CN108530094A - Magnesium oxide-based ceramic foam filter of a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhancing and preparation method thereof - Google Patents
Magnesium oxide-based ceramic foam filter of a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhancing and preparation method thereof Download PDFInfo
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- 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
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- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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Abstract
The invention discloses it is a kind of can realize at low temperature sintering, chemical stability and the excellent alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel of thermal shock resistance enhance magnesium oxide-based ceramic foam filter and preparation method thereof, preparation method 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 containing alkali magnesium sulfate crystal whisker, 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
Technical field
The present invention relates to a kind of magnesium oxide-based ceramic foam filter and preparation method thereof, specifically a kind of alkali magnesium sulfates
Whisker in-situ synthetic MgAl spinal enhances magnesium oxide-based ceramic foam filter and preparation method thereof, belongs to metal material and smelting
Golden collar domain.Filter prepared by the present invention especially suitable for magnesium and its filtration, purification of alloy melt, can also be used for aluminium and
The filtration, purification of its alloy melt.
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
Alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhances 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 alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhancing, will contain alkali
The light calcined magnesia base ceramic slurry of formula magnesium sulfate crystal whisker is coated on polyurethane foam carrier, is obtained through drying, sintering.
A kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhances the preparation of magnesium oxide-based ceramic foam filter
Method includes the following steps：
(1) according to mass percent by 15%~25% nanometer of Aluminum sol, 0.8%~1.5% rheological agent, remaining is containing alkali
The magnesia ceramics powder of formula magnesium sulfate crystal whisker carries out dispensing, and solid content, which is made, after addition absolute ethyl alcohol ball milling mixing is uniform is
60%~70% ceramic slurry.The alkali formula sulfuric acid that the nanometer Aluminum sol of addition disperses in light calcined magnesia particle and high uniformity
Magnesium whisker surface forms γ-Al2O3Coating film, the γ-Al in sintering process in nanometer Aluminum sol2O3It is reacted with MgO and generates tool
There is the high-melting-point magnesium aluminate spinel (MgAl of face-centered cubic lattice2O4, MA) and phase (2135 DEG C of fusing point).The nanometer Aluminum sol of addition is not
Binder can only be played the role of, and be distributed in magnesium oxide powder particle with magnesium oxide powder particle and high uniformity
It is brilliant to generate the magnalium point for having chemical stability to magnesium and its alloy melt for the decomposition product reaction in-situ of alkali magnesium sulfate crystal whisker
Stone MgAl2O4Phase avoids the damage that the binders such as Ludox, silester are added to foamed ceramics chemical stability in existing product
Evil.
The rheological agent is the mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for
The 50% of rheological agent quality, the cellulose ether be industrial hydroxypropyl methyl cellulose, one kind in hydroxyethyl cellulose or
Its mixture.Cellulose ether and the polyvinyl butyral not still fine dispersion agent of alkali magnesium sulfate crystal whisker powder, Neng Goufang
Only slurry generates agglomeration, and can play the role of bonding agent when preparing biscuit, and slurry can comparatively securely after dipping
Being attached on polyurethane foam plank makes biscuit have prodigious intensity, while easily escaping in sintering process and being made without polluting
Product, hereby it is ensured that the quality of ceramic foam filter.It does not use sodium carboxymethylcellulose etc. to contain the salt received in rheological agent, keeps away
The larger Na of remaining ionic radius is exempted from+To the obstruction of ceramic post sintering.
The ceramic powder is the mixture of light calcined magnesia and alkali magnesium sulfate crystal whisker.Wherein, the alkali magnesium sulfate
Whisker accounts for the 1%~3% of ceramic powder quality, a diameter of 1 μm of the alkali magnesium sulfate crystal whisker, and length is 50 μm~100 μm.Institute
The grain size for stating light calcined magnesia powder 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, and nanometer Aluminum sol can in sintering process
Being dissolved into the light-burned MgO lattices of high activity makes MgO crystal that distortion of lattice occur, and activates lattice, while by anti-between MgO particles
It should be sintered and generate new compound-magnesium aluminate spinel MgAl2O4Phase, to promote sintering and the alternate combination of particle.Another party
Face, nano-powder have the characteristics that large specific surface area, surface energy height, high activity, low-temperature sintering are added with nano aluminum solation
Auxiliary agent improves Al in nanometer Aluminum sol2O3With the mixing uniformity of magnesium oxide powder, sintering aid and MgO are intergranular fully
Contact makes the reaction speed of generation magnesium aluminate spinel phase improve rapidly, to further reduced sintering temperature, and sintering temperature
Reduction advantageously reduce the production cost of energy consumption and ceramic foam filter.
[molecular formula general formula is xMgSO to alkali magnesium sulfate crystal whisker4·yMg(OH)2·zH2O；MgSO4·5Mg(OH)2·3H2O
153 type whiskers it is relatively conventional] be a kind of novel needle-shaped short fiber reinforced material, a diameter of 0.5~1.0 μm, length 20
~80 μm, there is the excellent physical and mechanical properties such as high intensity, low-density, high elastic modulus.
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, alkali magnesium sulfate crystal whisker, rheological agent and absolute ethyl alcohol are mixed and sonicated for 30min~60min, make alkali magnesium sulfate
It is added in ball grinder after whisker 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 speeds
Ball milling 2h~4h make its be uniformly mixed obtain.
(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 polyurethane foam plastics masterplate specification is 10PPI~20PPI (Pores per inch, inches length
On average number of pores)；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, after being then immersed in the aqueous solution of 2%~4% dodecyl benzene sulfonic acid wetting agent
It is obtained after taking out drying.Make its surface roughening by NaOH etchings, then passes through the water-soluble of dodecyl benzene sulfonate wetting agent
After liquid 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 being added can not only play the role of reduce sintering temperature, and with MgO reaction in-situs
Generate MgAl2O4Magnesium oxide particle is mutually welded together by magnesium aluminate spinel, while having the alkali magnesium sulfate of certain orientation brilliant
The form of palpus is mutually inherited by being formed by magnesium aluminate spinel, and therefore, ceramic foam filter has good intensity, chemical stabilization
Property and thermal shock resistance it is molten also to can be used for aluminium and its alloy especially suitable for the field trash in filtration, purification magnesium and its alloy melt
Body filtration, purification.Compared with the prior art scheme, technique effect of the invention：
One, alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel of the invention enhances magnesium oxide-based ceramic foam filter
With excellent chemical stability.Although containing the γ-Al reacted with Serum Magnesium in raw material Aluminum sol component2O3, but what is be added receives
Rice Aluminum sol forms γ-Al on the alkali magnesium sulfate crystal whisker surface that light calcined magnesia particle and high uniformity disperse2O3Coating film,
γ-Al in sintering process in nanometer Aluminum sol2O3The high-melting-point magnalium point with face-centered cubic lattice is generated with MgO reactions
Spar (MgAl2O4, MA) and phase (2135 DEG C of fusing point).
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 (1), 5), the Gibbs Gibbs free Δs G of (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.
In the alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhancing magnesia ceramic foam filter of the present invention not
Containing any component for reducing its chemical stability, the nanometer Aluminum sol of addition can not only play the role of binder, Er Qieyu
The decomposition product that magnesium oxide powder particle and high uniformity are distributed to the alkali magnesium sulfate crystal whisker in magnesium oxide powder particle is in situ
Reaction generates the magnesium aluminate spinel MgAl for having chemical stability to magnesium and its alloy melt2O4Phase avoids existing product 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 alkali formula sulfuric acid
Magnesium whisker in-situ synthetic MgAl spinal enhancing magnesia ceramic foam filter can also be used for aluminium and its melting of alloy is net
Change.
Two, alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel of the invention enhances magnesium oxide-based ceramic foam filter
With good low-temperature sintering performance.Light calcined magnesia fine powder itself of the present invention has very high sintering activity, receives
Rice Aluminum sol, which can be dissolved into sintering process in the light-burned MgO lattices of high activity, makes MgO crystal that distortion of lattice occur, and activation is brilliant
Lattice, while new compound-magnesium aluminate spinel MgAl is generated by reaction-sintered between MgO particles2O4Phase is burnt to promote
The knot combination alternate with particle.On the other hand, nano-powder has the characteristics that large specific surface area, surface energy height, high activity, to receive
Low-temperature sintering auxiliary agent is added in rice Aluminum sol form, improves Al in nanometer Aluminum sol2O3With the mixing uniformity of magnesium oxide powder,
Sintering aid makes the reaction speed of generation magnesium aluminate spinel phase improve rapidly with intergranular come into full contact with of MgO, to further
Sintering temperature is reduced, and the reduction of sintering temperature advantageously reduces the production cost of energy consumption and ceramic foam filter.Experiment
The result shows that sintering structure combines and is not enough and causes its low strength between magnesium oxide particle when sintering temperature is less than 1350 DEG C,
It is 1350 DEG C~1550 DEG C that tissue, which combines the sintering temperature of good magnesia ceramic foam filter,.
Three, alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel of the invention enhances magnesium oxide-based ceramic foam filter
With good thermal shock resistance.Solid-phase component is the porous gamma-Al of high activity in Aluminum sol2O3, with magnesium aluminate spinel
(MgAl2O4) crystal structure is identical.The mechanical property of ceramic matric composite can be improved as reinforcement using fiber and whisker
Energy.Whisker (whisker) refers to having certain draw ratio (generally higher than 10), and sectional area is less than 5.2 × 10-4cm2Monocrystalline it is fine
Tie up material.[molecular formula general formula is xMgSO to alkali magnesium sulfate crystal whisker4·yMg(OH)2·zH2O；MgSO4·5Mg(OH)2·3H2O
153 type whiskers it is relatively conventional] be a kind of novel needle-shaped short fiber reinforced material, a diameter of 0.5~1.0 μm, length 20
~80 μm, there is the excellent physical and mechanical properties such as high intensity, low-density, high elastic modulus.In scheme provided by the present invention
In, height is sintered active light calcined magnesia particle and the alkali magnesium sulfate crystal whisker of high degree of dispersion is surrounded by nano aluminum dissolved glue film,
Reaction in-situ generates nano magnalium spinelle (MgAl in sintering process2O4) phase, cristobalite MgO crystal grain is directly fused together；
When squeezing the polyurethane foam plastics masterplate of leaching hanging material by roll squeezer simultaneously, the alkali magnesium sulfate crystal whisker in made biscuit
It is arranged to a certain extent along rolling direction, the form of the alkali magnesium sulfate crystal whisker with certain orientation is by being formed by magnalium
Spinel is inherited, and therefore, wraps up the magnesium aluminate spinel (MgAl of periclase MgO crystal grain2O4) mutually make to have between the ceramic crystalline grain of sintering
There is the tissue combined closely, while the pinning effect of magnesium aluminate spinel phase inhibits the growth of magnesium oxide particle to refine bubble
The tissue of foam ceramics simultaneously improves the consistency between ceramic crystalline grain, and prepared alkali magnesium sulfate crystal whisker fabricated in situ magnalium point is brilliant
Stone, which enhances magnesium oxide-based 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 alkali magnesium sulfate crystal whisker 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 that alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhances magnesium oxide-based ceramic foam filter
Process flow chart.
Specific implementation mode
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
A kind of magnesium oxide-based ceramic foam filter of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhancing, will contain alkali
The light calcined magnesia base ceramic slurry of formula magnesium sulfate crystal whisker is coated on polyurethane foam carrier, is obtained through drying, sintering.Specifically
Preparation process it is as shown in Figure 1.
Embodiment 1
1% proportioning that ceramic powder quality is accounted for according to alkali magnesium sulfate crystal whisker, weighs commercialization alkali magnesium sulfate crystal whisker
(about 1 μm of diameter, length are 50 μm~100 μm) and grain size are 250 mesh (central diameter d50Be 58 μm) light calcined magnesia powder prepare
Ceramic powder；It is 1 according to the mass ratio of polyvinyl butyral and hydroxypropyl methyl cellulose:1 ratio mixed preparing rheology
Agent.
(commercialization of pH value weakly acidic pH is selected to receive the nanometer Aluminum sol 15% that solid content is 20% 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, alkali magnesium sulfate crystal whisker, 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, keep alkali magnesium sulfate crystal whisker powder fully dispersed
After be added in ball grinder, according still further to ratio of grinding media to material 2:Corundum ball is added in 1 ratio, keeps its mixing equal with 60rpm rotating speed ball millings 4h
The even ceramic slurry for obtaining solid content and being 60%.
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
3% proportioning that ceramic powder quality is accounted for according to alkali magnesium sulfate crystal whisker, weighs commercialization alkali magnesium sulfate crystal whisker
It is 500 mesh (central diameter d with grain size50Be 25 μm) light calcined magnesia powder prepare ceramic powder；According to polyvinyl butyral and
The mass ratio of hydroxypropyl methyl cellulose is 1:1 ratio mixed preparing rheological agent.
The nanometer Aluminum sol 20% for being 25% 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, nanometer Aluminum sol, alkali magnesium sulfate is brilliant
Palpus, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 60min, add after keeping alkali magnesium sulfate crystal whisker 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 120rpm rotating speed ball millings 2h
The ceramic slurry for being 65% to solid content.
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
2% proportioning that ceramic powder quality is accounted for according to alkali magnesium sulfate crystal whisker, weighs commercialization alkali magnesium sulfate crystal whisker
It is 325 mesh (central diameter d with grain size50Be 45 μm) light calcined magnesia powder prepare ceramic powder；According to polyvinyl butyral and
The mass ratio of hydroxyethyl cellulose is 1:1 ratio mixed preparing rheological agent.
The nanometer Aluminum sol 25% 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, nanometer Aluminum sol, alkali magnesium sulfate is brilliant
Palpus, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 45min, add after keeping alkali magnesium sulfate crystal whisker 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 90rpm rotating speed ball millings 3h
The ceramic slurry for being 70% to solid content.
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, 1500 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
2% proportioning that ceramic powder quality is accounted for according to alkali magnesium sulfate crystal whisker, weighs commercialization alkali magnesium sulfate crystal whisker
It is 300 mesh (central diameter d with grain size50Be 48 μm) light calcined magnesia powder prepare ceramic powder；According to polyvinyl butyral：Hydroxyl
Propyl methocel：The mass ratio of hydroxyethyl cellulose is 5:2:3 ratio mixed preparing rheological agent.
The nanometer Aluminum sol 20% 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, nanometer Aluminum sol, alkali magnesium sulfate is brilliant
Palpus, rheological agent and suitable absolute ethyl alcohol are mixed and sonicated for 45min, add after keeping alkali magnesium sulfate crystal whisker 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 100rpm rotating speed ball millings 3h
The ceramic slurry for being 65% to solid content.
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, 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.
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 3MPa.
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 alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhances magnesium oxide-based ceramic foam filter, feature exists
In：Light calcined magnesia base ceramic slurry containing alkali magnesium sulfate crystal whisker is coated on polyurethane foam carrier, through drying, sintering
It obtains.
2. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel enhances the preparation side of magnesium oxide-based ceramic foam filter
Method, it is characterised in that include the following steps：
(1) according to mass percent by 15%~25% nanometer of Aluminum sol, 0.8%~1.5% rheological agent, remaining is the sulphur of formula containing alkali
The magnesia ceramics powder of sour magnesium whisker carries out dispensing, be made after addition absolute ethyl alcohol ball milling mixing is uniform solid content be 60%~
70% ceramic slurry；The rheological agent is the mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl alcohol
Butyral accounts for the 50% of rheological agent quality, and the 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 alkali magnesium sulfate crystal whisker；
(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 alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that：The nanometer Aluminum sol solid content is 20%~25%, pH value >=4.
4. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that：The alkali magnesium sulfate crystal whisker accounts for the 1%~3% of ceramic powder quality.
5. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that：The grain size of the light calcined magnesia powder is the mesh of 250 mesh~500.
6. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that：A diameter of 1 μm of the alkali magnesium sulfate crystal whisker, length are 50 μm~100 μ
m。
7. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that the preparation method of the ceramic slurry is：According to proportioning by light calcined magnesia
Powder is added in ball grinder, and nanometer Aluminum sol, alkali magnesium sulfate crystal whisker, rheological agent and absolute ethyl alcohol are mixed and sonicated for
30min~60min makes to be added in ball grinder after alkali magnesium sulfate crystal whisker is fully dispersed, according still further to ratio of grinding media to material 2:1 ratio adds
Enter corundum ball, so that it is uniformly mixed with 60~120rpm rotating speed ball millings 2h~4h and obtain.
8. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that：The polyurethane foam plastics masterplate specification is 10PPI~20PPI；It uses
It is preceding to be washed certainly with clear water after immersion surface etch 40min~60min in 40 DEG C~50 DEG C of 15%~20%NaOH aqueous solutions
It so dries, is obtained after taking out drying after being then immersed in the aqueous solution of 2%~4% dodecyl benzene sulfonic acid wetting agent.
9. a kind of alkali magnesium sulfate crystal whisker fabricated in situ magnesium aluminate spinel according to claim 2 enhances magnesium oxide-based foam
The preparation method of ceramic filter, it is characterised in that in the step (3), the sintering process is：With the heating of 30 DEG C/h
Speed is heated to the organic matters decomposition gasification such as the polyurethane foam that 550 DEG C make in ceramic foam filter biscuit and rheological agent row
Go out, 1100 DEG C of temperature are then heated to the heating rate of 200 DEG C/h, are finally heated to 1350 DEG C with the heating rate of 50 DEG C/h
~1550 DEG C of temperature simultaneously keep the temperature 2~3h at such a temperature.
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| CN116003156A (en) * | 2022-11-24 | 2023-04-25 | 浙江锦诚新材料股份有限公司 | MgAlON ceramic filter with multiple pore structures for magnesium alloy and preparation method thereof |
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