CN102275974B - Preparation method of ultra-micrometer copper oxide powdery material - Google Patents
Preparation method of ultra-micrometer copper oxide powdery material Download PDFInfo
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Abstract
The invention relates to a preparation method of an ultra-micrometer copper oxide powdery material. The invention belongs to the field of high property and high performance materials. According to the invention, raw materials can be pure copper wires (or pure copper blocks), or partially oxidized oxide scales produced during pure copper processing procedures. When pure copper wires (or pure copper blocks) are adopted as raw materials, the pure copper wires (or pure copper blocks) are cut into blocks with small volumes, wherein no impurity is allowed to be mixed in during the cutting process; when oxide scales are adopted as raw materials, the oxide scales are dried by heating, such that vapor on absorption surfaces is removed. The processed raw materials are processed through oxidization and ball milling in a ball milling tank, such that the ultra-micrometer copper oxide powdery material is obtained. The method provided by the invention is advantaged in that: high temperature or precursor synthesizing is not required in the preparation process; the process flow in the preparation process is short; oxidization and powder production are accomplished in a single process; and a dosageof acidic (basic) agent is low, such that the method is environment-friendly. With the method, the prepared copper oxide powdery material has a high purity equal to or higher than 99% and small particle sizes, wherein an average particle size is equal to or smaller than 1mum.
Description
Technical field:
A kind of method for preparing the ultra-micrometer copper oxide powdery material provided by the invention belongs to the performance function Material Field.
Background technology:
Cupric oxide is a kind of material with multiple catalytic activity.Be widely used in glass, pottery and enamel, fuel, catalyst and make other mantoquitas; Cupric oxide also is used for artificial silk industry, the anti-creasing agent of grease sweetening agent, paint and electron trade etc.Cupric oxide can not only improve combustion speed as the burningrate catalyst of solid rocket propellant, reduces Pressure Exponent, and the AP compositepropellent is also had preferably catalytic effect; Coating film as sensor can improve the right selectivity of sensor and sensitivity greatly, because copper oxide makes it become again important model compound at the abnormal characteristic in high-temperature superconductor field, is used for explaining the spectral signature of complex oxide.In addition, because cupric oxide has higher catalytic activity to the complete oxidation of carbon monoxide, be expected to the scavenging material as vehicle exhaust.Therefore superfine powder has interfacial effect, and dimensional effect and volume effect have than stronger functional of general powder.The preparation superfine copper oxide powder has become a hot issue of vast scholar's research.At present, superfine copper oxide powder the preparation method room temperature solid reaction process, Low Temperature Solid-Phase coordination chemistry method, sonochemistry method, pure hot method, improved sol-gel method, quick liquid-phase precipitation method etc. are arranged.Weak point when having its own advantages, these methods is also arranged.Preparation cost is high, and technical process is complicated, the seriously polluted basic reason that becomes restriction aforesaid method realization industrialization.Therefore develop a kind of with low costly, simple to operate, it is convenient to process, and reaction conditions is gentle, environmental friendliness, and the superfine copper oxide powder material that is easy to suitability for industrialized production is significant.Do not generate superfine copper oxide powder if under high temperature or alkali (acid) property liquid condition, directly do not prepare, will save a large amount of tooling costs, and be conducive to the protection of environment.
Mechanical alloying (Mechanical Alloying, be called for short MA) be a kind of new and high technology [4] for preparing powdered alloy, it is under the effect of high-energy ball milling, utilizes between the repeated deformation, fracture, seam, atom of metal powder mixture the phase mutual diffusion or solid state reaction occurs to form powdered alloy.Mechanical alloy is turned to one of technology of preparing of novel material, and particularly it has caused the extensive concern of material supply section educational circles occupying an important position aspect the research of trickle, superfine powder material.This patent adopts high-energy ball milling method in conjunction with the standby cupric oxide powder of oxygenation legal system, has both shortened preparation technology's flow process, cuts down finished cost, and has also avoided in the ordinary method acid (alkalescence) material to the pollution of environment.
Summary of the invention:
The invention provides a kind of method for preparing the ultra-micrometer copper oxide powdery material---oxidation ball milled, namely once obtain cupric oxide powder by ball milled in conjunction with the oxygenation technology.Its raw material can be pure copper wire (or fine copper piece), also can be the oxide skin that oxidation partly occurs that produces in the fine copper course of processing.This method does not only need high temperature or synthetic presoma, and technical process is short in the preparation process, and acid (alkalescence) dosing is few, environmentally friendly.The cupric oxide powder material purity high (〉=99%) of preparation, granularity little (mean particle size≤1 μ m), the part powder size can reach nano level.
The present invention is for achieving the above object, and the scheme of employing is:
1) as adopting pure copper wire (or fine copper piece) when being raw material, pure copper wire (or fine copper piece) is cut into small volume piece (≤10mm
3), and guarantee that inclusion-free is sneaked in the cutting process; As when adopting oxide skin to be raw material, oxide skin needs heat drying, 100～200 ℃ of drying temperatures, and soaking time 1～5h removes the steam of adsorption surface.
2) ball grinder of ready little fine copper volume piece or oxide skin being put into ball mill carries out ball milling, ratio of grinding media to material: 10: 1～100: 1, and revolution speed: 100～450r/min, rotational velocity: 100～750r/min, Ball-milling Time: 1～10h.
3) in mechanical milling process, ball grinder is carried out oxygenation, oxygenation number of times in the preparation process: 1～10 time.Copper and oxygen reaction process are expressed as follows with chemical equation in ball grinder:
2Cu+O
2＝2CuO (1)
Cu+Cu
2+＝2Cu
+ (2)
2Cu
2O+O
2＝4CuO (3)
Raw material described in the present invention can be pure copper wire (or fine copper piece), also can be the oxide skin that oxidation partly occurs that produces in the fine copper course of processing.The content of copper 〉=99% in the pure copper wire (or fine copper piece).
Advantage of the present invention and positively effect are embodied in:
1) compare with the technique that tradition prepares the superfine copper oxide powder material, avoided high temperature and a large amount of chemical agents that use, such as acid, alkali, salt etc. do not pollute environment.
2) in mechanical milling process, the temperature that ball grinder raises can realize the chemosynthesis of copper and oxygen.When in the sufficient situation of oxygen, can form cupric oxide.Greatly shortened process is finished in the oxidation of copper and the generation of cupric oxide powder simultaneously.
3) cupric oxide powder of the method preparation has higher purity (〉=99%), less granularity (mean particle size≤1 μ m), and the part powder size has reached the nanometer utmost point (1～100nm).
Description of drawings:
Fig. 1 is the pattern (* 3000) of the embodiment of the invention one gained cupric oxide powder.
Fig. 2 is the X-ray diffraction spectrum of the embodiment of the invention one gained cupric oxide powder.
Fig. 3 is the pattern (* 3000) of the embodiment of the invention two gained cupric oxide powders.
Fig. 4 is the X-ray diffraction spectrum of the embodiment of the invention two gained cupric oxide powders.
Embodiment:
Below in conjunction with specific embodiment ultra micro rice cupric oxide powder preparation method of the present invention is further described.
Embodiment one
1) with the fine copper wire of Φ 2mm, being cut into length with pliers is 2-3mm small volume piece, and weight is 20g.
2) the little fine copper volume piece that will prepare is put in the ball grinder of planetary ball mill (QM-ISP4) and is carried out ball milling, ratio of grinding media to material: 50: 1, and revolution speed: 200r/min, rotational velocity: 300r/min, Ball-milling Time: 5h.
3) in mechanical milling process, ball grinder is carried out oxygenation, oxygenation number of times in the whole preparation process: 4 times.With products therefrom in the present embodiment, carry out after spray carbon in surface processes, the pattern to product under scanning electronic microscope characterizes, and as can be seen from Figure 1, the mean particle size of products therefrom is less than 1 μ m, and part has reached nano level.Fig. 2 is the X-ray diffraction spectrum that the present embodiment obtains product, and as can be seen from the figure, inclusion-free in the product is pure cupric oxide (consistent with the 05-0661JCPDS card).In 2 θ=35.512
0, 61.612
0There is the characteristic diffraction peak of obvious monocline CuO at the place, wherein in 2 θ=35.512
0, the diffraction peak at d=2.5257nm place is highest peak, crystallization is complete to show the CuO powder, and composition is single.
Embodiment two
The oxide skin that 1) oxidation will occur partly is to carry out drying treatment under 180 ℃ of conditions in temperature, and soaking time 1h gets weight 50g after the drying.
2) ready oxide skin is put in the ball grinder of planetary ball mill (QM-ISP4) and carried out ball milling, ratio of grinding media to material: 20: 1, revolution speed: 300r/min, rotational velocity: 400r/min, Ball-milling Time: 4h.
3) in mechanical milling process, ball grinder is carried out oxygenation, oxygenation number of times in the whole preparation process: 2 times.
With products therefrom in the present embodiment, carry out after spray carbon in surface processes, the pattern to product under scanning electronic microscope characterizes, and as can be seen from Figure 3, the mean particle size of products therefrom is less than 1 μ m, and part has reached nano level.Fig. 4 is the X-ray diffraction spectrum that the present embodiment obtains product, and as can be seen from the figure, inclusion-free in the product is pure cupric oxide (consistent with the 05-0661JCPDS card).
Claims (2)
1. ultra-micrometer copper oxide powdery material preparation method is characterized in that:
1) oxide skin that adopts the part that produces in pure copper wire, fine copper piece or the fine copper course of processing that oxidation occurs is raw material, when adopting pure copper wire or fine copper piece to be raw material, pure copper wire or fine copper piece is cut into the small volume piece, and volume is less than≤10mm
3, and guarantee that inclusion-free is sneaked in the cutting process; When adopting oxide skin to be raw material, oxide skin needs heat drying, removes the steam of adsorption surface;
2) ball grinder that the little fine copper piece that will prepare or oxide skin are put into ball mill carries out ball milling, ratio of grinding media to material: 10: 1～100: 1, and revolution speed: 100～450r/min, rotational velocity: 100～750r/min, Ball-milling Time: 1～10h;
3) in mechanical milling process ball grinder is carried out oxygenation, the oxygenation number of times is 1-10 time in the preparation process, and copper and oxygen reaction process are expressed as follows with chemical equation in ball grinder:
2Cu+O
2＝2CuO
Cu+Cu
2+＝2Cu
+
2Cu
2O+O
2＝4CuO。
2. it is characterized in that in accordance with the method for claim 1: the content of copper 〉=99% in pure copper wire or the fine copper piece.
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| CN103524208B (en) * | 2013-09-27 | 2015-10-14 | 北京市农林科学院 | The purposes of water insoluble solids micro-powder |
| CN103553114A (en) * | 2013-11-15 | 2014-02-05 | 湖南大学 | Preparation method of high-purity copper oxide powder material |
| CN104591258A (en) * | 2015-02-08 | 2015-05-06 | 福建紫鑫金属材料科技有限公司 | Method for producing oxide copper powder from copper sand |
| CN108265191A (en) * | 2018-01-23 | 2018-07-10 | 苏州聚康新材料科技有限公司 | The preparation method of oil solubility nanometer copper metallic composite |
| CN114702311B (en) * | 2022-04-20 | 2023-01-17 | 江苏迪丞光电材料有限公司 | TZO ceramic target preparation method and processing device |
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| CN101633519A (en) * | 2009-08-07 | 2010-01-27 | 北京工业大学 | Preparation method of pure-phase superfine nano-crystalline CuO bulk material |
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| CN101633519A (en) * | 2009-08-07 | 2010-01-27 | 北京工业大学 | Preparation method of pure-phase superfine nano-crystalline CuO bulk material |
Non-Patent Citations (8)
| Title |
|---|
| Bianchi, AE er al..Grain growth of CuO nanocrystal activated by high energy ball milling.《PHYSICA B-CONDENSED MATTER》.2007,第389卷(第1期),135-139. |
| Grain growth of CuO nanocrystal activated by high energy ball milling;Bianchi, AE er al.;《PHYSICA B-CONDENSED MATTER》;20070201;第389卷(第1期);135-139 * |
| 在酸性条件下采用高能球磨法制备Cu2O纳米粉末;陈鼎等;《无机材料学报》;20071130;第22卷(第6期);1251-1254 * |
| 水磨法制备金属氧化物粉末研究;陈振华等;《矿冶工程》;20080430;第28卷(第2期);76-78 * |
| 肖廷等.超声波固液反应球磨法制备纳米氧化铜粉末.《人工晶体学报》.2010,第39卷(第3期),633-637. |
| 超声波固液反应球磨法制备纳米氧化铜粉末;肖廷等;《人工晶体学报》;20100630;第39卷(第3期);第634、636页 * |
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| 陈鼎等.在酸性条件下采用高能球磨法制备Cu2O纳米粉末.《无机材料学报》.2007,第22卷(第6期),1251-1254. |
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