs to be controlled to 100cm2Kg and 100mm3The normal use requirements can be met only when the dosage is less than/kg. Therefore, a purification process for removing inclusions in a magnesium melt to improve the purity of the melt during the casting process becomes a key to the production of magnesium alloys.
The melt purification process can be divided into two main categories of flux purification and non-flux purification. The flux purification process is a purification process commonly adopted in the production of magnesium alloy due to high impurity removal efficiency, low cost and convenient operation, but the flux purification also has the defects of increased metal loss, inclusion of flux, incapability of degassing and the like, and particularly when the rare earth magnesium alloy is smelted, the flux can also consume a large amount of rare earth elements in the alloy. The non-flux purification process not only can make up the defects of the flux purification process, but also has excellent purification effect, becomes an important melt purification process applied and developed at present, and develops a plurality of non-flux purification technologies such as filtration purification, rotary blowing purification, electromagnetic purification, ultrasonic treatment and the like in succession. Compared with simple metal mesh melt filtration, the three-dimensional porous ceramic foam ceramic filter with the three-dimensional porous ceramic structure has the advantages of high porosity (70-90%), strong adsorption capacity, chemical corrosion resistance and the like, and can have good filtering effect on impurity particles in the alloy melt through filter cake effect, adsorption effect and rectification effect. The foamed ceramic filtering method can not only filter out fine inclusion particles as small as 10-20 microns in the alloy melt, but also filter out liquid flux inclusions which are difficult to filter out by common filter media.
U.S. patent publication No. US3962081A (Ceramic foam filter), U.S. patent publication No. US4024212A (Ceramic foam and method of preparation), and Chinese patent publication No. CN103787691A (a method for preparing alumina Ceramic foam) disclose Al-containing materials for filtering inclusions from aluminum alloys and steel melts2O3，ZrO2，SiC、SiO2However, the standard free enthalpy of formation of MgO is very low, and the magnesium melt with high activity is very easy to react with the foam ceramic matrix material to dissolve rapidly, thereby blocking the filtration pores or corroding into the magnesium and its alloy melt to become harmful components, therefore, these prior art foam filters are not suitable for filtering magnesium and magnesium alloy melts.
3Mg(l)+Al2O3(s)＝3MgO(s)+2Al(l)(1)
2Mg(l)+ZrO2(s)＝2MgO(s)+Zr(s) (2)
6Mg(l)+4Al(l)+3SiC(s)＝3Mg2Si(s)+Al4C3(s) (3)
4Mg(l)+SiO2(s)＝2MgO(s)+Mg2Si(s) (4)
MgO is a cubic NaCl type structure with a lattice constant of 0.411nm, belongs to an ionic bond compound, has a melting point of 2852 ℃, and is much higher than that of common Al2O3(2054 ℃ C.) and SiO2(1650 +/-50 ℃), so that the magnesium oxide product has good chemical stability, high resistivity and strong anti-erosion capability on metal, slag and alkaline solutionAnd (4) characteristics. Compared with common ceramic materials, MgO, magnesium and alloy melt thereof have good high-temperature chemical stability, do not react with flux inclusion slag formed by molten chloride and fluonate, have small wetting angle with the flux and are easy to adsorb the flux inclusion in the magnesium melt, so the MgO foamed ceramic is an ideal material for smelting and purifying magnesium alloy liquid.
Firing below the melting point of the oxide composition is the most critical step necessary for the preparation of the ceramic material, and the sintering, grain growth, etc. that occurs at high temperatures determines the microstructure and properties of the ceramic material. Chinese patent documents CN1011306B (pure magnesium oxide ceramic foam filter and preparation process thereof), CN101138691A (preparation method of magnesium ceramic foam filter for casting) and the like, and the MgO has very high melting point and thermal expansion coefficient (13.5 multiplied by 10)-6/° c), which results in difficulty in sintering (sintering temperature not lower than 0.8 times of its melting point) and poor thermal shock resistance, limiting the application and development of MgO foam ceramic.
The research shows that: the heat consumption of unit products can be reduced by more than 10 percent when the firing temperature is reduced by 100 ℃ in the ceramic sintering process, and the addition of the sintering aid is an important technical means for reducing the sintering temperature of the MgO foamed ceramic. Addition of V2O5In the case of powder, MgO reacts with V at 1190 DEG C2O5Form an approximate composition of Mg3V2O8Can remarkably lower the sintering temperature of the MgO foamed ceramics, but V2O5Has damage to the respiratory system and the skin during the use process, and has strict limitation on the operation. And V2O5Similarly, cobalt oxide is a good low temperature sintering aid, but has limited application as a highly toxic substance and a scarce resource. Fluoride is a strong cosolvent and a mineralizer commonly used in the sintering of ceramic industry, and fluorite (melting point 1423 ℃) and fluoride are added into Chinese patent documents CN100536986C (magnesia foam ceramic filter), CN1473947A (foam ceramic for purifying magnesium and magnesium alloy melts) and CN101785944B (preparation method of magnesium oxide foam ceramic filter for filtering magnesium and magnesium melts)Magnesium (melting point 1248 ℃), the crystal lattice distortion of the matrix magnesium oxide is increased by the solid solution of fluoride in the sintering process, and a low-melting-point liquid phase is easily formed, so that the sintering temperature of the magnesium oxide ceramic is reduced; however, F in fluoride is combined with Si, Al, Fe and Ca in the sintering process, most of the F (accounting for about 70 percent in the production of ceramic tiles) volatilizes in a gaseous state to erode a blank body and damage the quality of the sintered ceramic, more serious the F pollution is caused by the emission of the fluoride into the atmosphere, the fluoride can enter a human body through respiratory tract, digestive tract and skin, has toxic effect on the central nervous system and cardiac muscle, the low-concentration fluorine pollution can cause brittle calcification of teeth and bones, and the emission standard of the fluoride is required to be lower than 5.0mg/m in the emission standard of ceramic industrial pollutants (GB25464-2010)3The fluoride is used as the low-temperature sintering aid of the magnesium oxide ceramic, so that the emission of gaseous fluoride is increased inevitably, and the burden of environmental protection is increased; in addition, fluorine ions in solid-solution fluorides remaining in ceramics exist in the form of substituted oxygen ions, which causes a decrease in chemical stability of intergranular bonding, and makes it difficult to resist long-term erosion by flux inclusion in a magnesium melt. In the slurry for producing the ceramic foam filter disclosed in Chinese patent document CN101138691A or the like, water glass, silica sol and ethyl silicate are used as a binder, and SiO is formed between sintered ceramic foam particles2The existence of the components makes the components easy to react with magnesium and magnesium alloy melt according to the formula (4), and the chemical stability of the foamed ceramic is also reduced. In chinese patent documents CN100536986C (magnesia ceramic foam filter), CN103553686A (magnesium aluminate spinel ceramic foam filter and its preparation method), and the like, boron trioxide and borax are used as low temperature sintering aids for magnesia ceramics, and when the boron trioxide is higher than 450 ℃, it forms a liquid phase, and when the sintering temperature exceeds 1350 ℃, it reacts with magnesia to generate magnesium borate in the form of a liquid phase, thereby lowering the sintering temperature. However, boron trioxide is liable to react with magnesium and aluminum and is unstable in magnesium and aluminum alloy melts; meanwhile, as the diboron trioxide is dissolved in solvents such as water, ethanol and the like, the diboron trioxide can strongly absorb water in the air to generate boric acid, and the diboron trioxide added in the preparation process of the foamed ceramic is dissolved in water to form a boric acid aqueous solution which is easy to react with magnesium oxideThe effect of which is reduced by the formation of magnesium borate precipitates. Gallium oxide is a family oxide of diboron trioxide, and forms spinel-shaped MgGa with magnesium oxide at a lower temperature2O4But the sintering temperature is reduced, but the resource amount of gallium is very small (gallium is a strategic reserve metal), and the application of gallium oxide in common ceramics is limited due to the higher price of gallium oxide.
Disclosure of Invention
The invention aims to provide a basic magnesium sulfate whisker in-situ synthesized magnesia-alumina spinel reinforced magnesia-based foamed ceramic filter which can be sintered at low temperature and has excellent chemical stability and thermal shock resistance and a preparation method thereof.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a magnesium aluminate spinel reinforced magnesia-based foam ceramic filter synthesized in situ by basic magnesium sulfate whiskers is prepared by coating light-burned magnesia-based ceramic slurry containing basic magnesium sulfate whiskers on a polyurethane foam carrier, drying and sintering.
A preparation method for in-situ synthesis of a magnesium aluminate spinel reinforced magnesia-based foamed ceramic filter by basic magnesium sulfate whiskers comprises the following steps:
(1) according to the mass percentage, 15 to 25 percent of nano alumina sol, 0.8 to 1.5 percent of rheological agent and the balance of magnesia ceramic powder containing alkali magnesium sulfate whisker are mixed, added with absolute ethyl alcohol and ball-milled and mixed evenly to prepare ceramic slurry with the solid content of 60 to 70 percent. The added nano alumina sol forms gamma-Al on the surfaces of the light-burned magnesium oxide particles and the highly uniformly dispersed basic magnesium sulfate whiskers2O3Coating film, gamma-Al in nano aluminium sol in sintering process2O3Reacting with MgO to obtain high melting point magnesium aluminate spinel (MgAl) with face-centered cubic lattice2O4MA) phase (melting point 2135 ℃ C.). The added nano alumina sol not only can play a role of a binder, but also reacts with magnesium oxide powder particles and decomposition products of basic magnesium sulfate whiskers highly and uniformly dispersed in the magnesium oxide powder particles in situ to generate magnesium aluminate spinel MgAl with chemical stability on magnesium and magnesium alloy melt2O4And the damage of the prior product added with binders such as silica sol, ethyl silicate and the like to the chemical stability of the foamed ceramic is avoided.
The rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is industrial hydroxypropyl methyl cellulose, hydroxyethyl cellulose or a mixture thereof. The cellulose ether and polyvinyl butyral are not only good dispersing agents for basic magnesium sulfate whisker powder, can prevent slurry from agglomerating, but also can play a role of a bonding agent when a biscuit is prepared, the soaked slurry can be firmly attached to a polyurethane foam template, so that the biscuit has high strength, and meanwhile, the impregnated slurry can easily escape in a sintering process without polluting products, thereby ensuring the quality of the foam ceramic filter. Sodium carboxymethyl cellulose and other sodium-containing salts are not adopted in the rheological agent, so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
The ceramic powder is a mixture of light-burned magnesium oxide and basic magnesium sulfate whisker. The basic magnesium sulfate whisker accounts for 1-3% of the mass of the ceramic powder, and has a diameter of 1 μm and a length of 50-100 μm. The particle diameter of the light-burned magnesium oxide powder is 250-500 meshes (medium diameter d)5025 to 58 μm).
The adopted light-burned magnesia fine powder has high sintering activity, the nano alumina sol can be dissolved into the high-activity light-burned MgO crystal lattice in a solid solution mode in the sintering process to enable the MgO crystal to generate lattice distortion and activate the crystal lattice, and meanwhile, a new compound, namely magnesia-alumina spinel MgAl, is generated through reaction and sintering between the nano alumina sol and the MgO particles2O4Phase, thereby promoting sintering and particle-phase bonding. On the other hand, the nano powder has the characteristics of large specific surface area, high surface energy, high activity and the like, and the low-temperature sintering aid is added in the form of nano aluminum sol, so that Al in the nano aluminum sol is improved2O3The mixing uniformity with the magnesia powder and the full contact between the sintering aid and MgO particles lead the reaction speed of the generated magnesia-alumina spinel phase to be rapidly improved, thereby further reducing the sintering temperature which isThe reduction of (2) is beneficial to reducing the energy consumption and the production cost of the foamed ceramic filter.
Basic magnesium sulfate whisker (molecular formula is xMgSO)4·yMg(OH)2·zH2O；MgSO4·5Mg(OH)2·3H2153 type O whiskers are more common]The composite material is a novel needle-shaped short fiber reinforced material, the diameter is 0.5-1.0 mu m, the length is 20-80 mu m, and the composite material has excellent physical and mechanical properties such as high strength, low density, high elastic modulus and the like.
Preferably, the solid content of the nano-alumina sol is 20-25%, and the PH value of the nano-alumina sol is more than or equal to 4.
The preparation method of the ceramic slurry comprises the following steps: adding light-burned magnesium oxide powder into a ball milling tank according to the proportion, mixing nano alumina sol, basic magnesium sulfate whisker, a rheological agent and absolute ethyl alcohol, carrying out ultrasonic treatment for 30-60 min, fully dispersing the basic magnesium sulfate whisker, adding the basic magnesium sulfate whisker into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 2-4 h at the rotating speed of 60-120 rpm to uniformly mix the mixture to obtain the magnesium oxide powder.
(2) Immersing the polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove the redundant immersed slurry to prepare a biscuit, and then removing the ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit.
The specification of the polyurethane foam plastic template is 10 PPI-20 PPI (Pores per inch, average number of Pores per inch of length); before use, the material is soaked in 15-20% NaOH aqueous solution at 40-50 ℃ for etching the surface for 40-60 min, then washed by clean water and naturally dried, and then soaked in 2-4% dodecyl benzene sulfonic acid wetting agent aqueous solution and then taken out and dried to obtain the finished product. The surface of the ceramic slurry is roughened by NaOH etching, and then the ceramic slurry is treated by the aqueous solution of the dodecyl benzene sulfonate wetting agent, so that the ceramic slurry is easily and uniformly coated and hung on a polyurethane foam template.
(3) And (3) putting the dried biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesia-based foamed ceramic filter.
The sintering process is that organic matters (polyurethane foam, rheological agent and the like) in a biscuit of the foam ceramic filter are decomposed, gasified and discharged by heating to 550 ℃ at a temperature rise speed of 30 ℃/h, and then heated to 1100 ℃ at the temperature rise speed of 200 ℃/h, and in a low-temperature sintering stage, the biscuit collapse or deformation damage caused by the excessively high decomposition speed of the polyurethane foam and the rheological agent can be prevented due to a low temperature rise speed. And finally heating to 1350-1550 ℃ at a heating rate of 50 ℃/h and preserving heat for 2-3 h at the temperature. In the high-temperature sintering stage, after the sintering temperature exceeds 1100 ℃, the temperature in the sintered body can be ensured to be consistent by the lower temperature rise speed, the uniform generation speed of the generated spinel is avoided, and the deformation and the cracking of the sintered body caused by the phase change stress generated too fast are avoided.
The preparation method of the magnesium oxide based foamed ceramic filter provided by the invention has the advantages of simple process, low cost, high efficiency, suitability for large-scale production and the like, the prepared magnesium oxide based foamed ceramic filter does not contain any component for reducing the chemical stability of the magnesium oxide based foamed ceramic filter, the added nano aluminum sol not only can play a role of reducing the sintering temperature, but also can react with MgO in situ to generate MgAl2O4The magnesium aluminate spinel phase fuses magnesium oxide particles together, and the form of the basic magnesium sulfate whisker with certain directionality is inherited by the formed magnesium aluminate spinel phase, so that the foamed ceramic filter has good strength, chemical stability and thermal shock resistance, is particularly suitable for filtering and purifying inclusions in magnesium and magnesium alloy melt, and can also be used for filtering and purifying aluminum and magnesium alloy melt. Compared with the prior art, the invention has the technical effects that:
firstly, the basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter has excellent chemical stability. Although the raw material alumina sol component contains gamma-Al which reacts with the magnesium melt2O3However, the added nano alumina sol forms gamma-Al on the surfaces of the light-burned magnesium oxide particles and the highly uniformly dispersed basic magnesium sulfate whiskers2O3Coating film, gamma-Al in nano aluminium sol in sintering process2O3Reacting with MgO to obtain high melting point magnesium aluminate spinel (MgAl) with face-centered cubic lattice2O4MA) phase (melting point 2135 ℃ C.).
In the magnesium melt and MgO-Al added with alumina2O3In addition to the reaction formula (1), the following reaction may be present in the reaction system for sintering ceramics:
3Mg(l)+4Al2O3(s)＝3MgAl2O4(s)+2Al(l)(5)
magnesium aluminate spinel MgAl generated by alumina and magnesia2O4The reaction of (a) is:
MgO(s)+Al2O3(s)＝MgAl2O4(s)(6)
magnesium melt and magnesium aluminate spinel MgAl2O4The reactions that occur are:
3Mg(l)+MgAl2O4(s)＝2Al(l)+4MgO(s)(7)
according to the pure substance thermochemistry data handbook (edited by Sudoku of Helh Sanger Valenchen, Chengmelin et al, Beijing: scientific Press, 2003), the Gibbs free energy data of the reaction system of magnesium melt and magnesium aluminate spinel at 900-1200K and the Gibbs free energy change delta G of the reactions (1), (5), (6) and (7)1、ΔG5、ΔG6、ΔG7The calculation results of (a) are shown in table 1.
TABLE 1 Gibbs free energy change delta G calculation results of each reaction in a 900-1200K magnesium melt and magnesium aluminate spinel reaction system
Reaction formula Gibbs free energy delta G of formula (5) for forming magnesium aluminate spinel by magnesium melt and alumina5The temperature difference is minimal, which indicates that the reaction can preferentially occur at the common melting temperature of magnesium alloy. Although the reaction formula (7) of the magnesium liquid and the magnesium aluminate spinel is thermodynamically feasible, the reaction is essentially a reaction between the magnesium liquid and alumina, which is a decomposition product of the magnesium aluminate spinel, but as can be seen from table 1, the magnesium aluminate spinel is decomposed into alumina and oxygen at the melting temperature of the magnesium alloyThe reaction of magnesium oxide is difficult to proceed (reverse reaction of reaction formula (6)), and residual alumina in the sintered ceramic and magnesium liquid generate magnesium aluminate spinel preferentially according to reaction formula (5); on the other hand, MgO-Al2O3In the phase diagram, the MgO side is a periclase solid solution and MA spinel solid solution eutectic phase diagram, and almost no O is generated in the process of generating MA through in-situ reaction2-Diffusion, only Mg2+And Al3+Through mutual diffusion of fixed oxygen lattices, Al with slower diffusion speed is generated3+Determined that the MA phase is mainly in Al2O3One side is grown by means of an epitaxial growth, resulting in the formation of a limited solid solution between the MA phase and MgO, while the MgO content in the MA outer layer in contact with the MgO particles is much higher than its average value, while MgO does not react with the magnesium melt, so that the magnesium aluminate spinel phase fusing together the magnesium oxide particles in the sintered ceramic structure is stable in the magnesium melt.
The magnesium aluminate spinel reinforced magnesium oxide foamed ceramic filter synthesized by the basic magnesium sulfate whiskers in situ does not contain any component for reducing the chemical stability of the magnesium aluminate spinel reinforced magnesium oxide foamed ceramic filter, and the added nano alumina sol not only can play the role of a binder, but also can react with magnesium oxide powder particles and decomposition products of the basic magnesium sulfate whiskers highly and uniformly dispersed in the magnesium oxide powder particles in situ to generate the magnesium aluminate spinel MgAl with chemical stability to magnesium and alloy melt thereof2O4The damage of the prior product added with binders such as silica sol, ethyl silicate and the like to the chemical stability of the foamed ceramic is avoided; meanwhile, the ceramic component does not contain sodium salt (for example, sodium carboxymethylcellulose is not adopted in the rheological agent), so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
Because the reaction formulas (1) and (5) can spontaneously proceed at the common melting temperature of the magnesium alloy, and the melting temperature of the aluminum and the aluminum alloy is the same as that of the magnesium and the aluminum alloy, the reverse reactions of the reaction formulas (1) and (5) can not occur between the MgO spinel phase and the aluminum alloy melt; the same as that used for the magnesium and the alloy melt thereof, avoids the damage of adding the bonding agents such as silica sol, ethyl silicate and the like to the chemical stability of the foamed ceramics in the aluminum and the alloy melt thereof (even if the materials contain1% SiO2The melt of aluminum and its alloy will also react with SiO in the ceramic at high temperature2Generation of Al + SiO2→Al2O3Reaction of + Si); therefore, the prepared basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide foamed ceramic filter can also be used for smelting and purifying aluminum and aluminum alloy.
Secondly, the basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter has good low-temperature sintering performance. The light-burned magnesia fine powder adopted by the invention has high sintering activity, the nano alumina sol can be dissolved into the high-activity light-burned MgO crystal lattice in a solid solution manner in the sintering process to enable the MgO crystal to generate lattice distortion and activate the crystal lattice, and simultaneously, a new compound, namely magnesia-alumina spinel MgAl, is generated by reaction and sintering between the nano alumina sol and the MgO particles2O4Phase, thereby promoting sintering and particle-phase bonding. On the other hand, the nano powder has the characteristics of large specific surface area, high surface energy, high activity and the like, and the low-temperature sintering aid is added in the form of nano aluminum sol, so that Al in the nano aluminum sol is improved2O3The magnesium aluminate spinel powder is uniformly mixed with the magnesium oxide powder, and the reaction speed of the generated magnesium aluminate spinel phase is rapidly improved due to the full contact between the sintering aid and MgO particles, so that the sintering temperature is further reduced, and the reduction of the sintering temperature is favorable for reducing the energy consumption and the production cost of the foamed ceramic filter. The test result shows that when the sintering temperature is lower than 1350 ℃, the sintering structure combination among magnesium oxide particles is insufficient, so that the strength is low, and the sintering temperature of the magnesium oxide foamed ceramic filter with good structure combination is 1350-1550 ℃.
Thirdly, the basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter has good thermal shock resistance. The solid phase component in the aluminum sol is high-activity porous gamma-Al2O3With magnesium aluminate spinel (MgAl)2O4) The crystal structure is the same. The mechanical property of the ceramic matrix composite material can be improved by adopting the fibers and the whiskers as the reinforcement. Whiskers (whisker) are understood to mean whiskers having a certain aspect ratio (generally greater than 10) and a cross-sectional area of less than 5.2X 10-4cm2Of a single crystal fiberA material. Basic magnesium sulfate whisker (molecular formula is xMgSO)4·yMg(OH)2·zH2O；MgSO4·5Mg(OH)2·3H2153 type O whiskers are more common]The composite material is a novel needle-shaped short fiber reinforced material, the diameter is 0.5-1.0 mu m, the length is 20-80 mu m, and the composite material has excellent physical and mechanical properties such as high strength, low density, high elastic modulus and the like. In the scheme provided by the invention, light-burned magnesium oxide particles with high sintering activity and highly dispersed basic magnesium sulfate whiskers are surrounded by a nano aluminum sol film and undergo in-situ reaction in the sintering process to generate nano magnesium aluminate spinel (MgAl)2O4) Directly welding the cristobalite MgO grains together; meanwhile, when the polyurethane foam plastic template for dipping and hanging the slurry is extruded by a roller press, the basic magnesium sulfate whiskers in the prepared biscuit are arranged along the rolling direction to a certain extent, and the form of the basic magnesium sulfate whiskers with certain directionality is inherited by the formed magnesium aluminate spinel, so that the magnesium aluminate spinel (MgAl) wrapping periclase MgO grains2O4) The sintered ceramic grains have tightly combined tissues, meanwhile, the pinning effect of the magnesium aluminate spinel phase inhibits the growth of magnesium oxide particles, so that the tissues of the foamed ceramic are refined, the density among the ceramic grains is improved, and the prepared basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter has higher mechanical property, high-temperature impact resistance and thermal shock resistance.
In addition, in the preparation method, the polyurethane foam plastic template is roughened by NaOH etching, and then is treated by the aqueous solution of the dodecylbenzene sulfonate wetting agent, so that the ceramic slurry is easily and uniformly coated on the polyurethane foam template; meanwhile, the cellulose ether and the polyvinyl butyral which are used as rheological agents are good dispersants for basic magnesium sulfate whisker powder, can prevent slurry from agglomerating, can play a role of a bonding agent when a biscuit is prepared, and the soaked slurry can be firmly attached to a polyurethane foam template so that the biscuit has high strength and can easily escape in a sintering process without polluting products, thereby ensuring the quality of the foam ceramic filter.
Drawings
FIG. 1 is a flow chart of a preparation process of a magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ synthesized by basic magnesium sulfate whiskers.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A magnesium aluminate spinel reinforced magnesia-based foam ceramic filter synthesized in situ by basic magnesium sulfate whiskers is prepared by coating light-burned magnesia-based ceramic slurry containing basic magnesium sulfate whiskers on a polyurethane foam carrier, drying and sintering. The specific preparation process is shown in figure 1.
Example 1
Weighing commercial alkali magnesium sulfate whisker (diameter about 1 μm and length 50-100 μm) and particle size 250 mesh (medium diameter d)5058 μm) of light-burned magnesia powder to prepare ceramic powder; mixing polyvinyl butyral and hydroxypropyl methyl cellulose in the mass ratio of 1 to prepare the rheological agent.
According to the mass percentage, 15 percent of nano aluminum sol with the solid content of 20 percent (commercial nano aluminum sol with the pH value close to neutral is selected, the same is applied below), 0.8 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, basic magnesium sulfate whisker, a rheological agent and a proper amount of absolute ethyl alcohol (the addition amount is determined according to the solid content of ceramic slurry, the same applies below) and carrying out ultrasonic treatment for 30min to ensure that the basic magnesium sulfate whisker powder is fully dispersed and then added into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 4h at the rotating speed of 60rpm to uniformly mix the materials to obtain the ceramic slurry with the solid content of 60%.
Selecting a 10PPI polyurethane foam plastic template, soaking the template in a 15% NaOH aqueous solution at 40 ℃ for 60min, washing the template with clear water, naturally drying the template, then soaking the template in a 2% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove redundant immersion slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at 40 ℃ to dry the biscuit, and the ethanol solvent can be recovered by a recovery device.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1550 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2.5h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foam ceramic filter.
Example 2
Weighing commercial basic magnesium sulfate whisker and the particle size of 500 meshes (medium diameter d) according to the proportion that the basic magnesium sulfate whisker accounts for 3 percent of the mass of the ceramic powder5025 μm) of light-burned magnesia powder to prepare ceramic powder; mixing polyvinyl butyral and hydroxypropyl methyl cellulose in the mass ratio of 1 to prepare the rheological agent.
According to the mass percentage, 20 percent of nano aluminum sol with the solid content of 25 percent, 1.5 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, basic magnesium sulfate whisker, a rheological agent and a proper amount of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, fully dispersing the basic magnesium sulfate whisker powder, adding the basic magnesium sulfate whisker powder into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and carrying out ball milling at a rotating speed of 120rpm for 2h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 65%.
Selecting a 20PPI polyurethane foam plastic template, soaking the template in a 20% NaOH aqueous solution at 50 ℃ for 40min, washing the template with clear water, naturally drying the template, then soaking the template in a 4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at 50 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1350 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 3h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foam ceramic filter.
Example 3
Weighing commercial basic magnesium sulfate whisker and 325 mesh (medium diameter d) according to the proportion of the basic magnesium sulfate whisker accounting for 2 percent of the mass of the ceramic powder5045 μm) of light-burned magnesia powder to prepare ceramic powder; mixing the polyvinyl butyral and the hydroxyethyl cellulose according to the mass ratio of 1:1 to prepare the rheological agent.
According to the mass percentage, 25 percent of nano-alumina sol with the solid content of 22 percent, 1.0 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, basic magnesium sulfate whisker, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 45min to fully disperse the basic magnesium sulfate whisker powder, adding the basic magnesium sulfate whisker powder into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and performing ball milling at a rotating speed of 90rpm for 3h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 70%.
Selecting a 15PPI polyurethane foam plastic template, soaking the template in a 45 ℃ 18% NaOH aqueous solution, etching the surface for 50min, washing the template with clear water, naturally drying the template, then soaking the template in a 3% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at the temperature of 45 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foamed ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1500 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foamed ceramic filter.
Example 4
Weighing commercial basic magnesium sulfate whisker and the particle size of 300 meshes (medium diameter d) according to the proportion that the basic magnesium sulfate whisker accounts for 2 percent of the mass of the ceramic powder5048 μm) of light-burned magnesia powder to prepare ceramic powder; according to the weight ratio of polyvinyl butyral: hydroxypropyl methylcellulose: the hydroxyethyl cellulose is mixed according to the mass ratio of 5:2:3 to prepare the rheological agent.
According to the mass percentage, 20 percent of nano aluminum sol with the solid content of 20 percent, 1.0 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, basic magnesium sulfate whisker, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 45min to ensure that the basic magnesium sulfate whisker powder is fully dispersed and then added into the ball milling tank, then adding corundum balls according to a ball-to-material ratio of 2:1, and performing ball milling at a rotating speed of 100rpm for 3h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 65%.
Selecting a 15PPI polyurethane foam plastic template, soaking the template in a 15% NaOH aqueous solution at 45 ℃ for 50min, washing the template with clear water, naturally drying the template, then soaking the template in a 4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at the temperature of 45 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1450 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foam ceramic filter.
In the embodiment, experiments show that the prepared foamed ceramic has excellent thermal shock resistance and strength, and does not crack after being cooled in air at 900 ℃ for 50 times; 75mm is 25mm, and the normal temperature strength of the foamed ceramic filter of 10PPI is not lower than 3 MPa.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (9)
1. A basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter is characterized in that: coating the light-burned magnesia-based ceramic slurry containing the alkali magnesium sulfate whiskers on a polyurethane foam carrier, and drying and sintering the polyurethane foam carrier to obtain the light-burned magnesia-based ceramic slurry containing the alkali magnesium sulfate whiskers, wherein the light-burned magnesia-based ceramic slurry containing the alkali magnesium sulfate whiskers comprises 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent, and the balance is magnesia ceramic powder containing the alkali magnesium sulfate whiskers; the rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose or a mixture thereof; the ceramic powder is a mixture of light-burned magnesium oxide and basic magnesium sulfate whisker.
2. A preparation method for in-situ synthesis of a magnesium aluminate spinel reinforced magnesia-based foamed ceramic filter by basic magnesium sulfate whiskers is characterized by comprising the following steps:
(1) preparing 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent and the balance of magnesium oxide ceramic powder containing alkali magnesium sulfate whiskers according to the mass percentage, adding absolute ethyl alcohol, and performing ball milling and mixing uniformly to prepare ceramic slurry with the solid content of 60-70%; the rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose or a mixture thereof; the ceramic powder is a mixture of light-burned magnesium oxide and basic magnesium sulfate whiskers;
(2) immersing a polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove redundant immersion slurry to prepare a biscuit, and then removing an ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit;
(3) and (3) putting the dried biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesia-based foamed ceramic filter.
3. The method for preparing the magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ by using the basic magnesium sulfate whiskers, according to claim 2, is characterized in that: the solid content of the nano aluminum sol is 20-25%, and the PH value of the nano aluminum sol is more than or equal to 4.
4. The method for preparing the magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ by using the basic magnesium sulfate whiskers, according to claim 2, is characterized in that: the basic magnesium sulfate whisker accounts for 1-3% of the mass of the ceramic powder.
5. The method for preparing the magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ by using the basic magnesium sulfate whiskers, according to claim 2, is characterized in that: the particle size of the light-burned magnesium oxide powder is 250-500 meshes.
6. The method for preparing the magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ by using the basic magnesium sulfate whiskers, according to claim 2, is characterized in that: the diameter of the basic magnesium sulfate whisker is 1 mu m, and the length of the basic magnesium sulfate whisker is 50-100 mu m.
7. The method for preparing the magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ by using the basic magnesium sulfate whiskers as claimed in claim 2, is characterized in that the method for preparing the ceramic slurry comprises the following steps: adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, basic magnesium sulfate whiskers, a rheological agent and absolute ethyl alcohol, carrying out ultrasonic treatment for 30-60 min, fully dispersing the basic magnesium sulfate whiskers, adding the basic magnesium sulfate whiskers into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and carrying out ball milling at a rotating speed of 60-120 rpm for 2-4 h to uniformly mix the materials to obtain the magnesium oxide powder.
8. The method for preparing the magnesium aluminate spinel reinforced magnesia-based ceramic foam filter in situ by using the basic magnesium sulfate whiskers, according to claim 2, is characterized in that: the specification of the polyurethane foam plastic template is 10 PPI-20 PPI; before use, the surface of the material is soaked in 15-20% NaOH aqueous solution at 40-50 ℃ for etching for 40-60 min, then the material is washed by clean water and naturally dried, and then the material is soaked in 2-4% aqueous solution of dodecyl benzene sulfonic acid wetting agent and then taken out and dried to obtain the material.
9. The method for preparing the magnesium oxysulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based ceramic foam filter according to claim 2, wherein in the step (3), the sintering process comprises: heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters in the biscuit of the foam ceramic filter and discharge the organic matters, then heating to 1100 ℃ at a heating rate of 200 ℃/h, finally heating to 1350-1550 ℃ at a heating rate of 50 ℃/h and preserving heat at the temperature for 2-3 h.
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