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CN108546094A - Magnesium oxide-based ceramic foam filter of a kind of MA-MF composite spinelles enhancing and preparation method thereof - Google Patents

Magnesium oxide-based ceramic foam filter of a kind of MA-MF composite spinelles enhancing and preparation method thereof Download PDF

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Publication number
CN108546094A
CN108546094A CN201810307627.XA CN201810307627A CN108546094A CN 108546094 A CN108546094 A CN 108546094A CN 201810307627 A CN201810307627 A CN 201810307627A CN 108546094 A CN108546094 A CN 108546094A
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nanometer
magnesium oxide
sintering
composite
spinelles
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CN108546094B (en
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刘希琴
刘子利
刘思雨
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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    • 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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    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
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Abstract

The invention discloses it is a kind of can realize at low temperature sintering, chemical stability and the excellent MA MF composite spinelles of thermal shock resistance enhance magnesium oxide-based ceramic foam filter and preparation method thereof, which includes the following steps：(1) according to mass percent by 15%~25% nanometer of Aluminum sol, 0.8%~1.5% rheological agent, remaining carries out dispensing for the magnesia ceramics powder of the sintering aid of di-iron trioxide containing nanometer, and the ceramic slurry that solid content is 60%~70% is made after addition absolute ethyl alcohol ball milling mixing is uniform；(2) polyurethane foam plastics masterplate is immersed in ceramic slurry, is squeezed after polyurethane foam plastics masterplate removes extra leaching hanging material by roll squeezer and biscuit is made, then so that biscuit is dried in 40 DEG C~50 DEG C draft chamber's removal alcohol solvents；(3) dry biscuit is put into sintering furnace, high temperature sintering is carried out at a temperature of being warming up to 1350 DEG C~1550 DEG C, cooled to room temperature with the furnace and obtain magnesium oxide-based ceramic foam filter.

Description

A kind of MA-MF composite spinelles enhance magnesium oxide-based ceramic foam filter and its system Preparation Method
Technical field
The present invention relates to a kind of magnesium oxide-based ceramic foam filters and preparation method thereof, and specifically a kind of MA-MF is compound Spinelle enhances magnesium oxide-based ceramic foam filter and preparation method thereof, belongs to metal material and field of metallurgy.Institute of the present invention The filter of preparation can also be used for the filtering of aluminium and its alloy melt especially suitable for magnesium and its filtration, purification of alloy melt Purification.
Background technology
The chemical property of magnesium is active, in casting and process, is easily chemically reacted with oxygen, nitrogen and vapor, The product of generation remains in magnesium, influences the internal soundness of product, deteriorates product properties.According to the type of field trash in magnesium alloy And property, field trash is generally divided into metal inclusion and nonmetal inclusion two major classes：(1) metallic inclusion：Magnesium alloy is in former magnesium During production and post-production, it can inevitably introduce some metal simple-substances or metallic compound is mingled with, they are with grain The forms such as sub- shape, tufted remain on the matrix or crystal boundary of magnesium alloy, and main includes metal simple-substance α-Fe particles, manganese-iron Metallic compound such as (Fe, Mn)3Si, (Fe, Mn)5Si3Deng；(2) non-metallic inclusion：Nonmetal inclusion owner in magnesium alloy It will be based on the oxynitrides of magnesium, such as MgO, Mg3N2Deng；Magnesium alloy added in fusion process with chloride (KCl, NaCl, MgCl2Deng) based on refining agent, flux cannot completely remove in refining process, and having a small amount of flux remains in Serum Magnesium, Magnesium metal flux is caused to be mingled with.The oxide inclusion of suspension is pushed to crystal boundary in crystallization by crystallization front, and field trash is generally with thin Membranaceous, particle shape, the form of tufted remain in magnesium alloy grain boundaries.There is statistics to show that MgO accounts for all of magnesium alloy and is mingled with 80% or more of object, distributional pattern are film-form, particle shape and tufted.The field trash generated in Normal Casting of Magnesium Alloy is not only tight Deteriorate the mechanical property and corrosion resisting property of alloy again, and reduces the surface quality of its machining and anodized.It is right For diecast magnesium alloy, the content of film-form and particle shape oxide inside alloy needs to control in 100cm2/ kg and 100mm3/ kg or less could meet normal requirement.Therefore, the field trash in Serum Magnesium is removed in fusion-casting process to carry The purification technique of the degree of purity of high melt becomes the key of magnesium alloy production.
Cleaning molten technique can be divided into flux refining and non-flux purification two major classes.Flux refining technique is because of dust removal rate It is high, at low cost, easy to operate and as the purification technique that generally uses in magnesium alloy production, but there is also gold for flux refining Category loss increases, flux is mingled with, is unable to the deficiencies of degasification, and especially in melting magnesium-rare earth, flux can also be consumed largely Rare earth element in alloy.Non-flux purification technique not only can overcome the disadvantages that the deficiency of flux refining technique but also have excellent purification Effect becomes the important cleaning molten technique of current application development and develops filtration, purification, rotary blowing purification, electromagnetism in succession A variety of non-flux purification technologies such as purification, ultrasonication.Compared to simple metal mesh melt filtration, have special three-dimensional more Hole ceramic structure ceramic foam filter, because of its porosity high (70%~90%), adsorption capacity is strong, the spies such as resistant to chemical etching Point can have filtering well by filter cake effect, adsorption effect and rectifying effect to the inclusion particle in alloy melt Effect.Foam ceramic filter method can not only filter as low as 10 μm~20 μm in alloy melt of microinclusions particle, and The liquid flux that general filter medium is difficult to filter out can be filtered out to be mingled with.
American documentation literature US3962081A (Ceramic foam filter), US4024212A (Ceramic foam And method of preparation), a kind of Chinese patent literature CN103787691A (preparations of Alumina Foam Ceramics Method) etc. all disclose some for aluminium alloy, steel fusant filter field trash Al2O3, ZrO2, SiC, SiO2Base foam is made pottery The method of porcelain, however, the standard of MgO generates, free enthalpy is very low, and the very high Serum Magnesium of activity is very easy to and foamed ceramics matrix Material occurs the reaction of (1)~(4) formula and dissolves rapidly, and to block, it filters hole or corrode enters in magnesium and its alloy melt As harmful components, therefore, the foam filter of these existing materials is not suitable for the filtering of magnesium and magnesium alloy fused mass.
3Mg(l)+Al2O3(s)=3MgO(s)+2Al(l) (1)
2Mg(l)+ZrO2(s)=2MgO (s) (2)+Zr (s)
6Mg (l)+4Al (l)+3SiC (s)=3Mg2Si(s)+Al4C3(s) (3)
4Mg(l)+SiO2(s)=2MgO (s)+Mg2Si(s) (4)
MgO is cubic system NaCl type structures, and lattice constant 0.411nm belongs to ion key compound, and fusing point is 2852 DEG C, it is far above common Al2O3(2054 DEG C) and SiO2(1650 ± 50 DEG C), therefore, magnesia product have goodization It learns stability, high resistivity and has the characteristics such as stronger corrosion resistance to metal, slag and alkaline solution.With it is common Ceramic material is compared, and MgO has good stability at elevated temperature, villaumite and fluorate with melting with magnesium and its alloy melt The flux mixture of composition does not react, and is mingled with the flux in the smaller and easy absorption Serum Magnesium of angle of wetting with flux and presss from both sides Miscellaneous, therefore, MgO material foamed ceramicses are the ideal materials of liquid magnesium alloy melting and purifying.
Carried out under the melting temperature formed less than oxide firing prepare necessary to ceramic material, most critical Step, and the sintering that is occurred at high temperature, crystal grain are grown up etc., processes decide the microscopic structure and performance of ceramic material.China Patent document CN1011306B (filter of purifying magnesium oxide foam pottery and its reparation technology), CN101138691A (casting magnesium The preparation method of foam ceramic filter) etc. prepare foamed ceramics using pure zirconia magnesium as raw material, because MgO have very high fusing point With coefficient of thermal expansion (13.5 × 10-6/ DEG C) high, therefore, cause its sintering difficult (sintering temperature is not less than 0.8 times of its fusing point) It is poor with thermal shock resistance, limit the application and development of MgO foamed ceramicses.
Research shows that：Firing temperature often reduces by 100 DEG C during being sintered ceramics, unit product heat consumption can reduce by 10% with On, it is the important technical for reducing MgO foamed ceramics sintering temperatures by adding sintering aid.Add V2O5When powder, MgO Meeting and V at 1190 DEG C2O5Formation proximate composition is Mg3V2O8Liquid phase, acceleration of sintering can significantly reduce MgO foamed ceramicses Sintering temperature, but V2O5There is detrimental effect to respiratory system and skin in use, has stringent limitation to operation. With V2O5Identical, cobalt oxide is also good low-temperature sintering auxiliary agent, but also limits application as highly toxic substance and scarce resource. Fluoride is common strong cosolvent and mineralizer, Chinese patent literature CN100536986C (magnesia in ceramic industry sintering Foam ceramic filter), CN1473947A (magnesium and magnesium alloy fused mass purification foamed ceramics), CN101785944B (be used for The preparation method of magnesium and Serum Magnesium filtering magnesia ceramic foam filter) in addition fluorite (1423 DEG C of fusing point) and magnesium fluoride (1248 DEG C of fusing point), in sintering process the solid solution of fluoride not only increase the distortion of lattice of matrix magnesia, and itself Low melting point liquid phase is easily formed, to reduce the sintering temperature of magnesia ceramics；However, F in sintering process in fluoride with Si, Al, Fe, Ca are combined, most of (accounting for about 70% in ceramic tile production) volatilize in a gaseous form not only itself corrode green body and Damage sintering ceramics quality, fluoride pollution can be caused by being more seriously discharged into air, fluoride can through respiratory tract, Alimentary canal and skin enter human body, Central nervous system, the toxic effect of cardiac muscle, and low dose fluoride pollution can lead to tooth and bone The crisp calcification of bone,《Ceramic industry pollutant emission standard》(GB25464-2010) discharge standard of regulation fluoride has to be lower than in 5.0mg/m3, the low-temperature sintering auxiliary agent using fluoride as magnesia ceramics necessarily increases the discharge of vapor-phase fluoride and aggravates ring Protect input burden；In addition, fluorine ion is existed in the form of replacing oxonium ion in remaining solid solution fluoride in ceramics, crystalline substance is caused The chemical stability that intergranular combines reduces, it is difficult to resist the long-time that flux in Serum Magnesium is mingled with and corrode.Chinese patent literature Preparing for ceramic foam filter disclosed in CN101138691A etc. uses waterglass, Ludox and silester conduct in slurry Bonding agent, SiO between the foamed ceramics particle of sintering2The presence of ingredient makes it easily be reacted by (4) formula with magnesium and its alloy melt, Equally reduce the chemical stability of foamed ceramics.(magnesium oxide foam ceramic filters Chinese patent literature CN100536986C Device), in the patent documents such as CN103553686A (a kind of magnesium aluminate spinel foamed ceramic filter and preparation method thereof), three oxygen Change the low-temperature sintering auxiliary agent of two boron and borax as magnesia ceramics, diboron trioxide forms liquid phase when being higher than 450 DEG C, burning When junction temperature is more than 1350 DEG C, is reacted with magnesia and generate antifungin so that liquid form exists and reduces sintering temperature.However, Diboron trioxide is in magnesium, aluminium alloy melt and unstable easily with magnesium, reactive aluminum；Simultaneously as diboron trioxide be dissolved in water and Ethyl alcohol equal solvent can consumingly absorb water generate boric acid in air, three oxidations two added in the preparation process of foamed ceramics Boron is dissolved in water and forms boric acid aqueous solution, easily reacts to form boric acid magnesium precipitate and reduce its effect with magnesia.Gallium oxide is three oxygen Change the oxide of the same clan of two boron, forms the MgGa of spinel-type with magnesia at a lower temperature2O4And play reduction sintering temperature The effect of degree, but gallium stock number is seldom (gallium is strategic reserves metal), the higher price limit of gallium oxide its in conventional ceramic In application.
Invention content
The object of the present invention is to provide it is a kind of can realize at low temperature sintering, chemical stability and thermal shock resistance it is excellent MA-MF composite spinelles enhance magnesium oxide-based ceramic foam filter and preparation method thereof.
In order to reach above-mentioned technical purpose, the technical scheme is that：
A kind of magnesium oxide-based ceramic foam filter of MA-MF composite spinelles enhancing, is that will contain a nanometer di-iron trioxide The light calcined magnesia base ceramic slurry of sintering aid is coated on polyurethane foam carrier, is obtained through drying, sintering.
A kind of MA-MF composite spinelles enhance the preparation method of magnesium oxide-based ceramic foam filter, include the following steps：
(1) according to mass percent by 15%~25% nanometer of Aluminum sol, 0.8%~1.5% rheological agent, remaining is containing receiving The magnesia ceramics powder of rice di-iron trioxide sintering aid carries out dispensing, is made after addition absolute ethyl alcohol ball milling mixing is uniform solid The ceramic slurry that content is 60%~70%.The nanometer Aluminum sol of addition not only can be in light calcined magnesia particle and high uniformity point Scattered nanometer Fe2O3Powder surface forms γ-Al2O3Coating film and play the role of binder, the Al in sintering process2O3With Fe2O3There is with MgO fabricated in situ to magnesium and its alloy melt the MA-MF composite spinelle solid solution phases of chemical stability together, It avoids existing product and the damages of the binders to foamed ceramics chemical stability such as Ludox, silester is added.
The rheological agent is the mixture of polyvinyl butyral and cellulose ether, and wherein polyvinyl butyral accounts for rheology The 50% of agent quality, cellulose ether are or mixtures thereof one kind in industrial hydroxypropyl methyl cellulose, hydroxyethyl cellulose. Cellulose ether and the polyacrylic acid not still fine dispersion agent of nano titania can prevent slurry from generating agglomeration, And bonding agent can also be played the role of when preparing biscuit, slurry can comparatively be firmly attached to polyurethane foam mould after dipping On plate, make biscuit that there is prodigious intensity, while easily escaping in sintering process without polluting product, hereby it is ensured that foam The quality of ceramic filter.It does not use sodium carboxymethylcellulose etc. to contain the salt received in rheological agent, avoids remaining ion half The larger Na of diameter+To the obstruction of ceramic post sintering.
The ceramic powder is the mixture of light calcined magnesia and nanometer di-iron trioxide.Wherein, the nanometer three aoxidizes Two iron account for the 1%~2% of ceramic powder quality, and the grain size of the nanometer di-iron trioxide is 30~60nm.The light-burned oxidation The grain size of magnesium powder body is mesh (the central diameter d of 250 mesh~50050It it is 25 μm~58 μm).
Light calcined magnesia fine powder of use itself has very high sintering activity, nanometer Aluminum sol and nanometer di-iron trioxide Can be dissolved into sintering process in the lattice of MgO make MgO crystal occur distortion of lattice, activate lattice, while by with MgO Reaction-sintered generates MA-MF composite spinelle phases between particle, to promote sintering and the alternate combination of particle.On the other hand, Nano-powder has the characteristics that large specific surface area, surface energy height, high activity, with the shape of nanometer Aluminum sol and nanometer di-iron trioxide Low-temperature sintering auxiliary agent is added in formula, optimizes ceramic particle grading and mixing uniformity, at the same nano-powder because of the surface of its own and Interfacial effect, sintering of nano-material auxiliary agent make the reaction speed of generation Spinel improve rapidly with intergranular come into full contact with of MgO, from And sintering temperature is further reduced, and the reduction of sintering temperature advantageously reduces being produced into for energy consumption and ceramic foam filter This.
The nanometer Fe of addition2O3It is easily dissolved into MgO phases, reaction generates the magnoferrite with high-temperature stability (MgFe2O4, MF) and phase (2030 DEG C of fusing point).Height is sintered active light calcined magnesia particle and is enclosed in sintering by nano aluminum dissolved glue film Reaction in-situ generates magnesium aluminate spinel MA phases in the process.Fe2O3Solubility in periclase MgO is much larger than Al2O3, 1600 DEG C When Fe2O3And Al2O3Effective solubility in periclase is respectively about 60% and 1%.Nanometer Fe is added2O3, Fe3+To MgO Middle diffusion velocity is fast, makes periclase MgO spinels, while also having and promoting Al2O3The effect spread into MgO, it is therefore, in situ It reacts the MA generated and has close continuous combination interface between MF and periclase solid solution.Since MA and MF can dissolve each other, MgO The MA-MF composite spinelles that grain is formed with surrounding are mutually directly joined together, while the pinning effect of composite spinelle phase inhibits The growth of magnesium oxide particle, to having refined the tissue of foamed ceramics and improve the consistency between ceramic crystalline grain.
Preferably, the nanometer Aluminum sol solid content is 20%~25%, pH value >=4.
The preparation method of the ceramic slurry is：Light calcined magnesia powder is added in ball grinder according to proportioning, by nanometer Aluminum sol, nanometer di-iron trioxide, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 30min~60min, make nanometer It is added in ball grinder after lanthanum oxide powder is fully dispersed, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, with 60~ 120rpm rotating speed ball millings 2h~4h makes it be uniformly mixed.
(2) polyurethane foam plastics masterplate is immersed in ceramic slurry, polyurethane foam plastics is squeezed by roll squeezer Biscuit is made after removing extra leaching hanging material in masterplate, then keeps biscuit dry in 40 DEG C~50 DEG C draft chamber's removal alcohol solvents It is dry.
The specification of the polyurethane foam plastics masterplate is that (Pores per inch, inches are long by 10PPI~20PPI Average number of pores on degree), using it is preceding impregnated in 40 DEG C~50 DEG C of 15%~20%NaOH aqueous solutions surface etch 40min~ Naturally dry is washed with clear water after 60min, is then immersed in the aqueous solution of 2%~4% dodecyl benzene sulfonic acid wetting agent, takes It is obtained after going out drying.Make its surface roughening, then the aqueous solution by dodecyl benzene sulfonate wetting agent by NaOH etchings After processing, ceramic slurry, which is easy to uniformly apply, to be suspended on polyurethane foam plank.
(3) dry biscuit is put into sintering furnace, high temperature sintering is carried out at a temperature of being warming up to 1350 DEG C~1550 DEG C, with Stove is cooled to room temperature to obtain magnesium oxide-based ceramic foam filter.
The sintering process is to be heated to 550 DEG C with the heating rate of 30 DEG C/h to make having in ceramic foam filter biscuit Machine object (polyurethane foam and rheological agent etc.) decomposition gasification is discharged, and is then heated to 1100 DEG C of temperature with the heating rate of 200 DEG C/h Degree, in the low-temperature sintering stage, lower heating rate can prevent polyurethane foam and rheological agent decomposition rate is too fast leads to element Base collapses or deformed damaged.1350 DEG C~1550 DEG C temperature are finally heated to the heating rate of 50 DEG C/h and are protected at such a temperature 2~3h of temperature.In the high temperature sintering stage, sintering temperature is more than after 1100 DEG C, and lower heating rate can ensure in sintered body Temperature is consistent, while avoiding the formation speed for generating spinelle uniform and the transformation stress of too fast generation is avoided to cause sintered body Deformation and cracking.
The preparation method of magnesium oxide-based ceramic foam filter provided by the present invention has simple for process, at low cost, effect Rate is high, is suitble to the advantages that large-scale production, its chemistry is steady without any reduction for prepared magnesium oxide-based ceramic foam filter Qualitative component, the nanometer Aluminum sol and nanometer di-iron trioxide being added can not only play the role of reducing sintering temperature, And high uniformity is distributed in magnesia ceramics powder granule and reacts generation to magnesium and its alloy melt with chemistry The MgAl of stability2O4And MgFe2O4Magnesium oxide particle is mutually welded together by composite spinelle, therefore, ceramic foam filter With good intensity, chemical stability and thermal shock resistance, especially suitable for being mingled in filtration, purification magnesium and its alloy melt Object also can be used for aluminium and its alloy melt filtration, purification.Compared with the prior art scheme, technique effect of the invention：
One, MA-MF composite spinelles of the invention enhancing magnesia ceramic foam filter has excellent chemical stabilization Property.With Al2O3、Cr2O3It compares, Fe2O3Solid solubility in periclase MgO phases is maximum.The nanometer Fe of addition2O3Easily it is dissolved into In MgO phases, reaction generates the magnoferrite (MgFe with high-temperature stability2O4, MF) and phase (2030 DEG C of fusing point).Although raw material Contain the γ-Al reacted with magnesium liquid in Aluminum sol component2O3, but the nanometer Aluminum sol being added is in light calcined magnesia particle and height Evenly dispersed nanometer Fe2O3Powder surface forms γ-Al2O3Coating film, the γ-Al in sintering process in Aluminum sol2O3With Light-burned MgO particle in-situs reaction generates the high-melting-point magnesium aluminate spinel (MgAl with face-centered cubic lattice2O4, MA) and phase (fusing point 2135℃).MA and MF can dissolve each other completely, and according to XRD analysis, the result shows that, the ceramic foam filter prepared by the present invention is only There is periclase MgO and MA-MF composite spinelle solid solution phase.
In the MgO-Al of Serum Magnesium and addition aluminium oxide2O3It is sintered in the reaction system of ceramics, in addition to there are reaction equation (1), There is likely to be following reactions：
3Mg(l)+4Al2O3(s)=3MgAl2O4(s)+2Al(l) (5)
Aluminium oxide generates magnesium aluminate spinel MgAl with magnesia2O4Reaction be：
MgO(s)+Al2O3(s)=MgAl2O4(s) (6)
Serum Magnesium and magnesium aluminate spinel MgAl2O4The reaction of generation is：
3Mg(l)+MgAl2O4(s)=2Al(l)+4MgO(s) (7)
According to《Pure material thermochemical data handbook》(Yi Hesang baluns are edited, and Cheng Nailiang etc. is translated, Beijing：Scientific publication Society, 2003), the substance Gibbs free energys data of Serum Magnesium and magnesium aluminate spinel reaction system and instead in 900~1200K Answer the Gibbs Gibbs free Δs G of (1), (5), (6) and (7)1、ΔG5、ΔG6、ΔG7Result of calculation it is as shown in table 1.
Table 1 is in 900~1200K Serum Magnesiums and each gibbs free energy change Δ G reacted in magnesium aluminate spinel reaction system Result of calculation
Reaction equation Serum Magnesium generates the Gibbs free energy Δs G of (5) formula of magnesium aluminate spinel with aluminium oxide5In different temperatures It is lower minimum, illustrate that the reaction can preferentially occur under the common smelting temperature of magnesium alloy.Magnesium liquid is reacted with magnesium aluminate spinel Formula (7) is the decomposition product oxygen of magnesium liquid and magnesium aluminate spinel in the reacting quintessence although from can thermodynamically carry out Change and react between aluminium, but as shown in Table 1, under the smelting temperature of magnesium alloy, magnesium aluminate spinel is decomposed into aluminium oxide and magnesia Reaction is difficult to carry out (back reaction of reaction equation (6)), while remaining aluminium oxide also can preferentially be pressed with magnesium liquid in the ceramics being sintered Reaction equation (5) generates magnesium aluminate spinel；On the other hand, MgO-Al2O3The sides MgO are that periclase solid solution and MA points are brilliant in phasor Stone solid solution eutectic phasor, in situ reaction generate MA in the process almost without O2-Diffusion, only Mg2+And Al3+By fixed Oxygen lattice phase counterdiffusion, formation speed is by spreading slower Al3+It is determined, MA phases are mainly in Al2O3Side passes through Nei Yansheng Long mode generates, and leads to content of MgO in the MA outer layers for forming limit solid solution between MA phases and MgO, while being contacted with MgO particles Far above its average value, and MgO is not reacted with Serum Magnesium, therefore, is sintered magnesium oxide particle welding in ceramic structure one The magnesium aluminate spinel risen is mutually that can be stabilized in Serum Magnesium.
Without any reduction, its chemistry is steady in the MA-MF composite spinelles enhancing magnesia ceramic foam filter of the present invention The nanometer Aluminum sol of qualitative component, addition not only can be in light calcined magnesia particle and the nanometer Fe of high uniformity dispersion2O3Powder Surface forms γ-Al2O3Coating film and play the role of binder, the Al in sintering process2O3With Fe2O3It is in situ with MgO together The MA-MF composite spinelle solid solution phases that there is chemical stability to magnesium and its alloy melt are synthesized, existing product is avoided and adds Enter damage of the binders such as Ludox, silester to foamed ceramics chemical stability；Meanwhile sodium salt is also free of in ceramic composition (not using sodium carboxymethylcellulose in such as rheological agent) avoids the larger Na of remaining ionic radius+Resistance to ceramic post sintering Hinder.
Because reaction equation (1), (5) spontaneous can carry out under the common smelting temperature of magnesium alloy, and aluminium and its alloy is molten It is identical with magnesium and its alloy melting temp to refine temperature, MgO and MA Spinels and aluminium and its alloy melt will not react formula (1), the back reaction of (5)；It is identical as magnesium and its alloy melt, it avoids and the binders pair such as Ludox, silester is added The damage of foamed ceramics chemical stability in aluminium and its alloy melt is (even if contain 1% SiO in material2, aluminium and its alloy Melt at high temperature also can be with SiO in ceramics2Al+SiO occurs2→Al2O3The reaction of+Si)；Therefore, prepared MA-MF is multiple The melting and purifying of aluminium and its alloy can also be used for by closing spinelle enhancing magnesia ceramic foam filter.
Two, MA-MF composite spinelles of the invention enhancing magnesia ceramic foam filter has good low-temperature sintering Performance.Light calcined magnesia fine powder itself of the present invention has very high sintering activity, three oxygen of nanometer Aluminum sol and nanometer Change two iron can be dissolved into sintering process in the lattice of MgO make MgO crystal occur distortion of lattice, activate lattice, simultaneously lead to It crosses between MgO particles reaction-sintered and generates MA-MF composite spinelle phases, to promote sintering and the alternate combination of particle.Separately On the one hand, nano-powder has the characteristics that large specific surface area, surface energy height, high activity, is aoxidized with nanometer Aluminum sol and nanometer three Low-temperature sintering auxiliary agent is added in the form of two iron, optimizes ceramic particle grading and mixing uniformity, while nano-powder is because of its own Surface and interface effect, sintering of nano-material auxiliary agent keeps the reaction speed of generation Spinel fast with intergranular come into full contact with of MgO Speed improves, and to further reduced sintering temperature, and the reduction of sintering temperature advantageously reduces energy consumption and foam ceramic filter The production cost of device.Test result shows that sintering structure combination is not enough filled between magnesium oxide particle when sintering temperature is less than 1350 DEG C Dividing causes its low strength, and tissue combines the sintering of good MA-MF composite spinelles enhancing magnesia ceramic foam filter Temperature is 1350 DEG C~1550 DEG C.
Three, MA-MF composite spinelles of the invention enhancing magnesia ceramic foam filter has good thermal shock resistance. Solid-phase component is the porous gamma-Al of high activity in Aluminum sol2O3, identical as magnesium aluminate spinel MA crystal structures.It is carried in the present invention In the scheme of confession, height is sintered active light calcined magnesia particle and is enclosed in reaction in-situ life in sintering process by nano aluminum dissolved glue film At magnesium aluminate spinel MA phases.Fe2O3Solubility in periclase MgO is much larger than Al2O3, Fe at 1600 DEG C2O3And Al2O3In side Effective solubility in magnesite is respectively about 60% and 1%.Nanometer Fe is added2O3, Fe3+Into MgO, diffusion velocity is fast, the side of making Magnesite MgO spinels, while also having and promoting Al2O3The effect spread into MgO, therefore, reaction in-situ generate MA and MF with There is close continuous combination interface between periclase solid solution.Since MA and MF can dissolve each other, the MA- of MgO particles and surrounding formation MF composite spinelles are mutually directly joined together, while the pinning effect of composite spinelle phase inhibits the life of magnesium oxide particle Long, to refine the tissue of foamed ceramics and improve the consistency between ceramic crystalline grain, therefore, prepared MA-MF is compound Spinelle, which enhances magnesia ceramic foam filter, has higher mechanical property, high temperature impact resistance and thermal shock resistance.
In addition, polyurethane foam plastics template makes its surface roughening by NaOH etchings in preparation method of the present invention, then After the aqueous solution processing of dodecyl benzene sulfonate wetting agent, ceramic slurry, which is easy to uniformly apply, is suspended to polyurethane foam plank On；Simultaneously as the cellulose ether and polyvinyl butyral of the rheological agent not still fine dispersion of nanometer ferric oxide powder Agent can prevent slurry from generating agglomeration, and can play the role of bonding agent when preparing biscuit, slurry energy ratio after dipping Being firmly attached on polyurethane foam plank compared with ground makes biscuit have prodigious intensity, at the same easily escape in sintering process and Product is not polluted, hereby it is ensured that the quality of ceramic foam filter.
Description of the drawings
Fig. 1 is the preparation technology flow chart that MA-MF composite spinelles enhance magnesium oxide-based ceramic foam filter.
Specific implementation mode
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
MA-MF composite spinelles enhance magnesium oxide-based ceramic foam filter, are sintered by that will contain nanometer di-iron trioxide The light calcined magnesia base ceramic slurry of auxiliary agent is coated on polyurethane foam carrier, is obtained through drying, sintering.It is specific to prepare work Skill is as shown in Figure 1.
Embodiment 1
1% proportioning that ceramic powder quality is accounted for according to nanometer di-iron trioxide aoxidizes the nanometer three that grain size is 30nm Two iron and grain size are 250 mesh (central diameter d50Be 58 μm) light calcined magnesia powder mixed preparing ceramic powder；According to polyvinyl alcohol The mass ratio of butyral and hydroxypropyl methyl cellulose is 1:1 ratio mixed preparing rheological agent.
(commercialization of pH value weakly acidic pH is selected to receive the nanometer Aluminum sol 25% that solid content is 25% according to mass percent Rice Aluminum sol, similarly hereinafter), rheological agent 0.8%, remaining carries out dispensing for ceramic powder.First, in accordance with proportioning by light-magnesite powder Material is added in ball grinder, by nanometer Aluminum sol, nanometer di-iron trioxide, rheological agent and suitable absolute ethyl alcohol (according to ceramic slurry The solid content of material determines its addition, similarly hereinafter) it is mixed and sonicated for 30min, add after keeping nano lanthanum oxide powder fully dispersed Enter into ball grinder, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, so that it is uniformly mixed with 60rpm rotating speed ball millings 4h The ceramic slurry for being 60% to solid content.
10PPI polyurethane foam plastics masterplates are selected, surface etch 60min is impregnated in 40 DEG C of 15%NaOH aqueous solutions Naturally dry is washed with clear water afterwards, is then immersed in the aqueous solution of 2% dodecyl benzene sulfonic acid wetting agent, drying is taken out.So Polyurethane foam plastics masterplate is immersed in ceramic slurry afterwards, it is more to squeeze the removal of polyurethane foam plastics masterplate by roll squeezer Biscuit is made after remaining leaching hanging material, then so that biscuit is dried in 40 DEG C of draft chamber's removal alcohol solvents, alcohol solvent can pass through Retracting device recycles.
Dry biscuit is put into sintering furnace, being heated to 550 DEG C with the heating rate of 30 DEG C/h makes foam ceramic filter The organic matters decomposition gasification such as polyurethane foam and rheological agent in device biscuit is discharged, and is then heated with the heating rate of 200 DEG C/h To 1100 DEG C of temperature, 1550 DEG C of temperature are finally heated to the heating rate of 50 DEG C/h and keep the temperature 2.5h at such a temperature, with stove It is cooled to room temperature to obtain magnesium oxide-based ceramic foam filter.
Embodiment 2
2% proportioning that ceramic powder quality is accounted for according to nanometer di-iron trioxide aoxidizes the nanometer three that grain size is 60nm Two iron and grain size are 500 mesh (central diameter d50Be 25 μm) light calcined magnesia powder mixed preparing ceramic powder；According to polyvinyl alcohol The mass ratio of butyral and hydroxypropyl methyl cellulose is 1:1 ratio mixed preparing rheological agent.
The nanometer Aluminum sol 15% for being 20% by solid content according to mass percent, rheological agent 1.5%, remaining is ceramic powder Material carries out dispensing.Light calcined magnesia powder is added in ball grinder first, in accordance with proportioning, by nanometer Aluminum sol, the oxidation of nanometer three two Iron, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 60min, make to be added to after nano lanthanum oxide powder is fully dispersed In ball grinder, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, so that it is uniformly mixed with 120rpm rotating speed ball millings 2h and is consolidated The ceramic slurry that content is 65%.
20PPI polyurethane foam plastics masterplates are selected, surface etch 40min is impregnated in 50 DEG C of 20%NaOH aqueous solutions Naturally dry is washed with clear water afterwards, is then immersed in the aqueous solution of 4% dodecyl benzene sulfonic acid wetting agent, drying is taken out.So Polyurethane foam plastics masterplate is immersed in ceramic slurry afterwards, it is more to squeeze the removal of polyurethane foam plastics masterplate by roll squeezer Biscuit is made after remaining leaching hanging material, then so that biscuit is dried in 50 DEG C of draft chamber's removal alcohol solvents.
Dry biscuit is put into sintering furnace, being heated to 550 DEG C with the heating rate of 30 DEG C/h makes foam ceramic filter The organic matters decomposition gasification such as polyurethane foam and rheological agent in device biscuit is discharged, and is then heated with the heating rate of 200 DEG C/h To 1100 DEG C of temperature, 1350 DEG C of temperature are finally heated to the heating rate of 50 DEG C/h and keep the temperature 3h at such a temperature, with furnace cooling But magnesium oxide-based ceramic foam filter is obtained to room temperature.
Embodiment 3
1.5% proportioning that ceramic powder quality is accounted for according to nanometer di-iron trioxide, by three oxygen of nanometer that grain size is 50nm It is 325 mesh (central diameter d to change two iron and grain size50Be 45 μm) light calcined magnesia powder mixed preparing ceramic powder；According to polyethylene The mass ratio of butyral and hydroxyethyl cellulose is 1:1 ratio mixed preparing rheological agent.
The nanometer Aluminum sol 20% for being 22% by solid content according to mass percent, rheological agent 1.0%, remaining is ceramic powder Material carries out dispensing.Light calcined magnesia powder is added in ball grinder first, in accordance with proportioning, by nanometer Aluminum sol, the oxidation of nanometer three two Iron, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 45min, make to be added to after nano lanthanum oxide powder is fully dispersed In ball grinder, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, so that it is uniformly mixed with 90rpm rotating speed ball millings 3h and is consolidated The ceramic slurry that content is 70%.
15PPI polyurethane foam plastics masterplates are selected, surface etch 50min is impregnated in 45 DEG C of 18%NaOH aqueous solutions Naturally dry is washed with clear water afterwards, is then immersed in the aqueous solution of 3% dodecyl benzene sulfonic acid wetting agent, drying is taken out.So Polyurethane foam plastics masterplate is immersed in ceramic slurry afterwards, it is more to squeeze the removal of polyurethane foam plastics masterplate by roll squeezer Biscuit is made after remaining leaching hanging material, then so that biscuit is dried in 45 DEG C of draft chamber's removal alcohol solvents.
Dry biscuit is put into sintering furnace, being heated to 550 DEG C with the heating rate of 30 DEG C/h makes foam ceramic filter The organic matters decomposition gasification such as polyurethane foam and rheological agent in device biscuit is discharged, and is then heated with the heating rate of 200 DEG C/h To 1100 DEG C of temperature, 1450 DEG C of temperature are finally heated to the heating rate of 50 DEG C/h and keep the temperature 2h at such a temperature, with furnace cooling But magnesium oxide-based ceramic foam filter is obtained to room temperature.
Embodiment 4
1% proportioning that ceramic powder quality is accounted for according to nanometer di-iron trioxide aoxidizes the nanometer three that grain size is 60nm Two iron and grain size are 300 mesh (central diameter d50Be 48 μm) light calcined magnesia powder mixed preparing ceramic powder；According to polyvinyl alcohol Butyral：Hydroxypropyl methyl cellulose：The mass ratio of hydroxyethyl cellulose is 5:2:3 ratio mixed preparing rheological agent.
The nanometer Aluminum sol 25% for being 20% by solid content according to mass percent, rheological agent 1.0%, remaining is ceramic powder Material carries out dispensing.Light calcined magnesia powder is added in ball grinder first, in accordance with proportioning, by nanometer Aluminum sol, the oxidation of nanometer three two Iron, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 45min, make to be added to after nano lanthanum oxide powder is fully dispersed In ball grinder, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, so that it is uniformly mixed with 100rpm rotating speed ball millings 3h and is consolidated The ceramic slurry that content is 65%.
15PPI polyurethane foam plastics masterplates are selected, surface etch 50min is impregnated in 45 DEG C of 15%NaOH aqueous solutions Naturally dry is washed with clear water afterwards, is then immersed in the aqueous solution of 4% dodecyl benzene sulfonic acid wetting agent, drying is taken out.So Polyurethane foam plastics masterplate is immersed in ceramic slurry afterwards, it is more to squeeze the removal of polyurethane foam plastics masterplate by roll squeezer Biscuit is made after remaining leaching hanging material, then so that biscuit is dried in 45 DEG C of draft chamber's removal alcohol solvents.
Dry biscuit is put into sintering furnace, being heated to 550 DEG C with the heating rate of 30 DEG C/h makes foam ceramic filter The organic matters decomposition gasification such as polyurethane foam and rheological agent in device biscuit is discharged, and is then heated with the heating rate of 200 DEG C/h To 1100 DEG C of temperature, 1400 DEG C of temperature are finally heated to the heating rate of 50 DEG C/h and keep the temperature 2h at such a temperature, with furnace cooling But magnesium oxide-based ceramic foam filter is obtained to room temperature.
In above-described embodiment, experiment shows that prepared foamed ceramics has excellent thermal shock resistance and intensity, at 900 DEG C It is cooled down 50 times in air and is showed no cracking；The normal temperature strength of the ceramic foam filter of 75mm × 75mm × 25mm, 10PPI is not low In 2MPa.
Above-described embodiment is not limit the invention in any way, every to be obtained by the way of equivalent substitution or equivalent transformation Technical solution all fall in protection scope of the present invention.

Claims (9)

1. a kind of MA-MF composite spinelles enhance magnesium oxide-based ceramic foam filter, it is characterised in that nanometer three will be contained and aoxidized The light calcined magnesia base ceramic slurry of two iron sintering aids is coated on polyurethane foam carrier, is obtained through drying, sintering.
2. a kind of MA-MF composite spinelles enhance the preparation method of magnesium oxide-based ceramic foam filter, it is characterised in that including Following steps：
(1) according to mass percent by 15%~25% nanometer of Aluminum sol, 0.8%~1.5% rheological agent, remaining is containing nanometer three The magnesia ceramics powder for aoxidizing two iron sintering aids carries out dispensing, and solid content is made after addition absolute ethyl alcohol ball milling mixing is uniform For 60%~70% ceramic slurry；The rheological agent is the mixture of polyvinyl butyral and cellulose ether, wherein poly- second Enol butyral accounts for the 50% of rheological agent quality, and cellulose ether is in industrial hydroxypropyl methyl cellulose, hydroxyethyl cellulose Or mixtures thereof one kind；The ceramic powder is the mixture of light calcined magnesia and nanometer di-iron trioxide；
(2) polyurethane foam plastics masterplate is immersed in ceramic slurry, polyurethane foam plastics masterplate is squeezed by roll squeezer Biscuit is made after removing extra leaching hanging material, then so that biscuit is dried in 40 DEG C~50 DEG C draft chamber's removal alcohol solvents；
(3) dry biscuit is put into sintering furnace, high temperature sintering is carried out at a temperature of being warming up to 1350 DEG C~1550 DEG C, with furnace cooling But magnesium oxide-based ceramic foam filter is obtained to room temperature.
3. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that：The nanometer Aluminum sol solid content is 20%~25%, pH value >=4.
4. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that：The nanometer di-iron trioxide accounts for the 1%~2% of ceramic powder quality.
5. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that：The grain size of the nanometer di-iron trioxide is 30~60nm.
6. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that：The grain size of the light calcined magnesia powder is the mesh of 250 mesh~500.
7. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that the preparation method of the ceramic slurry is：Light calcined magnesia powder is added in ball grinder according to proportioning, Nanometer Aluminum sol, nanometer di-iron trioxide, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 30min~60min, Make to be added in ball grinder after nano lanthanum oxide powder is fully dispersed, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, with 60 ~120rpm rotating speed ball millings 2h~4h makes it be uniformly mixed.
8. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that：The specification of the polyurethane foam plastics masterplate is 10PPI~20PPI, using preceding at 40 DEG C~50 DEG C 15%~20%NaOH aqueous solutions in impregnate and wash naturally dry with clear water after surface etch 40min~60min, be then immersed in Into the aqueous solution of 2%~4% dodecyl benzene sulfonic acid wetting agent, obtained after taking out drying.
9. a kind of MA-MF composite spinelles according to claim 2 enhance the preparation of magnesium oxide-based ceramic foam filter Method, it is characterised in that in the step (3), the sintering process is：Being heated to 550 DEG C with the heating rate of 30 DEG C/h makes Organic matter decomposition gasification discharge in ceramic foam filter biscuit, is then heated to 1100 DEG C with the heating rate of 200 DEG C/h Temperature is finally heated to 1350 DEG C~1550 DEG C temperature with the heating rate of 50 DEG C/h and keeps the temperature 2~3h at such a temperature.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110981539A (en) * 2019-12-30 2020-04-10 武汉科技大学 Magnesium oxide based filter containing functional coating multi-pore structure and preparation method thereof
JP2020203807A (en) * 2019-06-17 2020-12-24 東和耐火工業株式会社 Castable refractory and method for producing the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030146151A1 (en) * 2002-01-23 2003-08-07 Feng Chi Sintered magnesium oxide filter

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030146151A1 (en) * 2002-01-23 2003-08-07 Feng Chi Sintered magnesium oxide filter

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020203807A (en) * 2019-06-17 2020-12-24 東和耐火工業株式会社 Castable refractory and method for producing the same
CN110981539A (en) * 2019-12-30 2020-04-10 武汉科技大学 Magnesium oxide based filter containing functional coating multi-pore structure and preparation method thereof
CN110981539B (en) * 2019-12-30 2021-11-16 武汉科技大学 Magnesium oxide based filter containing functional coating multi-pore structure and preparation method thereof

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