Aluminium oxide foam ceramic filter
Technical field
The present invention relates to the purification of motlten metal, be specifically related to ceramic foam filter.More particularly, the present invention relates to contain the ceramic foam filter of aluminium oxide as ceramic composition, the filter of the present invention preparation is used for the filtration, purification of metal baths such as aluminium and aluminium alloy, copper to be handled.
Background technology
In the melting and casting process of various metal liquid alloys, because the casting wasted product rate that casting flaws such as the non-metallic inclusion and the pore that contracts cause is generally up to 50~60% of waste product sum.Inclusion defect not only seriously reduces the mechanical performance and the casting character of foundry goods, and also machining and the outward appearance to foundry goods produces adverse effect.Purify liquid casting alloy, reduce or eliminate wherein each kind of non-metallic inclusion and exhaust, obtain the important technique measure of high quality casting beyond doubt.
Filtering technique is applied to the Foundry Production history of existing decades, but only is at first with coming the filtering bulk inclusion in the simple filtering device insertion running gate systems such as wire netting, steel plate with holes, porous loam core.From the sixties, occurred two-dimensional structure type inner filtration nets such as alumina silicate fibre matter, molybdenum filament matter, boron nitride fiber matter in Russia, American and Britain, medium country successively, and be applied aborning, obtained certain effect.But all these screen packs can only be by bulk inclusion in the mechanical grading effect filtering molten metal and the little field trash of only a few.Because the refractoriness and the intensity of alumina silicate fibre screen pack are all lower, can only be used for the filtration of non-ferrous alloy, cast iron and small casting steel, are difficult to bear for a long time the impact of high-temperature metal fluid; Though the boron nitride fiber matter screen pack of the molybdenum filament matter of Britain's development and U.S.'s development can be used to filter high temperature alloys such as cast steel, because of it costs an arm and a leg, its application is restricted.Be used for straight hole core pattern ceramic filter and refractory particle filter in addition that casting alloy filters, but their porosity is all less, and the former filter efficiency is still lower, the filter effect instability, the latter makes its leakiness grain owing to do not have cementation between particle, uses also inconvenient.Though the slug type porous ceramic filter that the early seventies U.S. succeeds in developing has at first solved refractory particle filter leakiness grain and inconvenient problem with use, but the honeycomb straight-bore ceramic filter of succeeding in developing at first with the early eighties U.S. is the same, porosity is still less, be generally less than 50%, make that the mistake flow rate of molten metal is lower.
Ceramic foam filter is the third generation filtering product after refractory fibre screen pack, honeycomb straight-bore ceramic filter, ceramic foam filter the earliest is the aluminium alloy ceramic foam filter that U.S. Consolidated Aluminum company in 1978 succeeds in developing, and its commodity are called Selee/A1.Developed the ceramic foam filter Selee/Fe that is used to filter ferrous metal in 1984 again.Domestic casting alloy starts from early eighties with the development of ceramic foam filter, and the ceramic foam filter that Harbin University of Science and Technology succeeded in developing the earliest in nineteen eighty-two can only be used for the filtration of aluminium alloy.
Ceramic foam filter is that the employing polyurethane foam plastics is a carrier, it is immersed in the slurry of being made by ceramic powders, adhesive, sintering aid, suspending agent etc., squeeze out unnecessary slurry then, making ceramic size evenly be coated on carrier framework becomes base substrate, forms the base substrate oven dry and through high-temperature roasting again.Ceramic foam filter has the pore structure similar to foamed plastics, and through-hole rate reaches 85~90%.
Because the particular filter purification mechanism that unique 3 D stereo network structure is had (machinery interception; Exhaust rectification scum silica frost; Trickle slag inclusion deep layer absorption), the clean-up effect of ceramic foam filter is that refractory fibre screen pack and honeycomb straight-bore ceramic filter are incomparable, its feature is that rigid-skeleton is even, quality of molten metal decentralization after the filtration is little, filtering accuracy is good etc., most of little small solid suspension clamp foreign material to several microns in not only can the elimination molten metal, slag and gas that can also the elimination liquid state.Use ceramic foam filter filtering molten metal liquid, can also make the flow velocity of molten metal become mitigation in order, improve the microscopic structure and the mechanical property of foundry goods greatly, improve the quality and the compactness of foundry goods, the wearing and tearing of cutter when reducing the foundry goods machining.Facts have proved that the filter efficiency of ceramic foam filter is up to 75~97%, therefore, ceramic foam filter has been widely used in melting during body purifies of aluminium, copper, iron and steel, is subjected to increasing metallurgy, foundry enterprise favor.
Closely during the last ten years, the domestic and international characteristics of root a tree name different-alloy, the ceramic foam filter that has developed multiple unlike material comes filtering molten metal.Particularly, in United States Patent (USP) 3893917,3947363,3961081,4014056,4024212,4075303,4265659,4342644 and 4343104, all narrated the ceramic foam filter that is suitable for the aluminum filtration alloy for the filtration of aluminium and aluminium alloy.
Aluminium alloy absorbs gas easily and sneaks into nonmetal impurities in the process of melting and formation foundry goods, thereby reduces the serviceability and the processing characteristics of foundry goods.Using ceramic foam filter is the most effectual way of removing the out-phase impurity in the aluminum melt, studies show that, ceramic foam filter is used for the filtration of aluminium alloy melt, can also reduce the content of hydrogen in the aluminum melt in slagging-off.
Because the temperature of molten metals such as aluminium and aluminium alloy, copper is relatively low, the serviceability temperature of aluminium oxide foam ceramic filter is also lower, satisfying under the prerequisite of instructions for use, it is most economical rational adopting low temperature sintering technology to make aluminium oxide foam ceramic filter.Along with the requirement to aluminum product quality is more and more higher, also more and more higher to the requirement of aluminium oxide foam ceramic filter.
Summary of the invention
The purpose of this invention is to provide a kind of aluminium oxide foam ceramic filter that is suitable for aluminium, aluminium alloy and copper filtration, purification, this filter good filtration effect, production cost is low.
A kind of preparation method of above-mentioned aluminium oxide foam ceramic filter being provided, making the filter that makes have good sintering and comprehensive physical property, reduce the production cost of filter simultaneously, is another goal of the invention of the present invention.
Aluminium oxide foam ceramic filter of the present invention is the raw material with following percetage by weight:
Aluminium oxide 60~70%
Silica 1 5~25%
Talcum 5~10%
Kaolin 1~5%
Form ceramic powders, again according to following percetage by weight:
Carboxymethyl cellulose 0.4~0.8%
Polyvinyl alcohol 0.5~1.5%
Ludox 10~15%
Water 15~25%
The ceramic powders surplus
In ceramic powders, add auxiliary material, the preparation slip,
With the flexible polyurethane foams is carrier, floods above-mentioned slip, is crushed to blank, and dry back sintering obtains aluminium oxide foam ceramic filter.
Aluminium oxide ceramics claims the corundum porcelain again, is that purposes is the most extensive, and raw material is the abundantest, the cheapest a kind of high-temperature structural ceramics of price.The aluminium oxide ceramics of industrial indication generally is meant with α-Al
2O
3Ceramic material for principal crystalline phase.The fusing point of aluminium oxide is 2045 ℃, and pure alumina just begins creep and sintering about 1750 ℃ greatly.Therefore, it is uneconomical and irrational using alumina material to carry out sintering merely, needs to add certain auxiliary material and sintering agent, to reduce the sintering temperature of aluminium oxide.The present invention is to be principal crystalline phase with the aluminium oxide, is auxiliary material with high alumina refractories kaolin, and adds an amount of sintering agent talcum and form the ceramic powders sintering and prepare aluminium oxide foam ceramic filter.
According to the domestic literature report, aluminium oxide foam ceramic filter adopts aluminium dihydrogen phosphate as binding agent mostly.Use the product blank of this binding agent that very big moisture absorption tendency is arranged, be difficult for dry; The biphosphate al binder can produce pernicious gas and discharge in sintering process, environment is polluted; Simultaneously, because the existence of phosphorus in the product, also can cause to a certain degree influence to casting quality.
In view of above reason, the present invention adopts aqueous binders carboxymethyl cellulose, polyvinyl alcohol and the Ludox binding agent as aluminium oxide foam ceramic filter of the present invention through contrast test repeatedly.
Adopt the advantage of this binding agent to show the following aspects: the first, the whole voloxidation of binding agent in the sintering process, no pernicious gas is discharged, and helps environmental protection; Noresidue binding agent raw material helps guaranteeing product quality in the ceramic filter product, can not influence casting quality in the use.The second, adhesive preparation and product are stained with no pernicious gas volatilization in slurry, the drying course, help employee's operation.Three, ceramic filter blank (semi-finished product) rate of drying is fast, nonhygroscopic, and slurry is attached to and is easy in all kinds of vessel clean, and is convenient to recycle, and helps industrial scale production and prevents the waste of raw material.
The concrete preparation method of aluminium oxide foam ceramic filter of the present invention may further comprise the steps:
A) mix various raw materials according to following percetage by weight and obtain ceramic powders:
Aluminium oxide 60~70%
Silica 1 5~25%
Talcum 5~10%
Kaolin 1~5%
Based on above-mentioned ceramic powders, again according to following percetage by weight:
Carboxymethyl cellulose 0.4~0.8%
Polyvinyl alcohol 0.5~1.5%
Ludox 10~15%
Water 15~25%
The ceramic powders surplus
In ceramic powders, add auxiliary material, mix, make slurry;
B) be carrier with the flexible polyurethane foams, flood above-mentioned slurry, and be crushed to blank;
C) blank is put into drying box, 100~110 ℃ of dry sclerosis;
D) the blank sintering furnace of packing in dry back is warming up to 1350~1400 ℃ of high temperature sinterings, obtains aluminium oxide foam ceramic filter.
According to the inventive method, need provide the carrier of a kind of cancellated organic polymer foamed material as ceramic slurry.This carrier is preferably made by hydrophobic flexible foams, has many interconnected interstices of being surrounded by the nethike embrane of described flexible foams, and this foamed material must promptly burn before the firing temperature that is lower than used ceramic material or vaporize.Any flammable organic plastic foam material that has elasticity and can recover original form all can use, and the present invention adopts flexible polyurethane foams as carrier, and the flexible polyurethane foams of selecting for use has the aperture of 10PPI.
Among the present invention, be that described flexible polyurethane foams is soaked 20~30min earlier in pH value is 50~60 ℃ of aqueous slkalis of 7.5~8.5, remove aqueous slkali with the clear water rinsing again, after the air dry as the carrier use of ceramic slurry.
The present invention is that the specific embodiment of ceramic foam filter is with the blank high temperature sintering: blank is packed in the sintering furnace, programming rate with 90 ℃/h is warming up to 500 ℃ of low-temp plastic-removings at a slow speed by room temperature, after treating foamed plastics burning volatilization, programming rate with 150 ℃/h is rapidly heated to 1000 ℃ again, be warming up to 1350~1400 ℃ sintering temperature with the programming rate of 120 ℃/h, and under this temperature, be incubated 1~2h.
The aluminium oxide foam ceramic filter of the present invention's preparation is the space network structure, and wherein the cavity interconnects, and voidage can reach 80~95%.
Ceramic foam filter of the present invention has good high-temperature stability in molten aluminium alloy, do not pollute alloy, oxide inclusion in the molten metal and flux are mingled with good filtration and adsorption capacity, filtration, purification is effective, thermal capacitance is little, can preheating during use, the convection cell resistance is little, and filtration yield is big.
The aluminium oxide foam ceramic filter of the present invention preparation is through the filtration, purification test of aluminium and aluminium alloy, copper melt, and is every functional.
The specific embodiment
Embodiment 1
According to 68.5: 23: 6.5: 2 weight ratio, with the fully mixed ceramic powders of making of aluminium oxide, silica, talcum and kaolin.
With ceramic powders, carboxymethyl cellulose, polyvinyl alcohol, Ludox and water according to 65: 0.5: 1: 12: 25 weight ratio is mixed, and adds in the mixer to stir 2~3h, makes to stir, and makes ceramic slurry.
Select the flexible polyurethane foams of 10PPI for use, be processed into 50mm * 50mm * 22mm size, be placed on the pH value and be in 60 ℃ of aqueous slkalis of 7.5 and soak 20min, film with the plastic eyelet intraocular that defoams, remove aqueous slkali with the clear water rinsing then, moisture is removed in air dry afterwards, as the carrier of ceramic slurry.
Adopt roll-in to be stained with sizing process, on the foamed plastics carrier, add ceramic slurry, again the carrier input is stained with to push in the pulp grinder and is stained with slurry, extrude superfluous slip, make the ceramic foam filter blank.
The ceramic foam filter blank is put into drying box, and temperature is controlled in 100~105 ℃ of scopes, and dry 0.5~1h makes it sclerosis.
Dried blank is packed in the sintering furnace, programming rate with 90 ℃/h is warming up to 500 ℃ of low-temp plastic-removings at a slow speed by room temperature, after treating foamed plastics burning volatilization, programming rate with 150 ℃/h is rapidly heated to 1000 ℃ again, programming rate with 120 ℃/h is warming up to 1400 ℃, and under this temperature, be incubated 1h, and naturally cool to room temperature and come out of the stove, can obtain aluminium oxide foam ceramic filter.
Embodiment 2:
According to 70: 20: 5: 5 weight ratio, with the fully mixed ceramic powders of making of aluminium oxide, silica, talcum and kaolin.
With ceramic powders, carboxymethyl cellulose, polyvinyl alcohol, Ludox and water according to 72: 0.8: 0.6: 13: 18 weight ratio is mixed, and adds in the mixer to stir 2~3h, makes to stir, and makes ceramic slurry.
Select the flexible polyurethane foams of 10PPI for use, be processed into 50mm * 50mm * 22mm size, be placed on the pH value and be in 50 ℃ of aqueous slkalis of 8.5 and soak 30min, film with the plastic eyelet intraocular that defoams, remove aqueous slkali with the clear water rinsing then, moisture is removed in air dry afterwards, as the carrier of ceramic slurry.
Adopt roll-in to be stained with sizing process, on the foamed plastics carrier, add ceramic slurry, again the carrier input is stained with to push in the pulp grinder and is stained with slurry, extrude superfluous slip, make the ceramic foam filter blank.
The ceramic foam filter blank is put into drying box, and temperature is controlled in 100~105 ℃ of scopes, and dry 0.5~1h makes it sclerosis.
Dried blank is packed in the sintering furnace, programming rate with 90 ℃/h is warming up to 500 ℃ of low-temp plastic-removings at a slow speed by room temperature, after treating foamed plastics burning volatilization, programming rate with 150 ℃/h is rapidly heated to 1000 ℃ again, programming rate with 120 ℃/h is warming up to 1370 ℃, and under this temperature, be incubated 1.5h, and naturally cool to room temperature and come out of the stove, can obtain aluminium oxide foam ceramic filter.
Embodiment 3:
According to 65: 25: 7: 3 weight ratio, with the fully mixed ceramic powders of making of aluminium oxide, silica, talcum and kaolin.
With ceramic powders, carboxymethyl cellulose, polyvinyl alcohol, Ludox and water according to 65: 0.5: 1: 12: 25 weight ratio is mixed, and adds in the mixer to stir 2~3h, makes to stir, and makes ceramic slurry.
Select the flexible polyurethane foams of 10PPI for use, be processed into 50mm * 50mm * 22mm size, be placed on the pH value and be in 60 ℃ of aqueous slkalis of 8.5 and soak 30min, film with the plastic eyelet intraocular that defoams, remove aqueous slkali with the clear water rinsing then, moisture is removed in air dry afterwards, as the carrier of ceramic slurry.
Adopt roll-in to be stained with sizing process, on the foamed plastics carrier, add ceramic slurry, again the carrier input is stained with to push in the pulp grinder and is stained with slurry, extrude superfluous slip, make the ceramic foam filter blank.
The ceramic foam filter blank is put into drying box, and temperature is controlled in 100~105 ℃ of scopes, and dry 0.5~1h makes it sclerosis.
Dried blank is packed in the sintering furnace, programming rate with 90 ℃/h is warming up to 500 ℃ of low-temp plastic-removings at a slow speed by room temperature, after treating foamed plastics burning volatilization, programming rate with 150 ℃/h is rapidly heated to 1000 ℃ again, programming rate with 120 ℃/h is warming up to 1350 ℃, and under this temperature, be incubated 2h, and naturally cool to room temperature and come out of the stove, can obtain aluminium oxide foam ceramic filter.