A kind of mechanochemical reaction prepares the method for stabilizing zirconia
Technical field
The present invention relates to the nano material synthesis technical field, the Mechanochemical synthesis of specifically a kind of Mg stabilizing zirconia and Y stabilizing zirconia.
Background technology
Because the zirconium white in the monocline phase can produce bigger volume change in tetragonal phase converting, again bigger volume change can take place in the opposite direction in the time of refrigerative, causes the cracking of product easily, has limited the application of pure zirconia in the high temperature field.Yet add an amount of crystal stabilization MgO or Y
2O
3After, can make ZrO
2Transformation temperature is reduced to below the room temperature, and improves the toughness of stupalith, and therefore the sudden change of volume can not take place after heating, has expanded zirconic range of application greatly.Stably-doped tetragonal zircite mainly contains following important use:
1, structural ceramics: because stably-doped zirconia ceramics has excellent mechanical property: the thermal shock resistance that fracture toughness property is excellent, wearing resistance is good, corrosion-resistant, good etc.; Wear-resisting preferably and erosion resistance are also arranged simultaneously; It is little to add heat-conduction coefficient; Thermal insulation is fine, therefore can be used to make superhard abrading-ball, spot contact bearing etc.
Compare with the abrading-ball of other materials, the zirconium oxide ceramic grinding ball has characteristics such as density is big, hardness is high, toughness is strong, therefore have traditional abrading-ball incomparable mill efficiency.Simultaneous oxidation zirconia material density of material is big, quality is high, and Impact energy is strong when being used as grinding medium, can improve the grinding dispersion efficiency greatly, can effectively shorten milling time.
The life relations of bearing ball is to the safety and the life-span of bearing.Utilize the HS, H.T. of stabilized zirconia ceramic material, high temperature resistant, abrasion performance, advantage such as anti-oxidant, anticorrosive, can be used on the bearing arrangement.Improvement the zirconium white ball and the axle center that make are compared with the traditional metal parts, have that roughness is low, hardness is high, in light weight, temperature tolerance good, advantage such as wear-resisting, therefore prolonged work-ing life greatly.
In addition, partial stabilization zirconium oxide ceramic also can be made unlubricated bearing, wortle, impact extrusion pressing mold, spring, cutter, measurer, various nozzle, ceramic valve and lining, machinery sealing material, ball milling spare, various scissors, no magnetic screwdriver and bioceramic material etc.
2, function ceramics: the character of the multiple uniqueness of stably-doped zirconia ceramics makes its application that also has multiple function ceramics, for example SOFC, thermal barrier coating and oxygen sensor etc.
Stably-doped zirconia ceramics can be used as solid electrolyte and develops third generation fuel cell-SOFC, and it is by with the zirconia ceramics of stabilized with yttrium oxide, constitute to the ionogen of oxonium ion energising with by the fuel and the air pole of porous matter to the electronics energising.Airborne oxygen is oxidized at air pole/electrolyte interface; Under the partial pressure difference effect of oxygen between air and the fuel, oxonium ion in ionogen to fuel electrodes one side shifting, hydrogen in fuel electrodes electrolyte interface and fuel or reaction of carbon monoxide; Generate water vapour or carbonic acid gas, ejected electron.Electronics returns air pole once more through the outer loop, produces electric energy this moment.
Thermal barrier coating is for the air cooling metal parts of under the high temperature criticality, working heat-blocking action to be provided.The zirconium white of nano level stabilized with yttrium oxide has very high heat reflectivity; Chemicalstability is good; All be superior to other materials with the bonding force and the thermal shock resistance of base material; Therefore be present optimal heat barrier coat material, can be widely used in the heat insulating coat of aerospace mover, the lining of submarine, steamer diesel engine cylinder etc.
Zirconium oxide oxygen sensor is because Zr
4+With the metallic element ionic radius that adds, the difference of valence number, on lattice, produce the room (lattice imperfection) of oxonium ion, therefore generate oxygen ion conductor, have conductivity, temperature is high more, and specific conductivity is big more.Partially stabilized zirconia ceramics specific conductivity is than higher, if there is potential difference in the oxygen concn of its both sides, then oxygen just passes solid electrolyte guiding lower concentration side from the high density side with the oxonium ion form.Zirconium oxide oxygen sensor is widely used in the oxygen level that dissolves molten steel and process furnace institute emission gases in triple effect catalytic converter, industrial production, monitoring, quality inspection and the steel plant process of automobile engine system and detects.
If use wet chemistry method, prepare nano-powder like coprecipitation method, generally all there is the liquid phase production process, all there are dry, dehydration, improper if its method is selected for use, usually can cause the reunion of powder.And wet chemistry method needs a large amount of solvents, therefore also causes the pollution of environment easily.
Summary of the invention
The Mechanochemical synthesis that the purpose of this invention is to provide a kind of Mg stabilizing zirconia and Y stabilizing zirconia, it can prepare the Mg or the Y stabilizing zirconia of high cubic phase content quick, easy, effectively.
The concrete technical scheme that realizes the object of the invention is following:
A kind of mechanochemical reaction prepares the method for stabilizing zirconia, and this method comprises following concrete steps:
A, with MgO or Y
2O
3Powder and zirconium white powder are together put into ball grinder, add deionized water and zirconium oxide abrasive ball simultaneously; Wherein: zirconium white powder and Y
2O
3The mol ratio of powder is 97:3~95:5; The mol ratio of zirconium white powder and MgO powder is 86:14~90:10; The weight ratio of zirconium white powder and deionized water is 1:0.9~1:1.1; The weight ratio of zirconium white powder and zirconium oxide abrasive ball is 1:1.5~1:2.5.
B, ball grinder is placed on the ball mill, with 100~120 rev/mins speed, ball milling carried out batch mixing in 5~6 hours;
C, with filter screen with the elimination of zirconium oxide abrasive ball, slurry is placed in the baking oven under 100~120 ℃, dry 1~2 hour, the powder with caking pulverized with mortar then, crossed 20 mesh sieve granulations;
D, the granulation powder packed that will pulverize are in the grinding pot of screw abrasive machine, and granulation powder and grinding pot volume packing ratio are 2g/ml;
E, control shredder power are 2~3 KW, and its powder is ground, and are just changeing 15 minutes, reverse 1 minute, shut down 4 minutes for once, circulate 18~20 times, obtain Mg or Y stabilizing zirconia.
The present invention can prepare the Mg or the Y stabilizing zirconia of high cubic phase content quick, easy, effectively, and its technology is simple, with low cost, the preparation process temperature is low, environmentally friendly, is a kind of environmental protection synthesis technique.
Description of drawings
The XRD figure of the cubic phase Mg stabilizing zirconia that Fig. 1 obtains for the embodiment of the invention 1;
The XRD figure of the cubic phase Y stabilizing zirconia that Fig. 2 obtains for the embodiment of the invention 2.
Embodiment
Embodiment 1
A, take by weighing MgO powder 4 gram, take by weighing zirconium white powder 196 grams;
B, above-mentioned powder is put into ball grinder, add deionized water 200 grams simultaneously and restrain with zirconium oxide abrasive ball 400;
C, on ball mill, with 120 rev/mins speed, ball milling carried out batch mixing in 5 hours;
D, with filter screen with the mill ball elimination, be placed in the baking oven with 120 ℃ slurry carried out 1.5 hours drying treatment, the powder of dried caking is pulverized with mortar, cross 20 mesh sieve granulations;
E, with the granulation powder packed in screw abrasive machine, packing ratio is 2g/ml;
F, then above-mentioned powder is put into the screw shredder and grind, the power of shredder is controlled at 2.4kw, powder is ground, just changeing 15 minutes, reversed 1 minute, shut down 4 minutes.So circulation is 20 times, obtains 12mol% and mixes the Mg tetragonal phase zirconium oxide, and its XRD figure spectrum is consulted accompanying drawing 1.
Embodiment 2
A, take by weighing Y
2O
3Powder 5 grams take by weighing zirconium white powder 195 grams;
B, above-mentioned powder is put into ball grinder, add deionized water 200 grams simultaneously and restrain with zirconium oxide abrasive ball 400;
C, on ball mill, with 100 rev/mins speed, ball milling carried out batch mixing in 6 hours;
D, with filter screen with the mill ball elimination, be placed in the baking oven with 100 ℃ slurry carried out 2 hours drying treatment, the powder of dried caking is pulverized with mortar, cross 20 mesh sieve granulations;
E, with the granulation powder packed in screw abrasive machine, packing ratio is 2g/ml;
F, then above-mentioned powder is put into the screw shredder and grind, the power of shredder is controlled at 3kw, powder is ground, just changeing 15 minutes, reversed 1 minute, shut down 4 minutes.So circulation is 18 times,
Obtain 5mol% and mix the Y tetragonal phase zirconium oxide, its XRD figure spectrum is consulted accompanying drawing 2.