CN1032904C - Amorphous superfine metal particles and preparing process thereof - Google Patents
Amorphous superfine metal particles and preparing process thereof Download PDFInfo
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- CN1032904C CN1032904C CN 93117139 CN93117139A CN1032904C CN 1032904 C CN1032904 C CN 1032904C CN 93117139 CN93117139 CN 93117139 CN 93117139 A CN93117139 A CN 93117139A CN 1032904 C CN1032904 C CN 1032904C
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Abstract
The present invention relates to a method for the manufacture of superfine metal particles, particularly to the technical field of direct generation of amorphous superfine metal particles with the adoption of light irradiation to organic metal carbonyl compound solution, and the preparing method of the superfine metal particles. In order to save energy, the present invention utilizes ordinary light as a light source fully for the irradiation of a certain kind of metal carbonyl compound solution, and nanometer-stage metal particles are generated directly via photodissociation; the particles with the granule dimension of 50-70 nm and the purity of 98% is in amorphous state, namely, the metal particles are in unordered glass state with long period via X-ray diffraction measurement. The present invention has the advantages of simple method, no need of bulky facilities, multiple prepared varieties and high yield.
Description
The present invention relates to superfine metal particles.
Superfine metal particles is the important component part of new material, as a kind of new state of matter, is found by people for a long time, then starts from the eighties but really on purpose prepared and study by people.Because such material has and different new physics, chemical characteristic and the potential application prospects of common " bulk " material be familiar with of people, therefore, in the development high-tech in the works, all aim at this new material field, and impel its research, development and application to develop rapidly in the world.
The preparation method of nano level metal particulate can be divided into physics, chemistry and integrated approach, in recent years, utilize the high temperature characteristics of plasma, make variation material generation physics or chemistry prepare ultrafine tungsten powder, can be described as a kind of effective and rising method, but this method equipment is huge, and power consumption is big, complex process.And being published on " Nature " 353 (1991) 414 article that is entitled as " Sonochemical Synthesis of amorphous iron " recently, the willing. Su Silike of the upright university of report Illinois, USA and his colleagues are using the ultrasonic wave manufacturing to make chemical reaction catalyst one amorphous metal iron powder more rapidly.They adopt ultrasonic agitation carbonyls solution, make the more effective mixing of reactant, in addition, ultrasonic wave constantly produces minute bubbles and makes the vesicle fragmentation in solution, " hot spot " of this process in solution goes up and produces huge pressure, temperature variation, along with the generation and the fragmentation of bubble, the variations in temperature here can reach per second 10
9Degree centigrade.Though the time that " hot spot " exists is much smaller than 10
-6Second, the chemical reaction in " hot spot " has quickened.
When Su Silike is exposed to 5 carbonyl irons in the ultrasonic wave, they find that the carbonyl around the iron atom has been peeled off fully, the variations in temperature that hot spot causes is so big, make iron atom have little time to be arranged in crystal, and form a kind of amorphous particles, with the amorphous superfine iron powder of ultrasonic generation, its particle dimension is less than 10nm, good uniformity, purity per hour can be produced the ultra-fine iron granules of 1 gram up to 97%.But this method is only reported the amorphous superfine particulate of preparation iron, and other amorphous metal particulate is not reported.
The existing preparation metal fine powder need huge equipment, and energy consumption is very big, and the micro mist of gained is a crystalline structure, and granularity is bigger, and about about 1 μ m, purity is low, lack of homogeneity.
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art,, do not need bulky equipment, provide a kind of easier method to prepare amorphous superfine metal particles for energy savings.
The present invention realizes like this, under the room temperature condition of normal pressure, utilize natural daylight, ultraviolet light, xenon lamp, mercury lamp light, the solution that organic hydrocarbon solvent of irradiation organic metal carbonyls and n-hexane or cyclohexane is made into, after making it to dissolve fully, put into conical flask then, its concentration is 1～3 * 10
-2Mol was penetrated 0.5～5 hour through illumination, promptly generated sediment, this sediment contains the amorphous superfine particulate, then whole solution is poured in the centrifuge tube, be placed in the centrifugal trough centrifugal, centrifugal about 15 minutes, taking off centrifuge tube filters original solution, sediment at the bottom of staying bottle cleans two to three times repeatedly with solvent again, centrifugal after, sediment in the bottle is put into vacuum tank vacuumize drying, the nano level metal particle in dry back still is placed under the low vacuum environment to be preserved.
The amorphous superfine metal particles particle dimension of the present invention's preparation has the unordered glassy structure of long period at 50-70nm.
The said organic metal carbonyls of the present invention comprises tungsten carbonyl, chromium carbonyl, molybdenum carbonyl, manganese carbonyl, rhenium carbonyl.
The present invention's advantage is that implementation method is simple, and when utilizing sunshine to make light source, energy consumption is lower, and the gained initial product is the amorphous state particulate, has good uniformity.As handling and to change crystalline structure into from amorphous state through heat from hydrogenation.Therefore, this method is energy savings both, and equipment is also very simple, and prepared micro mist is an amorphous structure, and particle is little, purity height, good uniformity.
The present invention is described in detail below in conjunction with embodiment:
Accompanying drawing 1 is an amorphous state tungsten particulate Electronic Speculum micrograph
Accompanying drawing 2 is that x-ray photoelectron can spectrogram
Accompanying drawing 3 is amorphous state tungsten particulate X-ray diffractograms
Claim W (CO)
63mg joins in the 5ml hexane solution, is made into 1.7 * 10
-2The tungsten carbonyl solution of mol is placed in the conical flask, and vibration shakes up and makes it to dissolve fully repeatedly, places then under the 120w mercury lamp, and irradiation at room temperature is half an hour approximately, and promptly generating blue look sediment is amorphous superfine tungsten particulate.This metal particle generate fully be relation to be arranged not exclusively with irradiation time and light intensity, strong just irradiation time is short but institute uses up, the weak irradiation time that just needs of light is long, looking in its container sediment has no longer increased and illustrates and reacted completely.Then, whole solution is poured in the centrifuge tube, be put in the centrifugal trough, centrifugal about 15 minutes, take off centrifuge tube and original solution is filtered to pour measuring cup into standby, stay a bottle bottom sediment and put into vacuum tank and vacuumize drying, the nano level tungsten particulate in dry back is placed under the low vacuum to be preserved, in case oxidation.
This particulate shows deep blue color, it is to prevent the particulate bonding that sample is handled through ultrasonic wave, through scanning electron microscopic observation, Fig. 1 is an amorphous state tungsten Electronic Speculum micrograph, amplifies 7.5 ten thousand times, as calculated, show that the tungsten particle dimension is about 50～70nm, uniform particles is good, the composition of its sample, and Determination of Different Valence States result is as shown in Figure 2.Fig. 2 is the x-ray photoelectron energy spectrogram of tungsten particulate, and the composition of this figure working sample is a tungsten, and purity is better than 97%.The amorphous state analysis of this particulate shows that by Fig. 3 tungsten particulate X-ray diffractogram not seeing has tangible peak structure, and has the unordered glassy structure of long period.
Embodiment 2:
Be placed in the measuring bottle by the above-mentioned solution for preparing, dislocation sunlight is irradiation down, got under the strong sunlight at noon direct projection 3 hours, finish up to blue look precipitation reaction, take off measuring bottle through centrifugal 15 minutes, clean vacuum drying with n-hexane, be placed on the amorphous state tungsten particulate that preservation has generated under the low vacuum then, the productive rate of above after measured two embodiment W particulates (W particulate and W (CO)
5The weight ratio of middle W) can reach 50%.And has a unordered glassy structure of long period.
The amorphous superfine particulate of embodiment 3 Cr generates
Prepare ultra-fine Cr particulate as stated above, with assay balance weighing Cr (CO)
625mg puts into conical flask and adds the 5ml hexane solution altogether, and being mixed with concentration is 2.3 * 10
-2Mol solution was got the xenon lamp Continuous irradiation 5 hours, was precipitated as up to regeneration not and ended, and was poured in the centrifuge in the centrifuge tube containing sediment, centrifugal 15 minutes, took out the chromium powder preservation after the vacuum drying.Its gained Cr ultrafine dust dimension exists: be not more than 70nm, and have the unordered glassy structure of long period.
Embodiment 4 preparation amorphous superfine Mo particulates
Prepare ultra-fine Mo particulate, with assay balance weighing Mo (CO)
6About 25mg is placed in the conical flask hexane solution with 5ml, is made into concentration and is about ≈ 1.9 * 10
-2Mol solution, be placed on the Xe lamp before, with Xe lamp Continuous irradiation 5 hours, all produced precipitation in the bottle, promptly be the ultra-fine Mo particulate of amorphous state.It is centrifugal with centrifuge that it is injected centrifuge tube, and vacuum drying is then put into the measuring cup low vacuum to solid state powder and preserved, and its Mo particulate dimension exists: be not more than 70nm, have the unordered glassy structure of long period.
The amorphous superfine particulate of embodiment 5 Mn generates.
With assay balance weighing Mn
2(CO)
10About 35mg pours the cyclohexane solution of 5ml into, and its concentration is about 1.8 * 10
-2Mol, the measuring bottle that solution is housed is placed under the 120w Hg lamp irradiation, solution colour become immediately be with in the Huang light brown, after a few minutes, begin to occur to be with jade-green flocculent deposit in brown, 2 hour to be illuminated time made precipitation capacity more for a long time, and is centrifugal with centrifuge, and after the vacuum drying, promptly obtain the amorphous superfine particulate of Mn, the particle dimension equals 70nm, and has the unordered glassy structure of long period.Putting into measuring cup preserves under low vacuum.
The amorphous superfine particulate of embodiment 6 Re generates
Re weighs with scale
2(CO)
10About 60mg pours in the cyclohexane solution of 5ml, is made into concentration and is about 1.8 * 10
-2Mol, the measuring bottle that solution is housed is placed on irradiation under the 120wHg lamp, solution becomes milky and continues irradiation 3 hours after a few minutes, generate light-yellow precipitate, it has the unordered glassy structure of long period with centrifugal, the dried Re amorphous superfine of sediment particulate, its particle dimension is about 70nm, puts into measuring cup and preserves under low vacuum and get final product.
Claims (3)
1. photodissociation method for preparing amorphous superfine metal particles, it is characterized in that: under the room temperature normal pressure, utilize natural daylight, ultraviolet light, xenon lamp, mercury lamp light, the solution that organic hydrocarbon solvent of irradiation organic metal carbonyls and n-hexane or cyclohexane is made into, after making it to dissolve fully, put into conical flask then, its concentration is 1～3 * 10
-2Mol was penetrated 0.5～5 hour through illumination, promptly generated sediment, this sediment contains the amorphous superfine particulate, then whole solution is poured in the centrifuge tube, is placed in the centrifugal trough centrifugal, centrifugal about 15 minutes, take off centrifuge tube, original solution is filtered, sediment at the bottom of staying bottle, clean repeatedly two to three times with solvent again, after centrifugal, the sediment in the bottle put into vacuum tank vacuumize drying, the nano level metal particle in dry back still is placed under the low vacuum environment to be preserved.
2. by the photodissociation method of the described preparation amorphous superfine metal particles of claim 1, it is characterized in that: said organic metal carbonyls comprises: tungsten carbonyl, chromium carbonyl, molybdenum carbonyl, manganese carbonyl, rhenium carbonyl.
3. the amorphous superfine metal particles of the described method preparation of a claim 1, it is characterized in that: the particle dimension has the unordered glassy structure of long period at 50-70nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93117139 CN1032904C (en) | 1993-09-09 | 1993-09-09 | Amorphous superfine metal particles and preparing process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93117139 CN1032904C (en) | 1993-09-09 | 1993-09-09 | Amorphous superfine metal particles and preparing process thereof |
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| Publication Number | Publication Date |
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| CN1100017A CN1100017A (en) | 1995-03-15 |
| CN1032904C true CN1032904C (en) | 1996-10-02 |
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| CN 93117139 Expired - Fee Related CN1032904C (en) | 1993-09-09 | 1993-09-09 | Amorphous superfine metal particles and preparing process thereof |
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| CN1095411C (en) * | 1998-05-29 | 2002-12-04 | 中国科学院化学研究所 | Preparation of metal nanometre cluster |
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