CN108484181B - Alumina short fiber reinforced magnesium oxide based foamed ceramic filter and preparation method thereof - Google Patents

Alumina short fiber reinforced magnesium oxide based foamed ceramic filter and preparation method thereof Download PDF

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Publication number
CN108484181B
CN108484181B CN201810307628.4A CN201810307628A CN108484181B CN 108484181 B CN108484181 B CN 108484181B CN 201810307628 A CN201810307628 A CN 201810307628A CN 108484181 B CN108484181 B CN 108484181B
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China
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magnesia
ceramic
alumina short
short fiber
alumina
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CN108484181A (en
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刘子利
刘思雨
刘希琴
李健
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JIANGSU FAVOUR AUTOMOTIVE NEW STUFF SCI-TECH CO LTD
Nanjing University of Aeronautics and Astronautics
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JIANGSU FAVOUR AUTOMOTIVE NEW STUFF SCI-TECH CO LTD
Nanjing University of Aeronautics and Astronautics
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Priority to CN201810307628.4A priority Critical patent/CN108484181B/en
Priority to PCT/CN2018/089570 priority patent/WO2019196181A1/en
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Abstract

The invention discloses an alumina short fiber reinforced magnesia-based foamed ceramic filter which can realize sintering at low temperature and has excellent chemical stability and thermal shock resistance and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent and the balance of magnesia ceramic powder containing alumina short fiber and nano titanium dioxide according to the mass percentage, adding absolute ethyl alcohol, ball-milling and mixing uniformly to prepare ceramic slurry with the solid content of 60-70%; (2) immersing a polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove redundant immersion slurry to prepare a biscuit, and then removing an ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit; (3) and (3) putting the dried biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesia-based foamed ceramic filter.

Description

Alumina short fiber reinforced magnesium oxide based foamed ceramic filter and preparation method thereof
Technical Field
The invention relates to a magnesium oxide based foamed ceramic filter and a preparation method thereof, in particular to an aluminum oxide short fiber reinforced magnesium oxide based foamed ceramic filter and a preparation method thereof, belonging to the field of metal materials and metallurgy. The filter prepared by the invention is particularly suitable for filtering and purifying magnesium and magnesium alloy melts, and can also be used for filtering and purifying aluminum and aluminum alloy melts.
Background
The magnesium has active chemical property, and is easy to have chemical reaction with oxygen, nitrogen and water vapor in the casting and processing processes, and the generated product remains in the magnesium to influence the interior of a productMetallic inclusions are generally classified into two main types of metallic inclusions and non-metallic inclusions according to the kind and properties of the inclusions in magnesium alloys, (1) metallic inclusions, in which magnesium alloys inevitably introduce some metallic simple substances or metallic compound inclusions in the form of particles, clusters, etc. remaining on the matrix or grain boundary of magnesium alloys during the production and later processing of raw magnesium, and mainly include α -Fe particles of the metallic simple substances, and metallic compounds of Mn-Fe such as (Fe, Mn)3Si，(Fe,Mn)5Si3Etc.; (2) non-metallic inclusions: the non-metallic inclusions in the magnesium alloy are mainly based on magnesium oxynitrides, such as MgO, Mg3N2Etc.; the magnesium alloy is added with chloride (KCl, NaCl, MgCl) in the smelting process2Etc.) as the main refining agent, the flux can not be completely removed in the refining process, and a small amount of flux remains in the magnesium melt, causing the inclusion of magnesium metal flux. The suspended oxide inclusions are pushed to the grain boundary from the crystal front during crystallization, and the inclusions generally remain in the form of a film, particles, or clusters at the grain boundary of the magnesium alloy. Statistical data show that MgO accounts for more than 80% of all inclusions in the magnesium alloy, and the distribution form is film, particle and cluster. The inclusion produced in the process of casting the magnesium alloy not only seriously deteriorates the mechanical property and the corrosion resistance of the alloy, but also reduces the surface quality of the alloy after machining and anodic oxidation treatment. For die-cast magnesium alloy, the content of film-like and particle-like oxides in the alloy needs to be controlled to 100cm2Kg and 100mm3The normal use requirements can be met only when the dosage is less than/kg. Therefore, a purification process for removing inclusions in a magnesium melt to improve the purity of the melt during the casting process becomes a key to the production of magnesium alloys.
The melt purification process can be divided into two main categories of flux purification and non-flux purification. The flux purification process is a purification process commonly adopted in the production of magnesium alloy due to high impurity removal efficiency, low cost and convenient operation, but the flux purification also has the defects of increased metal loss, inclusion of flux, incapability of degassing and the like, and particularly when the rare earth magnesium alloy is smelted, the flux can also consume a large amount of rare earth elements in the alloy. The non-flux purification process not only can make up the defects of the flux purification process, but also has excellent purification effect, becomes an important melt purification process applied and developed at present, and develops a plurality of non-flux purification technologies such as filtration purification, rotary blowing purification, electromagnetic purification, ultrasonic treatment and the like in succession. Compared with simple metal mesh melt filtration, the three-dimensional porous ceramic foam ceramic filter with the three-dimensional porous ceramic structure has the advantages of high porosity (70-90%), strong adsorption capacity, chemical corrosion resistance and the like, and can have good filtering effect on impurity particles in the alloy melt through filter cake effect, adsorption effect and rectification effect. The foamed ceramic filtering method can not only filter out fine inclusion particles as small as 10-20 microns in the alloy melt, but also filter out liquid flux inclusions which are difficult to filter out by common filter media.
U.S. patent document US3962081A (Ceramic foam filter), US4024212A
(Ceramic foam and method of preparation), Chinese patent document CN103787691A (a preparation method of alumina foamed ceramics) and the like all disclose Al used for filtering inclusions in aluminum alloy and steel melts2O3，ZrO2，SiC、SiO2However, the standard free enthalpy of formation of MgO is very low, and the magnesium melt with high activity is very easy to react with the foam ceramic matrix material to dissolve rapidly, thereby blocking the filtration pores or corroding into the magnesium and its alloy melt to become harmful components, therefore, these prior art foam filters are not suitable for filtering magnesium and magnesium alloy melts.
3Mg(l)+Al2O3(s)＝3MgO(s)+2Al(l)(1)
2Mg(l)+ZrO2(s)＝2MgO(s)+Zr(s) (2)
6Mg(l)+4Al(l)+3SiC(s)＝3Mg2Si(s)+Al4C3(s) (3)
4Mg(l)+SiO2(s)＝2MgO(s)+Mg2Si(s) (4)
MgO is a cubic NaCl type structure with a lattice constant of 0.411nm, belongs to an ionic bond compound, has a melting point of 2852 ℃, and is much higher than that of common Al2O3(2054 ℃ C.) and SiO2(1650 +/-50 ℃), so that the magnesium oxide product has the characteristics of good chemical stability, high resistivity, strong erosion resistance to metal, slag and alkaline solution and the like. Compared with common ceramic materials, MgO, magnesium and alloy melt thereof have good high-temperature chemical stability, do not react with flux inclusion slag formed by molten chloride and fluonate, have small wetting angle with the flux and are easy to adsorb the flux inclusion in the magnesium melt, so the MgO foamed ceramic is an ideal material for smelting and purifying magnesium alloy liquid.
Firing below the melting point of the oxide composition is the most critical step necessary for the preparation of the ceramic material, and the sintering, grain growth, etc. that occurs at high temperatures determines the microstructure and properties of the ceramic material. Chinese patent documents CN1011306B (pure magnesium oxide ceramic foam filter and preparation process thereof), CN101138691A (preparation method of magnesium ceramic foam filter for casting) and the like, and the MgO has very high melting point and thermal expansion coefficient (13.5 multiplied by 10)-6/° c), which results in difficulty in sintering (sintering temperature not lower than 0.8 times of its melting point) and poor thermal shock resistance, limiting the application and development of MgO foam ceramic.
The research shows that: the heat consumption of unit products can be reduced by more than 10 percent when the firing temperature is reduced by 100 ℃ in the ceramic sintering process, and the addition of the sintering aid is an important technical means for reducing the sintering temperature of the MgO foamed ceramic. Addition of V2O5In the case of powder, MgO reacts with V at 1190 DEG C2O5Form an approximate composition of Mg3V2O8Can remarkably lower the sintering temperature of the MgO foamed ceramics, but V2O5Has damage to the respiratory system and the skin during the use process, and has strict limitation on the operation. And V2O5Similarly, cobalt oxide is a good low temperature sintering aid, but has limited application as a highly toxic substance and a scarce resource. Fluoride is a strong cosolvent and mineralizer commonly used in industrial sintering of ceramics, and Chinese patent document CN100536986C (magnesia foamed ceramics)The filter), CN1473947A (foamed ceramic for purifying magnesium and magnesium alloy melts), CN101785944B (preparation method of magnesium oxide foamed ceramic filter for filtering magnesium and magnesium melts) are added with fluorite (melting point 1423 ℃) and magnesium fluoride (melting point 1248 ℃), solid solution of fluoride in the sintering process not only increases lattice distortion of matrix magnesium oxide, but also easily forms low-melting-point liquid phase, thereby reducing the sintering temperature of the magnesium oxide ceramic; however, F in fluoride is combined with Si, Al, Fe and Ca in the sintering process, most of the F (accounting for about 70 percent in the production of ceramic tiles) volatilizes in a gaseous state to erode a blank body and damage the quality of the sintered ceramic, more serious the F pollution is caused by the emission of the fluoride into the atmosphere, the fluoride can enter a human body through respiratory tract, digestive tract and skin, has toxic effect on the central nervous system and cardiac muscle, the low-concentration fluorine pollution can cause brittle calcification of teeth and bones, and the emission standard of the fluoride is required to be lower than 5.0mg/m in the emission standard of ceramic industrial pollutants (GB25464-2010)3The fluoride is used as the low-temperature sintering aid of the magnesium oxide ceramic, so that the emission of gaseous fluoride is increased inevitably, and the burden of environmental protection is increased; in addition, fluorine ions in solid-solution fluorides remaining in ceramics exist in the form of substituted oxygen ions, which causes a decrease in chemical stability of intergranular bonding, and makes it difficult to resist long-term erosion by flux inclusion in a magnesium melt. In the slurry for producing the ceramic foam filter disclosed in Chinese patent document CN101138691A or the like, water glass, silica sol and ethyl silicate are used as a binder, and SiO is formed between sintered ceramic foam particles2The existence of the components makes the components easy to react with magnesium and magnesium alloy melt according to the formula (4), and the chemical stability of the foamed ceramic is also reduced. In chinese patent documents CN100536986C (magnesia ceramic foam filter), CN103553686A (magnesium aluminate spinel ceramic foam filter and its preparation method), and the like, boron trioxide and borax are used as low temperature sintering aids for magnesia ceramics, and when the boron trioxide is higher than 450 ℃, it forms a liquid phase, and when the sintering temperature exceeds 1350 ℃, it reacts with magnesia to generate magnesium borate in the form of a liquid phase, thereby lowering the sintering temperature. However, boron trioxide is liable to react with magnesium and aluminum and is unstable in magnesium and aluminum alloy melts; at the same time, since threeThe diboron oxide is dissolved in solvents such as water and ethanol, can absorb water strongly in the air to generate boric acid, and the diboron trioxide added in the preparation process of the foamed ceramic is dissolved in water to form a boric acid aqueous solution, and is easy to react with magnesium oxide to form magnesium borate precipitate so as to reduce the effect of the magnesium borate precipitate. Gallium oxide is a family oxide of diboron trioxide, and forms spinel-shaped MgGa with magnesium oxide at a lower temperature2O4But the sintering temperature is reduced, but the resource amount of gallium is very small (gallium is a strategic reserve metal), and the application of gallium oxide in common ceramics is limited due to the higher price of gallium oxide.
Disclosure of Invention
The invention aims to provide an alumina short fiber reinforced magnesia-based foamed ceramic filter which can be sintered at low temperature and has excellent chemical stability and thermal shock resistance and a preparation method thereof.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
an alumina short fiber reinforced magnesia-based foamed ceramic filter is prepared by coating light-burned magnesia-based ceramic slurry containing alumina short fibers and nano titanium dioxide on a polyurethane foam carrier, drying and sintering.
A preparation method of an alumina short fiber reinforced magnesia-based foamed ceramic filter comprises the following steps:
(1) according to the mass percentage, 15 to 25 percent of nano aluminum sol, 0.8 to 1.5 percent of rheological agent and the balance of magnesia ceramic powder containing alumina short fiber and nano titanium dioxide are mixed, and are added with absolute ethyl alcohol to be ball-milled and mixed evenly to prepare ceramic slurry with the solid content of 60 to 70 percent. The added nano aluminum sol not only bonds the light-burned magnesia particles, the nano titanium dioxide and the alumina short fibers together through forming a continuous film, and can play a role of a binder, but also reacts with the highly dispersed nano titanium dioxide powder together with the magnesia powder particles in situ to generate a spinel phase with chemical stability to magnesium and magnesium alloy melt, and the damage of the existing product on the chemical stability of the foamed ceramic caused by adding the binders such as silica sol, ethyl silicate and the like is avoided.
The solid phase component in the aluminum sol isHighly active porous gamma-Al2O3With magnesium aluminate spinel (MgAl)2O4) The crystal structure is the same. The mechanical property of the ceramic matrix composite material can be improved by adopting the fibers and the whiskers as the reinforcement.
The rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose or a mixture thereof. Cellulose ether and polyvinyl butyral are good dispersants for nano titanium dioxide and alumina short fiber powder, can prevent slurry from agglomerating, can play a role of a binder when preparing a biscuit, and the soaked slurry can be firmly attached to a polyurethane foam template so that the biscuit has high strength and can easily escape in a sintering process without polluting products, thereby ensuring the quality of the foam ceramic filter. Sodium carboxymethyl cellulose and other sodium-containing salts are not adopted in the rheological agent, so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
The ceramic powder is a mixture of light-burned magnesia, nano titanium dioxide and alumina short fibers. Wherein the nano titanium oxide accounts for 1-2% of the mass of the ceramic powder, the alumina short fiber accounts for 1-3% of the mass of the ceramic powder, the particle size of the nano titanium oxide is 30-60 nm, and the alumina short fiber is commercial polycrystalline Al with small length-diameter ratio2O3Short fibers having a diameter of 10 to 20 μm and a length of 50 to 100 μm. The particle diameter of the light-burned magnesium oxide powder is 250-500 meshes (medium diameter d)5025 to 58 μm).
The adopted light-burned magnesia fine powder has high sintering activity, nano titanium dioxide is added into the ceramic component, and titanium ions are diffused into a periclase crystal interface to form Ti4+Ion replacement of Mg2+Solid solutions of ions promote direct intercrystalline bonding. Al (Al)2O3The lattice constant of the MgO is similar to that of MgO, and the MgO can be dissolved into MgO lattice in a solid solution in the sintering process to cause the MgO crystal to generate lattice distortion; al (Al)3+Has a small diffusion rate of Al2O3Very low solubility in periclase MgO (Al)2O3The solubility of the nano alumina sol in periclase MgO at 1700 ℃ is only 3 percent), the nano alumina sol can be dissolved into a high-activity light-burned MgO crystal lattice in a solid solution in the sintering process to enable the MgO crystal lattice to generate lattice distortion and activate the crystal lattice, and simultaneously, a new compound, namely magnesia-alumina spinel MgAl, is generated by reaction and sintering between the nano alumina sol and the MgO particles2O4Phase, thereby promoting sintering and particle-phase bonding. On the other hand, the nano powder has the characteristics of large specific surface area, high surface energy, high activity and the like, so the nano powder is easy to combine with other atoms, and the melting point and the sintering temperature of the nano powder are much lower than those of the micro powder. The sintering aid added in the form of nano titanium oxide and nano aluminium sol can fill the gaps between the raw material micro powder particles, optimize the gradation and mixing uniformity of ceramic particles, and simultaneously, the nano powder has high reaction activity nano gamma-Al in the nano titanium oxide and the aluminium sol due to the surface and interface effect of the nano powder2O3The full contact with the light-burned MgO particles leads the reaction speed to be rapidly improved, the sintering temperature is reduced, the density and the mechanical property of the ceramic are improved, and the reduction of the sintering temperature is beneficial to reducing the energy consumption and the production cost of the foam ceramic filter.
The light-burned magnesia particles with high sintering activity, the highly dispersed nano titanium dioxide and alumina short fibers are surrounded by continuous nano alumina sol films, and the in-situ reaction is carried out in the sintering process to generate the magnesia-alumina spinel MA and the magnesia-titanium spinel M2Phase T, MA and M2T is completely mutually soluble at more than 1350 ℃, the crystal grains of the cristobalite MgO are directly welded together in the sintering process, and the secondary spinel (intercrystalline spinel) M is precipitated by desolventizing during cooling2T and MA can compensate the stress on each phase critical surface, and relax the stress generated when the material is sintered and cooled.
Preferably, the solid content of the nano-alumina sol is 20-25%, and the PH value of the nano-alumina sol is more than or equal to 4.
The preparation method of the ceramic slurry comprises the following steps: adding light-burned magnesium oxide powder into a ball milling tank according to the proportion, mixing nano aluminum sol, nano titanium dioxide, alumina short fibers, a rheological agent and absolute ethyl alcohol, carrying out ultrasonic treatment for 30-60 min, fully dispersing the alumina short fibers, adding the dispersed alumina short fibers into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 2-4 h at the rotating speed of 60-120 rpm to uniformly mix the mixture to obtain the magnesium oxide powder.
(2) Immersing the polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove the redundant immersed slurry to prepare a biscuit, and then removing the ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit.
When the polyurethane foam plastic template dipped with the slurry is extruded by a roller press, the alumina short fibers in the prepared biscuit are arranged along the rolling direction to a certain degree, and the form of the alumina short fibers with certain directionality is inherited by the formed magnesia-alumina spinel, so that the spinel phase wrapping the periclase MgO grains ensures that the sintered ceramic grains have a tightly combined tissue, and the pinning effect of the spinel phase inhibits the growth of the magnesia grains, thereby refining the tissue of the foam ceramic and improving the density of the ceramic grains.
The specification of the polyurethane foam plastic template is 10 PPI-20 PPI (Pores per inch, average number of Pores per inch of length); before use, the material is soaked in 15-20% NaOH aqueous solution at 40-50 ℃ for etching the surface for 40-60 min, then washed by clean water and naturally dried, and then soaked in 2-4% dodecyl benzene sulfonic acid wetting agent aqueous solution and then taken out and dried to obtain the finished product. The surface of the ceramic slurry is roughened by NaOH etching, and then the ceramic slurry is treated by the aqueous solution of the dodecyl benzene sulfonate wetting agent, so that the ceramic slurry is easily and uniformly coated and hung on a polyurethane foam template.
(3) And (3) putting the dried biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesia-based foamed ceramic filter.
The sintering process is that organic matters (polyurethane foam, rheological agent and the like) in a biscuit of the foam ceramic filter are decomposed, gasified and discharged by heating to 550 ℃ at a temperature rise speed of 30 ℃/h, and then heated to 1100 ℃ at the temperature rise speed of 200 ℃/h, and in a low-temperature sintering stage, the biscuit collapse or deformation damage caused by the excessively high decomposition speed of the polyurethane foam and the rheological agent can be prevented due to a low temperature rise speed. And finally heating to 1350-1550 ℃ at a heating rate of 50 ℃/h and preserving heat for 2-3 h at the temperature. In the high-temperature sintering stage, after the sintering temperature exceeds 1100 ℃, the temperature in the sintered body can be ensured to be consistent by the lower temperature rise speed, the uniform generation speed of the generated spinel is avoided, and the deformation and the cracking of the sintered body caused by the phase change stress generated too fast are avoided.
The preparation method of the alumina short fiber reinforced magnesia-based foamed ceramic filter provided by the invention has the advantages of simple process, low cost, high efficiency, suitability for large-scale production and the like, the prepared alumina short fiber reinforced magnesia-based foamed ceramic filter does not contain any component for reducing the chemical stability of the alumina short fiber reinforced magnesia-based foamed ceramic filter, the added nano alumina sol not only forms light-burned magnesia particles, nano titanium dioxide and alumina short fibers to be continuously bonded together and can play a role of a binder, but also reacts with highly dispersed nano titanium dioxide powder in situ to generate a spinel phase with chemical stability to magnesium and an alloy melt of the magnesium, the magnesia particles are fused together, and meanwhile, the form of the alumina short fiber with certain directionality is inherited by the formed magnesia-alumina spinel phase, so the foamed ceramic filter has good strength, Chemical stability and thermal shock resistance, is particularly suitable for filtering and purifying impurities in magnesium and alloy melts thereof, and can also be used for filtering and purifying aluminum and alloy melts thereof. Compared with the prior art, the invention has the technical effects that:
firstly, the alumina short fiber reinforced magnesia-based foamed ceramic filter has excellent chemical stability. The added nano titanium oxide in the scheme of the invention can promote the sintering of MgO and react with MgO to generate magnesium titanium spinel (Mg) with higher chemical stability2TiO4，M2T) phase. Although the raw material alumina sol component contains gamma-Al which reacts with the magnesium melt2O3And alumina staple fibers, but the nano-alumina sol can form gamma-Al on the surfaces of the lightly calcined magnesia particles, the nano-titanium dioxide and the alumina staple fibers2O3Coating film of Al during sintering2O3Reacting with high-activity light-burned MgO to generate high-melting point with face-centered cubic latticeMgAl2O4Phase (melting point 2135 ℃ C.), MA and M2T is completely mutually soluble at more than 1350 ℃, and the XRD analysis result shows that the foam ceramic filter prepared by the invention only contains periclase MgO and MA-M2A T-spinel solid solution phase.
In the magnesium melt and MgO-Al added with alumina2O3In addition to the reaction formula (1), the following reaction may be present in the reaction system for sintering ceramics:
3Mg(l)+4Al2O3(s)＝3MgAl2O4(s)+2Al(l)(5)
magnesium aluminate spinel MgAl generated by alumina and magnesia2O4The reaction of (a) is:
MgO(s)+Al2O3(s)＝MgAl2O4(s)(6)
magnesium melt and magnesium aluminate spinel MgAl2O4The reactions that occur are:
3Mg(l)+MgAl2O4(s)＝2Al(l)+4MgO(s)(7)
according to the pure substance thermochemistry data handbook (edited by Sudoku of Helh Sanger Valenchen, Chengmelin et al, Beijing: scientific Press, 2003), the Gibbs free energy data of the reaction system of magnesium melt and magnesium aluminate spinel at 900-1200K and the Gibbs free energy change delta G of the reactions (1), (5), (6) and (7)1、ΔG5、ΔG6、ΔG7The calculation results of (a) are shown in table 1.
TABLE 1 Gibbs free energy change delta G calculation results of each reaction in a 900-1200K magnesium melt and magnesium aluminate spinel reaction system
Figure BDA0001621444040000081
Figure BDA0001621444040000091
Reaction formula Gibbs free energy delta of formula (5) for forming magnesium aluminate spinel by magnesium melt and aluminaG5The temperature difference is minimal, which indicates that the reaction can preferentially occur at the common melting temperature of magnesium alloy. Although the reaction formula (7) of the magnesium liquid and the magnesium aluminate spinel is thermodynamically feasible, the reaction is essentially a reaction between the magnesium liquid and alumina, which is a decomposition product of the magnesium aluminate spinel, but it is known from table 1 that the reaction of the magnesium aluminate spinel to alumina and magnesia is difficult to proceed at the melting temperature of the magnesium alloy (reverse reaction of the reaction formula (6)), and the residual alumina in the sintered ceramic and the magnesium liquid preferentially form the magnesium aluminate spinel according to the reaction formula (5); on the other hand, MgO-Al2O3In the phase diagram, the MgO side is a periclase solid solution and MA spinel solid solution eutectic phase diagram, and almost no O is generated in the process of generating MA through in-situ reaction2-Diffusion, only Mg2+And Al3+Through mutual diffusion of fixed oxygen lattices, Al with slower diffusion speed is generated3+Determined that the MA phase is mainly in Al2O3One side is grown by means of an epitaxial growth, resulting in the formation of a limited solid solution between the MA phase and MgO, while the MgO content in the MA outer layer in contact with the MgO particles is much higher than its average value, while MgO does not react with the magnesium melt, so that the magnesium aluminate spinel phase fusing together the magnesium oxide particles in the sintered ceramic structure is stable in the magnesium melt.
The alumina short fiber reinforced magnesia ceramic foam filter does not contain any component for reducing the chemical stability of the alumina short fiber reinforced magnesia ceramic foam filter, the added nano alumina sol not only bonds light-burned magnesia particles, nano titanium dioxide and alumina short fibers together through forming a continuous film, and can play a role of a binder, but also reacts with highly dispersed nano titanium dioxide powder together with magnesia powder particles in situ to generate a spinel phase with chemical stability to magnesium and an alloy melt of the magnesium, so that the damage of the existing product on the chemical stability of the foam ceramic by adding the binders such as silica sol, ethyl silicate and the like is avoided; meanwhile, the ceramic component does not contain sodium salt (for example, sodium carboxymethylcellulose is not adopted in the rheological agent), so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
Because the reaction formulas (1) and (5) are at the common smelting temperature of the magnesium alloyThe smelting temperature of the aluminum and the aluminum alloy is the same as that of the magnesium and the aluminum alloy, and reverse reactions of the reaction formulas (1) and (5) can not occur between the MgO and MA spinel phase and the aluminum alloy melt; the same as that used for magnesium and alloy melt, avoids the damage of adding bonding agents such as silica sol, ethyl silicate and the like to the chemical stability of the foamed ceramics in aluminum and alloy melt (even if the material contains 1 percent of SiO)2The melt of aluminum and its alloy will also react with SiO in the ceramic at high temperature2Generation of Al + SiO2→Al2O3Reaction of + Si); therefore, the prepared alumina short fiber reinforced magnesia ceramic foam filter can also be used for smelting and purifying aluminum and aluminum alloy.
Secondly, the alumina short fiber reinforced magnesia-based foamed ceramic filter has good low-temperature sintering performance. The light-burned magnesia fine powder adopted in the technical scheme of the invention has high sintering activity, nano titanium dioxide is added into the ceramic component, and titanium ions are diffused into a periclase crystal interface to form Ti4+Ion replacement of Mg2+Solid solutions of ions promote direct intercrystalline bonding. Al (Al)2O3The lattice constant of the MgO is similar to that of MgO, and the MgO can be dissolved into MgO lattice in a solid solution in the sintering process to cause the MgO crystal to generate lattice distortion; al (Al)3+Has a small diffusion rate of Al2O3Very low solubility in periclase MgO (Al)2O3The solubility of the nano alumina sol in periclase MgO at 1700 ℃ is only 3 percent), the nano alumina sol can be dissolved into a high-activity light-burned MgO crystal lattice in a solid solution in the sintering process to enable the MgO crystal lattice to generate lattice distortion and activate the crystal lattice, and simultaneously, a new compound, namely magnesia-alumina spinel MgAl, is generated by reaction and sintering between the nano alumina sol and the MgO particles2O4Phase, thereby promoting sintering and particle-phase bonding. On the other hand, the nano powder has the characteristics of large specific surface area, high surface energy, high activity and the like, so the nano powder is easy to combine with other atoms, and the melting point and the sintering temperature of the nano powder are much lower than those of the micro powder. The sintering aid added in the form of nano titanium oxide and nano alumina sol can fill gaps among the raw material micro powder particles, optimize the grading and mixing uniformity of ceramic particles, and simultaneously, the nano powder is self-addedSurface and interface effects of (1), high reactivity nano gamma-Al in nano titanium oxide and alumina sol2O3The full contact with the light-burned MgO particles leads the reaction speed to be rapidly improved, the sintering temperature is reduced, the density and the mechanical property of the ceramic are improved, and the reduction of the sintering temperature is beneficial to reducing the energy consumption and the production cost of the foam ceramic filter. The test result shows that when the sintering temperature is lower than 1350 ℃, the sintering structure combination among magnesium oxide particles is insufficient, so that the strength is low, and the sintering temperature of the magnesium oxide foamed ceramic filter with good structure combination is 1350-1550 ℃.
And thirdly, the alumina short fiber reinforced magnesia-based foamed ceramic filter has good thermal shock resistance. The solid phase component in the aluminum sol is high-activity porous gamma-Al2O3With magnesium aluminate spinel (MgAl)2O4) The crystal structure is the same. The mechanical property of the ceramic matrix composite material can be improved by adopting the fibers and the whiskers as the reinforcement. In the scheme provided by the invention, light calcined magnesia particles with high sintering activity, highly dispersed nano titanium dioxide and alumina short fibers are surrounded by a continuous nano alumina sol film and undergo in-situ reaction in the sintering process to generate magnesium aluminate spinel MA and magnesium titanium spinel M2Phase T, MA and M2T is completely mutually soluble at more than 1350 ℃, the crystal grains of the cristobalite MgO are directly welded together in the sintering process, and the secondary spinel (intercrystalline spinel) M is precipitated by desolventizing during cooling2T and MA, which can compensate the stress on each critical surface and relax the stress generated when the material is sintered and cooled; meanwhile, when the polyurethane foam plastic template dipped with the slurry is extruded by a roller press, the alumina short fibers in the prepared biscuit are arranged along the rolling direction to a certain degree, the form of the alumina short fibers with certain directionality is inherited by the formed magnesia alumina spinel, therefore, the spinel phase wrapping the periclase MgO grains ensures that the sintered ceramic grains have a tightly combined tissue, and the pinning effect of the spinel phase inhibits the growth of the magnesia grains, thereby refining the tissue of the foamed ceramic and improving the density among the ceramic grains, and the prepared alumina short fiber reinforced magnesia-based foam ceramic filter has higher mechanical property, high resistance and high strengthThermal shock and thermal shock resistance.
In addition, in the preparation method, the polyurethane foam plastic template is roughened by NaOH etching, and then is treated by the aqueous solution of the dodecylbenzene sulfonate wetting agent, so that the ceramic slurry is easily and uniformly coated on the polyurethane foam template; meanwhile, the cellulose ether and the polyvinyl butyral which are used as rheological agents are good dispersants for nano titanium dioxide and alumina short fiber powder, can prevent slurry from generating agglomeration phenomenon, can play a role of adhesive when a biscuit is prepared, and the slurry after being soaked can be firmly attached to a polyurethane foam template so that the biscuit has great strength, and can easily escape in a sintering process without polluting products, thereby ensuring the quality of the foam ceramic filter.
Drawings
FIG. 1 is a flow chart of a process for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
An alumina short fiber reinforced magnesia-based foamed ceramic filter is prepared by coating light-burned magnesia-based ceramic slurry containing alumina short fibers and nano titanium dioxide on a polyurethane foam carrier, drying and sintering. The specific preparation process is shown in figure 1.
Example 1
According to the proportion that the nano titanium oxide accounts for 1 percent of the mass of the ceramic powder and the commercial alumina short fiber (the diameter is about 10-20 mu m, the length is 50-100 mu m) accounts for 1 percent of the mass of the ceramic powder, the nano titanium oxide with the grain diameter of 30nm, the commercial alumina short fiber and the grain diameter of 250 meshes (the medium diameter d is measured5058 μm) of light-burned magnesia powder to prepare ceramic powder; mixing polyvinyl butyral and hydroxypropyl methyl cellulose in the mass ratio of 1 to prepare the rheological agent.
According to the mass percentage, 15 percent of nano aluminum sol with the solid content of 20 percent (commercial nano aluminum sol with the pH value close to neutral is selected, the same is applied below), 0.8 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano titanium dioxide, alumina short fibers, a rheological agent and a proper amount of absolute ethyl alcohol (the addition amount of the inorganic ceramic slurry is determined according to the solid content of the ceramic slurry, the same applies below) and carrying out ultrasonic treatment for 30min to ensure that nano titanium dioxide and alumina short fiber powder are fully dispersed and then added into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 4h at the rotating speed of 60rpm to uniformly mix the mixture to obtain the ceramic slurry with the solid content of 60%.
Selecting a 10PPI polyurethane foam plastic template, soaking the template in a 15% NaOH aqueous solution at 40 ℃ for 60min, washing the template with clear water, naturally drying the template, then soaking the template in a 2% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove redundant immersion slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at 40 ℃ to dry the biscuit, and the ethanol solvent can be recovered by a recovery device.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1550 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2.5h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foam ceramic filter.
Example 2
According to the proportion that the nano titanium oxide accounts for 2 percent of the mass of the ceramic powder and the alumina short fiber accounts for 3 percent of the mass of the ceramic powder, the nano titanium oxide with the grain diameter of 60nm, the commercialized alumina short fiber and the grain diameter of 500 meshes (medium diameter d) are weighed5025 μm) of light-burned magnesia powder to prepare ceramic powder; mixing polyvinyl butyral and hydroxypropyl methyl cellulose in the mass ratio of 1 to prepare the rheological agent.
According to the mass percentage, 20 percent of nano aluminum sol with the solid content of 25 percent, 1.5 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano titanium dioxide, alumina short fibers, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 60min to ensure that alumina short fiber powder is fully dispersed and then added into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and performing ball milling for 2h at the rotating speed of 120rpm to uniformly mix the mixture to obtain ceramic slurry with the solid content of 65%.
Selecting a 20PPI polyurethane foam plastic template, soaking the template in a 20% NaOH aqueous solution at 50 ℃ for 40min, washing the template with clear water, naturally drying the template, then soaking the template in a 4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at 50 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1350 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 3h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foam ceramic filter.
Example 3
According to the proportion that the nano titanium oxide accounts for 1.5 percent of the mass of the ceramic powder and the alumina short fiber accounts for 2 percent of the mass of the ceramic powder, the nano titanium oxide with the grain diameter of 50nm, the commercial alumina short fiber and the grain diameter of 325 meshes (medium diameter d) are weighed5045 μm) of light-burned magnesia powder to prepare ceramic powder; mixing the polyvinyl butyral and the hydroxyethyl cellulose according to the mass ratio of 1:1 to prepare the rheological agent.
According to the mass percentage, 25 percent of nano-alumina sol with the solid content of 22 percent, 1.0 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano titanium dioxide, alumina short fibers, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 45min to ensure that alumina short fiber powder is fully dispersed and then added into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and performing ball milling at a rotating speed of 90rpm for 3h to uniformly mix the mixture to obtain ceramic slurry with the solid content of 70%.
Selecting a 15PPI polyurethane foam plastic template, soaking the template in a 45 ℃ 18% NaOH aqueous solution, etching the surface for 50min, washing the template with clear water, naturally drying the template, then soaking the template in a 3% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at the temperature of 45 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foamed ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1400 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foamed ceramic filter.
Example 4
According to the proportion that the nano titanium oxide accounts for 2 percent of the mass of the ceramic powder and the alumina short fiber accounts for 2 percent of the mass of the ceramic powder, the nano titanium oxide with the grain diameter of 60nm, the commercialized alumina short fiber and the grain diameter of 300 meshes (medium diameter d) are weighed5048 μm) of light-burned magnesia powder to prepare ceramic powder; according to the weight ratio of polyvinyl butyral: hydroxypropyl methylcellulose: the hydroxyethyl cellulose is mixed according to the mass ratio of 5:2:3 to prepare the rheological agent.
According to the mass percentage, 20 percent of nano aluminum sol with the solid content of 20 percent, 1.0 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano titanium dioxide, alumina short fibers, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 45min to ensure that alumina short fiber powder is fully dispersed and then added into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and performing ball milling for 3h at the rotating speed of 100rpm to uniformly mix the mixture to obtain ceramic slurry with the solid content of 65%.
Selecting a 15PPI polyurethane foam plastic template, soaking the template in a 15% NaOH aqueous solution at 45 ℃ for 50min, washing the template with clear water, naturally drying the template, then soaking the template in a 4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at the temperature of 45 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1450 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2h, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based foam ceramic filter.
In the embodiment, experiments show that the prepared foamed ceramic has excellent thermal shock resistance and strength, and does not crack after being cooled in air at 900 ℃ for 50 times; 75mm is 25mm, and the normal temperature strength of the foamed ceramic filter of 10PPI is not lower than 3 MPa.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.

Claims (9)

1. An alumina short fiber reinforced magnesia-based ceramic foam filter is characterized in that: coating light-burned magnesia-based ceramic slurry containing alumina short fibers and nano titanium dioxide on a polyurethane foam carrier, drying and sintering to obtain the light-burned magnesia-based ceramic slurry containing the alumina short fibers and the nano titanium dioxide, wherein the light-burned magnesia-based ceramic slurry containing the alumina short fibers and the nano titanium dioxide comprises 15 to 25 percent of nano aluminum sol, 0.8 to 1.5 percent of rheological agent, and the balance of magnesia ceramic powder containing the alumina short fibers and the nano titanium dioxide; the rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose or a mixture thereof; the ceramic powder is a mixture of light-burned magnesia, nano titanium dioxide and alumina short fibers.
2. A preparation method of an alumina short fiber reinforced magnesia-based foamed ceramic filter is characterized by comprising the following steps:
(1) preparing 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent and the balance of magnesia ceramic powder containing alumina short fiber and nano titanium dioxide according to the mass percentage, adding absolute ethyl alcohol, ball-milling and mixing uniformly to prepare ceramic slurry with the solid content of 60-70%; the rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose or a mixture thereof; the ceramic powder is a mixture of light-burned magnesia, nano titanium dioxide and alumina short fibers;
(2) immersing a polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove redundant immersion slurry to prepare a biscuit, and then removing an ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit;
(3) and (3) putting the dried biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesia-based foamed ceramic filter.
3. The method for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the solid content of the nano-alumina sol is 20-25%, and the PH value is more than or equal to 4.
4. The method for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the nano titanium oxide accounts for 1-2% of the mass of the ceramic powder, and the alumina short fiber accounts for 1-3% of the mass of the ceramic powder.
5. The method for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the grain diameter of the light-burned magnesium oxide powder is 250-500 meshes.
6. The method for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the particle size of the nano titanium oxide is 30-60 nm, and the alumina short fiber is commercial polycrystalline Al with small length-diameter ratio2O3Short fibers having a diameter of 10 to 20 μm and a length of 50 to 100 μm.
7. The method for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein the ceramic slurry is prepared by the following steps: adding light-burned magnesium oxide powder into a ball milling tank according to the proportion, mixing nano aluminum sol, nano titanium dioxide, alumina short fibers, a rheological agent and absolute ethyl alcohol, carrying out ultrasonic treatment for 30-60 min, fully dispersing the alumina short fibers, adding the dispersed alumina short fibers into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 2-4 h at the rotating speed of 60-120 rpm to uniformly mix the mixture to obtain the magnesium oxide powder.
8. The method for preparing an alumina short fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the specification of the polyurethane foam plastic template is 10 PPI-20 PPI; before use, the material is soaked in 15-20% NaOH aqueous solution at 40-50 ℃ for etching the surface for 40-60 min, then washed by clean water and naturally dried, and then soaked in 2-4% dodecyl benzene sulfonic acid wetting agent aqueous solution and then taken out and dried to obtain the finished product.
9. The method for preparing an alumina staple fiber reinforced magnesia-based ceramic foam filter according to claim 2, wherein in the step (3), the sintering process is: heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foamed ceramic filter and discharge the organic matters, then heating to 1100 ℃ at a heating rate of 200 ℃/h, finally heating to 1350-1550 ℃ at a heating rate of 50 ℃/h and preserving heat at the temperature for 2-3 h.
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CN101259347A (en) * 2007-12-14 2008-09-10 济南圣泉集团股份有限公司 Zirconium oxide foamed ceramic filter
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