CN102730738B - Preparation method of binary or multi-constituent composite rare earth oxide nanoparticles - Google Patents
Preparation method of binary or multi-constituent composite rare earth oxide nanoparticles Download PDFInfo
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- CN102730738B CN102730738B CN201210193369.XA CN201210193369A CN102730738B CN 102730738 B CN102730738 B CN 102730738B CN 201210193369 A CN201210193369 A CN 201210193369A CN 102730738 B CN102730738 B CN 102730738B
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Abstract
The invention provides a preparation method of binary or multi-constituent composite rare earth oxide nanoparticles, comprising the following steps: (1) smelting two or more rare earth metals into alloy ingot according to a certain proportion in an inert atmosphere, repeatedly smelting to uniformly distribute components of the alloy ingot; (2) in an argon and hydrogen atmosphere with a certain proportion under a certain pressure, melting the alloy ingot under the effect of hot plasma, reacting the rare earth metals with hydrogen plasma, and preparing composite rare earth hydride nanoparticles by chemical vapor deposition; (3) after finishing the reaction, taking out the composite rare earth hydride nanoparticles from the reactor; and (4) carrying out heat treatment on the prepared composite rare earth hydride nanoparticles at a certain temperature in an oxygen or air atmosphere to convert the composite rare earth hydride nanoparticles into composite rare earth oxide nanoparticles. According to the invention, the preparation method of the invention uses the rare earth metals and hydrogen as main raw materials, the prepared nanoparticles have high purity and uniform distribution of particle size, and the advantages of few working procedures of the method, simple device, and low energy consumption are achieved.
Description
Technical field
The invention belongs to the preparing technical field of binary or multiplex composite rare-earth oxide nano particles.
Background technology
Nanoparticle has quantum size effect, small-size effect, surface effects and macro quanta tunnel effect.In the time that the particle size of rare earth oxide reaches nano level, it has shown a lot of distinctive optical properties, makes it have wide application prospect.Binary or multiplex composite rare-earth oxide nano particles are a kind of luminescent materials that has potentiality, and in laser technology, opticfiber communication, has broad application prospects in the fields such as x-ray imaging and a transmitting.
At present, in laboratory and industrial production, there are a variety of methods can prepare Study of Nanoscale Rare Earth Luminescent Materials.As: high-temperature solid phase reaction method, chemical precipitation method, combustion synthesis method, sol-gel method, hydrothermal synthesis method, microemulsion method etc.But the rare earth oxide particles particle diameter that high-temperature solid phase reaction method is prepared is larger, must be through ball milling processing treatment when application, technique is more complicated; Chemical precipitation method complex procedures, easily mixes impurity; In combustion synthesis method, combustion flame temperature can reach thousands of degrees Celsius, even several thousand degrees Celsius, produces the gas that has contaminate environment in combustion processes; The cost of material of sol-gel method is relatively high, and sol-gel process has great effect to final material character, the more difficult expection product that makes sometimes, and operation is more complicated, and preparation cycle is long, and alkoxide is harmful; Microemulsion method output is lower, and conventional tensio-active agent cost is high, is difficult for reclaiming, and makes it be not suitable for producing in enormous quantities, and uses a large amount of organic solvents in reaction, easily causes environmental pollution.Visible, the synthetic method of existing binary or multiplex composite rare-earth oxide nano particles all exists some shortcomings part, is difficult to meet the requirement of practical application.
Summary of the invention
According to an aspect of the present invention, provide a kind of preparation method of rare-earth oxide nano particles, it is characterized in that comprising:
A) in inert atmosphere, two or more rare earth metal is smelted into alloy pig by predetermined proportion;
B) repeatedly alloy pig makes its composition even described in melting;
C) described uniform alloy pig is melted in reactor, and make its reaction, prepare rare earth hydride nanoparticle;
D) after reaction finishes, nano particle is taken out from reactor;
E) rare earth hydride nanoparticle is heat-treated, prepare rare-earth oxide nano particles.
According to another aspect of the present invention, provide the rare-earth oxide nano particles of preparing with aforesaid method.
Brief description of the drawings
Fig. 1 is YH prepared by the present invention
2: Er
2+and Y
2o
3: Er
3+the X ray diffracting spectrum of compound rare earth nano particle.
Fig. 2 (a) is 1 hour Y of 500 DEG C of thermal treatments
2o
3: Er
3+the transmission electron microscope photo of composite rare-earth oxide nano particle, Fig. 2 (b) is the X-ray energy spectrum face scan image of a nano particle in (a).
Fig. 3 is LaH prepared by the present invention
3: Dy
3+and La
2o
3: Dy
3+the X ray diffracting spectrum of compound rare earth nano particle.
Fig. 4 is La and Nd complex hydride and La prepared by the present invention
2o
3: Nd
3+the X-ray diffractogram spectrogram of composite oxides nano particle.
Embodiment
The object of this invention is to provide a kind of novel method of preparing binary or multiplex composite rare-earth oxide nano particles, the raw material of employing is rare earth metal, will first binary or multielement rare earth be smelted into alloy in inert atmosphere; Subsequently, under the argon gas and hydrogen atmosphere of certain proportion and certain pressure, alloy is melted under thermal plasma effect, and rare earth metal and hydrogen plasma are reacted, prepare compound rare-earth hydride nano-particle by chemical vapour deposition; Finally, in oxygen-containing atmosphere, the thermal treatment through certain temperature again, prepares rare-earth oxide nano particles.In the method, inclusion-free mixes, and prepared nano particle purity is high, and operation is few, and equipment is simple, and energy consumption is low.
According to multiple embodiment of the present invention, the step of composite rare-earth oxide nanometer grain preparation method comprises:
A) in inert atmosphere by a certain proportion of two or more rare earth metals, be smelted into alloy pig by thermal plasma, repeatedly melting is evenly distributed its composition;
B) under the argon gas and hydrogen atmosphere of certain proportion and certain pressure, alloy pig is melted under thermal plasma effect, rare earth and hydrogen plasma are reacted, prepare compound rare-earth hydride nano-particle by chemical vapour deposition;
C), after reacting completely, compound rare-earth hydride nano-particle is taken out from reactor;
D) by the compound rare-earth hydride nano-particle of preparation above at a certain temperature, in oxygen or air, heat-treat, make compound rare-earth hydride nano-particle be converted into composite rare-earth oxide nano particle.
According to a specific embodiment of the present invention, above-mentioned steps A) in multielement rare earth alloy melting mode be thermal plasma melting.
According to a specific embodiment of the present invention, described step B) in thermal plasma as thermal source, carry out chemical vapour deposition, plasma current is more than or equal to 50A.
According to a specific embodiment of the present invention, described step B) the plasma body that uses of chemical vapor deposition processes be containing hydrogen plasma.
According to a specific embodiment of the present invention, described step B) melting process in, hydrogen accounts for 1%～90% in the gas mixture of argon gas and hydrogen, total gas pressure is 0.01MPa～0.1MPa,
According to a specific embodiment of the present invention, described step D) in heat treatment mode be to carry out in oxygen-containing atmosphere (as oxygen, air, or the gas mixture of oxygen and rare gas element), use resistance furnace heat.
According to a specific embodiment of the present invention, described step D) in thermal treatment temp be generally more than 200 DEG C, this temperature determines by rare earth element is active.Heat treatment time is 0.1～6 hour.
Advantage of the present invention and positively effect: it is raw material that the present invention adopts rare earth metal and hydrogen, synthesizes binary or multiplex composite rare-earth hydride nano-particle by PCVD.Rare earth alloy forms metal vapors under hydrogeneous action of plasma, with hydrogen generation chemical reaction and be condensed into compound rare-earth hydride nano-particle.Subsequently, by thermal treatment in oxygen-containing atmosphere, make hydride nano-particle be further converted to nano-oxide particles.In whole technological process, inclusion-free mixes, and prepared nano particle purity is high, and operation is few, and equipment is simple, and energy consumption is low.
A kind of mechanism of the formation of the compound rare earth nano particle that the present invention is relevant can be described below: first rare earth metal is become metal vapors by forced evaporation under hydrogen plasma effect, and thermal plasma central zone can reach 6000～10000 DEG C.At so high temperature, according to the thermodynamic behaviour of following reaction, rare earth metal can not with hydrogen direct reaction.
RE+H
2→REH
x+Q
Wherein RE represents rare earth element; The thermal discharge of Q representative reaction.In the process of rare earth metal condensation, rare earth alloy elementide is collided and grown up into the rare earth of gaseous state mutually.Along with the reduction of temperature, further form tiny rare earth alloy drop.In the time that temperature drops to the fusing point of rare earth alloy, alloy liquid droplet starts homogeneous nucleation and forms nano particle.Because the specific surface area of nano particle is large and active high, make compound rare earth nano particle in temperature-fall period with hydrogen reaction, form compound rare earth nano hydride.After compound rare-earth hydride nano-particle contacts with air, partial oxidation becomes rare earth oxide, and at a certain temperature subsequently, heat-treat in oxygen-containing atmosphere, final rare earth hydride is converted into rare-earth oxide nano particles completely.
Embodiment 1, Y
2o
3: Er
3+synthesizing of composite nanometer particle
Adopt yttrium and erbium metal block to prepare Y
2o
3: Er
3+compound rare earth nano particle, step is as follows:
In argon gas atmosphere, adopting thermal plasma melting preparation quality mark is the alloy pig of 95% yttrium-5% erbium, and melting mixes it four times; Be in the atmosphere that is 0.08MPa of 5: 3, total gas pressure at argon gas and hydrogen volume ratio, the above-mentioned alloy pig of using plasma melting, plasma current is 200A, prepares YH by chemical vapour deposition
2: Er
2+nano particle; After reacting completely, by YH
2: Er
2+nano particle takes out from reactor; Above nano particle is carried out respectively to thermal treatment in 1 hour at 300,500 and 700 DEG C in air.
The test result of gained sample shows in Fig. 1, and its transmission electron microscope photo provides in Fig. 2; Wherein, curve (a) in Fig. 1 is the X ray diffracting spectrum of the hydride nano-particle sample of PCVD acquisition, curve (b) in Fig. 1 is the X ray diffracting spectrum of 1 hour sample of 300 DEG C of thermal treatment, and the curve (c) in Fig. 1 is the X ray diffracting spectrum of 1 hour sample of 500 DEG C of thermal treatment; Curve (d) in Fig. 1 is the X ray diffracting spectrum of 1 hour sample of 700 DEG C of thermal treatment.
From the curve in Fig. 1 (a), the nano particle that PCVD obtains is YH
2: Er
2+binary rare-earth hydride nano-particle, and contain a small amount of rare earth oxide phase, there is partial oxidation after due to nano particle ingress of air and causes in this.By the curve in Fig. 1 (b)～(e) can find out, more than 500 DEG C thermal treatment is after 1 hour, and rare earth hydride is converted into Y completely
2o
3: Er
3+rare-earth oxide nano particles.Can find out the Y of thermal treatment preparation in 1 hour in 500 DEG C of air from the transmission electron microscope photo of Fig. 2 (a)
2o
3: Er
3+nano particle diameter is 40～50nm, even particle size distribution.Can find out from the X-ray energy spectrum face scan image of Fig. 2 (b), Y and Er element are distributed among nano particle equably.
Embodiment 2, La
2o
3: Dy
3+synthesizing of composite nanometer particle
Adopt lanthanum and dysprosium metal block to prepare La
2o
3: Dy
3+multielement rare earth nano particle, step is as follows:
In argon gas atmosphere, adopt thermal plasma melting to prepare the alloy pig that molar fraction is 95% lanthanum-5% dysprosium, melting mixes it four times; Be in the atmosphere that is 0.09MPa of 1: 1, total pressure at argon gas and hydrogen volume ratio, adopt the above-mentioned rare earth alloy of thermal plasma melting, plasma current is 180A, prepares LaH by chemical vapour deposition
3: Dy
3+nano particle; After reacting completely, by LaH
3: Dy
3+nano particle takes out from reactor; Prepared hydride nano-particle is carried out respectively to thermal treatment in 1 hour at 400,600,800 and 1000 DEG C in air.
The test result of gained sample shows in Fig. 3, wherein, curve (a) is the X ray diffracting spectrum of the hydride nano-particle sample of PCVD acquisition, curve (b), (c), (d) and (e) for respectively 400,600, the X-ray diffractogram spectrogram of 1 hour sample of thermal treatment at 800 and 1000 DEG C.
As seen from Figure 3, the LaH that PCVD obtains
3: Dy
3+thermal treatment is after 1 hour more than 800 DEG C for nano particle, and rare earth hydride is converted into La completely
2o
3: Dy
3+rare-earth oxide nano particles.
Adopt lanthanum and neodymium metal block to prepare La
2o
3: Nd
3+multielement rare earth nano particle, step is as follows:
In argon gas atmosphere, adopt thermal plasma melting to prepare the alloy pig that molar fraction is 95% lanthanum-5% neodymium, melting mixes it four times; Be in the atmosphere that is 0.09MPa of 3: 2, total pressure at argon gas and hydrogen volume ratio, adopt the above-mentioned rare earth alloy of thermal plasma melting, plasma current is 150A, prepares LaH by chemical vapour deposition
3: Nd
3+nano particle; After reacting completely, by LaH
3: Nd
3+nano particle takes out from reactor; Prepared nano particle is carried out respectively to thermal treatment in 1 hour at 800 and 1000 DEG C in air.
The test result of gained sample shows in Fig. 4, wherein, curve (a) is the X ray diffracting spectrum of hydride nano-particle sample that PCVD obtains, curve (b) and (c) be the X-ray diffractogram spectrogram of 1 hour sample of thermal treatment at 800 and 1000 DEG C respectively.
As seen from Figure 4, LaH
3: Nd
3+thermal treatment is after 1 hour more than 800 DEG C for nano particle sample, and rare earth hydride is converted into La completely
2o
3: Nd
3+rare-earth oxide nano particles.
Claims (4)
1. a preparation method for binary or multiplex composite rare-earth oxide nano particles, is characterized in that comprising:
A) in inert atmosphere, two or more rare earth metal is smelted into alloy pig by predetermined proportion;
B) repeatedly alloy pig makes its composition even described in melting;
C) described uniform alloy pig is melted in reactor, and make its reaction, prepare rare earth hydride nanoparticle;
D) after reaction finishes, nano particle is taken out from reactor;
E) rare earth hydride nanoparticle is heat-treated, prepare rare-earth oxide nano particles;
Wherein
Adopting rare earth metal and hydrogen is raw material, synthesizes binary or multiplex composite rare-earth oxide nano particles by PCVD; Rare earth alloy forms metal vapors under hydrogeneous action of plasma, with hydrogen generation chemical reaction and be condensed into compound rare-earth hydride nano-particle; Subsequently, by thermal treatment in oxygen-containing atmosphere, make hydride nano-particle be further converted to nano-oxide particles, in whole technological process, inclusion-free mixes;
Described steps A) mode of interalloy ingot melting is thermal plasma melting;
Described step C) the mode melting in reactor be plasma body fusing;
Described step C) under argon gas and hydrogen atmosphere, carry out, wherein hydrogen accounts for 1%～90% in the gas mixture of argon gas and hydrogen, and total gas pressure is 0.01MPa～0.1MPa;
Step C) melting process adopt and be more than or equal to the plasma current of 50A;
Described step e) heat treated temperature for being more than or equal to 200 DEG C, heat treatment time is 0.1～6 hour;
Described step e) in thermal treatment be the thermal treatment of carrying out in resistance furnace.
2. the preparation method of binary as claimed in claim 1 or multiplex composite rare-earth oxide nano particles, is characterized in that: step e) the described rare-earth oxide nano particles that makes is Y
2o
3: Er
3+compound rare earth nano particle.
3. the preparation method of binary as claimed in claim 1 or multiplex composite rare-earth oxide nano particles, is characterized in that: step e) the described rare-earth oxide nano particles that makes is La
2o
3: Dy
3+multielement rare earth nano particle.
4. the preparation method of binary as claimed in claim 1 or multiplex composite rare-earth oxide nano particles, is characterized in that: step e) the described rare-earth oxide nano particles that makes is La
2o
3: Nd
3+multielement rare earth nano particle.
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Citations (4)
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| CN1034285A (en) * | 1987-09-16 | 1989-07-26 | 株式会社半导体能源研究所 | Form the method and apparatus of superconducting oxide material |
| CN1255237C (en) * | 2003-06-25 | 2006-05-10 | 中国科学院金属研究所 | Method for bulk preparing intermetallic compound nanometer powder of titanium and aluminium |
| CN1803816A (en) * | 2006-01-24 | 2006-07-19 | 北京工业大学 | Method for in-situ synthesizing preparation of high-purity GdH2 block material |
| CN101113009A (en) * | 2007-06-29 | 2008-01-30 | 中国科学院上海光学精密机械研究所 | Preparation method of rare earth oxide nanoparticles |
-
2012
- 2012-06-12 CN CN201210193369.XA patent/CN102730738B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034285A (en) * | 1987-09-16 | 1989-07-26 | 株式会社半导体能源研究所 | Form the method and apparatus of superconducting oxide material |
| CN1255237C (en) * | 2003-06-25 | 2006-05-10 | 中国科学院金属研究所 | Method for bulk preparing intermetallic compound nanometer powder of titanium and aluminium |
| CN1803816A (en) * | 2006-01-24 | 2006-07-19 | 北京工业大学 | Method for in-situ synthesizing preparation of high-purity GdH2 block material |
| CN101113009A (en) * | 2007-06-29 | 2008-01-30 | 中国科学院上海光学精密机械研究所 | Preparation method of rare earth oxide nanoparticles |
Non-Patent Citations (4)
| Title |
|---|
| Hydrogen absorption and its influence on the thermal stability of Zr65Al10Ni10Cu15 amorphous alloy;Tong Liu et al.;《International Journal of Hydrogen Energy》;20120420;第37卷;9148-9154 * |
| Synthesis and structures of Al-Ti nanoparticles by hydrogen plasma-metal reaction;Tong Liu et al.;《Journal of Nanoparticle Research》;20120209;第14卷(第3期) * |
| Tong Liu et al..Hydrogen absorption and its influence on the thermal stability of Zr65Al10Ni10Cu15 amorphous alloy.《International Journal of Hydrogen Energy》.2012,第37卷9148-9154. |
| Tong Liu et al..Synthesis and structures of Al-Ti nanoparticles by hydrogen plasma-metal reaction.《Journal of Nanoparticle Research》.2012,第14卷(第3期), |
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