CN104607648A - Method for preparing nanometer or submicron order tin or tin alloy microspheres - Google Patents
Method for preparing nanometer or submicron order tin or tin alloy microspheres Download PDFInfo
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- CN104607648A CN104607648A CN201510018962.4A CN201510018962A CN104607648A CN 104607648 A CN104607648 A CN 104607648A CN 201510018962 A CN201510018962 A CN 201510018962A CN 104607648 A CN104607648 A CN 104607648A
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Abstract
The invention relates to the technical field of surface metallization and the technical field of new material preparation, in particular to a method for preparing nanometer or submicron order tin or tin alloy microspheres using an electric spark deposition technique. The method adopts the electric spark deposition technique, a pure tin wire (bar) with lower melting point or Sn-X composite wire (bar) is used as a positive pole, a conductive substrate with higher melting point is used as a negative pole, and the negative pole is placed in a silicone oil both, the positive pole is allowed to move close to the negative pole slowly, contact and friction of the positive pole and the negative pole are conducted, thus a phenomenon of spark discharge occurs, instantaneous high temperature generated by the spark discharge melts metal in the tip end of the positive pole, formed metal or an alloy micro-droplet is diffused around the positive pole under burst impact force generated by the instantaneous spark discharge, and the formed metal or an alloy micro-droplet deposits on the surface of the negative pole gradually under the effect of gravity; formed nano-microspheres reach a submicron or nanometer order, and the size distribution of the nano-microspheres is uneven; The method for preparing nanometer or submicron order tin or tin alloy microspheres is simple in technique, small in damage to staff, high in efficiency, and suitable for large-scale and large-area production.
Description
Technical field
The present invention relates to surface metallurgical technology and technical field of new material preparation, be specifically related to a kind of method utilizing electric spark deposition technology to prepare nanometer or submicron order tin or ashbury metal microballoon.
Background technology
Tin ball is mainly used in the aspect such as assembling, flux, alloy manufacture of circuit board, and the industrial preparation method for tin ball product is varied at present, common are: aerosolization method, centrifugal atomization, chopping remelting process, casting method and cold heading methodologies etc.Aerosolization method utilizes gas pressure the method for hydraulic shock fragmentation flowing through nozzle, when producing tin ball due to the pressure height of atomization gas and the decentralization of the factors such as character on atomized tin grain of atomization gas medium and the impact of shape, make the decentralization of the tin grain of generation wider, also must through repeatedly sieving to obtain required size.Centrifugal atomization is that the metal liquid of melting is flow on the disk of rotation, under centrifugal action, make drop depart from disk, fall into a kind of method that cooling medium solidifies, its major influence factors is the charging rate of liquid metals, the rotating speed of disk and shape etc., the production efficiency of the method is higher, but the particle dispersion produced is wider and out of roundness is not high.Chopping remelting process is, with shearing machine, tin silk is cut into uniform segmentation, segmentation is immersed in high-temperature hot oil and make it a kind of method that Melting And Solidification becomes spheric granules, but in practical operation, the tin ball that production granularity is less is difficult to shear evenly, and in reflow process, the temperature, remelting time etc. of deep fat all can affect quality and the crystalline structure of tin ball.Casting method is that Xi Shui is injected the mould cooling forming being connected with cooling circulating water, and the method easily produces slag point, endless belt and gas hole defect.Cold heading methodologies first material is cast into ingot to be squeezed into bar again, then carries out cold-heading molding, and in extrusion process, two ingot joints easily produce fracture, and the method operation is more loaded down with trivial details simultaneously.
In sum, tin spherolite footpath prepared by these traditional methods is larger, and more than millimeter rank, grain size dispersity is wider, and often can only be used for preparing one-component tin ball.
On the one hand, along with electronic product is towards compact, high frequency, the future development such as multi-functional, the precision of tin ball quality and the requirement of kind is also improved constantly, requires tin and the alloy microballoon thereof of more small particle diameter.On the other hand, in field of functional materials, gold, silver and platinum-group noble metals are all good electrocatalysis materials, but due to their prices costly, limit its large-scale application, the micro-/ nano spherical structure of alloying is formed with transition metal Sn, both can augmenting response contact area, improve the utilization rate of material; Can the consumption of noble metal be reduced by alloying thus reduce costs again; By " synergy " effect between contiguous heteroatom, the chemism of metal can also be improved.Therefore, micro/nano level alloy micro-sphere structure can also as function admirable, cheap electro catalytic electrode material.Simultaneously, the kamash alloy of nanostructured is regarded as optimal lithium ion battery negative material after carbon, can improve specific capacity and the security of lithium battery on a large scale, micro-/ nano tin and ashbury metal microballoon are expected to the ion cathode material lithium becoming a kind of function admirable.By retrieval, we prepare the proper method of nanoscale Sn and Sn-X microballoon disclosed in finding also not have at present, the present invention mainly lays particular emphasis on the manufacture method with being different from traditional tin ball, fast, easy, economical prepare tin and alloy microballoon thereof, and the particle diameter of microballoon can reach sub-micron and Nano grade.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, and technical problem to be solved is a kind of method that electric spark deposition technology prepares nanometer or sub-micron Sn microballoon and Sn-X alloy microballoon.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon, comprises the steps:
1) pretreatment of base material
Conductive substrates ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
The fusing point of base material should be not less than 1000 DEG C; Preferred base material is the one in metallic nickel, titanium, molybdenum, tungsten, cobalt, palladium.
2) pretreatment of anode material
When pure tin selected by anode material, require the pure tin silk into purity 90wt.%-99.9wt.%, diameter 0.5-10mm or pure tin rod;
When Sn-X selected by anode material, require the composite filament into diameter 2-10mm or compound bar, described composite filament or compound bar for core, take tin as skin with component X, make both combine closely, similar pencil wick-like structure; The diameter of component X is 0.05-5mm; Wherein the purity of the purity of tin and the single metal of component X all requires 90wt.%-99.9wt.%;
In Sn-X composite filament or compound bar, component X can select the alloy of Pt, Pd, Au, Ag, Ni, Co, Cu wherein a kind or any 2 kinds.
The described Sn-X composite filament of pencil wick-like structure or the preparation method of compound bar have multiple, as long as combine closely between outer tin and inner core X, just do not affect outward appearance and the performance of formed complex microsphere.
The preparation of Sn-X composite filament or compound bar can be the one in following methods:
Hole in the axial centre of Xi Si or tin bar, in duct, put into X metal core, composition Sn-X composite filament or compound bar;
Or, comprise X metal core with tin, then make it combine closely 100-230 DEG C of hot extrusion, obtain Sn-X composite filament or compound bar;
Or, X metal core is stretched in tin melt, then takes out cooling, repeat this process and obtain Sn-X composite filament or the compound bar of wrapping up and needing thickness tin shell.
Wherein, the ratio of Sn and component X and X adopt metal ratio during alloy, all adjust according to the electrode that will obtain what performance, can accomplish easily.
3) connection of device
Pretreated base material immersed in the silicone oil bath of 10-50 DEG C, the upper surface of base material is 1-200mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
The upper surface of base material is to the preferred 1-100mm of distance of liquid level;
4) coating procedure
Arranging electric spark deposition supply voltage is 20-60 volt, electric capacity is 400-800 microfarad, frequency is 40-80 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 1-10 time;
After having applied, take out base material ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up is dried, and the condition of drying is 10-60 DEG C, preferred 10-40 DEG C.
Above-mentioned steps 1) and step 2) there is no strict ordinal relation.
Step 1) and 4) in the ultrasonic cleaning that relates to, the time of three ultrasonic cleaning is each 5-60min, preferred 10-50min.
In step 4), preferred process conditions are: voltage 40-60 volt, electric capacity 500-600 microfarad, frequency 50-60 hertz; 1-3 time per second of spark discharge coating speed.
Physical mechanism of the present invention can do description below:
Electric spark deposition technology is by spark discharge effect, produce TRANSIENT HIGH TEMPERATURE (up to 5000-25000 DEG C), anode material infiltration is entered metallic matrix top layer, forms metallurgical binding with matrix skin, make the physical chemistry of matrix surface and a kind of improved method of mechanical property.When using tin silk or Sn-X as anode, because anode material fusing point is lower, under the TRANSIENT HIGH TEMPERATURE that spark discharge produces, be in the tin silk of anode tip or melt instantaneously containing tin metal, depart from anode, the metal or alloy microlayer model formed, under " blast " impulsive force that moment spark discharge is formed in the silicone oil environment of disperse around anode, sedimentation is also solidified again gradually under gravity.Silicone oil has viscosity, and the buoyancy of generation has delayed the whereabouts of metal microlayer model, makes microlayer model have sufficient time formation rule under surface tension effects spherical, then sinks to cathode substrate surface.
Compared with prior art the present invention has following beneficial effect.
1, the tin ball prepared of this method, particle diameter is little, sub-micron and Nano grade can be reached, and even size distribution, without endless belt, can be good at meeting the demand to tin ball high accuracy, high-quality and low dimensional, is the ideal material of the aspects such as Electronic Packaging, fine chemistry industry, electro-catalysis and lithium cell cathode material.
2, utilize electric spark instantaneous discharge deposition technique, production process environmental protection, little to the injury of operating personnel, preparation method is simple, and metal ingredient is adjustable, reproducible.
3, in tradition application, electric spark deposition technology is mainly for the preparation of wear-resisting, anti-corrosion, fatigue proof superficial layer, meet the requirement of production field to material working surface mechanical property, and we propose to utilize this technology to produce tin and the ashbury metal microballoon of micro-/ nano yardstick first, this is different from the existing method being used for producing tin ball.
Accompanying drawing explanation
Nanometer tin microballoon low power stereoscan photograph prepared by Fig. 1 embodiment 1.
Nanometer tin microballoon high power stereoscan photograph prepared by Fig. 2 embodiment 1.
Nanometer tin palladium alloy microsphere stereoscan photograph prepared by Fig. 3 embodiment 2.
Nanometer tin palladium alloy microsphere EDX composition energy spectrogram prepared by Fig. 4 embodiment 2.
Nanometer tin silver alloy microballoon stereoscan photograph prepared by Fig. 5 embodiment 3.
Nanometer tin silver alloy microballoon EDX composition energy spectrogram prepared by Fig. 6 embodiment 3.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Nanometer tin microballoon prepared by a kind of electric spark deposition technology, deposition substrate used is disc-shaped leaf, diameter is 15 millimeters, be highly 2 millimeters, described leaf purity is 99.5wt.%, tin filament diameter used is 1 millimeter, and purity is 99.9wt.%, and after coating, substrate surface is obviously distributed with one deck nanoscale chondritic.
Concrete preparation method is as following step:
(1) it is 15 millimeters by diameter, thickness is 2 millimeters, purity is that the leaf of 99.5wt.% is ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, is polished to light, ultrasonic cleaning 15min in acetone, absolute ethyl alcohol and ultra-pure water respectively successively, and taking-up is dried for subsequent use;
(2) leaf of drying in step (1) is immersed in the silicone oil bath at 30 DEG C, leaf is placed in the lower 15 millimeters of places of liquid level, draw wire from its surface and be connected to the working electrode end of electrospark impregnation equipment as negative electrode, its source terminal connect purity be the tin silk of 99.9wt.% as anode, described tin filament diameter is 1 millimeter;
(3) the deposition supply voltage arranging electrospark impregnation equipment is 50 volts, and electric capacity is 500 microfarads, and frequency is 50 hertz.The anode that tin silk is equipped with in slow movement makes Xi Si contact with substrate leaf, produce spark discharge, most advanced and sophisticated tin silk fusing is made to depart from anode, micro-molten drop under gravity sedimentation also solidifies formation micro-/ nano tin ball again, mobile tin silk repeats the process producing electric discharge, until whole leaf is covered by micro-/ nano tin ball, discharge rate is 2 times per second, after coating, leaf is taken out, ultrasonic cleaning 10min in acetone, absolute ethyl alcohol and ultra-pure water respectively, dry at 30 DEG C, namely the micro/nano level tin microballoon of preparation deposits to the top layer of substrate.
Embodiment 2
A tin palladium alloy microsphere prepared by electric spark deposition technology, deposited base material used is disc-shaped leaf, and diameter is 15 millimeters, is highly 4 millimeters, and described leaf purity is 99.5wt.%, and tin filament diameter used is 3 millimeters, and purity is 99.9wt.%; Palladium filament diameter used is 0.5 millimeter, and purity is 99.9wt.%, observes the visible obviously chondritic of surface microscopic topographic, can reach submicron order after coating.
Concrete preparation method is as following step:
(1) it is 15 millimeters by diameter, thickness is 4 millimeters, purity is that the leaf of 99.5wt.% is ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, is polished to light, ultrasonic cleaning 15min in acetone, absolute ethyl alcohol and ultra-pure water respectively successively, and taking-up is dried for subsequent use;
(2) get length 40 millimeters, diameter is 3 millimeters, and purity is the tin silk of 99.9wt.%, and central punch also penetrates the palladium silk that diameter is 0.5 millimeter, purity is 99.9wt.%, makes both combine closely, forms the composite construction electrode of similar pencil wick-like as anode;
(3) leaf of drying in step (1) is immersed in the silicone oil bath at 35 DEG C, leaf is placed in the lower 30 millimeters of places of liquid level, draw wire from its surface and be connected to the working electrode end of electrospark impregnation equipment as negative electrode, the tin processed in its source terminal Connection Step (2)/palladium composite construction electrode is as anode;
(4) the deposition supply voltage arranging electrospark impregnation equipment is 50 volts, and electric capacity is 600 microfarads, and frequency is 60 hertz.The composite anode that tin/palladium metal is equipped with in slow movement makes its tip contact with substrate leaf, produce spark discharge, make most advanced and sophisticated tin palladium metal fusing, the microlayer model of synchronous formation alloying, and depart from anode, micro-molten drop under gravity sedimentation also solidifies formation chondritic again, mobile tin/palladium bimetallic composite anode, repeat to produce spark discharge process, until whole leaf is covered by tin palladium alloy microsphere, discharge rate is 2 times per second, after coating, leaf is taken out, respectively at acetone, ultrasonic cleaning 10min in absolute ethyl alcohol and ultra-pure water, dry at 35 DEG C, the superficial layer of substrate is the tin palladium alloy microsphere that will prepare, be present in alloy microballoon by carrying out X-ray energy spectrum analysis (EDX) known tin palladium element to prepared specimen surface, C, the signal of Si element derives from silicone oil, the signal of W element derives from matrix.
Embodiment 3
A sn-ag alloy microballoon prepared by electric spark deposition technology, deposited base material used is disc-shaped palladium sheet, and diameter is 13 millimeters, is highly 1 millimeter, and described palladium sheet purity is 99.5wt.%, and tin filament diameter used is 3 millimeters, and purity is 99.9wt.%; Filamentary silver diameter used is 1 millimeter, and purity is 99.9wt.%, and coating rear surface microscopic appearance is obvious chondritic, even size distribution.
Concrete preparation method is as following step:
(1) it is 13 millimeters by diameter, thickness is 1 millimeter, purity is that the palladium sheet of 99.5wt.% grinds with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, is polished to light, ultrasonic cleaning 15min in acetone, absolute ethyl alcohol and ultra-pure water respectively successively, and taking-up is dried for subsequent use;
(2) getting length is 35 millimeters, and diameter is 3 millimeters, and purity is the tin silk of 99.9wt.%, central punch to penetrate diameter be 1 millimeter, and purity is the filamentary silver of 99.9wt.%, makes both combine closely, forms the composite construction electrode of similar pencil wick-like as anode;
(3) the palladium sheet dried in step (1) is immersed in the silicone oil bath at 40 DEG C, palladium sheet is placed in the lower 20 millimeters of places of liquid level, draw wire from its surface and be connected to the working electrode end of electrospark impregnation equipment as negative electrode, in its source terminal Connection Step (2), tin/silver composite structure electrode is as anode;
(4) the deposition supply voltage arranging electrospark impregnation equipment is 50 volts, and electric capacity is 600 microfarads, and frequency is 50 hertz.The composite anode that tin/silver bimetal is equipped with in slow movement makes its tip contact with substrate palladium sheet, produce spark discharge, make most advanced and sophisticated tin silver metal fusing, the microlayer model of synchronous formation alloying, and depart from anode, there is sedimentation under gravity and again solidify formation chondritic, mobile tin/silver bimetal composite anode, repeat to produce discharge process, until whole palladium sheet is covered by sn-ag alloy microballoon, discharge rate is 3 times per second, after coating, palladium sheet is taken out, respectively at acetone, ultrasonic cleaning 10min in absolute ethyl alcohol and ultra-pure water, dry at 40 DEG C, superficial layer is the sn-ag alloy microballoon that will prepare, be present in alloy microballoon by carrying out the known tin silver element of X-ray energy spectrum analysis (EDX) to prepared specimen surface, C, the signal of Si element derives from silicone oil, the signal of Pd element derives from matrix,
Embodiment 4
The present embodiment except following characteristics with embodiment 2: selected base material is diameter is 10 millimeters, and thickness is 2 millimeters, and purity is the molybdenum sheet of 99.9wt.%.Anode used is Sn-X (X=PdCu) composite filament of diameter 1.5 millimeters, and wherein palladium brass wire diameter used is 0.5 millimeter, is 10wt.% containing palladium, cupric 90wt.%.The deposition supply voltage of electrospark impregnation equipment is 40 volts, and electric capacity is 500 microfarads, and frequency is 50 hertz, each second electro-arc depositing 3 times.After coating, molybdenum sheet is taken out, ultrasonic cleaning 10min in acetone, absolute ethyl alcohol and ultra-pure water, dries at 40 DEG C respectively, and superficial layer is the tin palladium-copper alloy microballoon that will prepare.
Embodiment 5
Prepare a method for nanometer or submicron order tin microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Co sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
The pure tin silk of diameter 2mm selected by anode material, requires as purity 99.5wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 20 DEG C, the upper surface of base material is 150mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 60 volts, electric capacity is 700 microfarads, frequency is 75 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 5 times;
After having applied, take out base material ultrasonic cleaning 10 min in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up high pure nitrogen dries up.
Embodiment 6
Prepare a method for nanometer or submicron order tin microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Ti sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
The pure tin silk of diameter 6mm selected by anode material, requires as purity 99.5wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 50 DEG C, the upper surface of base material is 60mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 40 volts, electric capacity is 800 microfarads, frequency is 80 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 8 times;
After having applied, take out base material ultrasonic cleaning 30min in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up high-purity argon gas dries up.
Embodiment 7
Prepare a method for nanometer or submicron order ashbury metal microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Pd sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
Anode material is with the Cu wire of diameter 3mm for core, and outside parcel Sn layer, obtains the compact composite filament of diameter 5mm through 200 DEG C of hot extrusions;
Wherein the purity of Sn, Cu is 95wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 35 DEG C, the upper surface of base material is 1mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 50 volts, electric capacity is 550 microfarads, frequency is 70 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 5 times;
After having applied, take out base material ultrasonic cleaning 5min in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up high pure nitrogen dries up.
Embodiment 8
Prepare a method for nanometer or submicron order ashbury metal microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Mo sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
Anode material is with the B alloy wire of Ag, Co mass ratio 1:1 of diameter 1mm for core, and outside parcel Sn layer, obtains the compact composite filament of diameter 4mm through 220 DEG C of hot extrusions;
Wherein the purity of Sn, Ag, Co is 99wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 40 DEG C, the upper surface of base material is 3mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 55 volts, electric capacity is 800 microfarads, frequency is 80 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 10 times;
After having applied, take out base material ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up high-purity argon gas dries up.
Embodiment 9
Prepare a method for nanometer or submicron order ashbury metal microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Ti sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
Anode material is with the B alloy wire of Co, Au mass ratio 1:0.5 of diameter 5mm for core, and outside parcel Sn, obtains the compact composite filament of diameter 10mm through 150 DEG C of hot extrusions;
Wherein the purity of Sn, Co, Au is 95wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 45 DEG C, the upper surface of base material is 1-50mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 40 volts, electric capacity is 500 microfarads, frequency is 50 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 4 times;
After having applied, take out base material ultrasonic cleaning 50 min in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up high pure nitrogen dries up.
Embodiment 10
Prepare a method for nanometer or submicron order ashbury metal microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Co sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
Anode material for core with the B alloy wire of Au, Cu mass ratio 1:5 of diameter 2mm, immerses in tin melt, then takes out cooling, repeat this process, obtains the compound bar of diameter 3.5mm;
Wherein the purity of Sn, Au, Cu is 99wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 25 DEG C, the upper surface of base material is 10mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 45 volts, electric capacity is 600 microfarads, frequency is 55 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 6 times;
After having applied, take out base material ultrasonic cleaning 25 min in acetone, absolute ethyl alcohol and ultra-pure water successively, dry under taking out the environment of 60 DEG C.
Embodiment 11
Prepare a method for nanometer or submicron order ashbury metal microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Co sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
Anode material for core with the B alloy wire of Au, Cu mass ratio 1:0.5 of diameter 2.5mm, immerses in tin melt, then takes out cooling, repeat this process, obtains the compound bar of diameter 5mm;
Wherein the purity of Sn, Au, Cu is 99wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 10 DEG C, the upper surface of base material is 200mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 20 volts, electric capacity is 400 microfarads, frequency is 50 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 2 times;
After having applied, take out base material ultrasonic cleaning 15 min in acetone, absolute ethyl alcohol and ultra-pure water successively, take out and dry under the environment of temperature 50 C.
Embodiment 12
Prepare a method for nanometer or submicron order ashbury metal microballoon, comprise the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by the Ni sheet of conductive substrates and purity 99wt.%, the conductive substrates after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
Anode material for core with the B alloy wire of Au, Cu mass ratio 1:1 of diameter 1.5mm, immerses in tin melt, then takes out cooling, repeat this process, obtains the composite filament of diameter 2mm;
Wherein the purity of Sn, Au, Cu is 99wt.%;
3) connection of device
Immersed by pretreated base material in the silicone oil bath of 50 DEG C, the upper surface of base material is 15mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Ready anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 30 volts, electric capacity is 500 microfarads, frequency is 40 hertz, slow moving anode metal electrode, it is made to immerse below silicone oil liquid level gradually and Contact cathod substrate surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 3 times;
After having applied, take out base material ultrasonic cleaning 60 min in acetone, absolute ethyl alcohol and ultra-pure water successively, take out and dry under the environment of temperature 60 C.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought explanation of the present invention and can not limit invention, claims indicate scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (10)
1. prepare a method for nanometer or submicron order tin or ashbury metal microballoon, it is characterized in that comprising the steps:
The material selection pure tin of anode or Sn-X composite, dystectic conducting metal selected by the base material of negative electrode, negative electrode is placed in silicone oil bath, slow moving anode, it is made to immerse below silicone oil liquid level gradually and Contact cathod surface, produce spark discharge, repeat said process until anode material is even in whole cathode surface coating;
In described Sn-X composite, component X is the alloy of Pt, Pd, Au, Ag, Ni, Co, Cu or any 2 kinds;
The fusing point of described base material is not less than 1000 DEG C.
2. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 1, is characterized in that: the material of described base material is Ni, Ti, Mo, W, Co or Pd.
3. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 1, is characterized in that comprising the steps:
1) pretreatment of base material
Ground with 360 orders, 1000 orders, 2000 object abrasive paper for metallograph, be polished to light successively by base material, the base material after polishing is ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, and taking-up is dried for subsequent use;
2) pretreatment of anode material
When pure tin selected by anode material, require the pure tin silk into purity 90wt.%-99.9wt.%, diameter 0.5-10mm or pure tin rod;
When Sn-X selected by anode material, require the composite filament into diameter 2-10mm or compound bar, Sn-X composite filament or compound bar for core, take tin as skin with component X, and the diameter of core is 0.05-5mm; Wherein the purity of the purity of tin and the single metal of component X all requires 90wt.%-99.9wt.%;
3) connection of device
To immerse in the silicone oil bath of 10-50 DEG C through the pretreated base material of step 1), the upper surface of base material is 1-200mm to the distance of liquid level; Draw wire from base material lower surface, be connected to the working electrode end of metal surface electrospark impregnation equipment as negative electrode;
Using through step 2) pretreated anode material is connected to the source terminal of equipment as anode;
4) coating procedure
Arranging electric spark deposition supply voltage is 20-60 volt, electric capacity is 400-800 microfarad, frequency is 40-80 hertz, slow moving anode, it is made to immerse below silicone oil liquid level gradually and Contact cathod surface, produce spark discharge, repeat said process until anode material is even in whole base material upper surface coating, spark discharge coating speed is electric discharge per second 1-10 time;
After having applied, take out base material ultrasonic cleaning in acetone, absolute ethyl alcohol and ultra-pure water successively, taking-up is dried.
4. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 3, is characterized in that described step 2) in the preparation method of Sn-X composite filament or compound bar be:
Hole in the axial centre of Xi Si or tin bar, in duct, put into X metal core, composition Sn-X composite filament or compound bar;
Or, comprise X metal core with tin, then make it combine closely 100-230 DEG C of hot extrusion, obtain Sn-X composite filament or compound bar;
Or, X metal core is stretched in tin melt, then takes out cooling, repeat this process and obtain Sn-X composite filament or the compound bar of wrapping up and needing thickness tin shell.
5. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 3, is characterized in that: coating procedure arranges electric spark deposition power supply, and to arrange voltage be 40-60 volt, and electric capacity is 500-600 microfarad, and frequency is 50-60 hertz.
6. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 3, is characterized in that: coating procedure spark discharge coating speed is 1-3 time per second.
7. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 3, is characterized in that: in described step 3), the upper surface of base material is 1-100mm to the distance of liquid level.
8. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 3, is characterized in that: step 1) and 4) in the ultrasonic cleaning that relates to, the time of three ultrasonic cleaning is each 5-60min.
9. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 3, is characterized in that: after having applied, and after base material cleaning, dries up, or dry under the environment of temperature 10-60 DEG C with high pure nitrogen or argon gas.
10. a kind of method preparing nanometer or submicron order tin or ashbury metal microballoon according to claim 9, is characterized in that: described in dry temperature be 10-40 DEG C.
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| CN105506552A (en) * | 2016-01-15 | 2016-04-20 | 陕西科技大学 | Nanometer Sn ball preparing method |
| CN107541702A (en) * | 2017-09-08 | 2018-01-05 | 张家港创博金属科技有限公司 | A kind of is efficiently the method and apparatus of caryosphere coating |
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| CN107541702A (en) * | 2017-09-08 | 2018-01-05 | 张家港创博金属科技有限公司 | A kind of is efficiently the method and apparatus of caryosphere coating |
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| CN104607648B (en) | 2017-03-01 |
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