CN106925570B - A method of soil for electrical contact working face ester impurities are removed using electron beam - Google Patents

A method of soil for electrical contact working face ester impurities are removed using electron beam Download PDF

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Publication number
CN106925570B
CN106925570B CN201710102822.4A CN201710102822A CN106925570B CN 106925570 B CN106925570 B CN 106925570B CN 201710102822 A CN201710102822 A CN 201710102822A CN 106925570 B CN106925570 B CN 106925570B
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China
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electron beam
electrical contact
soil
working face
rivet
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CN201710102822.4A
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CN106925570A (en
Inventor
王珩
宋振阳
刘兰兰
翁桅
柏小平
颜小芳
李�杰
张秀芳
杨昌麟
周龙
林万焕
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Zhejiang Fuda Alloy Materials Technology Co Ltd
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Fuda Alloy Materials Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0035Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32009Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32366Localised processing

Abstract

The invention discloses a kind of methods using electron beam removal soil for electrical contact working face ester impurities, electron beam treatment is carried out to soil for electrical contact working face by electron beam in ester impurities electron beam removal device, it the steps include: that (1) opens hatch door, soil for electrical contact is fixed on console, and make exit direction of its working face towards electron beam, hatch door is closed, bleeding point starts to be evacuated, and cabin inner cavity vacuum degree reaches 10‑3‑10‑5Pa closes bleeding point;(2) power supply is opened, acceleration voltage is adjusted to 1-5KV, cathode issues electron beam, it adjusts control grid and changes the beam pulse time as 10-30ms, pulse frequency is 0.5-10Hz, and tentatively focus, by Electron Beam Focusing unit precisely by the rivet work face of the soil for electrical contact on Electron Beam Focusing to console, the covalent bond of ester impurities is destroyed using the pulse kinetic energy of electron beam.It can be limited on the basis of removing soil for electrical contact working face ester impurities by the device and form oxidation film on soil for electrical contact working face.

Description

A method of soil for electrical contact working face ester impurities are removed using electron beam
Technical field
It is handled the present invention relates to material surface, in particular to a kind of using electron beam removal soil for electrical contact working face esters The device and method of impurity.
Background technique
Soil for electrical contact is applied to the contactor of various relays, contactor, temperature controller, various current classes, is to influence An important factor for device for switching contact system functional reliability, preparation process are typically all to use upsetting that type, structure ginseng is made See attached drawing 1A and attached drawing 1B, in soil for electrical contact manufacturing process, due to the particularity of processing, working face a inevitably by To the pollution of some residual chemical agents (lubricant, grinding agent etc.), while (dust, organic high score microgranular existing for environment Son etc.) pollutant will also result in pollution, and this pollution impurity main component is esters.Therefore soil for electrical contact working face esters are miscellaneous The removal of matter has a very important significance to the raising of soil for electrical contact product quality is improved.
Currently, there are two ways to removal soil for electrical contact ester impurities, multiple one is using organic washing agent to carry out Cleaning, although this method can remove ester impurities, lotion direct emission causes environmental pollution after cleaning.Another kind side Method is high annealing, but when rivet is in hot environment is readily formed layer oxide film, it is difficult to be removed.
With the development of science and technology with the needs of material property, using pulse high energy beam (electron beam, laser beam etc.) into The processing of row material surface, the method for making material obtain the properties such as stable physics, chemistry, mechanics are rapidly developed.Work as high energy When metric density beam is applied to material surface, a large amount of energy can be heated in the thin layer that the short time deposits on the surface of the material Layer temperature under the action of Joule heat increases rapidly, and some impurity of material surface, especially some high-melting-point impurity can be rapid Fusing, so that material property be made to be stabilized.Great-power electronic beam is used as the close beam heat source of high energy and handles material surface, with Laser beam is compared, optical characteristics of the energy absorption of electron beam independent of material surface, so capacity usage ratio significantly improves.
By retrieval, Chinese Patent Application No. discloses " electron beam polishing of aluminium ", the technology for 201380023815.5 In scheme, the method on the press polished surface on aluminum substrate is formed using a variety of process for machining.In the process for machining Period, intermetallic compound usually by during the cutting technique between the cutting edge of aluminum substrate and cut end generated office It is generated at the top surface area of aluminum substrate caused by portion's heating.Since intermetallic compound is peeled off from the surface, in routine After mechanical polishing, intermetallic compound may leave surface defect so that the surface of the aluminum substrate be difficult to obtain it is desired High gloss.In order to remove the influence of the intermetallic compound, electron beam is applied to the surface, causes Joule heating to melt Top surface area.In this way, any mold-mart and intermetallic compound can be eliminated.
Intermetallic compound is referred in the patent document, usually by two or more or metal and metalloid group At the compound with integer stoichiometric ratio, since the ordered structure and metallic bond of its crystal coexist, thus have one The unique excellent properties of series, such as fusing point is high, high-temperature behavior is good.Therefore, which uses between electron beam removal metal Compound, cutting mechanisms are exactly the Joule heat bring high temperature that electron beam generation is utilized, and this high temperature can make dystectic Intermetallic compound fusing, is removed.
In addition, since the material of soil for electrical contact is generally copper Cu, fine silver Ag, Agcdo AgCdO, silver-colored nickel AgNi, silver Tin oxide AgSnO2, Ag-ZnO AgZnO, silver-tin oxide or indium oxide AgSnO2ln2O3, cupro-nickel CuNi, silver-colored cerium AgCe, silver-colored tungsten AgW, copper tungsten CuW, after these metal material surfaces are stained with ester impurities, in conjunction with the electronics of documents " electron beam polishing of aluminium " If beam removes technique, have the following problems: the Joule heat bring high temperature that electron beam generates makes soil for electrical contact working face Ester impurities high-temp combustion oxidation, but electron beam generate Joule heat and ester impurities burn caused by high temperature can make The metal material for obtaining working face is aoxidized with oxygen in air simultaneously, forms metal oxide layer, so that rivet electricity touches The electrical contact performance of head is greatly reduced, it is therefore necessary to be improved to this.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that providing a kind of using electron beam removal soil for electrical contact work The method for making face ester impurities can limit riveting on the basis of removing soil for electrical contact working face ester impurities by the device Oxidation film is formed on nail electrical contact working face.
To achieve the above object, the technical scheme is that passing through electron beam in ester impurities electron beam removal device Electron beam treatment is carried out to soil for electrical contact working face, the ester impurities electron beam removal device includes cabin, and It is set to the electron beam generating unit, Electron Beam Focusing unit and console of cabin inner cavity, console, which moves horizontally, is set to cabin Intracoelomic cavity, and it is additionally provided with the driving unit moved horizontally for drive control platform, electron beam generating unit includes cathode, sun Pole and control grid and for providing the power supply of beam voltage, be provided in the cabin hatch door, gas vent and For by the bleeding point of its inner cavity vacuum state;
It the steps include:
(1) hatch door is opened, soil for electrical contact is fixed on console, and make its working face towards the outgoing side of electron beam To closing hatch door, bleeding point starts to be evacuated, and cabin inner cavity vacuum degree reaches 10-3-10-5Pa closes bleeding point;
(2) power supply is opened, acceleration voltage is adjusted to 1-5KV, cathode issues electron beam, adjusts control grid and changes electron beam Burst length is 10-30ms, pulse frequency 0.5-10Hz, and is tentatively focused, and electron beam is accelerated by anode, passes through electricity Beamlet focusing unit precisely by the rivet work face of the soil for electrical contact on Electron Beam Focusing to console, utilizes electron beam The ester group covalent bond of pulse kinetic energy destruction ester impurities;
(3) it controls console by driving unit to move horizontally, movement speed 1-100mm/s, so that electron beam is to whole A rivet work face is irradiated, after open gas vent, open hatch door after atmospheric pressure to be restored, replace next batch rivet Electrical contact.
It is AgSnO that further setting, which is the soil for electrical contact,2Soil for electrical contact, the electron beam parameter of step (2) 5KV is adjusted to for acceleration voltage, the beam pulse time is 30ms, pulse frequency 1Hz.
It is AgCdO soil for electrical contact that further setting, which is the soil for electrical contact, and the electron beam parameter of step (2) is Acceleration voltage is adjusted to 3KV, the beam pulse time is 20ms, pulse frequency 0.8Hz.
It is AgNi soil for electrical contact that further setting, which is the soil for electrical contact, and the electron beam parameter of step (2) is Acceleration voltage is adjusted to 1KV, the beam pulse time is 10ms, pulse frequency 0.5Hz.
It further includes having the face-up collating unit of rivet work, rivet that further setting, which is ester impurities electron beam removal device, The face-up collating unit that works be turnover panel, the turnover panel include bottom plate, be set to bottom plate surrounding and height-adjustable peripheral frame and The movable plate being set in peripheral frame is arranged multiple soil for electrical contact by rivet work before the step (1) up Device arranges, so that rivet work planar orientation is consistent, operating procedure are as follows:
Turnover panel height is higher than height of rivet 0.1-0.5mm, and 100-10000 rivets is taken to be placed in turnover panel, and turnover panel level is shaken Dynamic 1-3min, rivet all work down under the effect of gravity, overturn 180 ° of bottom plate is placed below, flip-flop transitions of turnover panel 0.1-0.3s pumps movable plate rivet work face all upward;
The multiple rivets arranged by the face-up collating unit of rivet work turnover panel is connected in the step (2) to set together In on console.
Therefore, the present invention proposes a kind of method using electron beam removal soil for electrical contact working face ester impurities, passes through The parameter area of stringent limitation electron beam, can the flux matched ester impurities for just destroying soil for electrical contact working face it is covalent Key, and esters are decomposed and gasification finish, to realize the purification in rivet work face.In addition, the application electron beam parameter Under, for the ester impurities of soil for electrical contact, when covalent bond destroys and gasifies, since beam energy is decomposed by esters substantially And be finished, therefore, the contact material temperature rising of face surface is not high, to decompose after effectivelying prevent covalent bond to be destroyed Small molecule chemically reacted at high temperature with contact material, to effectively prevent the generationization on soil for electrical contact working face The spot and trace for learning reaction, improve removal efficiency and quality.
The present invention is entirely different using the mechanism of electron beam with documents " electron beam polishing of aluminium ".Documents " aluminium Electron beam polishing " in intermetallic compound be that metallic bond form exists, therefore fusing point is very high, utilize to be that electron beam generates burnt Bring of having burning ears high temperature makes its fusing, and the rivet work face ester impurities that the present invention removes, and what is utilized is the pulse of electron beam Function.In general, ester impurities contain ester group-COO-, deposited in the form of covalent bond containing 1 C=0 and 1 C-O, most of esters ?.Metallic bond is composed of free electron and the electrostatic attraction being arranged between the metal ion of lattice-like.Due to electricity The free movement of son, the direction that metallic bond is not fixed, thus be nonpolar bond.Metallic bond has many characteristics of metal.Such as: Fusing point, the boiling point of common metal are increased with the intensity of metallic bond.Covalent bond is that two or more atoms are used in conjunction with them Outer-shell electron reaches the state of electronics saturation in the ideal case, thus forms more stable chemical structure and be called covalent bond, Covalent bond is to be formed by interaction by share electron pair between atom in other words.Its essence is height after atomic orbital overlapping Appear in probability the electrical function between the electronics and two atomic nucleus between two atomic nucleus.Documents 1 refer to aluminium gold Compound between category, the fusing point of aluminium are 660 DEG C, and intermetallic compound fusing point can be higher, therefore extremely using beam voltage 10KV or more is wanted less, most of ester impurities are that covalent bond form exists in the present invention, and destroying covalent bond can remove it, because This, the rivet acceleration voltage of different materials controls 5KV or less, mainly utilizes the impulse action of electron beam, destroys altogether Valence link.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to These attached drawings obtain other attached drawings and still fall within scope of the invention.
The structure chart of Figure 1A plane rivet;
The structure chart of Figure 1B spherical surface rivet;
Fig. 2 ester impurities electron beam removal device is with reference to figure;
Fig. 3 reverse turning bed structure schematic diagram;
The schematic diagram of Fig. 4 turnover panel loading soil for electrical contact;
Fig. 5 turnover panel is packed into soil for electrical contact and shakes schematic diagram after arrangement;
Fig. 6 turnover panel is packed into overturning after soil for electrical contact shakes and pumps movable plate schematic diagram;
Fig. 7 grid sieve is packed into schematic diagram after rivet;
Rivet work face photo before Fig. 8 A electron beam irradiates (black punctate substance is ester impurities);
Rivet work face photo (removal of black punctate substance) after the irradiation of Fig. 8 B electron beam.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing Step ground detailed description.
The direction and position term that the present invention is previously mentioned, for example, "upper", "lower", "front", "rear", "left", "right", "inner", " Outside ", " top ", " bottom ", " side " etc. are only direction or position with reference to attached drawing.Therefore, the direction used and position term It is rather than the limitation to scope of protection of the utility model to illustrate and understand the utility model.
A specific embodiment of the invention as described in Fig. 2-7 passes through electronics in ester impurities electron beam removal device Beam carries out electron beam treatment, ester impurities electron beam removal device packet shown in Figure 2, described to soil for electrical contact working face Cabin 1 has been included, and has been set to the electron beam generating unit of cabin inner cavity 11, Electron Beam Focusing unit 3 and console 4, has been controlled Platform 4, which moves horizontally, is set to cabin inner cavity 11, and is additionally provided with the driving unit 41 moved horizontally for drive control platform 4, this The embodiment driving unit is preferably stepper motor, and concrete scheme is turned using the power drive screw rod that stepper motor provides It is dynamic, so that the screw rodb base that transmission is set on screw rod is moved horizontally, and console 4 and the fixed linkage of screw rodb base.
Electron beam generating unit includes cathode 21, anode 22 and control grid 23 and for providing electronics beam acceleration electricity The power supply 24 of pressure is provided with hatch door 12, gas vent 13 in the cabin 1 and for by the pumping of its inner cavity vacuum state Mouth 14;Electron beam generating unit described in the present embodiment is the manufacture of Bo Bin electron beam technology Co., Ltd.
It the steps include:
(1) hatch door 12 is opened, soil for electrical contact is fixed on console 4, and makes its working face going out towards electron beam Direction is penetrated, hatch door 12 is closed, bleeding point 14 starts to be evacuated, and 11 vacuum degree of cabin inner cavity reaches 10-3-10-5Pa closes bleeding point 14;
(2) power supply 24 is opened, acceleration voltage is adjusted to 1-5KV, cathode issues electron beam, adjusts control grid and changes electronics The beam pulse time is 10-30ms, pulse frequency 0.5-10Hz, and is tentatively focused, and electron beam is accelerated by anode 22, is led to Electron Beam Focusing unit 3 is crossed precisely on the rivet work face of the soil for electrical contact on Electron Beam Focusing to console, utilizes electricity The pulse kinetic energy of beamlet destroys the covalent bond of ester impurities;
(3) it controls console 4 by driving unit 41 to move horizontally, movement speed 1-100mm/s, so that electron beam pair Entire rivet work face is irradiated, after open gas vent, open hatch door 12 after atmospheric pressure to be restored, replace next batch Soil for electrical contact.
In addition, in order to improve treatment effeciency, ester impurities electron beam removal device further includes having rivet work whole up Device is managed, the face-up collating unit of rivet work is turnover panel 5, and as seen in figures 3-6, which includes bottom plate 51, is set to bottom 51 surrounding of plate and height-adjustable peripheral frame 52 and the movable plate 53 being set in peripheral frame will be more before the step (1) A soil for electrical contact is arranged by the face-up collating unit of rivet work, so that rivet work planar orientation is consistent, operating procedure Are as follows:
Turnover panel height is higher than height of rivet 0.1-0.5mm, and 100-10000 rivets is taken to be placed in turnover panel, and turnover panel level is shaken Dynamic 1-3min, rivet are whole under the effect of gravity
Down, 180 ° of turnover panel of overturning is placed below by bottom plate, and flip-flop transition 0.1-0.3s pumps movable plate rivet for work Working face is whole upward;
The multiple rivets arranged by the face-up collating unit of rivet work turnover panel is connected in the step (2) to set together In on console.
In addition, the face-up collating unit of rivet work can also be carried out using grid sieve 6, housekeeping face is consistent, and grid sieves Interior side length of element is greater than rivet bolster size 0.1-0.3mm and is less than working surface diameter, and grid sieve height is higher than rivet 0.1- 0.5mm takes 100-10000 rivets to be placed in grid sieve, shown in Fig. 7, puts one piece of rivet electricity touching in such as 7 in each grid Head.
Preferred embodiment 1
For in the embodiment of the present invention, contact sample uses AgNi, spherical surface rivet takes 1000, diameter 3mm, head thickness 0.5mm, Sufficient diameter 1.5mm, foot length 1mm, plane rivet take 1000, and size is consistent with spherical surface rivet.2000 rivets are placed in turnover panel Interior, turnover panel height 1.8mm, horizontal jitter 2min overturn turnover panel with 0.1s, 2000 rivet work face whole courts are checked after overturning On.Turnover panel is fixed on console, closes hatch door by device for opening hatch door, and bleeding point starts to be evacuated, and vacuum degree reaches 10-3When Pa After closing pumping, power supply is opened, adjusts acceleration voltage to 1KV, adjusting control grid makes beam pulse time 10ms, frequency For 0.5HZ, starting to irradiate after focusing, mobile console, speed 2mm/s, completely rear closing voltage to be illuminated opens gas vent, Hatch door is opened, next batch rivet is replaced.Referring to Fig. 8 A and Fig. 8 B, ester impurities are removed on soil for electrical contact working face.
Preferred embodiment 2
For in the embodiment of the present invention, contact sample uses AgSnO2, spherical surface rivet takes 3000, diameter 4mm, and head is thick 0.8mm, sufficient diameter 1.8mm, foot length 1.2mm, plane rivet take 3000, and size is consistent with spherical surface rivet.By 6000 rivets It is placed in turnover panel, turnover panel height 2.2mm, horizontal jitter 2min, overturns turnover panel with 0.1s, 6000 rivet work faces are checked after overturning All upward.Turnover panel is fixed on console, closes hatch door by device for opening hatch door, and bleeding point starts to be evacuated, and vacuum degree reaches 10-4After closing pumping when Pa, power supply is opened, adjusts acceleration voltage to 5KV, adjusting control grid makes the beam pulse time 30ms, frequency 1HZ start to irradiate, mobile console after focusing, and speed 2mm/s, completely rear closing voltage to be illuminated is opened Gas vent opens hatch door, replaces next batch rivet.Referring to Fig. 8 A and Fig. 8 B, ester impurities are gone on soil for electrical contact working face It removes.
Preferred embodiment 3
For in the embodiment of the present invention, contact sample uses AgCdO, spherical surface rivet takes 5000, diameter 5mm, head thickness 1mm, Sufficient diameter 2mm, foot length 1.5mm, plane rivet take 5000, and size is consistent with spherical surface rivet.10000 rivets are placed in turnover panel Interior, turnover panel height 2.8mm, horizontal jitter 2min overturn turnover panel with 0.1s, 10000 rivet work face whole courts are checked after overturning On.Turnover panel is fixed on console, closes hatch door by device for opening hatch door, and bleeding point starts to be evacuated, and vacuum degree reaches 10-4When Pa After closing pumping, power supply is opened, adjusts acceleration voltage to 3KV, adjusting control grid makes beam pulse time 20ms, frequency For 0.8HZ, starting to irradiate after focusing, mobile console, speed 2mm/s, completely rear closing voltage to be illuminated opens gas vent, Hatch door is opened, next batch rivet is replaced.Referring to Fig. 8 A and Fig. 8 B, ester impurities are removed on soil for electrical contact working face.

Claims (5)

1. a kind of method using electron beam removal soil for electrical contact working face ester impurities, it is characterised in that: in ester impurities Electron beam treatment, the ester impurities electronics are carried out to soil for electrical contact working face by electron beam in electron beam removal device Beam removal device includes cabin, and is set to the electron beam generating unit of cabin inner cavity, Electron Beam Focusing unit and control Platform, console, which moves horizontally, is set to cabin inner cavity, and is additionally provided with the driving unit moved horizontally for drive control platform, electricity Beamlet generating unit includes cathode, anode and control grid and for providing the power supply of beam voltage, described Hatch door, gas vent are provided in cabin and for by the bleeding point of its inner cavity vacuum state;
It the steps include:
(1) hatch door is opened, soil for electrical contact is fixed on console, and make exit direction of its working face towards electron beam, Hatch door is closed, bleeding point starts to be evacuated, and cabin inner cavity vacuum degree reaches 10-3-10-5Pa closes bleeding point;
(2) power supply is opened, acceleration voltage is adjusted to 1-5KV, cathode issues electron beam, adjusts control grid and changes beam pulse Time is 10-30ms, pulse frequency 0.5-10Hz, and is tentatively focused, and electron beam is accelerated by anode, passes through electron beam Focusing unit precisely by the rivet work face of the soil for electrical contact on Electron Beam Focusing to console, utilizes the pulse of electron beam The covalent bond of kinetic energy destruction ester impurities;
(3) it controls console by driving unit to move horizontally, movement speed 1-100mm/s, so that electron beam is to entire riveting Nail working face is irradiated, after open gas vent, open hatch door after atmospheric pressure to be restored, replacement next batch rivet electricity touching Head.
2. a kind of method using electron beam removal soil for electrical contact working face ester impurities according to claim 1, Be characterized in that: the soil for electrical contact is AgSnO2Soil for electrical contact, the electron beam parameter of step (2) are acceleration voltage tune To 5KV, the beam pulse time be 30ms, pulse frequency 1Hz.
3. a kind of method using electron beam removal soil for electrical contact working face ester impurities according to claim 1, Be characterized in that: the soil for electrical contact is AgCdO soil for electrical contact, and the electron beam parameter of step (2) is acceleration voltage tune To 3KV, the beam pulse time be 20ms, pulse frequency 0.8Hz.
4. a kind of method using electron beam removal soil for electrical contact working face ester impurities according to claim 1, Be characterized in that: the soil for electrical contact is AgNi soil for electrical contact, and the electron beam parameter of step (2) is adjusted to for acceleration voltage 1KV, beam pulse time be 10ms, pulse frequency 0.5Hz.
5. a kind of method using electron beam removal soil for electrical contact working face ester impurities according to claim 1, Be characterized in that: ester impurities electron beam removal device further includes having the face-up collating unit of rivet work, and rivet work is face-up Collating unit is turnover panel, which includes bottom plate, be set to bottom plate surrounding and height-adjustable peripheral frame, be set in peripheral frame Movable plate is arranged multiple soil for electrical contact by the face-up collating unit of rivet work before the step (1), so that Rivet work planar orientation is consistent, operating procedure are as follows:
Turnover panel height is higher than height of rivet 0.1-0.5mm, takes 100-10000 rivets to be placed in turnover panel, turnover panel horizontal jitter 1- 3min, rivet all work down under the effect of gravity, overturn 180 ° of turnover panel bottom plate is placed below, flip-flop transition 0.1- 0.3s pumps movable plate rivet work face all upward;
The multiple rivets arranged by the face-up collating unit of rivet work are connected to turnover panel in the step (2) and are placed in control together On platform processed.
CN201710102822.4A 2017-02-24 2017-02-24 A method of soil for electrical contact working face ester impurities are removed using electron beam Active CN106925570B (en)

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Effective date of registration: 20220128

Address after: 325025 No. 308, Binhai fifth road, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province

Patentee after: Zhejiang Fuda alloy material technology Co.,Ltd.

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Patentee before: FUDA ALLOY MATERIALS Co.,Ltd.