CN107176836A - A kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder and preparation method thereof - Google Patents
A kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder and preparation method thereof, and wherein preparation method comprises the following steps：Mixed solution is prepared, by the mixed solution and precipitant mix, hydroxide colloid is obtained；By the hydroxide colloid separating, washing, precipitated；By the precipitation press filtration, semisolid hydroxide gel is obtained；The semisolid hydroxide gel is uniformly mixed with dispersant, mixture is obtained；The mixture is distilled, then dried, solid powder is obtained；The solid powder is calcined, cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder is obtained.The present invention also provides a kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder obtained using above-mentioned preparation method, and its structural formula is (La1‑2xCexCax)2(Zr0.7Ce0.3)2O7, in formula：0.05≤x≤0.2.The preparation method technological process that the present invention is provided is few, easily controllable.
Description
Technical field
The present invention relates to inorganic non-metallic material preparation and application field, more particularly to a kind of cerium calcium dual element codope zirconium
Sour lanthanum nano-ceramic powder and preparation method thereof.
Background technology
Zirconic acid lanthanum material has unique crystal structure, and its chemical stability is good, thermal conductivity is low, is a kind of important structure
And function ceramics.Cerium dopping zirconic acid lanthanum material has fusing point height, thermal conductivity is small, thermal coefficient of expansion is big, chemical stability good and high
The characteristics of under temperature without phase transformation, be the important candidate material of high-temp heat barrier coating material.Meanwhile, although zirconic acid lanthanum material is with excellent
Thermodynamic property, but its thermal coefficient of expansion is smaller (25 DEG C~1200 DEG C about 9.7 × 10-6K-1), therefore it applies as thermal boundary
During layer material, exist and the unmatched problem of matrix material.CeO2Intrinsic thermal coefficient of expansion is higher, in addition, Ce4+And Zr4+'s
Ionic radius and relative atomic mass difference are obvious.Ce4+Replace La2Zr2O7In Zr4+It is advantageously possible for improving the hot thing of material
Rationality energy.
Y.F.Wang et al. have studied La2(Zr0.7Ce0.3)2O7Thermophysical property influence factor.Result of study shows,
CeO2Incorporation significantly reduce La2Zr2O7Thermal conductivity, while the amplitude that thermal conductivity is varied with temperature is shallower.Doped chemical
Specific mass difference is wanted more effectively to influence point defect phon scattering with the ionic radius difference of corresponding matrix element, so as to also influence
The trend that thermal conductivity is varied with temperature.In addition, mixing the element of larger quality, especially larger-size element can effectively drop
The theoretical minimum thermal conductivity of low material.
Another effective doping way is to use divalent metal element (Mg, Ca, Sr etc.), and crystalline substance can be distorted to a greater extent
Lattice, increase oxygen vacancy concentration, and enhancing phon scattering effect reduces the thermal conductivity of material.H.S.Zhang et al. have studied Sr, Ca,
Mg doping La2Ce2O7Influence to its thermal conductivity.As a result show, after diad Sr, Ca, Mg part doping La,
(La0.95M0.05)2Ce2O7The thermal conductivity of (M=Sr, Ca, Mg) is compared with La2Ce2O7There is obvious reduction.
The content of the invention
In view of this, the invention provides a kind of high cerium calcium dual element codope zirconic acid lanthanum nano ceramics of thermal coefficient of expansion
Powder, additionally provides a kind of preparation method of the few cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder of technological process.
The present invention provides a kind of preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder, including following step
Suddenly:
S1, prepares the mixed solution of cerium salt, calcium salt, zirconates and lanthanum salt, by the mixed solution and precipitant mix, stirring
It is still aging afterwards, obtain hydroxide colloid；
S2, the hydroxide colloid separating, washing is precipitated and solution；
S3, using filter press by the precipitation press filtration, obtains semisolid hydroxide gel；
S4, the semisolid hydroxide gel is uniformly mixed with dispersant, mixture is obtained；
S5, the mixture is placed in distilling apparatus and distilled, then dries, obtains solid powder；
S6, the solid powder is calcined, and obtains cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder.
Further, in step S1, the cerium salt, calcium salt, the concentration of zirconates and lanthanum salt are 0.1~1mol/L, the cerium
Salt is ceric sulfate or cerous nitrate, and the calcium salt is calcium nitrate, calcium chloride or calcium sulfate, and the zirconates is basic zirconium chloride, described
Lanthanum salt is lanthanum nitrate or lanthanum chloride, and calcium ion in the mixed solution, cerium ion, the mol ratio of zirconium ion and lanthanum ion are 1:7:
14:18~2:5:7:6.
Further, in step S1, the precipitating reagent is ammoniacal liquor or ammonium oxalate, the volumetric concentration of ammoniacal liquor for 25%~
100%.
Further, in step S1, the time of stirring is 2~4h, stirs the pH value of the reaction system into the precipitating reagent
10~14 are maintained at, the still aging time is 9~12h.
Further, in step S2, using Inorganic Ceramic Membranes by the hydroxide colloid separating, washing, stop
Only the Rule of judgment of separation process be the pH value of solution obtained after separation be 7 and solution do not produced with nitric acid silver reaction it is cotton-shaped
Thing.
Further, in step S3, by weight percentage, the solid content of the semisolid hydroxide gel for 8~
20%.
Further, in step S4, the mode of mixing is to utilize milling treatment of colloid or strong stirring, and dispersant is alcohols point
Powder, dispersant selects appointing in diglycol, n-butanol, normal propyl alcohol, ethylene glycol, isobutanol, isopropanol or n-amyl alcohol
The mass ratio of one kind, the dispersant and semisolid hydroxide gel is 2：1~6:1.
Further, in step S5, the detailed process of distillation is：The mixture is placed in distilling apparatus, by adding
Heat is by the temperature control of distilling apparatus at 80~180 DEG C, so as to distill the absorption water in removing mixture, water to be adsorbed takes off completely
After removing, the temperature of rise distilling apparatus evaporates dispersant, then dries 2~8h, obtains solid powder.
Further, in step S6, the solid powder is calcined into 2~5h at 1300 DEG C~1600 DEG C, cerium calcium is obtained
Dual element codope zirconic acid lanthanum nano-ceramic powder.
Present invention also offers a kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder, above-mentioned preparation method is utilized
Obtain, its structural formula is (La1-2xCexCax)2(Zr0.7Ce0.3)2O7, in formula：0.05≤x≤0.2, the nano-ceramic powder is burning
Green stone structure.
The beneficial effect that the technical scheme that the present invention is provided is brought is：
1. the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder that the present invention is provided is pyrochlore constitution, possess excellent
Hot expansibility and anti-sintering property, nano-ceramic powder particle diameter distribution uniform, controllable, the regular appearance, structure is steady under high temperature
It is fixed, with zirconic acid lanthanum (thermal coefficient of expansion：25 DEG C~1500 DEG C reach 9.37 × 10-6K-1, thermal conductivity：25 DEG C~1450 DEG C are
1.571W·m-1·K-1) compare, the nano-ceramic powder has more excellent thermal coefficient of expansion, and (25 DEG C~1500 DEG C reach 12.34
×10-6K-1) and thermal conductivity (25 DEG C~1450 DEG C be 1.183Wm-1·K-1)；
2. the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder that the present invention is provided can be to a greater extent in application
Improve coating service life and heat-proof quality in ground, it is adaptable to various high temperature resistance thermal barrier coating or high-temperature wearable consumptions, corrosion-resistant finishes
The preparation of material, can be widely used in the fields such as Aero-Space, gas turbine, ship, automobile, machinery, chemical industry；
3. the preparation method technological process for the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder that the present invention is provided is few,
Required equipment is simple, and preparation process is easily controllable, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 is a schematic diagram of the preparation method of the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder of the present invention.
Fig. 2 be the present invention cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder preparation in embodiment 1 obtain
Nano-ceramic powder X-ray powder diffraction pattern.
Fig. 3 be the present invention cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder preparation in embodiment 2 obtain
Nano-ceramic powder X-ray powder diffraction pattern.
Fig. 4 be the present invention cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder preparation in embodiment 3 obtain
Nano-ceramic powder X-ray powder diffraction pattern.
Fig. 5 be the present invention cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder preparation in embodiment 4 obtain
Nano-ceramic powder X-ray powder diffraction pattern.
Fig. 6 be the present invention cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder preparation in embodiment 4 obtain
Nano-ceramic powder the curve that varies with temperature of thermal coefficient of expansion.
Fig. 7 be the present invention cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder preparation in embodiment 4 obtain
Nano-ceramic powder the curve that varies with temperature of thermal conductivity.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with drawings and examples to this hair
Bright embodiment is further described.
Fig. 1 is refer to, The embodiment provides a kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder
Preparation method, comprise the following steps：
S1, concentration is mixed for 0.1~1mol/L cerium salt, calcium salt, zirconates and lanthanum salt, mixed solution is configured to, and is utilized
Mixed solution is added in precipitating reagent by back titration method, still aging after stirring, obtains hydroxide colloid.
In step S1, cerium salt is ceric sulfate or cerous nitrate, and calcium salt is calcium nitrate, calcium chloride or calcium sulfate, and zirconates is chlorine
Zirconium oxide, lanthanum salt is lanthanum nitrate or lanthanum chloride, and calcium ion in mixed solution, cerium ion, the mol ratio of zirconium ion and lanthanum ion are
1:7:14:18~2:5:7:6, precipitating reagent is ammoniacal liquor or ammonium oxalate, and the volumetric concentration of ammoniacal liquor is 25%~100%, stirring when
Between be 2~4h, stirring pH value of reaction system into precipitating reagent is maintained at 10~14, and the still aging time is 9~12h.
S2, using Inorganic Ceramic Membranes by the hydroxide colloid separating, washing obtained in step S1, is sunk
Form sediment and solution；Inorganic Ceramic Membranes are to realize the separating of different component, pure of feed liquid using the Selective Separation of film
A kind of technology changed and concentrated, it, which has, to be carried out at normal temperatures, without phase-state change, without chemical change, the good, adaptability of selectivity
The strong and low advantage of energy consumption.
In step S2, the effect of separation is to remove the foreign ion in hydroxide colloid, stops the judgement of separation process
Condition is that the pH value of solution obtained after separation is 7 and solution does not produce floccule with nitric acid silver reaction.
S3, press filtration will be precipitated using filter press, obtain semisolid hydroxide gel；By weight percentage, semisolid
The solid content of hydroxide gel is 8~20%.
S4, the semisolid hydroxide gel obtained in step S3 is uniformly mixed with dispersant, mixture is obtained.
In step S4, the mode of mixing is to utilize milling treatment of colloid or strong stirring, and dispersant is alcohols dispersant, is disperseed
Agent is disperseed from any of diglycol, n-butanol, normal propyl alcohol, ethylene glycol, isobutanol, isopropanol or n-amyl alcohol
The mass ratio of agent and semisolid hydroxide gel is 2：1~6:1.
S5, the mixture obtained in step S4 is placed in distilling apparatus and distilled, then dries, obtains solid powder.
Specifically, in step S5, mixture is placed in distilling apparatus, existed by the temperature control heated distilling apparatus
80~180 DEG C, so as to distill the absorption water in removing mixture, after water to be adsorbed removing completely, raise the temperature of distilling apparatus
Evaporate dispersant, then dry 2~8h, obtain being stirred continuously in solid powder, drying process, so as to get solid powder it is equal
Even drying.
S6, solid powder is calcined, and is co-doped with by controlling the temperature of calcining to obtain varigrained cerium calcium dual element
Miscellaneous zirconic acid lanthanum nano-ceramic powder.
Specifically, in step S6, solid powder is calcined into 2~5h at 1300 DEG C~1600 DEG C, cerium calcium dual element is obtained
Codope zirconic acid lanthanum nano-ceramic powder.
Present invention also offers a kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder, above-mentioned preparation method is utilized
Obtain, the nano-ceramic powder is pyrochlore constitution, the structural formula of the nano-ceramic powder is：(La1-2xCexCax)2
(Zr0.7Ce0.3)2O7, in formula：0.05≤x≤0.2.
Several realities of the preparation method of the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder of the present invention are given below
Example is applied, above-mentioned preparation method is illustrated with reference to the embodiment.
Embodiment 1：
Zirconium oxychloride solution that the cerous nitrate solution for being 0.2mol/L by concentration, concentration are 0.356mol/L, concentration are
0.5mol/L calcium nitrate solution and concentration mixes for 0.5mol/L lanthanum nitrate hexahydrate, is configured to calcium ion, cerium ion, zirconium
The mol ratio of ion and lanthanum ion is 1:7:14:18 mixed solution, volume is added to using back titration method by mixed solution
Concentration is in 40% ammoniacal liquor, stirring pH value of reaction system into ammoniacal liquor reaches 10, still aging 12h, obtains hydroxide
Colloid；Using Inorganic Ceramic Membranes by hydroxide colloid separating, washing, precipitated and solution, measure the pH of solution
Value, if the pH value of solution be more than 7, continue separate until solution pH value for 7 and solution do not produced with nitric acid silver reaction it is cotton-shaped
Thing；Using filter press by the precipitation press filtration obtained after separation, semisolid hydroxide gel is obtained；Using colloid mill by n-butanol
It is 2 in mass ratio with semisolid hydroxide gel:1 is well mixed, and obtains mixture；Mixture is placed in distilling apparatus,
By heating after the complete removing of absorption water by the temperature control in distilling apparatus in 150 DEG C, thing to be mixed, rise distillation dress
The temperature put evaporates n-butanol, then dries 2h, obtains solid powder；Solid powder is calcined into 4h at 1350 DEG C, obtained
Cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder.
The cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder prepared using embodiment 1 progress X-ray is spread out
(X-ray diffraction, XRD) test is penetrated, Fig. 2 is that the cerium calcium dual element codope zirconic acid lanthanum obtained using embodiment 1 is received
The X-ray powder diffraction pattern of rice ceramic powder, it is pyrochlore constitution that obtained nano-ceramic powder can be analyzed by Fig. 2.
Embodiment 2：
Zirconium oxychloride solution that the cerous nitrate solution for being 0.15mol/L by concentration, concentration are 0.45mol/L, concentration are
0.6mol/L calcium nitrate solution and concentration for 0.65mol/L lanthanum nitrate hexahydrate mix, be configured to calcium ion, cerium ion,
The mol ratio of zirconium ion and lanthanum ion is 1:4:7:8 mixed solution, volume is added to using back titration method by mixed solution
Concentration is in 30% ammoniacal liquor, stirring pH value of reaction system into ammoniacal liquor reaches 11, still aging 11h, obtains hydroxide
Colloid；Using Inorganic Ceramic Membranes by hydroxide colloid separating, washing, precipitated and solution, measure the pH of solution
Value, if the pH value of solution be more than 7, continue separate until solution pH value for 7 and solution do not produced with nitric acid silver reaction it is cotton-shaped
Thing；Using filter press by the precipitation press filtration obtained after separation, semisolid hydroxide gel is obtained；Using colloid mill by one contract two
Ethylene glycol is 5 in mass ratio with semisolid hydroxide gel:2 are well mixed, and obtain mixture；Mixture is placed in distillation dress
In putting, by heating after the complete removing of absorption water by the temperature control in distilling apparatus in 135 DEG C, thing to be mixed, rise
The temperature of distilling apparatus evaporates diglycol, then dries 4h, obtains solid powder；By solid powder at 1350 DEG C
3h is calcined, cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder is obtained.
The cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder prepared using embodiment 2 is subjected to XRD tests,
Fig. 3 is the X-ray powder diffraction pattern of the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder obtained using embodiment 2,
It is pyrochlore constitution that obtained nano-ceramic powder can be analyzed by Fig. 3.
Embodiment 3：
Zirconium oxychloride solution that the cerous nitrate solution for being 0.35mol/L by concentration, concentration are 0.65mol/L, concentration are
0.8mol/L calcium nitrate solution and concentration for 0.85mol/L lanthanum nitrate hexahydrate mix, be configured to calcium ion, cerium ion,
The mol ratio of zirconium ion and lanthanum ion is 3:9:14:14 mixed solution, body is added to using back titration method by mixed solution
Product concentration is in 30% ammoniacal liquor, stirring pH value of reaction system into ammoniacal liquor reaches 12, still aging 10h, obtains hydroxide
Thing colloid；Using Inorganic Ceramic Membranes by hydroxide colloid separating, washing, precipitated and solution, measurement solution
PH value, if the pH value of solution is more than 7, continues to separate until the pH value of solution is 7 and solution does not produce wadding with nitric acid silver reaction
Shape thing；Using filter press by the precipitation press filtration obtained after separation, semisolid hydroxide gel is obtained；Using colloid mill by second two
Alcohol is 5 in mass ratio with semisolid hydroxide gel:2 are well mixed, and obtain mixture；Mixture is placed in distilling apparatus
In, by heating after the complete removing of absorption water by the temperature control in distilling apparatus in 135 DEG C, thing to be mixed, rise is steamed
The temperature of distillation unit evaporates ethylene glycol, then dries 3h, obtains solid powder；Solid powder is calcined at 1450 DEG C
2.5h, obtains cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder.
The cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder prepared using embodiment 3 is subjected to XRD tests,
Fig. 4 is the X-ray powder diffraction pattern of the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder obtained using embodiment 3,
It is pyrochlore constitution that obtained nano-ceramic powder can be analyzed by Fig. 4.
Embodiment 4：
Zirconium oxychloride solution that the cerous nitrate solution for being 0.2mol/L by concentration, concentration are 1.0mol/L, concentration are
0.5mol/L calcium nitrate solution and concentration for 0.75mol/L lanthanum nitrate hexahydrate mix, be configured to calcium ion, cerium ion,
The mol ratio of zirconium ion and lanthanum ion is 2:5:7:6 mixed solution, volume is added to using back titration method by mixed solution
Concentration is in 30% ammoniacal liquor, stirring pH value of reaction system into ammoniacal liquor reaches 14, still aging 9h, obtains hydroxide glue
Body；Using Inorganic Ceramic Membranes by hydroxide colloid separating, washing, precipitated and solution, measure the pH of solution
Value, if the pH value of solution be more than 7, continue separate until solution pH value for 7 and solution do not produced with nitric acid silver reaction it is cotton-shaped
Thing；Using filter press by the precipitation press filtration obtained after separation, semisolid hydroxide gel is obtained；Using colloid mill by isobutanol
It is 5 in mass ratio with semisolid hydroxide gel:2 are well mixed, and obtain mixture；Mixture is placed in distilling apparatus,
By heating after the complete removing of absorption water by the temperature control in distilling apparatus in 150 DEG C, thing to be mixed, rise distillation dress
The temperature put evaporates isobutanol, then dries 5h, obtains solid powder；Solid powder is calcined into 4h at 1500 DEG C, obtained
Cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder.
By the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder prepared using embodiment 4 carry out XRD tests,
Semiconductor cooler (Thermo Electric Cooler, TEC) is tested and thermal conductivity test, and Fig. 5 is to be obtained using embodiment 4
Cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder X-ray powder diffraction pattern, Fig. 6 is obtains using embodiment 4
Cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder the curve that varies with temperature of thermal coefficient of expansion, Fig. 7 is using real
The curve that the thermal conductivity for the cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder that example 4 is obtained is varied with temperature is applied, can by Fig. 5
To analyze obtained nano-ceramic powder as pyrochlore constitution, from fig. 6, it can be seen that cerium calcium dual element codope zirconic acid lanthanum is received
The thermal coefficient of expansion (25 DEG C~1500 DEG C) of rice ceramic powder reaches 12.34 × 10-6K-1, from figure 7 it can be seen that cerium calcium double base
(25 DEG C~1450 DEG C) of the thermal conductivity of plain codope zirconic acid lanthanum nano-ceramic powder is 1.183Wm-1·K-1。
The cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder that the present invention is provided is pyrochlore constitution, possesses excellent
Structure is steady under hot expansibility and anti-sintering property, nano-ceramic powder particle diameter distribution uniform, controllable, the regular appearance, high temperature
It is fixed, with zirconic acid lanthanum (thermal coefficient of expansion：25 DEG C~1500 DEG C reach 9.37 × 10-6K-1, thermal conductivity：25 DEG C~1450 DEG C are
1.571W·m-1·K-1) compare, the nano-ceramic powder has more excellent thermal coefficient of expansion, and (25 DEG C~1500 DEG C reach 12.34
×10-6K-1) and thermal conductivity (25 DEG C~1450 DEG C be 1.183Wm-1·K-1)；The cerium calcium dual element codope that the present invention is provided
Zirconic acid lanthanum nano-ceramic powder can improve coating service life and heat-proof quality to a greater extent in application, it is adaptable to various
High temperature resistance thermal barrier coating or high-temperature wearable consumption, the preparation of corrosion-resistant finishes material, can be widely used in Aero-Space, combustion gas wheel
The fields such as machine, ship, automobile, machinery, chemical industry；The cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder that the present invention is provided
Preparation method technological process is few, and required equipment is simple, and preparation process is easily controllable, is adapted to large-scale industrial production.
In the case where not conflicting, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder, it is characterised in that including following step
Suddenly:
S1, prepares the mixed solution of cerium salt, calcium salt, zirconates and lanthanum salt, by the mixed solution and precipitant mix, quiet after stirring
Ageing is put, hydroxide colloid is obtained；
S2, the hydroxide colloid separating, washing is precipitated and solution；
S3, using filter press by the precipitation press filtration, obtains semisolid hydroxide gel；
S4, the semisolid hydroxide gel is uniformly mixed with dispersant, mixture is obtained；
S5, the mixture is placed in distilling apparatus and distilled, then dries, obtains solid powder；
S6, the solid powder is calcined, and obtains cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder.
2. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In, in step S1, the cerium salt, calcium salt, the concentration of zirconates and lanthanum salt are 0.1~1mol/L, the cerium salt be ceric sulfate or
Cerous nitrate, the calcium salt be calcium nitrate, calcium chloride or calcium sulfate, the zirconates be basic zirconium chloride, the lanthanum salt be lanthanum nitrate or
Calcium ion in lanthanum chloride, the mixed solution, cerium ion, the mol ratio of zirconium ion and lanthanum ion are 1:7:14:18~2:5:7:
6。
3. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S1, the precipitating reagent is ammoniacal liquor or ammonium oxalate, and the volumetric concentration of ammoniacal liquor is 25%~100%.
4. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S1, time of stirring is 2~4h, and stirring pH value of reaction system into the precipitating reagent is maintained at 10~14, quiet
The time for putting ageing is 9~12h.
5. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S2, using Inorganic Ceramic Membranes by the hydroxide colloid separating, washing, stopping sentencing for separation process
Broken strip part is that the pH value of solution obtained after separation is 7 and solution does not produce floccule with nitric acid silver reaction.
6. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S3, by weight percentage, the solid content of the semisolid hydroxide gel is 8~20%.
7. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S4, the mode of mixing is to utilize milling treatment of colloid or strong stirring, and dispersant is alcohols dispersant, dispersant choosing
It is described scattered with any of diglycol, n-butanol, normal propyl alcohol, ethylene glycol, isobutanol, isopropanol or n-amyl alcohol
The mass ratio of agent and semisolid hydroxide gel is 2: 1~6:1.
8. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S5, the detailed process of distillation is：The mixture is placed in distilling apparatus, by heating distilling apparatus
Temperature control is at 80~180 DEG C, so that the absorption water in removing mixture is distilled, after water to be adsorbed removing completely, rise distillation
The temperature of device evaporates dispersant, then dries 2~8h, obtains solid powder.
9. the preparation method of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder as claimed in claim 1, its feature exists
In in step S6, the solid powder is calcined into 2~5h at 1300 DEG C~1600 DEG C, cerium calcium dual element codope zirconium is obtained
Sour lanthanum nano-ceramic powder.
10. a kind of cerium calcium dual element codope zirconic acid lanthanum nano-ceramic powder, it is characterised in that the cerium calcium dual element codope
Zirconic acid lanthanum nano-ceramic powder is obtained according to preparation method according to any one of claims 1 to 9, and its structural formula is (La1- 2xCexCax)2(Zr0.7Ce0.3)2O7, in formula：0.05≤x≤0.2, the nano-ceramic powder is pyrochlore constitution.
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| CN108178631A (en) * | 2018-01-15 | 2018-06-19 | 中国地质大学（武汉） | A kind of preparation method of thermal spraying spherical shape lanthanum zirconate powder |
| CN109796206A (en) * | 2019-03-26 | 2019-05-24 | 武汉理工大学 | A kind of high infrared radiation ceramic material and its preparation method and application |
| US10322409B1 (en) | 2018-03-05 | 2019-06-18 | King Fahd University Of Petroleum And Minerals | Low temperature hydrothermal method for the preparation of LaCO3OH nanoparticles |
| CN112960980A (en) * | 2021-03-02 | 2021-06-15 | 中国人民解放军国防科技大学 | Ultralow-thermal-conductivity co-doped modified pyrochlore thermal barrier coating material and preparation method thereof |
| CN113121227A (en) * | 2021-03-08 | 2021-07-16 | 江苏大学 | Gadolinium-nickel co-doped magnesium-based lanthanum hexaaluminate ceramic and preparation method thereof |
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| CN102659403A (en) * | 2012-05-31 | 2012-09-12 | 北京科技大学 | Ceramic material for high-temperature-resistant thermal barrier coating and preparation method thereof |
| CN102718485A (en) * | 2012-06-27 | 2012-10-10 | 中国地质大学（武汉） | Cerium-doped lanthanum zirconate nano powder and preparation method thereof |
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| CN102659403A (en) * | 2012-05-31 | 2012-09-12 | 北京科技大学 | Ceramic material for high-temperature-resistant thermal barrier coating and preparation method thereof |
| CN102718485A (en) * | 2012-06-27 | 2012-10-10 | 中国地质大学（武汉） | Cerium-doped lanthanum zirconate nano powder and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178631A (en) * | 2018-01-15 | 2018-06-19 | 中国地质大学（武汉） | A kind of preparation method of thermal spraying spherical shape lanthanum zirconate powder |
| US10322409B1 (en) | 2018-03-05 | 2019-06-18 | King Fahd University Of Petroleum And Minerals | Low temperature hydrothermal method for the preparation of LaCO3OH nanoparticles |
| US10512900B2 (en) | 2018-03-05 | 2019-12-24 | King Fahd University Of Petroleum And Minerals | Method for making LaCO3OH nanoparticles from aqueous salt solutions |
| US10646856B2 (en) | 2018-03-05 | 2020-05-12 | King Fahd University Of Petroleum And Minerals | Method for forming lanthanum hydroxycarbonate nanoparticles |
| CN109796206A (en) * | 2019-03-26 | 2019-05-24 | 武汉理工大学 | A kind of high infrared radiation ceramic material and its preparation method and application |
| CN109796206B (en) * | 2019-03-26 | 2021-11-16 | 武汉理工大学 | High-infrared-radiation ceramic material and preparation method and application thereof |
| CN112960980A (en) * | 2021-03-02 | 2021-06-15 | 中国人民解放军国防科技大学 | Ultralow-thermal-conductivity co-doped modified pyrochlore thermal barrier coating material and preparation method thereof |
| CN113121227A (en) * | 2021-03-08 | 2021-07-16 | 江苏大学 | Gadolinium-nickel co-doped magnesium-based lanthanum hexaaluminate ceramic and preparation method thereof |
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