CN115504506B - Large-scale production method of yttrium-doped zirconia - Google Patents
Large-scale production method of yttrium-doped zirconia Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000011031 large-scale manufacturing process Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 47
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 150000003746 yttrium Chemical class 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 150000003754 zirconium Chemical class 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000011858 nanopowder Substances 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000011268 mixed slurry Substances 0.000 claims description 23
- 229920002401 polyacrylamide Polymers 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229920000084 Gum arabic Polymers 0.000 claims description 15
- 241000978776 Senegalia senegal Species 0.000 claims description 15
- 239000000205 acacia gum Substances 0.000 claims description 15
- 235000010489 acacia gum Nutrition 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 11
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 11
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 11
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 42
- 238000002360 preparation method Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000006070 nanosuspension Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 6
- 238000000703 high-speed centrifugation Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- -1 zirconium ions Chemical class 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 238000012356 Product development Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012671 ceramic insulating material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to the technical field of powder materials, and particularly discloses a large-scale production process of yttrium-doped zirconia. The method comprises the following steps: adding zirconium salt and yttrium salt with the mass ratio of 10:1 into a hydrothermal reaction kettle, adding deionized water, and obtaining a reaction solution after the zirconium salt and yttrium salt are completely dissolved; regulating the pH value of the reaction solution to 8-14, and carrying out heat preservation reaction for 4 hours at 120 ℃ to obtain a suspension; centrifugally separating the suspension, and thoroughly separating the nano powder and water to obtain dry yttrium-doped zirconia nano powder; according to 10:0.03:0.03:10, mixing yttrium-doped zirconia nano-powder, a dispersing agent, a binder and water, and calcining at 1000 ℃ for 3 hours to obtain yttrium-doped zirconia particles. The invention effectively solves the problems of stability, crystal form and uniformity of zirconia at the same time, and is beneficial to the application of yttrium-doped zirconia products in multiple scenes.
Description
Technical Field
The invention relates to the technical field of powder materials, and particularly discloses a large-scale production process of yttrium-doped zirconia.
Background
Zirconia is the primary oxide of zirconium, and is an important refractory material, ceramic insulating material, and ceramic opacifier due to its inert chemical nature and its properties of high melting point, high resistivity, high refractive index, and low coefficient of thermal expansion.
Both the tetragonal phase and the cubic phase of the zirconia are octahedral structures, the stability of the structure can be maintained only at high temperature through lattice vibration balance, and zirconium ions tend to form an unstable monoclinic phase structure at lower temperature, and the thermal shock property of the material is reduced due to the increase of shear stress caused by the volume change caused by phase change, so that the mechanical property of the material is reduced, therefore, the stability of the zirconia is improved by regulating and controlling the preparation method of the zirconia from the aspect of material structural design to overcome the volume change caused by phase change. In addition, the existing zirconia production process has low product purity and uneven particles, which is a problem to be solved. More urgent, a large-scale production process for effectively solving the key problems of zirconia stability, crystal form, uniformity and other powder materials at the same time is not available at present, and the large-scale production process is a difficult problem in the technical field of new material preparation, which needs to be broken through.
Disclosure of Invention
In order to solve the problems in the existing zirconia production process, the invention aims to provide a large-scale production process of yttrium-doped zirconia, yttrium salt is doped in the hydrothermal preparation process of zirconia as a crystal stabilizer to obtain yttrium-doped zirconia, tetragonal phase zirconia can be stabilized to room temperature, so that the stability of zirconia is improved, and yttrium-doped zirconia nano-powder is granulated to obtain particles with uniform size by adopting a high-temperature calcination mode, so that the stability of the powder is further improved.
The invention discloses a large-scale production process of yttrium-doped zirconia, which adopts the following technical scheme:
a large-scale production process of yttrium-doped zirconia comprises the following steps:
s1: adding zirconium salt and yttrium salt with the mass ratio of 10:0.5-10 into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium salt and the yttrium salt in water of 0.04-0.2 Kg/L, and obtaining a reaction solution after the zirconium salt and the yttrium salt are completely dissolved;
s2: adjusting the pH value of the reaction solution to 8-14, and carrying out heat preservation reaction for 2-24 h at 80-300 ℃ to obtain suspension after the hydrothermal reaction is finished;
s3: carrying out centrifugal separation on the suspension by a horizontal centrifuge, and thoroughly separating the nano powder and water by a centrifugal atomizer to obtain dry yttrium-doped zirconia nano powder;
s4: according to 10:0.01 to 0.1:0.1 to 1: mixing the yttrium-doped zirconia nano-powder with a dispersing agent, a binder and water according to the mass ratio of 10-50, stirring uniformly to obtain mixed slurry, and calcining the mixed slurry at 800-1000 ℃ for 0.5-5 h to obtain yttrium-doped zirconia particles.
Preferably, in the step S4, the calcination temperature is 1000 ℃ and the calcination time is 2-3 hours. .
Preferably, the binder is gum arabic.
Preferably, the dispersing agent is one or more of polyacrylamide, ammonium polyacrylate and polyvinyl alcohol.
Preferably, the zirconium salt is one or more of zirconium nitrate pentahydrate, zirconium tetrachloride and zirconium oxychloride octahydrate; the yttrium salt is one or two of yttrium nitrate hexahydrate and yttrium chloride.
Preferably, the mass ratio of the zirconium salt to the yttrium salt in the S1 is 10:1.
Preferably, the hydrothermal reaction conditions of S2 are: the temperature was kept at 120℃for 4 hours.
Preferably, the suspension in the step S3 is pumped by a vacuum pump into a horizontal centrifuge, the centrifugation time is 5-30 min at the rotation speed of 4000-12000 rpm, and the nano particles in the nano suspension are efficiently cleaned and separated.
Preferably, the pH regulator is one or more of sodium hydroxide aqueous solution, ammonia water and ethylenediamine.
It is further preferable to adjust the pH of the reaction solution with an aqueous sodium hydroxide solution having a concentration of 0.5 to 4 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, yttrium ions are introduced into the preparation process of zirconium oxide as a crystal form stabilizer, meanwhile, a specific ratio of zirconium salt to yttrium salt is adopted to carry out hydrothermal reaction at 80-300 ℃, and then yttrium-doped zirconium oxide nano-powder is prepared through a horizontal centrifuge and a centrifugal atomizer, so that high-temperature tetragonal zirconium oxide can be stabilized to room temperature, and the volume change caused by phase change can be overcome, so that the mechanical property and the thermal stability of the material are improved; granulating yttrium-doped zirconia nano-powder by adopting a high-temperature calcination mode at 800-1000 ℃ to obtain particles with uniform size, so that the stability of the powder is further improved; the large-scale production process of the yttrium-doped zirconia can effectively solve the problems of purity, stability, crystal form and uniformity of the zirconia at the same time, and is beneficial to the application of yttrium-doped zirconia products in multiple scenes.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of yttrium-doped zirconia produced in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of yttrium-doped zirconia particles produced in comparative example 3 of the present invention.
FIG. 3 is a scanning electron microscope image of yttrium-doped zirconia particles prepared in example 1 of the present invention.
FIG. 4 is a scanning electron microscope image of yttrium-doped zirconia particles prepared in example 2 of the present invention.
FIG. 5 is a scanning electron microscope image of yttrium-doped zirconia particles prepared in example 3 of the present invention.
FIG. 6 is a scanning electron microscope image of yttrium-doped zirconia particles produced in example 5 of the present invention.
FIG. 7 is a scanning electron microscope image of yttrium-doped zirconia particles prepared in example 6 of the present invention.
FIG. 8 is a scanning electron microscope image of yttrium-doped zirconia particles produced in comparative example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the detailed description below, in order to make the above objects, features and advantages of the present invention more comprehensible.
Example 1
A large-scale production process of yttrium-doped zirconia comprises the following steps:
S1: adding 100Kg of zirconium oxychloride octahydrate and 10Kg of yttrium chloride into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium oxychloride octahydrate and the yttrium chloride in water of 0.05Kg/L, and completely dissolving the zirconium oxychloride octahydrate and the yttrium chloride under the action of mechanical stirring to obtain a reaction solution;
s2: adjusting the pH value of the reaction solution to 10 by adopting a 2mol/L sodium hydroxide aqueous solution, preserving the temperature at 120 ℃ for 4 hours, and obtaining a suspension after the reaction is finished;
S3: centrifuging the suspension by a vacuum pump for 20min at 8000rpm, performing high-efficiency cleaning and separation on the nano particles in the nano suspension by high-speed centrifugation, and further thoroughly separating the nano powder from water by a centrifugal atomizer to obtain dry yttrium-doped zirconium oxide nano powder;
S4: mixing yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water according to the mass ratio of 10:0.03:0.3:10, mixing materials, stirring uniformly to obtain mixed slurry, placing the mixed slurry into a rotary kiln, calcining at 800 ℃ for 1h, and granulating to obtain yttrium-doped zirconia particles.
The X-ray powder diffraction pattern of the yttrium-doped zirconia prepared in the embodiment 1 of the invention is shown in figure 1, which shows that the yttrium-doped zirconia is tetragonal phase and has very high purity.
Example 2
A large-scale production process of yttrium-doped zirconia comprises the following steps:
S1: adding 100Kg of zirconium nitrate pentahydrate and 10Kg of yttrium nitrate hexahydrate into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium nitrate pentahydrate and the yttrium nitrate hexahydrate in water of 0.05Kg/L, and completely dissolving the zirconium nitrate pentahydrate and the yttrium nitrate hexahydrate under the action of mechanical stirring to obtain a reaction solution;
S2: ammonia water is adopted to adjust the pH value of the reaction solution to 12, and the temperature is kept at 120 ℃ for 4 hours, and after the reaction is finished, suspension is obtained;
S3: centrifuging the suspension by a vacuum pump for 20min at 8000rpm, performing high-efficiency cleaning and separation on the nano particles in the nano suspension by high-speed centrifugation, and further thoroughly separating the nano powder from water by a centrifugal atomizer to obtain dry yttrium-doped zirconium oxide nano powder;
S5: mixing yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water according to the mass ratio of 10:0.03:0.3:10, mixing materials, stirring uniformly to obtain mixed slurry, placing the mixed slurry into a rotary kiln, calcining at 800 ℃ for 2 hours, and granulating to obtain yttrium-doped zirconia particles.
Example 3
A large-scale production process of yttrium-doped zirconia comprises the following steps:
S1: adding 100Kg of zirconium nitrate pentahydrate and 10Kg of yttrium chloride into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium nitrate pentahydrate and the yttrium chloride in water of 0.05Kg/L, and completely dissolving the zirconium nitrate pentahydrate and the yttrium chloride under the action of mechanical stirring to obtain a reaction solution;
S2: ammonia water is adopted to adjust the pH value of the reaction solution to 12, and the temperature is kept at 120 ℃ for 4 hours, and after the reaction is finished, suspension is obtained;
S3: centrifuging the suspension by a vacuum pump for 20min at 8000rpm, performing high-efficiency cleaning and separation on the nano particles in the nano suspension by high-speed centrifugation, and further thoroughly separating the nano powder from water by a centrifugal atomizer to obtain dry yttrium-doped zirconium oxide nano powder;
S4: mixing yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water according to the mass ratio of 10:0.03:0.3:10, mixing materials, stirring uniformly to obtain mixed slurry, placing the mixed slurry into a rotary kiln, calcining at 800 ℃ for 3 hours, and granulating to obtain yttrium-doped zirconia particles.
Example 4
A large-scale production process of yttrium-doped zirconia comprises the following steps:
S1: adding 100Kg of zirconium oxychloride octahydrate and 10Kg of yttrium nitrate hexahydrate into a hydrothermal reaction kettle, adding deionized water according to the concentration of the zirconium oxychloride octahydrate and the yttrium nitrate hexahydrate in water of 0.05Kg/L, and completely dissolving the zirconium oxychloride octahydrate and the yttrium nitrate hexahydrate under the action of mechanical stirring to obtain a reaction solution;
S2: ammonia water is adopted to adjust the pH value of the reaction solution to 12, and the temperature is kept at 120 ℃ for 4 hours, and after the reaction is finished, suspension is obtained;
S3: centrifuging the suspension by a vacuum pump for 20min at 8000rpm, performing high-efficiency cleaning and separation on the nano particles in the nano suspension by high-speed centrifugation, and further thoroughly separating the nano powder from water by a centrifugal atomizer to obtain dry yttrium-doped zirconium oxide nano powder;
S4: mixing yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water according to the mass ratio of 10:0.03:0.3:10, mixing materials, stirring uniformly to obtain mixed slurry, placing the mixed slurry into a rotary kiln, calcining at 1000 ℃ for 1h, and granulating to obtain yttrium-doped zirconia particles.
Example 5
A large-scale production process of yttrium-doped zirconia comprises the following steps:
S1: adding 100Kg of zirconium oxychloride octahydrate and 10Kg of yttrium chloride into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium oxychloride octahydrate and the yttrium chloride in water of 0.05Kg/L, and completely dissolving the zirconium oxychloride octahydrate and the yttrium chloride under the action of mechanical stirring to obtain a reaction solution;
S2: ammonia water is adopted to adjust the pH value of the reaction solution to 12, and the temperature is kept at 120 ℃ for 4 hours, and after the reaction is finished, suspension is obtained;
S3: centrifuging the suspension by a vacuum pump for 20min at 8000rpm, performing high-efficiency cleaning and separation on the nano particles in the nano suspension by high-speed centrifugation, and further thoroughly separating the nano powder from water by a centrifugal atomizer to obtain dry yttrium-doped zirconium oxide nano powder;
S4: mixing yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water according to the mass ratio of 10:0.03:0.3:10, mixing materials, stirring uniformly to obtain mixed slurry, placing the mixed slurry into a rotary kiln, calcining at 1000 ℃ for 2 hours, and granulating to obtain yttrium-doped zirconia particles.
Example 6
S1: adding 100Kg of zirconium nitrate pentahydrate and 10Kg of yttrium nitrate hexahydrate into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium nitrate pentahydrate and the yttrium nitrate hexahydrate in water of 0.05Kg/L, and completely dissolving the zirconium nitrate pentahydrate and the yttrium nitrate hexahydrate under the action of mechanical stirring to obtain a reaction solution;
s2: adjusting the pH value of the reaction solution to 10 by adopting a 2mol/L sodium hydroxide aqueous solution, preserving heat at 120 ℃ for 4, and obtaining a suspension after the reaction is finished;
S3: centrifuging the suspension by a vacuum pump for 20min at 8000rpm, performing high-efficiency cleaning and separation on the nano particles in the nano suspension by high-speed centrifugation, and further thoroughly separating the nano powder from water by a centrifugal atomizer to obtain dry yttrium-doped zirconium oxide nano powder;
S4: mixing yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water according to the mass ratio of 10:0.03:0.3:10, mixing materials, stirring uniformly to obtain mixed slurry, placing the mixed slurry into a rotary kiln, calcining at 1000 ℃ for 3 hours, and granulating to obtain yttrium-doped zirconia particles.
Comparative example
Comparative example 1 differs from example 4 only in that in S4 the yttrium-doped zirconia particles were obtained by granulating the mixed slurry after calcination in a rotary kiln at 600 ℃ for 1 hour.
Comparative example 2 differs from example 5 only in that in S4 the yttrium-doped zirconia particles were obtained by calcining the mixed slurry in a rotary kiln at 600 ℃ for 2 hours and then granulating.
Comparative example 3 differs from example 6 only in that in S4 the yttrium-doped zirconia particles were obtained by granulating the mixed slurry after calcination in a rotary kiln at 600 ℃ for 3 hours.
Comparative example 4 differs from example 4 only in that in S4 the yttrium-doped zirconia particles were obtained by granulating the mixed slurry after calcination in a rotary kiln at 1100 ℃ for 1 hour.
Comparative example 5 differs from example 5 only in that in S4 the yttrium-doped zirconia particles were obtained by granulating the mixed slurry after calcination in a rotary kiln at 1100 ℃ for 2 hours.
Comparative example 6 differs from example 6 only in that in S4 the yttrium-doped zirconia particles were obtained by granulating the mixed slurry after calcination in a rotary kiln at 1100 ℃ for 3 hours.
The scanning electron microscope of the yttrium-doped zirconia particles prepared according to the mass production process of the yttrium-doped zirconia of the comparative example 3 is shown in fig. 2, and it can be seen from fig. 2 that the particle size after calcination for 3 hours at 600 ℃ is not uniform and has breakage. Further increases in calcination temperature to 800 ℃ were found in examples 1-3 to improve particle uniformity and longer calcination time was more beneficial to obtain regular particles (fig. 3-5). Calcination was carried out at 1000℃in examples 4-6, the yttrium-doped zirconia particles being very conventional and intact, especially at calcination times of 2-3h (FIGS. 6-7). At the higher calcination temperatures of comparative examples 4-6 (1100 ℃ C.), the calcined particles were again subject to cracking (FIG. 8).
As can be seen from the comparison of the properties of the products produced by the yttrium-doped zirconia particle production processes of examples 1-6 and comparative examples 1-6 above, calcination at 1000℃for 2-3 hours is the most desirable condition for producing yttrium-doped zirconia particles, mainly due to the fact that high temperature calcination can completely remove the dispersant and binder from the mixed slurry, and in addition, high temperature can refine the grains and promote grain growth, improving creep and stress rupture resistance. However, when the temperature is higher than 1000 ℃, sintering of the particles is caused, resulting in breakage of the particles. Therefore, the yttrium-doped zirconia particle production process disclosed by the invention has an surprise product performance turning point at the calcining temperature of 1000 ℃, and has great economic value for large-scale production of yttrium-doped zirconia.
Besides, the invention also discusses the influence of the proportions of yttrium-doped zirconia nano-powder, a dispersing agent, a binder and water and the types of the binder on the quality of yttrium-doped zirconia particles, and the invention is shown in comparative examples 7-19.
Comparative example 7 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water are mixed in a mass ratio of 10:0.05:0.3:10, carrying out batching.
Comparative example 8 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water are mixed in a mass ratio of 10:0.03:0.5:10, carrying out batching.
Comparative example 9 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water are mixed in a mass ratio of 10:0.05:0.5:10, carrying out batching.
Comparative example 10 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water are mixed in a mass ratio of 10:0.03:0.7:10, carrying out batching.
Comparative example 11 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water are mixed in a mass ratio of 10:0.07:0.3:10, carrying out batching.
Comparative example 12 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, gum arabic and water are mixed in a mass ratio of 10:0.07:0.7:10, carrying out batching.
Comparative example 13 differs from example 5 only in that in S4, yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.03:0.3:10, carrying out batching.
Comparative example 14 differs from example 5 only in that in S4, yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.05:0.3:10, carrying out batching.
Comparative example 15 differs from example 5 only in that in S4 yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.03:0.5:10, carrying out batching.
Comparative example 16 differs from example 5 only in that in S4, yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.05:0.5:10, carrying out batching.
Comparative example 17 differs from example 5 only in that in S4, yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.03:0.7:10, carrying out batching.
Comparative example 18 differs from example 5 only in that in S4, yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.07:0.3:10, carrying out batching.
Comparative example 19 differs from example 5 only in that in S4, yttrium-doped zirconia nano-powder, polyacrylamide, polyurethane adhesive and water are mixed according to a mass ratio of 10:0.07:0.7:10, carrying out batching.
Comparative examples 7-19 the proportions of yttrium-doped zirconia nanopowder, dispersant, binder and water and the types of binders were adjusted, and the yttrium-doped zirconia particles produced showed the product quality shown in table 1 below:
TABLE 1 quality of products of yttrium-doped zirconia particles prepared from comparative examples 7-19
| Project | Particle uniformity | Particle integrity | Product quality rating |
| Example 5 | Very uniform | Is very complete | Primary product |
| Comparative example 7 | Uniformity of | In general | Secondary product |
| Comparative example 8 | In general | Complete and complete | Secondary product |
| Comparative example 9 | In general | In general | Three-stage product |
| Comparative example 10 | Uniformity of | In general | Secondary product |
| Comparative example 11 | Uniformity of | In general | Secondary product |
| Comparative example 12 | In general | In general | Three-stage product |
| Comparative example 13 | In general | In general | Three-stage product |
| Comparative example 14 | In general | In general | Three-stage product |
| Comparative example 15 | In general | In general | Three-stage product |
| Comparative example 16 | In general | In general | Three-stage product |
| Comparative example 17 | In general | In general | Three-stage product |
| Comparative example 18 | In general | In general | Three-stage product |
| Comparative example 19 | In general | In general | Three-stage product |
The results are shown in Table 1, where changing the type of binder and adjusting the proportions of the components all had an effect on the regularity and integrity of the yttrium-doped zirconia particles.
The preparation methods provided in preparation examples 1-6 of the yttrium-doped zirconia powder according to the present invention can obtain tetragonal yttrium-doped zirconia nano-powder with stable structure, and can obtain yttrium-doped zirconia particles with more uniform and more complete size. As can be seen from the comparison of the quality of the products of example 5 and comparative examples 7-19, the uniformity and integrity of the yttrium-doped zirconia particles were more desirable when the mass ratio of yttrium-doped zirconia nano-powder, dispersant, binder and water was 10:0.03:0.3:10, and the binder was gum arabic.
In the invention, yttrium salt is used as a crystal form stabilizer, and a pH value regulator is used as a hydrolysis accelerator, so that tetragonal zirconia can be stabilized to room temperature, and the volume change caused by phase change can be overcome, thereby improving the mechanical property and the thermal stability of the material. The invention adopts a high-temperature calcination mode to further improve the stability of the yttrium-doped zirconia nano-powder, and obtains the preparation conditions of yttrium-doped zirconia particles with standard crystal form, consistent shape and high purity through condition optimization. In addition, the invention also provides a whole set of yttrium-doped zirconia preparation process and equipment, realizes full-automatic production, and solves the problems of safety, high energy consumption, large pollution, high cost, low purity, uneven particles and the like in the production of nano zirconia.
The large-scale production process greatly improves the comprehensive production efficiency, obviously reduces the manufacturing cost, the product development period, the product reject ratio and the energy consumption of unit output value, realizes the full-automatic production, and obtains the yttrium-doped zirconia product with good crystal form quality and uniform particles.
The foregoing has outlined rather broadly the more detailed description of the invention in order that the detailed description of the invention that follows may be better understood, and in order that the present principles and embodiments may be better understood; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (6)
1. The large-scale production method of the yttrium-doped zirconia is characterized by comprising the following steps of:
s1: adding zirconium salt and yttrium salt with the mass ratio of 10:0.5-10 into a hydrothermal reaction kettle, adding deionized water according to the total concentration of the zirconium salt and the yttrium salt in water of 0.04-0.2 Kg/L, and obtaining reaction liquid after the zirconium salt and the yttrium salt are completely dissolved under the action of mechanical stirring;
s2: adjusting the pH value of the reaction solution to 8-14, and carrying out heat preservation reaction for 2-24 h at 80-300 ℃ to obtain suspension after the hydrothermal reaction is finished;
S3: pumping the suspension into a horizontal centrifuge by a vacuum pump, centrifuging for 5-30 min at 4000-12000 rpm, centrifuging the suspension by the horizontal centrifuge, and thoroughly separating the nano powder and water by a centrifugal atomizer to obtain dry yttrium-doped zirconia nano powder;
S4: mixing yttrium-doped zirconia nano-powder, a dispersing agent, a binder and water according to the mass ratio of 10:0.03:0.3:10, stirring uniformly to obtain mixed slurry, and calcining the mixed slurry at 800-1000 ℃ for 1-3 h to obtain yttrium-doped zirconia particles;
The binder is gum arabic;
the dispersing agent is one or more of polyacrylamide, ammonium polyacrylate and polyvinyl alcohol;
the zirconium salt is one or more of zirconium nitrate pentahydrate, zirconium tetrachloride and zirconium oxychloride octahydrate; the yttrium salt is one or two of yttrium nitrate hexahydrate and yttrium chloride.
2. The method for mass production of yttrium-doped zirconia according to claim 1, wherein in S4, the calcination temperature is 1000 ℃ and the calcination time is 2-3 hours.
3. The method for mass production of yttrium-doped zirconia according to claim 1, wherein the mass ratio of zirconium salt to yttrium salt in S1 is 10:1.
4. The method for mass production of yttrium-doped zirconia according to claim 1, wherein the hydrothermal reaction conditions of S2 are: the temperature was kept at 120℃for 4 hours.
5. The method for mass production of yttrium-doped zirconia according to claim 1, wherein the pH regulator for regulating the pH value of the reaction solution of S2 is one or more of aqueous sodium hydroxide solution, aqueous ammonia and ethylenediamine.
6. The method for mass production of yttrium-doped zirconia according to claim 5, wherein the pH value of the reaction solution is adjusted by using sodium hydroxide aqueous solution with the concentration of 0.5-4 mol/L.
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| CN101275212A (en) * | 2008-03-31 | 2008-10-01 | 中国地质大学（武汉） | Preparation for nanostructured Yt-stable spherical zircite powder for thermal spraying |
| KR20100081105A (en) * | 2009-01-05 | 2010-07-14 | 한국표준과학연구원 | Method of synthesizing zirconia nano powders |
| CN104129991A (en) * | 2014-07-23 | 2014-11-05 | 西安航天复合材料研究所 | Preparation method of low-cost hollow spherical YSZ powder for plasma spraying |
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| CN101275212A (en) * | 2008-03-31 | 2008-10-01 | 中国地质大学（武汉） | Preparation for nanostructured Yt-stable spherical zircite powder for thermal spraying |
| KR20100081105A (en) * | 2009-01-05 | 2010-07-14 | 한국표준과학연구원 | Method of synthesizing zirconia nano powders |
| CN104129991A (en) * | 2014-07-23 | 2014-11-05 | 西安航天复合材料研究所 | Preparation method of low-cost hollow spherical YSZ powder for plasma spraying |
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