CN102173389B - Microwave-assisted solid-liquid reaction ball-milling device and process for preparing nano-oxide powder - Google Patents
Microwave-assisted solid-liquid reaction ball-milling device and process for preparing nano-oxide powder Download PDFInfo
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- CN102173389B CN102173389B CN 201110004753 CN201110004753A CN102173389B CN 102173389 B CN102173389 B CN 102173389B CN 201110004753 CN201110004753 CN 201110004753 CN 201110004753 A CN201110004753 A CN 201110004753A CN 102173389 B CN102173389 B CN 102173389B
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Abstract
The invention relates to a microwave-assisted solid-liquid reaction ball-milling device and process for preparing nano-oxide powder, and discloses a ball-milling device for improving the quality of powder obtained from ball milling and a method using the ball-device to prepare fine nano-oxide powder. The microwave-assisted solid-liquid reaction ball-milling device comprises a stirring shaft, a microwave oven, a ceramic ballo-milling jar, milling balls, a crossbar, a sealing device, the door of the microwave oven and a fixing device. The microwave-assisted solid-liquid reaction ball-milling device is combined with a related technique to realize milling by using the ceramic ballo-milling jar, the motor drives the stirring shaft to perform milling, and during the milling process, the microwave produces a microwave environment. The invention has the advantage that block reactant can fully react and finer particles are produced at the same time so as to promote the reaction to be better, faster and more thorough.
Description
Technical field
The present invention relates to stainless material, powder metallurgy and ceramic field provide a kind of microwave-assisted solid-liquid reaction ball mill device and technology for preparing nano-oxide powder.
Background technology
Because the nanoparticle volume is very little; Has very large specific surface area; Thereby show many and macroscopical different physics and chemical properties of volume physics greatly; Show that mainly it has high-performances such as surface effects, quantum size effect, volume effect and macro quanta tunnel effect, show peculiar physics and chemical property at aspects such as magnetic, photoabsorption, chemically reactive, thermal resistance, catalyzer and fusing points, so nano material has received people's common concern.
Ball mill can be good at the pulverized particles material owing to pass through the effect of impact between the abrading-ball, thereby pulverizes at solid material, and widespread use in the fields such as colliery separation has the people to solve the crushing efficiency problem of hard brittle material through the microwave grinding aid.Yet because the high energy of ball milling bump; Powder particle after the fragmentation again can seam in follow-up mechanical milling process together; Thereby the particle of the final product that obtains is still bigger, and will seek out more tiny product particle, must traditional ball mill be improved.
Summary of the invention
The technical problem that the present invention solved is to provide a kind of microwave-assisted solid-liquid reaction ball mill device and technology for preparing nano-oxide powder, to solve the shortcoming in the above-mentioned background technology.
The technical problem that the present invention solved adopts following technical scheme to realize:
The present invention at first provides a kind of microwave-assisted solid-liquid reaction ball mill device for preparing nano-oxide powder; Comprise: tetrafluoroethylene rotating shaft, microwave oven, ceramic ball grinder, abrading-ball, tetrafluoroethylene agitator arm, tightness system, door for microwave oven and stationary installation; Wherein the tetrafluoroethylene rotating shaft is connected in phonomoter; Driving the tetrafluoroethylene agitator arm that is connected in above it when being rotated by the rotating shaft of motor drives tetrafluoroethylene rotates; The tetrafluoroethylene agitator arm places tiny abrading-ball, thereby causes the stirring of abrading-ball and collision each other.
In the present invention, abrading-ball is contained in the ball grinder, and ball grinder is fixed in the microwave oven by stationary installation.The part of tetrafluoroethylene rotating shaft places microwave oven, and microwave oven leaves a circular hole atop so that rotation axis can enter in the microwave oven, increases by a tightness system, the pollution and the human injury that cause environment to avoid microwave leakage on it simultaneously.
In the present invention, whole microwave oven by screw retention on worktable, in order to reduce the concussion that is produced in the device operational process.
Abrading-ball is of a size of radius below 1.5 millimeters, is processed by stainless steel or pottery, makes that the radiation reflection of microwave is even; Ball grinder is whole to be placed in the microwave oven, makes microwave radiation even; Agitator arm is pressed on the ball grinder, in order to fixing ball grinder; Ball grinder is fixed in the microwave oven, and microwave oven is fixed on the worktable, and the stirring of ball milling bar drives abrading-ball work in the time of ball milling work.
In addition, ceramic pot, the material of stir shaft and agitator arm also can adopt multiple materials such as aluminum oxide, zirconium white or macromolecular material.
In the present invention, a kind of related process for preparing nano-oxide powder is provided also, in order to be used, in order to the preparation nano-oxide powder with said apparatus.
Obtained multiple nano functional powder through the solid-liquid reaction ball-milling technology under the microwave-assisted adopting under the situation of said apparatus, mainly contained through decomposition reaction and prepared nano-oxide powder, like cupric oxide, zinc oxide and red stone etc.; Nanometer powders such as Ni ferrite, Mn ferrite, Zn ferrite and Mn-Zn ferrite have been prepared through building-up reactions; Nanometer powders such as zinc oxide, cupric oxide and red stone have been prepared through replacement(metathesis)reaction.
Key step comprises:
Select the microwave oven of 2450MHZ frequency, power selection 1024W puts into the tiny abrading-ball of 500 units earlier in ball grinder, and a certain amount of reactant adds 600 unit water then inward.Open the fire door of microwave oven, put into the ceramic ball grinder that adds reactant the centre of microwave oven.
Be rotated counterclockwise tightness system, open apical pore, rotating shaft is inserted in the ball grinder through apical pore; And be inserted into the bottom of tetrafluoroethylene agitator arm to ball grinder, mechanism, fixedly ball grinder then are locked; The cover upper sealing device, it is tight to turn clockwise, and shuts door of microwave oven.
Rotating shaft is screwed on the shaft of motor, and device connects to be accomplished.
Start motor, open microwave, adjusting power is peak, is 1024W, and microwave treatment time is 15 minutes.
After half hour, the motor that stops is opened tightness system; Take out agitator arm, open fire door, take out ball grinder; Marginal not entry inward makes that adding water water afterwards is total up to 600 units, puts into ball grinder in the microwave oven then; Insert agitator arm from the microwave oven top, cover tightness system then, screw.
With screw motor is started in rotating shaft and phonomoter, regulating microwave power is 80%, and the time is decided to be 15 minutes, opens microwave and drives the phonomoter that rotating shaft is mixed, and continues experiment.
Repeat above-mentioned ball milling step, up to obtaining title product.
Working method of the present invention; In the process of experiment, must notice that water volume wherein must keep abundant; Otherwise it is will can not get nano-oxide powder, and also can burn out equipment, but simultaneously also cannot the aqueous solution too many; Can burn out equipment otherwise solution overflows equally, even cause the generation of accident.
Beneficial effect:The present invention has the following advantages compared with prior art:
1, whole ball grinder is placed in the microwave oven, thereby makes microwave radiation even;
2, absorb microwave through liquid medium (water); And the microwave non-thermal effect that takes place; Making the common high-energy ball milling of script needs increase temperature roasting just can obtain can directly obtaining in nickel-zinc ferrite is being no more than 100 degrees centigrade under present method the water; Not only greatly reduce the high problem of this type of nano-oxide powder preparation temperature, also successful solution the seriously polluted problem that is prone to reunion and grows up with powder in the dry type ball milling;
3. be in the present invention through in the solid-liquid system by mechanical force and microwave and an effect of intercoupling; Utilize the mechanical force ball milling to the strike of reactant-peel off decomposition, synthetic and replacement(metathesis)reaction that effect is brought out; And obtain nano level oxide powder through forming core growth process again; So the formation mechanism of the nanometer powder among the present invention and traditional dry type high-energy ball milling prepare the fine powder Cracking Mechanism and exist essential distinction; In fact the effect that just reduces powder diameter that traditional dry type ball milling in most cases plays, not through the reactant forming core grow up can not arrive nanometer powder;
4. what adopt in apparatus of the present invention is diameter in the Stainless Steel Ball below 1.5 millimeters or Ceramic Balls as abrading-ball; Relevant principle according to the metal-powder microwave sintering; Undersized stainless steel abrading-ball can be so that microwave radiation time reflection evenly in the ball grinder; And then make medium (water) fully to absorb micro-wave energy, make solid-liquid reaction be able to efficiently carry out fast.
Description of drawings
Fig. 1 is the device synoptic diagram of preferred embodiment of the present invention;
Fig. 2 is the TEM figure of 5 hours after product nano cupric oxides of microwave ball milling ventilation breather;
Fig. 3 is that ventilation breather microwave ball milling generates the nano cupric oxide XRD figure after 5 hours;
Fig. 4 is the microwave ball milling basic nickel carbonate Ni ferrite XRD figure of surviving after 15 hours.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect and be easy to understand and understand, below in conjunction with concrete diagram, further set forth the present invention.
With specific examples practical feasibility and the meliority that this is bright is described now.
Instance 1: selecting power is the microwave oven of 1300W, puts into 500 gram ceramic grinding balls 4 and 10 gram basic carbonate copper powder 3 li of ceramic ball grinders earlier, adds entry then inward, water IR be that 600 of container restrains.Open the fire door 7 of microwave oven then, put into the centre of microwave oven 2 to the ceramic ball grinder 3 that adds ventilation breather, the bottom is fixing with firm banking 11.
Be rotated counterclockwise tightness system 6, open apical pore, rotating shaft 1 is inserted in the ceramic ball grinder 3 through apical pore; And be inserted into the bottom of tetrafluoroethylene agitator arm 5 to ceramic ball grinder 3, the mechanism 8 that then is locked, and the exhaust hole 12 of assurance fixed mechanism 8 is opened; Fixing simultaneously ceramic ball grinder 3; Cover upper sealing device 6, it is tight to turn clockwise, and shuts door of microwave oven 7.At last rotating shaft 1 is screwed in the rotating shaft of phonomoter 9, device connects to be accomplished.
Next just begin test: start phonomoter 9, open microwave oven 2, inject window 10 at the microwave of microwave oven 2 both sides and carry out microwave and inject that to regulate power be 80%, the time is 15 minutes, and motor speed is 235 r/min.
After half hour, the motor that stops is opened tightness system 6, and marginal not entry inward makes the content of water keep 600 grams, covers tightness system 6 then, screws.Start phonomoter 9, regulate power 80%, the time is decided to be 15 minutes.
Repeat above-mentioned ball milling step, close microwave equipment and ball-grinding machine after 2 hours, open fire door, take out ceramic ball grinder 3.
With spoon the aqueous solution of 3 li of ceramic ball grinders is scooped out; Filter through qualitative filter paper; The product of staying above the filter paper is put in the loft drier that temperature is 50 degree; Obtain the exsiccant powder after 8 hours, again the exsiccant powder is detected through technique means such as XRD and TEM, the adding like accompanying drawing 2 of detection with shown in the accompanying drawing 3.
Experimental result finds that ventilation breather has been converted into cupric oxide, and particle remains on 30nm～50nm.
Instance 2: the equal particle diameter of making even is put into ball grinder 3 at 1 to 3 millimeter basic nickel carbonate particle 10 grams, adds the stainless steel abrading-ball 4 of 500 gram diameters below 1.5mm then in wherein, in ball grinder 3, adds 600 gram deionized waters again as ball-milling medium.
According to the method for embodiment 1 ball grinder 3 is put in the microwave oven 2 again; Build the fixed mechanism 8 of ball grinder 3 and the tightness system 6 of microwave oven 2; Connect tetrafluoroethylene agitator arm 5 on phonomoter 9; Another section of tetrafluoroethylene agitator arm 5 is inserted into the bottom of ball grinder 3, and fire door is closed in being connected of be locked then phonomoter 9 and tetrafluoroethylene agitator arm 5.
The rotating speed of regulating phonomoter is 235 r/min, and then opens the switch of microwave oven 2, makes it launched microwave, and the power regulation of microwave is 1024W.Time location 15 minutes.Close microwave oven after 15 minutes finish and the rotation of phonomoter 9 and tetrafluoroethylene agitator arm 5 does not stop.Stop phonomoter 9 after 30 minutes and rotate, unload being connected of tetrafluoroethylene agitator arm 5 and phonomoter 9, open tightness system 6; Take out tetrafluoroethylene agitator arm 5, open 2 of microwave ovens then, take out ball grinder 3; Adding in the ball grinder 3 again makes the water in the ball grinder 3 remain 600 grams.
Again ball grinder 3 is put back in the microwave oven 2 and fixed.The test that continues according to earlier examples.Finish test after 12 hours; The liquid that takes out in the ball grinder 3 filters, and being deposited in the loft drier that powder on the filter paper is put into 50 degree of obtaining of filtration was carried out drying 8 hours, and then the dried powder that obtains is carried out the XRD detection; As shown in Figure 4; From figure, can know that basic nickel carbonate has changed the Ni ferrite nanometer powder fully into, cuts diameter at 20～40nm.
Embodiment 3: the equal particle diameter of making even is 1～3mm metallic zinc granule, 10 grams, and diameter is: ceramic grinding ball 400 grams of 1.5mm, ball-to-powder weight ratio is 40:1, places in the ball grinder 3, adds about 500g deionized water as ball milling liquid.
Controlled microwave stove 2 microwave powers are 1024 W, and ball mill control rotating speed is that 235 r/min carry out wet ball-milling; After 30 hours, sampling Detection, powder size has reached production engineering specifications, stops ball milling; Suction filtration, at 50 ℃, vacuum tightness is 10 with filter residue
-1Under the Pa, oven dry promptly obtains pure ZnO nanometer powder.Through detecting, the granularity of gained ZnO nanometer powder is about 50nm, and purity reaches more than 98%.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (2)
1. the microwave-assisted solid-liquid reaction ball-milling technology of preparation nano-oxide powder is characterized in that, need be used with microwave-assisted solid-liquid reaction ball mill device,
Said microwave-assisted solid-liquid reaction ball mill device comprises: tetrafluoroethylene rotating shaft, microwave oven, ball grinder, abrading-ball, tetrafluoroethylene agitator arm, tightness system, door for microwave oven and stationary installation; Wherein the tetrafluoroethylene rotating shaft is connected in phonomoter; The tetrafluoroethylene agitator arm is connected in the tetrafluoroethylene rotating shaft; The tetrafluoroethylene agitator arm places the abrading-ball of ball grinder; Ball grinder is fixed in the microwave oven by stationary installation, and the part of tetrafluoroethylene rotating shaft places microwave oven, and microwave oven leaves a circular hole atop so that rotation axis can enter in the microwave oven; Simultaneously it goes up increase by one tightness system, whole microwave oven by screw retention on worktable;
Said technology key step comprises:
(1) microwave oven of selection 2450MHz frequency; Power selection 1024W; Earlier putting into 500 units, the radius stainless steel abrading-ball below 1.5 millimeters in the ball grinder, a certain amount of reactant adds 600 unit water then inward; Open the fire door of microwave oven, put into the ceramic ball grinder that adds reactant the centre of microwave oven;
(2) be rotated counterclockwise tightness system, open apical pore, rotating shaft is inserted in the ball grinder through apical pore; And be inserted into the bottom of tetrafluoroethylene agitator arm to ball grinder, mechanism, fixedly ball grinder then are locked; The cover upper sealing device, it is tight to turn clockwise, and shuts door of microwave oven;
(3) rotating shaft is screwed on the shaft of motor, device connects to be accomplished;
(4) start motor, open microwave, adjusting power is peak, and microwave treatment time is 15 minutes;
(5) after half hour, the motor that stops is opened tightness system; Take out agitator arm, open fire door, take out ball grinder; Marginal not entry inward makes that adding water water afterwards is total up to 600 units, puts into ball grinder in the microwave oven then; Insert agitator arm from the microwave oven top, cover tightness system then, screw;
(6) start motor, open microwave, regulating microwave power is 80%, and the time is decided to be 15 minutes;
(7) repeat above-mentioned steps (5) and step (6), up to obtaining title product.
2. the microwave-assisted solid-liquid reaction ball-milling technology of preparation nano-oxide powder according to claim 1; It is characterized in that; The material of said ceramic ball grinder is aluminum oxide or zirconium white; The material of said rotating shaft and agitator arm replaces tetrafluoroethylene with aluminum oxide or zirconium white, and the material of said abrading-ball replaces stainless steel with pottery.
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| CN103521763A (en) * | 2013-11-01 | 2014-01-22 | 赣州中瑞材料科技有限公司 | Process for preparing superfine tungsten-base alloy powder by microwave-assisted ball-milling |
| CN105289806B (en) * | 2015-11-17 | 2017-08-25 | 绍兴文理学院 | A kind of lithium battery material microwave radiation technology ball-grinding machine and Ginding process |
| CN107742713A (en) * | 2017-10-27 | 2018-02-27 | 天津先众新能源科技股份有限公司 | A kind of synthetic method of graphene/lithium ferric manganese phosphate material |
| CN107790193B (en) * | 2017-10-30 | 2020-07-14 | 贵州理工学院 | High-frequency magnetic field assisted ball milling preparation method of catalyst for sewage treatment |
| CN107716002B (en) * | 2017-11-06 | 2023-03-28 | 齐鲁工业大学 | Device and method for preparing hexagonal boron nitride nanosheet through pure shear ball milling and ultrasonic cooperation |
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| CN201168628Y (en) * | 2008-07-18 | 2008-12-24 | 西安科技大学 | Multifunctional lab microwave mixing globe mill |
| CN101712005A (en) * | 2009-11-12 | 2010-05-26 | 湖南大学 | Method for preparing ZnO nanometer powder by ultrasonic ball milling |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201168628Y (en) * | 2008-07-18 | 2008-12-24 | 西安科技大学 | Multifunctional lab microwave mixing globe mill |
| CN101712005A (en) * | 2009-11-12 | 2010-05-26 | 湖南大学 | Method for preparing ZnO nanometer powder by ultrasonic ball milling |
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