CN1680214A - Solid-phase reacting synthesis of composite ceramic powder non-toxic gel - Google Patents
Solid-phase reacting synthesis of composite ceramic powder non-toxic gel Download PDFInfo
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- CN1680214A CN1680214A CN 200410030878 CN200410030878A CN1680214A CN 1680214 A CN1680214 A CN 1680214A CN 200410030878 CN200410030878 CN 200410030878 CN 200410030878 A CN200410030878 A CN 200410030878A CN 1680214 A CN1680214 A CN 1680214A
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- 239000000843 powder Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 5
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- 239000007790 solid phase Substances 0.000 title abstract 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 21
- 239000000661 sodium alginate Substances 0.000 claims abstract description 21
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 24
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- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- UHWJJLGTKIWIJO-UHFFFAOYSA-L calcium iodate Chemical compound [Ca+2].[O-]I(=O)=O.[O-]I(=O)=O UHWJJLGTKIWIJO-UHFFFAOYSA-L 0.000 claims description 8
- 235000019390 calcium iodate Nutrition 0.000 claims description 8
- 238000003746 solid phase reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010671 solid-state reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004151 Calcium iodate Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 31
- 238000005516 engineering process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001879 gelation Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000009413 insulation Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
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- 239000004743 Polypropylene Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- -1 polypropylenes Polymers 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 210000003811 finger Anatomy 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
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- 239000003999 initiator Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 210000003813 thumb Anatomy 0.000 description 3
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
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- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
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- 230000007135 neurotoxicity Effects 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Abstract
A non-toxic gel solid phase reacting synthesis of composite ceramic powder is carried out by proportioning, preparing sodium alginate solution, mixing, ball milling, adding catalyst, gelating, drying and calcining. Its advantages include low cost, simple operation, no pollution and higher powder quality.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to the improvement of multicomponent ceramic composite powder solid state reaction synthetic technology.
Background technology
The characteristic of ceramic powder has material impact to the preparation technology and the microtexture of special ceramic material, and the performance to ceramic component produces considerable influence then.Therefore, research prepares the importance that high performance ceramic powder is the stupalith development always with advanced processing method.At present traditional ceramic powder preparation method has solid phase method, liquid phase method, vapor phase process, mechanical process and solvent evaporated method etc., adopts these traditional methods to prepare ceramic powder and has usually that the purity of powder composition inequality, synthesis temperature height, complex procedures, equipment requirements height and powder is not high, granularity is difficult to reach problems such as requirement.The A.Douy of France in 1989 and P.Odier have proposed a kind of way (Mat.Res.Bull. with polyacrylamide liquid phase gel method synthesize ceramic oxide powder, Vol.24, pp.1119-1126,1989, Printed in the USA, Pergamon Press plc.), but this method can only adopt water-soluble salt as raw material, cost is higher, and certain environmental pollution is arranged, and makes its range of application be subjected to certain limitation.Old afterwards big bright method---the gel solid reaction process (China Patent No.: 99100590.2) that waits the people to propose a kind of new synthesize ceramic composite granule.This method adopts water-soluble organic monomer (third rare acid amides) and linking agent (N, the N-methylene-bisacrylamide) is added to mix again in the water slip that contains the required raw material of preparation ceramic powder and makes monomer and linking agent gel at certain condition, the raw material and the water solvent that mix are strapped in the high molecular three-dimensional network dehydration then, dry, calcining synthesizing ceramic powder.There is following shortcoming in this method: at first, gel mode in its technology is heating gel or catalyzer gel, if adopt the mode gel of heating, then need slurry is heated to 60-90 ℃ high temperature, cause process complications, the production cycle prolongs, and has increased energy consumption and equipment cost, and heating may cause that some raw material has just decomposed before gel, the quality of the final powder that obtains of influence.For catalyzer gel mode, find in the research if with in the disposable adding slip after initiator and the catalyst mix, then initiator can be followed blended catalyst reaction with it, makes initiator can't produce enough free radical trigger monomer polymerizations, thereby can't realize the gelation of slip.Both must be added respectively in the slip in two steps like this, because catalyzer is bigger to the influence of gel speed, aforesaid operations makes complex technical process and gel speed restive, and slip is prone to caking phenomenon.On the other hand, the price of the catalyzer Tetramethyl Ethylene Diamine that adopts in the above-mentioned technology is higher, can improve production cost undoubtedly in scale operation.Tetramethyl Ethylene Diamine has strong impulse smell and inflammable simultaneously, belongs to hazardous substance, therefore production environment is had certain pollution and harm.In addition, prepare in the technology of ceramic powder in the gel solid state reaction, because organic content very little, only contain the organic monomer that is no more than raw material weight 10wt%, the space that produces behind the binder removal is limited, can not be effectively that raw material powder is separated, and therefore calcining back powder has often formed firm block, be difficult to fragmentation, be difficult to obtain the loose powder of desirable particle size.Given this, people such as Xu Rongjiu has proposed a kind of method---liquid gel method (China Patent No.: 99100590.2) of new synthesize ceramic composite granule.This method also is with organic monomer (third rare acid amides) and linking agent (N, the N-methylene-bisacrylamide) is added to and mixes in the aqueous solution that contains the required raw material of preparation ceramic powder or the water slip that (these raw materials both can be water miscible, also can be non-water-soluble), make monomer and linking agent gel by the redox initiation mode, the raw material and the water solvent that mix are strapped in the high molecular three-dimensional network dehydration then, dry, calcining synthesizing ceramic powder.
Though above-mentioned patent is being advanced-is being gone on foot than conventional solid-state method aspect the preparation composite ceramic material, but all ignored a problem: nearly all organic monomer is all toxic, especially the acrylamide of all using in the above-mentioned relevant patent has neurotoxicity, it can directly enter blood of human body, participate in blood circulation, life-time service can destroy the nervous function of human body, and human body is caused fatal harm.This is that national environmental protection policy institute is unallowed, does not also meet the industry policy of country.
Summary of the invention
The objective of the invention is: propose a kind of multicomponent ceramic composite powder synthetic novel method-nontoxic gel synthesis by solid state reaction, can overcome that washing, filter operation that multicomponent that conventional solid-state method exists disperses inhomogeneous component segregation problem of bringing and conventional liquid phase method to exist are loaded down with trivial details, cost is high and can produce shortcoming such as etchant gas, overcome the toxicity problem that traditional high-molecular gel method exists again.Make the water slip of raw material at room temperature to carry out in safer, simple and direct and cheap mode, and after calcining the ceramic powder sufficient reacting of gained, and loose, evenly.
Technical scheme of the present invention is: the nontoxic gel solid state reaction of a kind of composite ceramic powder synthetic method is characterized in that the operation steps of this method is as follows:
(1) batching is according to the predetermined formulation preparation ceramic raw material of the composite ceramic powder that will prepare;
(2) compound concentration is the sodium alginate aqueous solution of 1～3wt%;
(3) mix, with sodium alginate aqueous solution and ceramic raw material and dispersant, dispersion agent is any material in the following material or the mixture of several materials: polyacrylic acid, poly-methyl polyacrylic acid ammonia, vinylformic acid-CALCIUM ACRYLATE copolymer, citric acid ammonia, Tetramethylammonium hydroxide, and the consumption of dispersion agent accounts for 0.5～3% of ceramic powder weight; Wherein the solid volume fraction of ceramic raw material is: 20vol%～60vol%.
(4) ball milling is put into the cylinder mill with compound or planetary mills is carried out the ball milling mixing, and the ball milling time is 5～50 hours;
(5) add catalyzer, add catalyzer in the ceramic slurry behind ball milling and stir, catalyzer be following material one of them: calcium iodate, secondary calcium phosphate, lime carbonate+hexanodioic acid, the add-on of catalyzer are 0.5～2% of ceramic powder weight;
(6) gel is heated to 40～100 ℃ with ceramic slurry, and being incubated after 10～20 minutes is solidifiable, obtains the gel base substrate;
(7) drying, with gel base substrate morsel, natural air drying or put into baking oven and carry out drying and dehydrating, oven temperature is 50～100 ℃, till parching;
(8) calcining places calcining furnace to be heated to 800 ℃～1300 ℃ dried ceramic gel piece, is incubated 1～5 hour, and the cooling of coming out of the stove obtains the synthetic powder agglomates of needed composite ceramics.
Advantage of the present invention is: compare with the synthetic flouring technology of gel in the past, this technology has many advantages.At first, use present method both can synthesize the ceramic powder of single component, again can the synthesize ceramic composite granule, raw materials used both can be water-soluble, also can be water-insoluble, applicable surface is very wide.Secondly, employed all raw material does not have toxicity in present method, can not bring problem of environmental pollution, and price is lower yet.Therefore, the present invention compares with gel flouring technology in the past, have widely applicable, cost is low, easy and simple to handle, non-environmental-pollution, gained powder quality advantages of higher, is suitable for suitability for industrialized production.
Embodiment
Below the present invention is described in further details.The nontoxic gel solid state reaction of composite ceramic powder of the present invention synthetic method is characterized in that the operation steps of this method is as follows:
(1) batching is according to the predetermined formulation preparation ceramic raw material of the composite ceramic powder that will prepare.Use and the essentially identical starting material of traditional synthesis by solid state reaction, wherein trace additives adopts water soluble salt, with the starting material of desiring synthetic powder in accordance with regulations proportioning prepare burden.
(2) compound concentration is the sodium alginate aqueous solution of 1～3wt%.
(3) mix, with sodium alginate aqueous solution and ceramic raw material and dispersant, dispersion agent is any material in the following material or the mixture of several materials: polyacrylic acid, poly-methyl polyacrylic acid ammonia, vinylformic acid-CALCIUM ACRYLATE copolymer, citric acid ammonia, Tetramethylammonium hydroxide, and the consumption of dispersion agent accounts for 0.5～3% of ceramic powder weight; Wherein the solid volume fraction of ceramic raw material is: 20vol%～60vol%.
(4) ball milling is put into the cylinder mill with compound or planetary mills is carried out the ball milling mixing, and the thickness degree of ball milling time according to raw material can be decided to be 5～50 hours.
(5) add catalyzer, ceramic slurry behind the ball milling is placed container, add catalyzer in the ceramic slurry behind ball milling and stir, the catalyzer of coagulation reaction be following material one of them: calcium iodate, secondary calcium phosphate, lime carbonate+hexanodioic acid, the add-on of catalyzer are 0.5～2% of ceramic powder weight.
(6) gel is heated to 40～100 ℃ with ceramic slurry, and being incubated after 10～20 minutes is solidifiable, obtains the mixed uniformly gel base substrate of various ceramic compositions.
(7) drying, with gel base substrate morsel, natural air drying or put into baking oven and carry out drying and dehydrating, oven temperature is 50～100 ℃, till parching.
(8) calcining places calcining furnace to be heated to 800 ℃～1300 ℃ dried ceramic gel piece, is incubated 1～5 hour, and the cooling of coming out of the stove obtains the synthetic powder agglomates of needed composite ceramics.
Recommend to adopt following method for calcinating: place calcining furnace to be warming up to 500～800 ℃ dried ceramic gel piece with stove, be incubated 30 minutes～2 hours, the burn off organism, and then bring up to synthetic (800 ℃～1300 ℃) temperature of regulation, be incubated 1～5 hour, promptly obtain needed synthetic powder, the gained powder generally need not to pulverize, and grinds a little and gets final product sieving for standby.
When synthetic multicomponent thermal sensitive ceramics PTC powder, can synthesize the PTC original washing powder earlier, carry out secondary doping according to the inventive method then, obtain multicomponent piezoelectricity PTC powder.
Embodiment
Embodiment 1: synthetic magnesium titanate MgTiO
3Powder.
Starting material adopt metatitanic acid H
2TiO
3With magnesium basic carbonate Mg (OH)
24MgCO
36H
2O, its proportioning is Mg: Ti=1: 1.In 200 ml waters, add 3 gram sodium alginate stirring and dissolving, make the aqueous solution of sodium alginate, add the above-mentioned ceramic raw material of 1000 grams then, add 8 ml polypropylenes acid dispersion agent.Mixed 5 hours by ball milling, obtain the ceramic slurry that solid content is about 50vol%, slip is poured in the container, under whipped state, adding 10 gram calcium iodates also mix, the container that will fill slip then is placed in 60 ℃ the thermostatic container, through 30 minutes, slip generation gelation in the container is taken out the wet gel piece and is placed 80 ℃ of baking ovens to be dried to constant weight, puts into retort furnace then and is warming up to 600 ℃ with stove, be incubated 30 minutes, the burn off organism, and then bring up to 900 ℃ of insulations 2 hours, both can obtain monophasic magnesium titanate MgTiO
3Powder.
Embodiment 2: synthetic W type ferrite BaZn
0.5Co
1..5Fe
16O
27Powder.
Starting material adopt non-water-soluble Fe
2O
3, BaCO
3With water miscible ZnCl
2, CoCl
2, its proportioning is Ba: Zn: Co: Fe=1: 0.5: 1.5: 7.8.In 250 ml waters, add 3 gram sodium alginate stirring and dissolving, make the aqueous solution of sodium alginate, add the above-mentioned ceramic raw material of 1000 grams then, add 8 gram ammonium citrate dispersion agents.Mixed 10 hours by ball milling, obtain finely disseminated ceramic slurry, slip is poured in the container, under whipped state, adding 4 gram secondary calcium phosphates also mix, and the container that will fill slip then is placed in the microwave oven and heats, through 1 minute, the wet gel piece is taken out in slip generation gelation, breaks off with the fingers and thumb into about 2cm
2Fritter place under the ventilation condition and be dried to constant weight, put into retort furnace then and be warming up to 700 ℃ with stove, be incubated 1 hour, burn off organism, and then bring up to 1200 ℃ of insulations 3 hours both can obtain monophasic W type plane hexad ferrite powder.
Embodiment 3: synthesis of barium titanate BaTiO
3Powder.
Starting material adopt BaCO
3And TiO
2, its proportioning is Ba: Ti=1: 1.In 300 ml waters, add 3 gram sodium alginate stirring and dissolving, make the aqueous solution of sodium alginate, add the above-mentioned ceramic raw material of 1000 grams then, add 10 ml polypropylenes acid ammonia dispersion agent.Mixed 15 hours by ball milling, obtain finely disseminated ceramic slurry, slip is poured in the container, under whipped state, adding 4 gram secondary calcium phosphates also mix, the container that will fill slip then is placed in 80 ℃ the thermostatic container, through 20 minutes, slip generation gelation in the container is taken out the wet gel piece and is placed 100 ℃ of baking ovens to be dried to constant weight, puts into retort furnace then and is warming up to 800 ℃ with stove, be incubated 30 minutes, the burn off organism, and then bring up to 1100 ℃ of insulations 2 hours, both can obtain monophasic barium titanate BaTiO
3Powder.
Embodiment 4: synthetic multicomponent piezoelectricity PZT powder.
Starting material adopt non-water-soluble Pb
3O
4, ZrO
2, TiO
2, La
2O
3, Nb
2O
5, MnO
2, its proportioning is Pb: Zr: Ti=1: 0.53: 0.47, add 0.01 La, 0.012 Nb, 0.002Mn.In 200 ml waters, add 4 gram sodium alginate stirring and dissolving, make the aqueous solution of sodium alginate, add the above-mentioned ceramic raw material of 1000 grams then, add 10 ml polypropylenes acid dispersion agent.Mixed 20 hours by ball milling, obtain finely disseminated ceramic slurry, slip is poured in the container, under whipped state, adding 10 gram calcium iodates also mix, and the container that will fill slip then is placed in the microwave oven and heats, through 30 seconds, the wet gel piece is taken out in slip generation gelation, breaks off with the fingers and thumb into about 2cm
2Fritter place under the ventilation condition and be dried to constant weight, put into retort furnace then and be warming up to 600 ℃ with stove, be incubated 1 hour, burn off organism, and then bring up to 850 ℃ of insulations 4 hours both can obtain uniform multicomponent piezoelectricity PZT powder.
Embodiment 5: synthetic multicomponent thermal sensitive ceramics PTC powder.
Earlier synthetic PTC original washing powder, starting material adopt Pb
3O
4, BaCO
3, CaCO
3, TiO
2With water miscible YCl
3Its proportioning is Ba: Pb: Ca: Ti: Y=0.93: 0.03: 0.04: 1.01: 0.0011, in 200 ml waters, add 4 gram sodium alginate stirring and dissolving, and make the aqueous solution of sodium alginate, add the above-mentioned ceramic raw material of 1000 grams then, add 10 ml polypropylenes acid dispersion agent.Mixed 20 hours by ball milling, obtain finely disseminated ceramic slurry, slip is poured in the container, under whipped state, adding 10 gram calcium iodates also mix, and the container that will fill slip then is placed in the microwave oven and heats, through 30 seconds, the wet gel piece is taken out in slip generation gelation, breaks off with the fingers and thumb into about 2cm
2Fritter place under the ventilation condition and be dried to constant weight, put into retort furnace then and be warming up to 800 ℃ with stove, be incubated 30 minutes, burn off organism, and then bring up to 1200 ℃ of insulations 2 hours both can obtain uniform multicomponent piezoelectricity PTC original washing powder.
With the hole sizer of original washing powder coarse crushing, carry out secondary doping by 0.5mm.The secondary doping raw material adopts Sb
2O
3, MnO
2, SiO
2, Al
2O
3, Li
2CO
3, consumption mixes with original washing powder according to the rules, adds 4 gram sodium alginate stirring and dissolving in 200 ml waters, makes the aqueous solution of sodium alginate, adds above-mentioned 1000 gram mixed powders, adds 10 ml polypropylenes acid dispersion agent.Mixed 15 hours by ball milling, obtain finely disseminated ceramic slurry, slip is poured in the container, under whipped state, adding 10 gram calcium iodates also mix, and the container that will fill slip then is placed in the microwave oven and heats, through 30 seconds, slip generation gelation, take out the wet gel piece, place under the ventilation condition and be dried to constant weight, put into retort furnace then and be warming up to 600 ℃ of insulations 2 hours with stove, burn organism, promptly to obtain uniform multicomponent piezoelectricity PTC powder.
Embodiment 6: with synthetic yttrium aluminum garnet (YAG) powder of liquid gel method
With Al
2O
3, Y (NO
3)
3Be raw material, wherein Al: Y=5: 3, with Al
2O
3Particle diameter be 2.6 μ m.In 200 ml waters, add 3 gram sodium alginate stirring and dissolving, make the aqueous solution of sodium alginate, add the above-mentioned ceramic raw material of 1000 grams then, add 8 ml polypropylenes acid dispersion agent.Mixed 5 hours by ball milling, obtain the ceramic slurry that solid content is about 50vol%, slip is poured in the container, under whipped state, adding 10 gram calcium iodates also mix, the container that will fill slip then is placed in 60 ℃ the thermostatic container, through 30 minutes, slip generation gelation in the container is taken out the wet gel piece and is placed 80 ℃ of baking ovens to be dried to constant weight, puts into retort furnace then and is warming up to 800 ℃ with stove, be incubated 30 minutes, the burn off organism, and then bring up to 1200 ℃ of insulations 3 hours, obtain the loose powder of white.The gained powder is carried out the analysis of X diffraction structure, and the result proves that raw material all is converted into the YAG ceramic powder.
Claims (3)
1, the nontoxic gel solid state reaction of a kind of composite ceramic powder synthetic method is characterized in that, the operation steps of this method is as follows:
(1) batching is according to the predetermined formulation preparation ceramic raw material of the composite ceramic powder that will prepare;
(2) compound concentration is the sodium alginate aqueous solution of 1～3wt%;
(3) mix, with sodium alginate aqueous solution and ceramic raw material and dispersant, dispersion agent is any material in the following material or the mixture of several materials: polyacrylic acid, poly-methyl polyacrylic acid ammonia, vinylformic acid-CALCIUM ACRYLATE copolymer, citric acid ammonia, Tetramethylammonium hydroxide, and the consumption of dispersion agent accounts for 0.5～3% of ceramic powder weight; Wherein the solid volume fraction of ceramic raw material is: 20vol%～60vol%.
(4) ball milling is put into the cylinder mill with compound or planetary mills is carried out the ball milling mixing, and the ball milling time is 5～50 hours;
(5) add catalyzer, add catalyzer in the ceramic slurry behind ball milling and stir, catalyzer be following material one of them: calcium iodate, secondary calcium phosphate, lime carbonate+hexanodioic acid, the add-on of catalyzer are 0.5～2% of ceramic powder weight;
(6) gel is heated to 40～100 ℃ with ceramic slurry, and being incubated after 10～20 minutes is solidifiable, obtains the gel base substrate;
(7) drying, with gel base substrate morsel, natural air drying or put into baking oven and carry out drying and dehydrating, oven temperature is 50～100 ℃, till parching;
(8) calcining places calcining furnace to be heated to 800 ℃～1300 ℃ dried ceramic gel piece, is incubated 1～5 hour, and the cooling of coming out of the stove obtains the synthetic powder agglomates of needed composite ceramics.
2, synthetic method according to claim 1 is characterized in that, during said calcining gel piece, is heated to 500～800 ℃ earlier, is incubated 30 minutes～2 hours, the burn off organism, and then bring up to 800 ℃～1300 ℃, be incubated 1～5 hour and calcine.
3, synthetic method according to claim 1 and 2 is characterized in that, when synthesizing multicomponent thermal sensitive ceramics PTC powder, earlier synthetic PTC original washing powder carries out secondary doping according to the inventive method then, obtains multicomponent piezoelectricity PTC powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072182A (en) * | 2013-01-08 | 2013-05-01 | 清华大学 | Gellan gum gel-based ceramic gel injection molding method |
| CN103739285A (en) * | 2013-11-21 | 2014-04-23 | 中北大学 | Oxide toughened porous lead zirconate titanate piezoelectric ceramic preparation method |
| CN104744045A (en) * | 2015-03-25 | 2015-07-01 | 武汉理工大学 | Method for preparing MgAlON transparent ceramic biscuit by direct coagulation casting |
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| US5380782A (en) * | 1993-10-04 | 1995-01-10 | Rohm And Haas Company | Polymeric dispersants for ceramic materials |
| CN1125794C (en) * | 1999-02-05 | 2003-10-29 | 北京航空材料研究院 | Process for synthesizing composite ceramic powder body |
| CN1172876C (en) * | 2002-07-17 | 2004-10-27 | 清华大学 | Process for preparing ceramic sheet by water-base doctor blading method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072182A (en) * | 2013-01-08 | 2013-05-01 | 清华大学 | Gellan gum gel-based ceramic gel injection molding method |
| CN103072182B (en) * | 2013-01-08 | 2014-09-24 | 清华大学 | Gellan gum gel-based ceramic gel injection molding method |
| CN103739285A (en) * | 2013-11-21 | 2014-04-23 | 中北大学 | Oxide toughened porous lead zirconate titanate piezoelectric ceramic preparation method |
| CN103739285B (en) * | 2013-11-21 | 2015-08-19 | 中北大学 | The preparation method of the toughness reinforcing porous lead titanate piezoelectric ceramics of oxide compound |
| CN104744045A (en) * | 2015-03-25 | 2015-07-01 | 武汉理工大学 | Method for preparing MgAlON transparent ceramic biscuit by direct coagulation casting |
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