CN104607648B - A kind of method preparing nanometer or submicron order stannum or tin alloy microsphere - Google Patents
A kind of method preparing nanometer or submicron order stannum or tin alloy microsphere Download PDFInfo
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- CN104607648B CN104607648B CN201510018962.4A CN201510018962A CN104607648B CN 104607648 B CN104607648 B CN 104607648B CN 201510018962 A CN201510018962 A CN 201510018962A CN 104607648 B CN104607648 B CN 104607648B
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Abstract
The present invention relates to surface metallurgical technology and technical field of new material preparation are and in particular to a kind of utilization electric spark deposition technology prepares nanometer or the method for submicron order stannum or tin alloy microsphere；The method is using electric spark deposition technology, using the relatively low pure tin silk of fusing point（Rod）Or Sn X composite filament（Rod）For anode, the conductive substrates of higher melt are negative electrode, and negative electrode is placed in silicone oil bath, allow anode slowly near negative electrode, contact and rub, thus producing Spark Discharges, the instantaneous high-temperature that spark discharge produces makes anode tip metal molten, the metal or alloy microlayer model being formed disperse under " blast " impulsive force that moment spark discharge is formed, around anode, and gradually deposits to cathode surface under self gravitation effect,；The Nano microsphere being formed reaches submicron and Nano grade, and even size distribution；Present invention process is simple, staff is injured little, efficiency high and be suitable for extensive, large area and produce.
Description
Technical field
The present invention relates to surface metallurgical technology and technical field of new material preparation are and in particular to one kind utilizes electric spark deposition
Technology prepares nanometer or the method for submicron order stannum or tin alloy microsphere.
Background technology
The aspect such as stannum ball is mainly used in the assembling of circuit board, flux, alloy manufacture, industrial at present for stannum ball product
Preparation method varied, common are：Gas atomization, centrifugal atomization, shredding remelting process, casting method and cold heading methodologies etc..
Gas atomization is the method hydraulic shock flowing through nozzle being crushed using gas pressure, when producing stannum ball due to atomization gas
Pressure height and the dispersion to atomized tin grain for the factor such as property of atomization gas medium and the impact of shape, make generation
The dispersion of stannum grain is wider, must also sieve through multiple to the size required for obtaining.Centrifugal atomization is the gold melting
Belong to liquid and flow on the disk of rotation, make drop depart from disk under the action of the centrifugal force, fall into one kind of solidification in cooling medium
Method, its major influence factors is charging rate, the rotating speed of disk and shape of liquid metals etc., and the production efficiency of the method is relatively
Height, but the particle dispersion that produced is wider and out of roundness is not high.Shredding remelting process is to be cut into uniformly stannum silk with shearing machine
Segmentation, segmentation is immersed in high-temperature hot oil and is allowed to Melting And Solidification and becomes a kind of method of spheroidal particle, but in practical operation,
It is difficult to shearing uniformly for producing granularity less stannum ball, and in reflow process, the temperature of deep fat, remelting time etc. all can shadows
Ring quality and the crystalline structure of stannum ball.Casting method is that Xi Shui injection is connected with cooling shaping in the mould of cooling circulating water, the party
Method is also easy to produce slag point, annulus and gas hole defect.Cold heading methodologies are first material to be cast into ingot to be squeezed into bar again, then carry out cold-heading one-tenth
Type, in extrusion process, two ingot joints are also easy to produce fracture, and the method operation is comparatively laborious simultaneously.
In sum, the stannum spherolite footpath ratio of these traditional method preparations is larger, more than millimeter rank, grain size dispersity
Wider, and often can only be used for preparing one-component stannum ball.
On the one hand, develop towards compact, high frequency, the direction such as multi-functional with electronic product, the essence to stannum ball quality
The requirement of degree and species also improves constantly it is desirable to the stannum of smaller particle and its alloy microsphere.On the other hand, lead in functional material
Domain, gold, silver and platinum-group noble metals are all preferable electrocatalysis materials, but due to their prices costly, limit it big
Sizable application, is formed the micro-/ nano spherical structure of alloying, both can increase reaction contact area with transition metal Sn, improves
The utilization rate of material；The consumption of noble metal can be reduced thus reduces cost by alloying again；Can also be by neighbouring heterogeneous
" synergism " effect between atom, improves the chemism of metal.Therefore, micro/nano level alloy micro-sphere structure is also used as
Function admirable, cheap electro catalytic electrode material.Meanwhile, the kamash alloy of nanostructured is considered the most preferable after carbon
Lithium ion battery negative material, specific capacity and the safety of lithium battery can be improved on a large scale, micro-/ nano stannum and tin alloy are micro-
Ball is expected to become a kind of ion cathode material lithium of function admirable.By retrieval it has been found that there is presently no disclosed preparation
Nanoscale Sn and the proper method of Sn-X microsphere, the present invention primarily focuses on the manufacture method different from traditional stannum ball, quick,
Easy, economical prepares stannum and its alloy microsphere, and the particle diameter of microsphere can reach submicron and Nano grade.
Content of the invention
The present invention overcomes the deficiencies in the prior art, and technical problem to be solved is the preparation of one kind electric spark deposition technology
Nanometer or the method for submicron Sn microsphere and Sn-X alloy microsphere.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is：One kind prepares nanometer or submicron order stannum
Or the method for tin alloy microsphere, comprise the steps：
1）The pretreatment of base material
Conductive substrates are ground, are polished to light, after polishing with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively
Conductive substrates are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, and taking-up is dried standby；
The fusing point of base material should be not less than 1000 DEG C；Preferably base material be metallic nickel, in titanium, molybdenum, tungsten, cobalt, palladium
One kind.
2）The pretreatment of anode material
Anode material is selected during pure tin it is desirable to be purity 90wt.%-99.9wt.%, the pure tin silk or pure of diameter 0.5-10mm
Tin bar；
Anode material is selected during Sn-X it is desirable to be composite filament or the compound bar of diameter 2-10mm, described composite filament or compound
Rod, with component X as core, with stannum as skin, makes both be tightly combined, similar pencil wick-like structure；A diameter of 0.05-5mm of component X；
The purity of the wherein single metal of the purity of stannum and component X is required to 90wt.%-99.9wt.%；
In Sn-X composite filament or compound bar, component X can select wherein a kind of Pt, Pd, Au, Ag, Ni, Co, Cu or any 2
The alloy planted.
The described Sn-X composite filament of pencil wick-like structure or the preparation method of compound bar have multiple, as long as outer layer stannum and inner core
It is tightly combined between 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 one of following methods：
In the axial centre boring of Xi Si or tin bar, put into X metal core, composition Sn-X composite filament or compound in duct
Rod；
Or, wrap up X metal core with stannum, then so that it is tightly combined in 100-230 DEG C of hot extrusion, obtain Sn-X and be combined
Silk or compound bar；
Or, X metal core is stretched in stannum melt, then takes out cooling, repeating this process acquisition parcel needs thickness
The Sn-X composite filament of stannum shell or compound bar.
Wherein, the ratio of Sn and component X and X, using metal ratio during alloy, are all according to what property to be obtained
Can electrode and adjust, can easily do.
3）The connection of device
Pretreated base material is immersed in 10-50 DEG C of silicone oil bath, the upper surface of base material to liquid level away from
From for 1-200mm；Draw wire from base material lower surface so as to be connected to the work electricity of metal surface electrospark impregnation equipment
Extremely 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
Setting electric spark deposition supply voltage is 20-60 volt, and electric capacity is 400-800 microfarad, and frequency is 40-80 hertz,
Slowly move anode metal electrodes so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produce electric spark and put
Electricity, repeats said process until anode material is uniform in the coating of whole base material upper surface, and spark discharge coating speed is
Per second electric discharge 1-10 time；
After the completion of coating, take out base material and be cleaned by ultrasonic in acetone, dehydrated alcohol and ultra-pure water successively, taking-up is dried in the air
Dry, condition of drying is 10-60 DEG C, preferably 10-40 DEG C.
Above-mentioned steps 1）With step 2）There is no strict ordering relation.
Step 1）With 4）In the ultrasonic cleaning that is related to, the time of three ultrasonic cleaning is each 5-60min, preferably 10-
50min.
Step 4）In preferably process conditions be：Voltage 40-60 volt, electric capacity 500-600 microfarad, frequency 50-60 hertz；
1-3 time per second of spark discharge coating speed.
The physical mechanism of the present invention can do description below：
Electric spark deposition technology is to be acted on by spark discharge, produces TRANSIENT HIGH TEMPERATURE（Up to 5000-25000 DEG C）,
Anode material infiltration enters metallic matrix top layer, forms metallurgical binding with matrix skin, makes physical chemistry and the mechanics of matrix surface
A kind of improved method of performance.When being used Xi Si or Sn-X as anode, because anode material fusing point is relatively low, in electricity fire
Under the TRANSIENT HIGH TEMPERATURE that flower electric discharge produces, it is in the stannum silk of anode tip or moment containing tin metal melts, depart from anode, the gold of formation
Belong to or alloy microlayer model, moment spark discharge formed " blast " impulsive force under disperse in the silicone oil environment around anode,
Gradually settle under gravity and again solidify.Silicone oil has viscosity, and the buoyancy of generation has delayed metal microlayer model
Whereabouts so that microlayer model has sufficient time formation rule under surface tension effects spherical, then sink to cathode substrate table
Face.
Compared with prior art the invention has the advantages that.
1st, the stannum ball of this method preparation, particle diameter is little, up to submicron and Nano grade, and even size distribution, no annulus,
Can be good at meeting the demand to stannum ball high accuracy, high-quality and low dimensional, be Electronic Packaging, fine chemistry industry, electro-catalysis and
The ideal material of the aspects such as lithium cell cathode material.
2nd, electric spark instantaneous discharge deposition technique, production process environmental protection are utilized, the injury to operator is little, preparation
Method is simple, and metal ingredient scalable is reproducible.
3rd, in tradition application, electric spark deposition technology, mainly for the preparation of wear-resisting, anti-corrosion, fatigue proof surface layer, is come
Meet the requirement to material working surface mechanical property for the production field, and we propose to produce micro-/ nano using this technology first
The stannum of yardstick and tin alloy microsphere, this is different from the existing method for producing stannum ball.
Brief description
Nanometer tin microsphere low power stereoscan photograph prepared by Fig. 1 embodiment 1.
Nanometer tin microsphere 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 spectrum diagram prepared by Fig. 4 embodiment 2.
Nanometer sn-ag alloy microsphere stereoscan photograph prepared by Fig. 5 embodiment 3.
Nanometer sn-ag alloy microsphere EDX composition energy spectrum diagram prepared by Fig. 6 embodiment 3.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of nanometer tin microsphere of use electric spark deposition technology preparation, deposition substrate used is disc-shaped leaf, a diameter of
15 millimeters, highly for 2 millimeters, described leaf purity is 99.5wt.%, a diameter of 1 millimeter of stannum silk used, and purity is 99.9wt.%,
After coating, substrate surface is substantially distributed with one layer of nanoscale chondritic.
Concrete preparation method such as following step：
（1）By a diameter of 15 millimeters, thickness be 2 millimeters, purity be 99.5wt.% leaf successively with 360 mesh, 1000 mesh,
The abrasive paper for metallograph of 2000 mesh grinds, is polished to light, is cleaned by ultrasonic 15min respectively, takes in acetone, dehydrated alcohol and ultra-pure water
Go out to dry standby；
（2）By step（1）In the leaf dried immerse 30 DEG C at silicone oil bath in, leaf is placed at lower 15 millimeters 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 connects purity and is
The stannum silk of 99.9wt.% as anode, a diameter of 1 millimeter of described stannum silk；
（3）The deposition supply voltage of setting electrospark impregnation equipment is 50 volts, and electric capacity is 500 microfarads, and frequency is 50 hertz
Hereby.Slowly moving the anode equipped with stannum silk makes Xi Si contact with substrate leaf, produces spark discharge, makes the stannum silk fusing at tip
Depart from anode, micro- molten drop settles under gravity and solidification forms micro-/ nano stannum ball again, and mobile stannum silk repeats to produce
The process of electric discharge, until whole leaf is covered by micro-/ nano stannum ball, discharge rate is 2 times per second, and coating after finishing takes leaf
Go out, be cleaned by ultrasonic 10min in acetone, dehydrated alcohol and ultra-pure water respectively, dry at 30 DEG C, the micro/nano level stannum of preparation
Microsphere deposits to the top layer of substrate.
Embodiment 2
A kind of stannum palladium alloy microsphere of use electric spark deposition technology preparation, deposited base material used is disc-shaped leaf, diameter
For 15 millimeters, highly for 4 millimeters, described leaf purity is 99.5wt.%, a diameter of 3 millimeters of stannum silk used, and purity is
99.9wt.%；A diameter of 0.5 millimeter of palladium silk used, purity is 99.9wt.%, observes surface microscopic topographic visible substantially after coating
Chondritic, up to submicron order.
Concrete preparation method such as following step：
（1）By a diameter of 15 millimeters, thickness be 4 millimeters, purity be 99.5wt.% leaf successively with 360 mesh, 1000 mesh,
The abrasive paper for metallograph of 2000 mesh grinds, is polished to light, is cleaned by ultrasonic 15min respectively, takes in acetone, dehydrated alcohol and ultra-pure water
Go out to dry standby；
（2）Take 40 millimeters of length, a diameter of 3 millimeters, purity is the stannum silk of 99.9wt.%, and central punch simultaneously penetrates a diameter of
0.5 millimeter, the palladium silk for 99.9wt.% for the purity, make both be tightly combined, and the composite construction electrode forming similar pencil wick-like is made
For anode；
（3）By step（1）In the leaf dried immerse 35 DEG C at silicone oil bath in, leaf is placed at lower 30 millimeters 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 Connection Step（2）
In stannum/palladium composite construction electrode of processing as anode；
（4）The deposition supply voltage of setting electrospark impregnation equipment is 50 volts, and electric capacity is 600 microfarads, and frequency is 60 hertz
Hereby.Slowly moving the composite anode equipped with stannum/palladium metal makes its tip contact with substrate leaf, produces spark discharge, makes point
The stannum palladium metal fusing at end, the synchronous microlayer model forming alloying, and depart from anode, micro- molten drop settles under gravity
And solidification forms chondritic again, mobile stannum/palladium bimetallic composite anode, repeats to produce spark discharge process, until whole
Leaf is covered by stannum palladium alloy microsphere, and discharge rate is 2 times per second, and coating after finishing is taken out leaf, respectively in acetone, anhydrous
It is cleaned by ultrasonic 10min in ethanol and ultra-pure water, dry at 35 DEG C, the stannum palldium alloy that the surface layer of substrate is as to be prepared is micro-
Ball, by carrying out X-ray energy spectrum analysis to prepared specimen surface（EDX）Understand that stannum palladium element is present in alloy microsphere, C,
The signal of Si element derives from silicone oil, and the signal of W element derives from matrix.
Embodiment 3
A kind of sn-ag alloy microsphere of use electric spark deposition technology preparation, deposited base material used is disc-shaped palladium piece, diameter
For 13 millimeters, highly for 1 millimeter, described palladium piece purity is 99.5wt.%, a diameter of 3 millimeters of stannum silk used, and purity is
99.9wt.%；A diameter of 1 millimeter of filamentary silver used, purity is 99.9wt.%, and after coating, surface microscopic topographic is obvious chondritic,
Even size distribution.
Concrete preparation method such as following step：
（1）By a diameter of 13 millimeters, thickness be 1 millimeter, purity be 99.5wt.% palladium piece successively with 360 mesh, 1000 mesh,
The abrasive paper for metallograph of 2000 mesh grinds, is polished to light, is cleaned by ultrasonic 15min respectively, takes in acetone, dehydrated alcohol and ultra-pure water
Go out to dry standby；
（2）Length is taken to be 35 millimeters, a diameter of 3 millimeters, purity is the stannum silk of 99.9wt.%, and central punch simultaneously penetrates diameter
For 1 millimeter, purity is the filamentary silver of 99.9wt.%, so that both is tightly combined, and the composite construction electrode forming similar pencil wick-like is made
For anode；
（3）By step（1）In the palladium piece that dries immerse 40 DEG C at silicone oil bath in, palladium piece is placed at lower 20 millimeters 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 Connection Step（2）
Middle tin silver composite construction electrode is as anode；
（4）The deposition supply voltage of setting electrospark impregnation equipment is 50 volts, and electric capacity is 600 microfarads, and frequency is 50 hertz
Hereby.Slowly move and so that its tip is contacted with substrate palladium piece equipped with the bimetallic composite anode of tin silver, produce spark discharge, make
Most advanced and sophisticated stannum silver metal fusing, the synchronous microlayer model forming alloying, and depart from anode, occur sedimentation to lay equal stress under gravity
New solidification forms chondritic, mobile tin silver bimetallic composite anode, repeats to produce discharge process, until whole palladium piece is by stannum
Silver alloy microsphere cover, discharge rate be 3 times per second, coating finish after palladium piece take out, respectively acetone, dehydrated alcohol and surpass
It is cleaned by ultrasonic 10min in pure water, dry at 40 DEG C, surface layer sn-ag alloy microsphere as to be prepared, by prepared
Specimen surface carries out X-ray energy spectrum analysis（EDX）Understand that stannum silver element is present in alloy microsphere, the signal source of C, Si element
In silicone oil, the signal of Pd element derives from matrix.
Embodiment 4
The present embodiment is in addition to following characteristics with embodiment 2：Selected base material is a diameter of 10 millimeters, and thickness is 2 millimeters, purity
Molybdenum sheet for 99.9wt.%.Anode used is Sn-X (X=PdCu) composite filament of 1.5 millimeters of diameter, palladium brass wire diameter wherein used
For 0.5 millimeter, it is 10wt.% containing palladium, cupric 90wt.%.The deposition supply voltage of electrospark impregnation equipment is 40 volts, and electric capacity is
500 microfarads, frequency be 50 hertz, each second electro-arc depositing 3 times.Coating is taken out molybdenum sheet, respectively in acetone, anhydrous second after finishing
It is cleaned by ultrasonic 10min in alcohol and ultra-pure water, dry at 40 DEG C, surface layer stannum palladium-copper alloy microsphere as to be prepared.
Embodiment 5
A kind of method preparing nanometer or submicron order stannum microsphere, comprises the steps：
1）The pretreatment of base material
The Co piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material selects the pure tin silk of diameter 2mm it is desirable to be purity 99.5wt.%；
3）The connection of device
Pretreated base material is immersed in 20 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
150mm；Draw wire from base material lower surface so as to the working electrode end being connected to metal surface electrospark impregnation equipment is made
For negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 60 volts, and electric capacity is 700 microfarads, and frequency is 75 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 5 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 10 min in acetone, dehydrated alcohol and ultra-pure water successively, take
Go out and dried up with high pure nitrogen.
Embodiment 6
A kind of method preparing nanometer or submicron order stannum microsphere, comprises the steps：
1）The pretreatment of base material
The Ti piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material selects the pure tin silk of diameter 6mm it is desirable to be purity 99.5wt.%；
3）The connection of device
Pretreated base material is immersed in 50 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
60mm；Draw wire from base material lower surface so as to the working electrode end being connected to metal surface electrospark impregnation equipment is made
For negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 40 volts, and electric capacity is 800 microfarads, and frequency is 80 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 8 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 30min in acetone, dehydrated alcohol and ultra-pure water successively, take
Go out and dried up with high-purity argon gas.
Embodiment 7
A kind of method preparing nanometer or submicron order tin alloy microsphere, comprises the steps：
1）The pretreatment of base material
The Pd piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
With the Cu tinsel of diameter 3mm as core, Sn layer is wrapped up in outside to anode material, obtains diameter 5mm through 200 DEG C of hot extrusions
Compact composite filament；
The purity of wherein Sn, Cu is 95wt.%；
3）The connection of device
Pretreated base material is immersed in 35 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
1mm；Draw wire from base material lower surface so as to be connected to the working electrode end conduct of metal surface electrospark impregnation equipment
Negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 50 volts, and electric capacity is 550 microfarads, and frequency is 70 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 5 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 5min in acetone, dehydrated alcohol and ultra-pure water successively, take out
Dried up with high pure nitrogen.
Embodiment 8
A kind of method preparing nanometer or submicron order tin alloy microsphere, comprises the steps：
1）The pretreatment of base material
The Mo piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material is with Ag, Co mass ratio 1 of diameter 1mm：1 B alloy wire is core, and Sn layer is wrapped up in outside, through 220 DEG C of heat
Extruding obtains the compact composite filament of diameter 4mm；
The purity of wherein Sn, Ag, Co is 99wt.%；
3）The connection of device
Pretreated base material is immersed in 40 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
3mm；Draw wire from base material lower surface so as to be connected to the working electrode end conduct of metal surface electrospark impregnation equipment
Negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 55 volts, and electric capacity is 800 microfarads, and frequency is 80 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Until anode material is uniform in the coating of whole base material upper surface, spark discharge coating speed is electric discharge 10 per second to process
Secondary；
After the completion of coating, take out base material and be cleaned by ultrasonic in acetone, dehydrated alcohol and ultra-pure water successively, taking-up is high
Pure argon dries up.
Embodiment 9
A kind of method preparing nanometer or submicron order tin alloy microsphere, comprises the steps：
1）The pretreatment of base material
The Ti piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material is with Co, Au mass ratio 1 of diameter 5mm：0.5 B alloy wire is core, and Sn is wrapped up in outside, through 150 DEG C of heat
Extruding obtains the compact composite filament of diameter 10mm；
The purity of wherein Sn, Co, Au is 95wt.%；
3）The connection of device
Pretreated base material is immersed in 45 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
1-50mm；Draw wire from base material lower surface so as to 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
Setting electric spark deposition supply voltage is 40 volts, and electric capacity is 500 microfarads, and frequency is 50 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 4 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 50 min in acetone, dehydrated alcohol and ultra-pure water successively, take
Go out and dried up with high pure nitrogen.
Embodiment 10
A kind of method preparing nanometer or submicron order tin alloy microsphere, comprises the steps：
1）The pretreatment of base material
The Co piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material is with Au, Cu mass ratio 1 of diameter 2mm：5 B alloy wire is core, in immersion stannum melt, then takes out cold
But, repeat this process, obtain the compound bar of diameter 3.5mm；
The purity of wherein Sn, Au, Cu is 99wt.%；
3）The connection of device
Pretreated base material is immersed in 25 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
10mm；Draw wire from base material lower surface so as to the working electrode end being connected to metal surface electrospark impregnation equipment is made
For negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 45 volts, and electric capacity is 600 microfarads, and frequency is 55 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 6 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 25 min in acetone, dehydrated alcohol and ultra-pure water successively, take
Dry in the environment of going out 60 DEG C.
Embodiment 11
A kind of method preparing nanometer or submicron order tin alloy microsphere, comprises the steps：
1）The pretreatment of base material
The Co piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material is with Au, Cu mass ratio 1 of diameter 2.5mm：0.5 B alloy wire is core, in immersion stannum melt, Ran Houqu
Go out cooling, repeat this process, obtain the compound bar of diameter 5mm；
The purity of wherein Sn, Au, Cu is 99wt.%；
3）The connection of device
Pretreated base material is immersed in 10 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
200mm；Draw wire from base material lower surface so as to the working electrode end being connected to metal surface electrospark impregnation equipment is made
For negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 20 volts, and electric capacity is 400 microfarads, and frequency is 50 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 2 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 15 min in acetone, dehydrated alcohol and ultra-pure water successively, take
Go out and dry in the environment of temperature 50 C.
Embodiment 12
A kind of method preparing nanometer or submicron order tin alloy microsphere, comprises the steps：
1）The pretreatment of base material
The Ni piece that conductive substrates are purity 99wt.% is ground with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively,
It is polished to light, the conductive substrates after polishing are cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, taking-up is dried standby
With；
2）The pretreatment of anode material
Anode material is with Au, Cu mass ratio 1 of diameter 1.5mm：1 B alloy wire is core, in immersion stannum melt, then takes out
Cooling, repeats this process, obtains the composite filament of diameter 2mm；
The purity of wherein Sn, Au, Cu is 99wt.%；
3）The connection of device
Pretreated base material is immersed in 50 DEG C of silicone oil bath, the distance of upper surface to the liquid level of base material is
15mm；Draw wire from base material lower surface so as to the working electrode end being connected to metal surface electrospark impregnation equipment is made
For negative electrode；
Ready anode material is connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 30 volts, and electric capacity is 500 microfarads, and frequency is 40 hertz, slowly mobile sun
Pole metal electrode, so as to be gradually immersed into below silicone oil liquid level Contact cathod substrate surface, produces spark discharge, repeats above-mentioned
Up to anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 3 times to process；
After the completion of coating, take out base material and be cleaned by ultrasonic 60 min in acetone, dehydrated alcohol and ultra-pure water successively, take
Go out and dry in the environment of temperature 60 C.
The present invention can be summarized without prejudice to the concrete form of the spirit or essential characteristics of the present invention with others.Therefore, no
By from the point of view of which point, the embodiment above of the present invention all can only be considered that the description of the invention can not limit invention,
Claims indicate the scope of the present invention, and the scope of the present invention is not pointed out in above-mentioned explanation, therefore, with the present invention
The suitable implication and scope of claims in any change, be all considered as being included within the scope of the claims.
Claims (10)
1. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere is it is characterised in that comprise the steps：
The material selection pure tin of anode or Sn-X composite, dystectic conducting metal selected by the base material of negative electrode, will
Negative electrode is placed in silicone oil bath, slowly moves anode so as to be gradually immersed into below silicone oil liquid level Contact cathod surface, produces electricity fire
Flower electric discharge, repeats said process until anode material coats uniformly in whole cathode surface；
In described Sn-X composite, component X is the alloy of Pt, Pd, Au, Ag, Ni, Co, Cu or wherein any 2 kinds；
The fusing point of described base material is not less than 1000 DEG C；
Specifically, the method being adopted comprises the following steps：
1）The pretreatment of base material
Base material is ground, is polished to light with the abrasive paper for metallograph of 360 mesh, 1000 mesh, 2000 mesh successively, the substrate after polishing
Material is cleaned by ultrasonic successively in acetone, dehydrated alcohol and ultra-pure water, and taking-up is dried standby；
2）The pretreatment of anode material
Anode material is selected during pure tin it is desirable to be purity 90wt.%-99.9wt.%, the pure tin silk of diameter 0.5-10mm or pure tin
Rod；
Anode material is selected during Sn-X it is desirable to for the composite filament of diameter 2-10mm or compound bar, Sn-X composite filament or compound bar with
Component X is core, with stannum as skin, a diameter of 0.05-5mm of core；The purity of the wherein single metal of the purity of stannum and component X is equal
Require 90wt.%-99.9wt.%；
3）The connection of device
Will be through step 1）The base material of pretreatment immerses in 10-50 DEG C of silicone oil bath, and the upper surface of base material is to liquid level
Distance is 1-200mm；Draw wire from base material lower surface so as to be connected to the work of metal surface electrospark impregnation equipment
Electrode tip is as negative electrode；
Will be through step 2）Pretreatment anode material be connected to the source terminal of equipment as anode；
4）Coating procedure
Setting electric spark deposition supply voltage is 20-60 volt, and electric capacity is 400-800 microfarad, and frequency is 40-80 hertz, slowly
Mobile anode, so as to be gradually immersed into below silicone oil liquid level Contact cathod surface, produces spark discharge, repeats said process straight
To anode material in the coating of whole base material upper surface uniformly, spark discharge coating speed is per second electric discharge 1-10 time；
After the completion of coating, take out base material and be cleaned by ultrasonic in acetone, dehydrated alcohol and ultra-pure water successively, taking-up is dried.
2. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In：The material of described base material is Ni, Ti, Mo, W, Co or Pd.
3. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In described step 2）The preparation method of middle Sn-X composite filament or compound bar is：
In the axial centre boring of Xi Si or tin bar, put into X metal core, composition Sn-X composite filament or compound bar in duct；
Or, with stannum wrap up X metal core, then so that it is tightly combined in 100-230 DEG C of hot extrusion, obtain Sn-X composite filament or
Compound bar；
Or, X metal core is stretched in stannum melt, then takes out cooling, repeating this process acquisition parcel needs outside thickness stannum
The Sn-X composite filament of shell or compound bar.
4. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 3, its feature exists
In：Coating procedure setting electric spark deposition supply voltage is 40-60 volt, and electric capacity is 500-600 microfarad, and frequency is that 50-60 is conspicuous
Hereby.
5. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In：Coating procedure spark discharge coating speed is 1-3 time per second.
6. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In：Described step 3）The distance of the upper surface of middle base material to liquid level is 1-100mm.
7. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In：Step 1）With 4）In the ultrasonic cleaning that is related to, the time of three ultrasonic cleaning is each 5-60min.
8. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In：After the completion of coating, after base material cleaning, dry in the environment of temperature 10-60 DEG C.
9. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 8, its feature exists
In：Described temperature of drying is 10-40 DEG C.
10. a kind of method preparing nanometer or submicron order stannum or tin alloy microsphere according to claim 1, its feature exists
In：After the completion of coating, after base material cleaning, will dry to replace with and be dried up with high pure nitrogen or argon.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001267730A (en) * | 2000-03-14 | 2001-09-28 | Hitachi Metals Ltd | Solder ball |
| WO2003080275A2 (en) * | 2002-03-23 | 2003-10-02 | Metal Nanopowders Limited | Powder and coating formation method and apparatus |
| EP1449605A1 (en) * | 2001-10-29 | 2004-08-25 | Phild Co., Ltd. | Method and apparatus for the production of metal powder |
| CN101402115A (en) * | 2008-10-13 | 2009-04-08 | 大连理工大学 | Synthesis in situ of intermetallic compound nano-particle |
| CN103022508A (en) * | 2012-12-07 | 2013-04-03 | 太原理工大学 | Coating type nano-palladium film catalytic electrode and its preparation method |
-
2015
- 2015-01-15 CN CN201510018962.4A patent/CN104607648B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001267730A (en) * | 2000-03-14 | 2001-09-28 | Hitachi Metals Ltd | Solder ball |
| EP1449605A1 (en) * | 2001-10-29 | 2004-08-25 | Phild Co., Ltd. | Method and apparatus for the production of metal powder |
| WO2003080275A2 (en) * | 2002-03-23 | 2003-10-02 | Metal Nanopowders Limited | Powder and coating formation method and apparatus |
| CN101402115A (en) * | 2008-10-13 | 2009-04-08 | 大连理工大学 | Synthesis in situ of intermetallic compound nano-particle |
| CN103022508A (en) * | 2012-12-07 | 2013-04-03 | 太原理工大学 | Coating type nano-palladium film catalytic electrode and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 火花等离子体制备粉末技术;郭双全等;《材料导报：综述篇》;20101031;第24卷(第10期);第112-116页 * |
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