CN109111230A - A kind of yttrium oxide-bitter earth nano composite granule and preparation method thereof - Google Patents
A kind of yttrium oxide-bitter earth nano composite granule and preparation method thereof Download PDFInfo
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- CN109111230A CN109111230A CN201811289297.2A CN201811289297A CN109111230A CN 109111230 A CN109111230 A CN 109111230A CN 201811289297 A CN201811289297 A CN 201811289297A CN 109111230 A CN109111230 A CN 109111230A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 26
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 24
- 239000008187 granular material Substances 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000000499 gel Substances 0.000 claims abstract description 28
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 28
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008139 complexing agent Substances 0.000 claims abstract description 23
- 239000011240 wet gel Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 5
- 239000000395 magnesium oxide Substances 0.000 abstract description 4
- 229910002106 crystalline ceramic Inorganic materials 0.000 abstract description 3
- 239000011222 crystalline ceramic Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 72
- 238000000034 method Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 235000019580 granularity Nutrition 0.000 description 3
- 239000008236 heating water Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 150000003746 yttrium Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 235000019587 texture Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Abstract
The present invention relates to a kind of yttrium oxide-bitter earth nano composite granules and preparation method thereof.The preparation method includes: to prepare the metal ion solution comprising ruthenium ion and magnesium ion, and dispersing agent is then added into metal ion solution, obtains reaction solution；Reaction solution and complexing agent are mixed, adjust the pH of mixed system, validity response when then carrying out mixed system obtains sol system；Sol system is subjected to sol gel processing, obtains wet gel；Wet gel is freeze-dried, dry gel powder is obtained；Dry gel powder is calcined, the yttrium oxide-bitter earth nano composite granule is obtained.The preparation method is introduced into yttrium oxide polycrystalline material using magnesia as the second phase, and nano composite ceramic is formed, and can improve the defect of single-phase polycrystalline crystalline ceramics, inhibits yttrium oxide combinations grain length big；By adjusting sol-gel flouring technology acquisition pattern, uniform, good dispersion, partial size are less than yttrium oxide-bitter earth nano composite granule of 20nm.
Description
Technical field
The present invention relates to ceramic powder material technical field more particularly to a kind of yttrium oxide-bitter earth nano composite granules
And preparation method thereof.
Background technique
Yttrium oxide is a kind of important ceramic material, while being also to apply more one of rare earth oxide.Yttrium oxide material
The purposes for having very more is expected, as superalloy, the sinterable pottery at high-intensity and high-tenacity can be obtained in its disperse in the alloy
Porcelain and yttrium oxide superfine powder can significantly improve the picture quality of colour TV and the luminous efficiency of fluorescent lamp, service life etc..With
The development of high-tech, Yttrium oxide material in fields such as electronics, Aeronautics and Astronautics, atomic energy using increasingly extensive, to yttrium oxide
The requirement of powder granularity is also higher and higher.
Conventional oxidation yttrium material due to raw material and technique limitation, crystal grain during the sintering process can abnormal growth, influence it
Mechanical behavior under high temperature.In addition, the nano ceramics of uniform texture in order to obtain, prepared sizes are uniform, the uniform nanometer of component
Powder is particularly important, and the partial size of current single-phase Yttrium oxide material is generally micron order, is extremely difficult to nanoscale, and at present
Yttrium oxide material that there is also granularities is inhomogenous, poor, the easy to reunite problem of dispersibility.
Summary of the invention
(1) technical problems to be solved
The present invention is to solve following one or more technical problem:
Conventional oxidation yttrium material due to raw material and technique limitation, crystal grain during the sintering process can abnormal growth, influence it
Mechanical behavior under high temperature；
The partial size of single-phase yttrium oxide powder material is generally micron order, is extremely difficult to nanoscale；
That there is also granularities is inhomogenous for current yttrium oxide powder material, poor, the easy to reunite problem of dispersibility.
(2) technical solution
In order to solve said one or multiple technical problems, the present invention provides the following technical scheme that
1, a kind of yttrium oxide-bitter earth nano composite granule preparation method, the preparation method include the following steps:
(1) metal ion solution comprising ruthenium ion and magnesium ion is prepared, dispersion is then added into metal ion solution
Agent obtains reaction solution；
(2) reaction solution and complexing agent are mixed, adjusts the pH of mixed system, it is anti-that mixed system is then carried out timeliness
It answers, obtains sol system；
(3) sol system is subjected to sol gel processing, obtains wet gel；
(4) wet gel is freeze-dried, obtains dry gel powder；
(5) dry gel powder is calcined, obtains the yttrium oxide-bitter earth nano composite granule.
2, preparation method according to technical solution 1, the complexing agent select EDTA and the pH tune by mixed system
It saves to 5~6.
3, the preparation method according to technical solution 1 or 2 adjusts the pH of mixed system using ammonium hydroxide and nitric acid solution；
Preferably, the concentration of ammonium hydroxide is 1~1.5mol/L, and the concentration of nitric acid solution is 1~1.5mol/L.
4, the preparation method according to any one of technical solution 1 to 3, the mole of the complexing agent and ruthenium ion and
The ratio of the sum of the mole of magnesium ion is (1~3): 1.
5, preparation method according to any one of technical solution 1 to 4, in the metal ion solution, ruthenium ion
Molar ratio with magnesium ion is 1:(1.8~2.2).
6, the preparation method according to any one of technical solution 1 to 5, ruthenium ion in the metal ion solution and
The total concentration of magnesium ion is 0.7~0.8mol/L.
7, the preparation method according to any one of technical solution 1 to 6, the dispersing agent are selected from ethylene glycol, poly- second two
Alcohol, stearic acid are any one or more of；Preferably, mole of the sum of mole of ruthenium ion and magnesium ion and the dispersing agent
The ratio of amount is 1:1~1:5.
8, it is solidifying to be carried out as follows the colloidal sol-for the preparation method according to any one of technical solution 1 to 7
Gelatinization processing:
Sol system is placed in heating in water bath and heating process is with stirring；
Preferably, the temperature of the water-bath is controlled at 60~80 DEG C；
Preferably, until stopping heating when there is the wet gel to lose flowability.
9, the preparation method according to any one of technical solution 1 to 8, it is described freeze-drying at -40~-70 DEG C into
Row；And/or
The calcining carries out at 600~800 DEG C.
10, a kind of yttrium oxide-bitter earth nano composite granule, using preparation side described in any one of technical solution 1 to 9
Method is made.
(3) beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
Preparation method provided by the invention is introduced into yttrium oxide polycrystalline material using magnesia as the second phase, and nanometer is formed
Composite ceramics can improve the defect of single-phase polycrystalline crystalline ceramics, inhibit yttrium oxide combinations grain length big, have infra-red china excellent
Mechanical property.
In order to which prepared sizes are uniform, the uniform composite nano-powder of component, the present invention is by adjusting sol-gel powder work
Skill obtain pattern uniformly, good dispersion, partial size be less than 20nm yttrium oxide-bitter earth nano composite granule.
Detailed description of the invention
Fig. 1 is yttrium oxide made from embodiment 1-bitter earth nano composite granule transmitted electron scanning figure.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of yttrium oxide-bitter earth nano composite granule preparation method, the preparation method includes
Following steps:
(1) reaction solution is prepared
First prepare include ruthenium ion and magnesium ion metal ion solution, ruthenium ion can use yttrium nitrate or it is other can
The yttrium salt of dissolution obtains, and magnesium ion can use magnesium nitrate or other soluble magnesium salts obtain；
Then dispersing agent is added into metal ion solution, preparation obtains reaction solution.
In this step, the molar ratio of ruthenium ion and magnesium ion is preferably 1:(1.8~2.2), it can be within the scope of this
Any number (including two endpoint values), for example, can be 1:1.8,1:1.9,1:2.0,1:2.1 or 1:2.2.In metal ion
In solution, the sum of molar concentration of ruthenium ion and magnesium ion is preferably 0.7~0.8mol/L, can be the arbitrary number within the scope of this
It is worth (including two endpoint values), for example, can be 0.7mol/L, 0.71mol/L, 0.72mol/L, 0.73mol/L, 0.74mol/
L、0.75mol/L、0.76mol/L、0.77mol/L、0.78mol/L、0.79mol/L、0.8mol/L。
The present invention is not particularly limited dispersing agent used in the step and its dosage, but in ruthenium ion and magnesium ion
The sum of molar concentration for 0.7~0.8mol/L in the case where, the dispersing agent is preferably selected from ethylene glycol, polyethylene glycol, tristearin
Acid is any one or more of, and the dosage of the dispersing agent is preferably determined according to such as under type: mole of ruthenium ion and magnesium ion
The ratio of the sum of amount and the mole of the dispersing agent is 1:1~1:5, can be any number (including the endpoint within the scope of this
Value) for example, can be 1:1,1:2,1:3,1:4,1:5.
(2) sol system is prepared by reaction
The prepared reaction solution of step (1) and complexing agent are mixed, the pH of mixed system is adjusted, then by mixed system
Validity response when progress, obtains sol system.
In this step, complexing agent is preferably EDTA (Ethylenediaminetetraacetic acid, ethylenediamine tetraacetic
Acetic acid).When complexing agent is EDTA, the pH of mixed system is adjusted to 5~6 in the next steps (for example, can for 5,5.1,
5.2,5.3,5.4,5.5,5.6,5.7,5.8,5.9,6).The dosage of complexing agent can be according to mole matter of ruthenium ion and magnesium ion
Amount is determined, and the ratio of preferably the sum of mole of complexing agent and ruthenium ion and the mole of magnesium ion is (1~3):
1, it can be any number (including endpoint value) within the scope of this, for example, can be 1:1,2:1,3:1.
When using EDTA as complexing agent, EDTA first can be configured to certain density solution, for example, making using EDTA
When for complexing agent, it is 7~8 that EDTA can be configured to pH, concentration be 1~1.5mol/L (for example, can be 1mol/L,
1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L) EDTA solution.
The present invention is not particularly limited reagent used when adjusting pH, but when complexing agent selects EDTA, preferably
It is the pH of mixed system to be adjusted using ammonium hydroxide and nitric acid solution, the concentration of ammonium hydroxide is preferably 1~1.5mol/L (for example, can be
1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L), the concentration of nitric acid solution is preferably 1~
1.5mol/L (for example, can be 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L).It adjusts
When the pH of mixed system, precipitating dissolution rapidly is generated when ammonium hydroxide is added dropwise in solution, solution is as clear as crystal after the completion of pH is adjusted.
When validity response can carry out at room temperature, the time of clock synchronization validity response of the present invention is not particularly limited, preferably
In 30min or more, such as 50~100min, preferably 60~70min can be reacted at room temperature, obtain transparent sol body
System.
(3) sol gel is handled
Sol system obtained in step (2) is subjected to sol gel processing, obtains wet gel.Promote colloidal sol to solidifying
There are many ways to glue converts, the present invention is not specifically limited it, adds for example, sol system can be placed in water bath
Heat and the adjoint stirring of heating process, to realize conversion of the colloidal sol to gel.Sol gel processing is carried out using this method
When, the temperature of the water-bath, which is preferably controlled in 60~80 DEG C, to be any number within the scope of this, for example, can for 60 DEG C,
61℃、62℃、63℃、64℃、65℃、66℃、67℃、68℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76
℃,77℃,78℃,79℃,80℃.The time of heating water bath is unsuitable too long, after there is gel, i.e. when gel loses flowability
It can stop heating, also contain the crystallization water in gel at this time, be a kind of wet gel.
(4) it is freeze-dried
The wet gel to lose flowability is freeze-dried, dry gel powder is obtained；Temperature of the present invention to freeze-drying
Degree is not particularly limited, for example, can be at -40~-70 DEG C (for example, can be -40 DEG C, -41 DEG C, -42 DEG C, -43 DEG C, -44
℃、-45℃、-46℃、-47℃、-48℃、-49℃、-50℃、-51℃、-52℃、-53℃、-54℃、-55℃、-56℃、-
57℃、-58℃、-59℃、-60℃、-61℃、-62℃、-63℃、-64℃、-65℃、-66℃、-67℃、-68℃、-69
DEG C, -70 DEG C) at a temperature of be freeze-dried.
(5) it calcines
Dry gel powder made from step (4) is calcined, calcination temperature is preferably 600~800 DEG C, can be the model
Any number (comprising endpoint value) in enclosing, for example, can be 600 DEG C, 610 DEG C, 620 DEG C, 630 DEG C, 640 DEG C, 650 DEG C, 660
℃、670℃、680℃、690℃、700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、
The yttrium oxide-bitter earth nano composite granule can be obtained in 790 DEG C, 800 DEG C after calcining.
More fully, the present invention provides preparation method include the following steps:
(1) reaction solution is prepared
First prepare include ruthenium ion and magnesium ion metal ion solution, ruthenium ion can use yttrium nitrate or it is other can
The yttrium salt of dissolution obtains, and magnesium ion can use magnesium nitrate or other soluble magnesium salts obtain；Then to metal ion solution
Middle addition dispersing agent, preparation obtain reaction solution.In this step, the molar ratio of ruthenium ion and magnesium ion be 1:(1.8~
2.2).In metal ion solution, the sum of molar concentration of ruthenium ion and magnesium ion is 0.7~0.8mol/L.The dispersing agent
Any one or more of selected from ethylene glycol, polyethylene glycol, stearic acid, the dosage of the dispersing agent is preferably true according to such as under type
Fixed: the ratio of the sum of mole of ruthenium ion and magnesium ion and the mole of the dispersing agent is 1:1~1:5.
(2) sol system is prepared by reaction
The prepared reaction solution of step (1) and complexing agent are mixed, the pH of mixed system is adjusted, then by mixed system
Validity response when progress, obtains sol system.
In this step, complexing agent is EDTA (Ethylenediaminetetraacetic acid, ethylenediamine tetrem
Acid).When complexing agent is EDTA, the pH of mixed system is adjusted to 5~6 in the next steps.The mole and yttrium of complexing agent
The ratio of the sum of the mole of ion and magnesium ion is (1~3): 1.
When using EDTA as complexing agent, EDTA is first configured to certain density solution, for example, using EDTA as network
When mixture, it is 7~8 that EDTA, which is configured to pH, and concentration is 1~1.5mol/L.
When adjusting pH, the pH of mixed system is adjusted using ammonium hydroxide and nitric acid solution, the concentration of ammonium hydroxide is 1~1.5mol/L,
The concentration of nitric acid solution is 1~1.5mol/L.When adjusting the pH of mixed system, generation precipitating is molten rapidly in solution when ammonium hydroxide is added dropwise
Solution, solution is as clear as crystal after the completion of pH is adjusted.
When validity response carry out at room temperature, the reaction time in 30min or more, obtains transparent sol system.
(3) sol gel is handled
Sol system obtained in step (2) is subjected to sol gel processing, obtains wet gel.In this step, will
Sol system is placed in heating in water bath and heating process is with stirring, to realize conversion of the colloidal sol to gel.Utilize this
When one method carries out sol gel processing, the temperature of the water-bath is controlled at 60~80 DEG C.The time of heating water bath should not mistake
It is long, after there is gel, it can stop heating when gel loses flowability, also contain the crystallization water in gel at this time, be a kind of
Wet gel.
(4) it is freeze-dried
The wet gel to lose flowability is freeze-dried, the temperature of freeze-drying is -40~-70 DEG C, is obtained dry solidifying
Rubber powder end.
(5) it calcines
The dry gel powder that volume is made in step (4) is calcined, calcination temperature is 600~800 DEG C, obtains the oxidation
Yttrium-bitter earth nano composite granule.
Yttrium oxide-bitter earth nano composite granule made from above-mentioned preparation method is utilized the present invention also provides a kind of.It should
Yttrium oxide-bitter earth nano composite granule magnesia is introduced into yttrium oxide polycrystalline material as the second phase, is formed nano combined
Ceramic powder can improve the defect of single-phase polycrystalline crystalline ceramics, inhibit yttrium oxide combinations grain length big, have infra-red china excellent
Mechanical property.The yttrium oxide-bitter earth nano composite granule homogeneous grain diameter, component is uniform, pattern uniformly, good dispersion, grain
Diameter is less than 20nm.
It is the embodiment that the present invention enumerates below.
Embodiment 1
Take the Y (NO of 0.05mol3)3·6H2Mg (the NO of O and 0.1mol3)2·6H2O prepares 200mL metal ion solution.
0.1mol ethylene glycol is added into metal ion solution as dispersing agent.
EDTA alkaline solution, pH value of solution 7 are prepared, EDTA concentration is 1mol/L.
The EDTA alkaline solution 150mL of preparation is taken, metal ion solution is added.
Adjusting above-mentioned mixed system pH by 1mol/L ammonium hydroxide and 1mol/L nitric acid is 5.2, during adjusting pH, is added dropwise
When ammonium hydroxide in solution generate precipitating rapidly dissolution, pH adjust after the completion of solution it is as clear as crystal, at room temperature when validity response 60min, obtain
To transparent sol system.
Sol system is placed in and heat while being stirred under 80 DEG C of water baths, wet gel is obtained.
The wet gel to lose flowability is freeze-dried, dry gel powder is obtained, freeze-drying temperature is -50 DEG C.
Dry gel powder is calcined at 650 DEG C, 2h is kept the temperature, obtains yttrium oxide-bitter earth nano composite granule, powder
Transmitted electron scanned photograph as shown in Figure 1, powder is spherical in shape, good dispersion, partial size is in 20nm or less.
Embodiment 1 is mixed to get female salt with yttrium nitrate, magnesium nitrate, and EDTA is complexing agent, using sol-gal process, by matching
Mixed solution processed adjusts the technical process such as pH and initial concentration, sol-gel, fast freezing, drying, calcining, prepares particle
Diameter is small and is evenly distributed, the yttrium oxide of good dispersion-magnesia composite nano powder.Technology preparation process is simple, at low cost
It is honest and clean, it is suitable for batch production.
Embodiment 2
Take the Y (NO of 0.05mol3)3·6H2Mg (the NO of O and 0.09mol3)2·6H2It is molten to prepare 200mL metal ion by O
Liquid.
0.14mol ethylene glycol is added into metal ion solution as dispersing agent.
EDTA alkaline solution, pH value of solution 7 are prepared, EDTA concentration is 1mol/L.
The EDTA alkaline solution 150mL of preparation is taken, metal ion solution is added.
Adjusting above-mentioned mixed system pH by 1mol/L ammonium hydroxide and 1mol/L nitric acid is 5.0, during adjusting pH, is added dropwise
When ammonium hydroxide in solution generate precipitating rapidly dissolution, pH adjust after the completion of solution it is as clear as crystal, at room temperature when validity response 60min, obtain
To transparent sol system.
Sol system is placed in and heat while being stirred under 60 DEG C of water baths, wet gel is obtained.
The wet gel to lose flowability is freeze-dried, dry gel powder is obtained, freeze-drying temperature is -60 DEG C.
Dry gel powder is calcined at 700 DEG C, 2h is kept the temperature, obtains yttrium oxide-bitter earth nano composite granule.Through examining
It surveys, powder is spherical in shape, and good dispersion, partial size is in 20nm or less.
Embodiment 3
Take the Y (NO of 0.05mol3)3·6H2Mg (the NO of O and 0.11mol3)2·6H2It is molten to prepare 200mL metal ion by O
Liquid.
0.8mol ethylene glycol is added into metal ion solution as dispersing agent.
EDTA alkaline solution, pH value of solution 7 are prepared, EDTA concentration is 1mol/L.
The EDTA alkaline solution 480mL of preparation is taken, metal ion solution is added.
Adjusting above-mentioned mixed system pH by 1mol/L ammonium hydroxide and 1mol/L nitric acid is 5.6, during adjusting pH, is added dropwise
When ammonium hydroxide in solution generate precipitating rapidly dissolution, pH adjust after the completion of solution it is as clear as crystal, at room temperature when validity response 60min, obtain
To transparent sol system.
Sol system is placed in and heat while being stirred under 60 DEG C of water baths, wet gel is obtained.
The wet gel to lose flowability is freeze-dried, dry gel powder is obtained, freeze-drying temperature is -60 DEG C.
Dry gel powder is calcined at 700 DEG C, 2h is kept the temperature, obtains yttrium oxide-bitter earth nano composite granule.Through examining
It surveys, powder is spherical in shape, and good dispersion, partial size is in 20nm or less.
Embodiment 4
That the preparation method is the same as that of Example 1 is substantially the same for embodiment 4, the difference is that: when adjusting pH, by mixture
The pH of system is adjusted to 4.8.Occur EDTA precipitating at this time, solution is irradiated by light beam, does not occur Tyndall effect, without molten in solution
Colloid system.Colloidal sol can be successfully made when the pH of mixed system is adjusted to 4.8 by repeating verification experimental verification in inventor once in a while.
Due to less reproducible, risk is too big, is not mature experiment condition.
Embodiment 5
That the preparation method is the same as that of Example 1 is substantially the same for embodiment 5, the difference is that: when adjusting pH, by mixture
The pH of system is adjusted to 7.Occur yttrium, magnesium hydroxide precipitating at this time, is not complexed with EDTA and generates collosol structure.
Embodiment 6
Using glucose as complexing agent, preparation method includes the following steps: the preparation method of embodiment 6
Take the Y (NO of 0.05mol3)3·6H2Mg (the NO of O and 0.1mol3)2·6H2O prepares 200mL metal ion solution.
0.1mol ethylene glycol is added into metal ion solution as dispersing agent.
It takes 5g glucose sugared, 600mL distilled water is added, is configured to glucose solution.
The glucose solution of preparation is taken, metal ion solution is added.
Mixed system is placed in and heat while being stirred under 80 DEG C of water baths, without sol system in solution.
Ruthenium ion and magnesium ion can not be complexed as a kind of polysaccharide in glucose, and utilizing it as " complexing agent " can only obtain
There is the phenomenon that polymerization, segregation and enrichment in mixture, the mixture.
Embodiment 7
That the preparation method is the same as that of Example 1 is substantially the same for embodiment 7, the difference is that: after obtaining wet gel,
Continue to dry at 80 DEG C, obtained powder reuniting is serious, and maximum aggregate reaches 200nm or more.Free water in wet gel passes through
Heating water bath is removed, but wherein there are also the crystallization water (or perhaps residual water).If being dried at this time to wet gel,
The problem of removing the crystallization water therein, making its complete dehydration, be easy to appear reunion instead.
Experimental result from embodiment 1 to embodiment 7 can be seen that can using the preparation process condition after present invention optimization
To obtain homogeneous grain diameter, component is uniform, pattern uniformly, good dispersion, partial size less than 20nm yttrium oxide-bitter earth nano it is compound
Powder can be used as the raw material for preparing infra-red china.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of yttrium oxide-bitter earth nano composite granule preparation method, it is characterised in that: the preparation method includes as follows
Step:
(1) metal ion solution comprising ruthenium ion and magnesium ion is prepared, dispersing agent is then added into metal ion solution, obtains
To reaction solution；
(2) reaction solution and complexing agent are mixed, adjusts the pH of mixed system, validity response when then carrying out mixed system obtains
To sol system；
(3) sol system is subjected to sol gel processing, obtains wet gel；
(4) wet gel is freeze-dried, obtains dry gel powder；
(5) dry gel powder is calcined, obtains the yttrium oxide-bitter earth nano composite granule.
2. preparation method according to claim 1, it is characterised in that: the complexing agent selects EDTA and by mixed system
PH be adjusted to 5~6.
3. preparation method according to claim 1 or 2, it is characterised in that: adjust mixture using ammonium hydroxide and nitric acid solution
The pH of system；Preferably, the concentration of ammonium hydroxide is 1~1.5mol/L, and the concentration of nitric acid solution is 1~1.5mol/L.
4. preparation method according to any one of claim 1 to 3, it is characterised in that: the mole of the complexing agent with
The ratio of the sum of the mole of ruthenium ion and magnesium ion is (1~3): 1.
5. preparation method according to any one of claim 1 to 4, it is characterised in that: in the metal ion solution,
The molar ratio of ruthenium ion and magnesium ion is 1:(1.8~2.2).
6. preparation method according to any one of claim 1 to 5, it is characterised in that: in the metal ion solution
The total concentration of ruthenium ion and magnesium ion is 0.7~0.8mol/L.
7. preparation method according to any one of claim 1 to 6, it is characterised in that: the dispersing agent be selected from ethylene glycol,
Polyethylene glycol, stearic acid are any one or more of；Preferably, the sum of mole of ruthenium ion and magnesium ion and the dispersing agent
Mole ratio be 1:1~1:5.
8. preparation method according to any one of claim 1 to 7, it is characterised in that: be carried out as follows described
Sol gel processing:
Sol system is placed in heating in water bath and heating process is with stirring；
Preferably, the temperature of the water-bath is controlled at 60~80 DEG C；
Preferably, heating stopping when wet gel loses flowability.
9. preparation method according to any one of claim 1 to 8, it is characterised in that: the freeze-drying -40~-
It is carried out at 70 DEG C；And/or
The calcining carries out at 600~800 DEG C.
10. a kind of yttrium oxide-bitter earth nano composite granule, it is characterised in that: using described in any one of claims 1 to 9
Preparation method be made.
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