CN101498034A - Preparation of transient metal doped nano zinc oxide crystal whisker - Google Patents
Preparation of transient metal doped nano zinc oxide crystal whisker Download PDFInfo
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- CN101498034A CN101498034A CNA2009100771272A CN200910077127A CN101498034A CN 101498034 A CN101498034 A CN 101498034A CN A2009100771272 A CNA2009100771272 A CN A2009100771272A CN 200910077127 A CN200910077127 A CN 200910077127A CN 101498034 A CN101498034 A CN 101498034A
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Abstract
The invention relates to a method for preparing nanometer zinc oxide whiskers doped with transitional mental. Zinc powder, zinc oxide, alkaline zinc carbonate or zinc hydroxide, and the like are used as zinc predecessors, and metal and metal chloride are used as doped element predecessors. After being mechanically mixed, the zinc predecessors and the doped element predecessors are added to plasma arcs to have a gas phase reaction after high-frequency induction plasma is instantaneously gasified at a high temperature, and then the uniformly doped nanometer zinc oxide whiskers are obtained by appearance control in a condensing process. The method is characterized by being applied to the doping of various elements and having high doping content and strong suitability, and the prepared nanometer zinc oxide whiskers are uniformly doped and have controllable appearance. The invention has short technological process and high yield and can continue mass production.
Description
Technical field
The present invention relates to the method that the high-frequency induction plasma body prepares transient metal doped nano zinc oxide crystal whisker, more precisely, the present invention relates to a kind of different material containing zincs and doped element metal or muriate of can utilizing and be precursor material, by high-frequency induction plasma body moment high-temperature gasification and reaction, in condensation process, obtain the method for even adulterated nano zinc oxide crystal whisker then by morphology control.
Technical background
Doping is a kind of very important semiconductor technology, can change semi-conductive character by mixing, and realizes device functionization, is the basis of modern microelectronics.In recent years along with going deep into to monodimension nanometer material research, the doping of one-dimensional nano structure material becomes new research focus, the interaction of its distinctive one-dimentional structure and foreign atom can make one-dimensional nano structure material show special physics, chemistry, electricity and optical property.
More successfully mainly contain two kinds in the adulterating method of one dimension Nano structure: liquid phase method and vapor phase process.The liquid phase method uniform doping, the product defective is few.But have only the physical form of selecting suitable doped element, could guarantee that doped element separates out crystallization simultaneously in the process of growth of one dimension Nano structure; In addition, also to keep activity that can mate, higher, these effects limit the kind of liquid phase method doping elements.Secondly, the liquid phase method reaction times is longer, and process is complicated, and introduces other ion easily.Vapor phase process generally adopts vacuum vapor deposition process, and vapor phase process is lower to the requirement of doped element material form, so adaptability is more eager to excel in whatever one does than liquid phase method.The doping of vapor phase process one dimension Nano structure can be divided into in-situ doped and the later stage mixes two kinds.In-situ doped being meant in the process of growth of one-dimentional structure introduced foreign atom in the lattice.For example Lee etc. mixes zinc powder in the time of 600 ℃ with Manganous chloride tetrahydrate, and co-evaporated under the argon gas atmosphere condition in silica tube has obtained having the adulterated ZnO nano-wire array of tangible ferromagnetic Mn.Zinc acetate and Cobaltous diacetate mixing solutions that Yang etc. will contain trioctylamine are heated to 310 ℃ rapidly, have obtained the adulterated zinc oxide nanowire of cobalt, and have observed unusual paramagnetic performance.In addition, the catalyst action that risen in the one-dimentional structure process of growth of impurity is not allowed to ignore yet.Later stage mixes and to comprise thermodiffusion, solid state reaction and ion implantation etc.For example Roy etc. places a vacuum vessel with four-needle-like zinc oxide and manganese powder, at 800 ℃ and 900 ℃ of heating 30min, obtained the adulterated four-needle-like zinc oxide of manganese respectively, interpretation of result shows that crystal has the trend of growing up, the needle point rust, but still keep four branched structures.Obtained using widely though vapor phase process mixes, because the vapor partial pressure of raw material is subjected to the influence of raw material boiling point, vaporization temperature and system vacuum tightness, therefore existing vapor phase process is difficult to the doping of accurate controlled doping element.Simultaneously, make proportion of raw materials change because the evaporation of product causes the change of evaporation area, thereby the skewness of doped element in the product that obtains.
We adopt the high-frequency thermal plasma technology to prepare one-D nano zinc oxide, have obtained the controlled one-D nano zinc oxide of magnanimity preparation.High frequency plasma has near 10
4The high temperature of K is very easy to fusion even gasified metal and raw materials of compound, and raw material enters in the reactor after gasification and reacts, and finishes process of growth under certain conditions, just can obtain controlled one dimension Nano structure.In reaction process, processes such as the evaporation of reaction species, reaction, condensation and growth all are in the successive flow state, and, raw material after the gasification has high condensate depression, these provide high growth power for reactant, and therefore, the difference of hotchpotch and matrix growth velocity will be dwindled, can guarantee like this doped element can with matrix synchronous growth, realize evenly mixing.Therefore, the doping of carrying out one-dimentional structure under the plasma condition can well remedy the shortcoming of existing vapor phase process.With raw material with treat to join in the plasma body after the doped element pre-mixing, evaporation back just can obtain equally distributed phase feed in arc.Under certain cooling conditions, gaseous feed condensation is simultaneously separated out, and follows the growth of one-dimentional structure, thereby obtains even adulterated one-dimensional nano structure material.Therefore by uniform temperature field in the controlling reactor, just can realize evenly separating out of raw material and doped element, obtain even adulterated one dimension product.The arc core temperature that plasma is high, the most metal that can gasify, thus enlarged the kind of selecting scope and doped element for use of raw material, simultaneously can large-scale production.
Summary of the invention
The present invention proposes on the basis of a kind of method (200610112739.7) for preparing nano zinc oxide crystal whisker of the patent of having applied for, this patent is that the using plasma technology prepares one-dimensional nano structure material, and patent has been introduced processing condition and the parameter that the using plasma technology prepares one-dimensional nano structure material.The purpose of this patent provides a kind of method of utilizing the high-frequency induction plasma body to prepare transient metal doped nano zinc oxide crystal whisker.The mixed precursor raw material is carried, is entered in the plasma arc through feeding gun by carrier gas, utilize isoionic high temperature and high reactivity atmosphere to gasify and react, in the morphology control device, realize the growth of condensation forming core then under the controlled condition, generate fibrous crystal whisker products.By to control of process parameters such as oxygen partial pressure and working gas flow velocity in raw material type, feed way, the morphology control device, realize control to ZnOw product pattern.This method technology is simple, can the mass-producing continuous production.The present invention prepares transient metal doped nano zinc oxide crystal whisker and comprises following step:
1. the plasma processing tool accompanying drawing for preparing transient metal doped nano zinc oxide crystal whisker is identical with patent (200610112739.7).
2. the selection of raw material: the raw material route of present method is wide, and multiple material containing zincs such as zinc subcarbonate, zinc oxide, zinc and zinc hydroxide all can be used as presoma; The precursor of doped element can be metal or muriate etc.
3. the mixing of raw material: the mixing of raw material adopts simple mechanically mixing to get final product, and mixed raw material is crossed 100 eye mesh screens, to guarantee that raw material can enter in the plasma body by feeding gun smoothly.
4. the selection of feed way and feeding quantity: feed way adopts the mode of centre charging, can make full use of the energy gasified raw material of plasma body like this; The feeding quantity scope is controlled at 1-200g/min, preferred 5-50g/min.
Oxidizing atmosphere selection: when raw material is zinc powder or doped element when being metal powder, must add atmosphere in the oxidizing gas control plasma body.Oxidizing gas comprises oxygen and air.The adding mode adopts with limit gas mixes the mode that adds, to guarantee having higher temperature.Add-on is 1-100l/min, preferred 2-50l/min.
6. the selection of plasma parameter: when plasma power was 30kw, each parameter was as follows: plasma generation gas is argon gas, and flow range is 0.5-5m
3/ h, preferred 0.8-2.5m
3/ h.Limit gas is nitrogen or air, and flow is 0.5-20m
3/ h, preferred 1-10m
3/ h; System pressure is a negative pressure, and pressure range is controlled at 1-50cm H
2The O water column, preferred 5-20cm H
2The O water column.
7. temperature in the morphology control device: temperature is controlled by adding cooling tolerance in the morphology control device, and cooling gas can be selected nitrogen or air, when raw material is zinc powder, should adopt air cooling.Cooling tolerance range of choice is generally 0-5m
3/ h, preferred 0-3m
3/ h.
Characteristics of the present invention:
1. raw material route is wide, and technical process is simple, and energy consumption is low, environmentally safe.
2. quality product height, uniform doping, pattern homogeneous.
3. can realize the doping of high boiling point refractory metal.
4. the output height has been realized the serialization scale production.
5. investment and running cost are lower, this Technology can grafting direct or indirect method zinc oxide production technique basis till now on, adaptability is strong.
Description of drawings:
Fig. 1 is the X-ray diffraction spectrogram according to the adulterated ZnOw of manganese of example 1 preparation;
Fig. 2 is the stereoscan photograph according to the adulterated ZnOw of manganese of example 1 preparation;
Fig. 3 is the transmission electron microscope photo according to the adulterated ZnOw of manganese of example 1 preparation;
Fig. 4 is the ultimate analysis according to the adulterated ZnOw of manganese of example 1 preparation;
Fig. 5 is the stereoscan photograph according to the adulterated ZnOw of manganese of example 2 preparations;
Fig. 6 is the stereoscan photograph according to the adulterated ZnOw of manganese of example 3 preparations;
Fig. 7 is the stereoscan photograph according to the adulterated ZnOw of nickel of example 4 preparations.
Embodiment:
Embodiment 1
Raw material is the Manganous chloride tetrahydrate of zinc powder and 2%, mixes the back of sieving and adds in the feed pot.During experiment, raw material adds in the plasma body with 20g/min.Plasma parameter is as follows:
| Central gas Ar 2 | Limit gas N 2 | Oxygen | System's negative pressure |
| 1.5m 3/h | 6m 3/h | 15L/h | The 10cm water column |
Product is collected by the rewinding jar, and accompanying drawing 1 is seen in the product structure analysis, and the product morphology analysis is seen accompanying drawing 2 and accompanying drawing 3, and accompanying drawing 4 is seen in the ultimate analysis of product.
Embodiment 2:
Raw material is the Manganous chloride tetrahydrate of zinc powder and 0.25%, mixes the back of sieving and adds in the feed pot.During experiment, raw material adds in the plasma body with 20g/min.Plasma parameter is as follows:
| Central gas Ar 2 | Limit gas (oxygen) | System's negative pressure |
| 1.5m 3/h | 6m 3/h | The 10cm water column |
Product is collected by the rewinding jar, and the product morphology analysis is seen accompanying drawing 5.
Embodiment 3:
Raw material is the Manganous chloride tetrahydrate of zinc powder and 0.25%, mixes the back of sieving and adds in the feed pot.During experiment, raw material adds in the plasma body with 20g/min.Plasma parameter is as follows:
| Central gas Ar 2 | Limit gas N 2 | Oxygen | System's negative pressure |
| 1.5m 3/h | 6m 3/h | 15L/h | The 10cm water column |
Product is collected by the rewinding jar, and the product morphology analysis is seen accompanying drawing 6.
Embodiment 4:
Raw material is the cupric chloride of zinc powder and 0.5%, mixes the back of sieving and adds in the feed pot.During experiment, raw material adds in the plasma body with 20g/min.Plasma parameter is as follows:
| Central gas Ar 2 | Limit gas N 2 | Oxygen | System's negative pressure |
| 1.5m 3/h | 6m 3/h | 15L/h | The 10cm water column |
Product is collected by the rewinding jar, and the product morphology analysis is seen accompanying drawing 7.
Claims (8)
1, a kind of transient metal doped nano zinc oxide crystal whisker preparation method is characterized in that:
(1) precursor that contains zinc raw material and doped element is carried out pre-mixing and form the uniform precursor raw material;
(2) under the conveying of carrier gas, the precursor raw material is entered in the plasma arcs with certain feed rate;
(3) precursor material that enters plasma arcs gasifies in the plasma arcs district;
(4) product after the gasification enters the also nucleating growth that reacts in the plasma body morphology control device under the drive of air-flow, forms transient metal doped nano zinc oxide crystal whisker product;
(5) the transient metal doped ZnOw product of Sheng Chenging enters collector with air-flow and collects.
2, preparation method according to claim 1 is characterized in that the used zinc raw material that contains can be the multiple zinc precursor things that contain such as zinc powder, zinc oxide, zinc subcarbonate or zinc hydroxide; The precursor of doped element can be metal, muriate etc.
3, preparation method according to claim 1 contains that the mass percent of zinc and doped element is 0-10% in the zinc raw material.
4, preparation method according to claim 1 mixes raw material, sieves then, and the screen cloth that wherein sieves makes it can form mixed uniformly precursor, and can add in the plasma arcs continuously smoothly greater than 100 orders.
5, preparation method according to claim 1, the precursor raw material that enters in the plasma arcs adopts the mode of centre charging to carry out, and the feed rate of precursor raw material is 1-200g/min, preferred 5-50g/min.
6, preparation method according to claim 1 need add oxygen when containing the zinc raw material for zinc powder, and the adding mode of oxygen adopts with limit gas mixes the mode that the back adds, and add-on is 1-100l/min, preferred 2-50l/min.
7, preparation method according to claim 1, the temperature in the morphology control device can be controlled by adding the cold gas scale of construction, and cooling gas can be selected nitrogen or air, and cooling gas flow range of choice is 0-5m
3/ h, preferred 0-3m
3/ h.
8, preparation method according to the transient metal doped nano zinc oxide crystal whisker of claim, it is characterized in that this method goes for various transient metal doped ZnOw products, and controlled, the uniform doping of nano zinc oxide crystal whisker length-to-diameter ratio of preparation, output height can be realized the production of serialization scale.
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| CNA2009100771272A CN101498034A (en) | 2009-01-16 | 2009-01-16 | Preparation of transient metal doped nano zinc oxide crystal whisker |
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|---|---|---|---|
| CNA2009100771272A CN101498034A (en) | 2009-01-16 | 2009-01-16 | Preparation of transient metal doped nano zinc oxide crystal whisker |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515233A (en) * | 2011-12-29 | 2012-06-27 | 中国科学院过程工程研究所 | Method and product for preparing aluminum oxide with hot plasma |
| CN103849934A (en) * | 2014-03-28 | 2014-06-11 | 四川理工学院 | Preparation method of nano Cr3C2 crystal whisker |
| CN105926029A (en) * | 2016-05-09 | 2016-09-07 | 郑州云江科技有限公司 | Method for quick synthesis of zinc oxide whiskers by means of microwaves |
| CN109877312A (en) * | 2019-04-18 | 2019-06-14 | 北京科技大学 | A kind of preparation method of spherical shape ferrite base ODS alloy powder |
| CN110014145A (en) * | 2019-04-18 | 2019-07-16 | 北京科技大学 | A kind of preparation method of spherical shape iron-based powder |
-
2009
- 2009-01-16 CN CNA2009100771272A patent/CN101498034A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515233A (en) * | 2011-12-29 | 2012-06-27 | 中国科学院过程工程研究所 | Method and product for preparing aluminum oxide with hot plasma |
| CN103849934A (en) * | 2014-03-28 | 2014-06-11 | 四川理工学院 | Preparation method of nano Cr3C2 crystal whisker |
| CN103849934B (en) * | 2014-03-28 | 2016-08-17 | 四川理工学院 | A kind of nanometer Cr3c2the preparation method of whisker |
| CN105926029A (en) * | 2016-05-09 | 2016-09-07 | 郑州云江科技有限公司 | Method for quick synthesis of zinc oxide whiskers by means of microwaves |
| CN109877312A (en) * | 2019-04-18 | 2019-06-14 | 北京科技大学 | A kind of preparation method of spherical shape ferrite base ODS alloy powder |
| CN110014145A (en) * | 2019-04-18 | 2019-07-16 | 北京科技大学 | A kind of preparation method of spherical shape iron-based powder |
| CN109877312B (en) * | 2019-04-18 | 2020-12-04 | 北京科技大学 | Preparation method of spherical ferrite-based ODS alloy powder |
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Open date: 20090805 |