CN106191933A - Method for processing parts based on supercritical fluid 3D electrodeposition - Google Patents

Method for processing parts based on supercritical fluid 3D electrodeposition Download PDF

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CN106191933A
CN106191933A CN201610590545.1A CN201610590545A CN106191933A CN 106191933 A CN106191933 A CN 106191933A CN 201610590545 A CN201610590545 A CN 201610590545A CN 106191933 A CN106191933 A CN 106191933A
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deposition
anode
electro
cathode
reactor
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CN106191933B (en
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雷卫宁
钱海峰
刘维桥
李奇林
谈衡
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Jiangsu University of Technology
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/0033D structures, e.g. superposed patterned layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00Apparatus for additive manufacturing; Details thereof or accessories therefor
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/12Process control or regulation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/003Electroplating using gases, e.g. pressure influence
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04Electroplating with moving electrodes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention provides a method for processing parts implemented by a supercritical fluid-based 3D electro-deposition processing device, which comprises a carbon dioxide gas cylinder, a high-pressure pump, a numerical control controller, a reactor, a movable anode assembly, a movable cathode assembly, a direct-current power supply and a cathode substrate serving as a processed part; a mechanical stirrer is arranged in the reactor; the movable anode assembly comprises a Z-direction linear motor, a driving screw rod, an anode connecting rod and a movable anode; the movable cathode assembly comprises linear motors in the X direction and the Y direction, a guide rail, a movable block and a clamp; when the device is used, the movable anode and the cathode base body are respectively electrically connected with the anode and the cathode of the direct current power supply. The processing method mainly comprises the steps of cathode matrix chemical plating treatment in advance, cathode matrix installation, supercritical fluid preparation, electrodeposition processing, post-treatment and the like. The invention can effectively improve the electrodeposition speed and the deposition quality, prepares complex and precise metal parts in a three-dimensional space by electrodeposition and widens the application field of the electrodeposition technology.

Description

A kind of method based on supercritical fluid 3D electro-deposition process component
The application is Application No. 201410762856.2, and filing date December in 2014 11 days, invention and created name is The divisional application of the application for a patent for invention of " based on supercritical fluid 3D electro-deposition processing unit (plant) and method ".
Technical field
The present invention relates to electrochemical deposition processing technique field, be specifically related to a kind of three-dimensional based on supercritical fluid 3D() electricity The device and method of deposition process part.
Background technology
A focus of research outside electro-deposition techniques is Present Domestic under supercritical environment.Supercritical fluid (Supercritical Fluid) refers to, when pure material is in more than critical point (critical pressure and critical temperature), be showed Out a kind of is between liquid with the fluid of gaseous state.In Near The Critical Point, the density of supercritical fluid, viscosity, dissolubility, thermal capacitance There is phenomenon jumpy in the physical property of all fluids such as amount, dielectric constant.CO2Gas have environmental protection, do not fire, nontoxic, lazy Property, deposit is abundant and critical pressure (7.39MPa) and temperature (31.1 DEG C) less advantages of higher, therefore supercritical CO2Fluid quilt Extensively use.Due to supercritical CO2There is relatively low viscosity (0.03-0.1 MPa s) and higher diffusion coefficient (10- 4 cm2·s-1), good condition can be provided for mass transfer in electro-deposition system.Metal Substrate is prepared at present under supercritical fluid environment Nano composite material finding existing with the process of micro-workpiece and device.If Authorization Notice No. is CN 101092716B Chinese patent literature discloses a kind of supercritical fluid trickle electroforming technique and device thereof, and it is with SCF-CO2For plating ring Border carries out the molding of micro-structure part, by the electrodeposition of metals surface depositing homogeneous of the method gained, without buildup, and cast layer group Knit fine and closely woven smooth, but the part that gained cast layer part is photoetching in advance (interior mould) shape, it is impossible to flexibility prepares different types of 3D Parts;And for example publication No. is that the Chinese patent literature of CN 102146573A proposes a kind of supercritical fluid electrotyping forming system The method of standby nano composite material, it is mainly electro-deposition under mechanical agitation subsidiary conditions and prepares metal-based nano composite wood Material, Electric Field Distribution is fixing, from the point of view of its parameter is arranged and anode and cathode is arranged, it is impossible to effectively carry out parts in three-dimensional Space is processed preparation by electro-deposition.Thus, by three-dimensionally shaped and motor in the most popular 3D printing technique Reason applies to supercritical electro-deposition and adds in technique, and design one can carry out electro-deposition processing preparation in three dimensions to parts Device and processing method, it appears the most necessary.
Summary of the invention
It is an object of the invention to: for the deficiencies in the prior art, it is provided that one can be effectively improved electrodeposition rate, improve and sink Amass quality, prepare complicated, precision metallic parts at three dimensions by electro-deposition, and electro-deposition techniques application can be widened Based on supercritical fluid 3D electro-deposition processing unit (plant) and the method that uses this device process component.
The technical scheme is that the method based on supercritical fluid 3D electro-deposition process component of the present invention, by Based on supercritical fluid 3D electro-deposition processing unit (plant) implement, this device include dioxide bottle, high-pressure pump, CNC controller, Reactor, DC source and the cathode base as processed parts;Above-mentioned reactor includes body and mechanical agitator; Body is provided with air inlet, leakage fluid dram and heating coil;To reaction when above-mentioned dioxide bottle and high-pressure pump are used for using Device provides carbon dioxide;It is characterized in that: also include mobile anode assemblies and swap cathode assembly;
Above-mentioned mobile anode assemblies includes Z-direction linear electric motors, drives leading screw, anode connecting rod and mobile anode;Z-direction straight-line electric Machine is fixedly mounted on the top of the body of reactor;Leading screw is driven to be in transmission connection with Z-direction linear electric motors;Anode connecting rod and driving Leading screw is fixing to be connected;Leading screw is driven to be built-in with the elastic conduction coil being insulated from;Mobile anode anode connecting rod is fixing to be connected; Mobile anode passes through the positive pole of the anode connecting rod elastic conduction coil external direct current power supply built-in with driving leading screw;Mobile anode The mobile anode of assembly by Z-direction linear electric motors by driving leading screw and the transmission of anode connecting rod, can be internal in the basis of reactor Pump;
Above-mentioned swap cathode assembly include X to linear electric motors, X direction guiding rail, X to movable block, Y-direction linear electric motors, Y-direction guide rail, Y To movable block and fixture;X is fixedly mounted on the body of reactor to linear electric motors;X direction guiding rail divides and is front and back provided with 2;Guide X Rail is fixedly mounted on the intrinsic lower surface of reactor;X is arranged on X direction guiding rail and at X to linear electric motors to movable block Driving under can rely on about X direction guiding rail to linear slide;
Y-direction linear electric motors are fixedly mounted on X on the upper surface of movable block;Y-direction guide rail divides left and right to be provided with 2;Y-direction guide rail is fixed On the upper surface of movable block and Y-direction guide rail is vertically arranged with X direction guiding rail to be arranged on X;Coat on the upper surface of Y-direction movable block 66 There are insulation engineering plastics;Before Y-direction movable block is arranged on Y-direction guide rail and can rely on Y-direction guide rail under the driving of Y-direction linear electric motors Backward linear slide;
The material of fixture is acidproof, high pressure resistant and the insulation engineering plastics of high rigidity;Fixture is arranged on the upper surface of Y-direction movable block On, clamp cathode base when being used for using;During use, cathode base is connected with the negative electricity of DC source.
The X of swap cathode assembly is to the Z-direction linear electric motors of linear electric motors and Y-direction linear electric motors and mobile anode assemblies Run by CNC controller control;
The above-mentioned material driving leading screw is rustless steel, inner hollow;Anode connecting rod be built-in copper framework and carry out outward insulation, The body of rod part of engineering plastics acidproof, high voltage bearing;The above-mentioned leading screw that drives is connected with junction and the anode of anode connecting rod Bar all seals with high-pressure seal ring with the junction of mobile anode;
Above-mentioned mobile anode includes matrix and electrode;The material of matrix is glass, and matrix is by upper cylinder body and lower cylinder Portion's one composition, the diameter of the upper cylinder body of matrix is less than the diameter of lower cylinder body, the upper cylinder body of matrix and anode Connecting rod is fixing to be connected;Electrode is arranged in matrix and is positioned on the axial line of matrix.
Use above-mentioned method based on supercritical fluid 3D electro-deposition processing unit (plant) process component, including following step Rapid:
1. cathode base chemical plating in advance process: the plated surface last layer at the cathode base as processed parts be prone to into The metal of row electro-deposition;
2. cathode base is installed: be fixed on the upper surface of Y-direction movable block by the fixture of swap cathode assembly by cathode base; The upward and downward position of the mobile anode of regulation so that it is do not interference with swap cathode assembly;
3. prepare supercritical fluid: add in the reactor configured containing surface additive and the diploid of electro-deposition slow releasing agent It it is electroplate liquid;After airtight, in reactor, it is passed through carbon dioxide, controls the temperature in reactor at 35~70 DEG C, pressure In the range of 8~20MPa, form the ternary electro-deposition system with supercritical carbon dioxide emulsion as carrier;
4. electro-deposition processing: switch on power, sets electro-deposition parameter and the position of mobile anode opposing cathode matrix;In numerical control control Carry out electro-deposition under the control of device processed and the stirring auxiliary of mechanical agitator and obtain required with the outer surface at cathode base Deposition layer;CNC controller controls mobile anode and swap cathode assembly by the orbiting motion set;Mobile anode relative to The maximum single direction stroke that moves up and down as the cathode base of cathode body is 5cm;The electro-deposition course of processing is by multiple processing districts Between in series, each processing interval is divided into deposition interval and cutter lifting interval;Electrodeposition time is 2~5 hours, each crystallizing field Between duration control as 30min, cutter lifting interval duration controls as 2min;In cutter lifting interval, swap cathode assembly is static;
During electro-deposition interval, the bottom of mobile anode controls as 1cm with the spacing of cathode base;
To horizontal intermittent stirring about mechanical agitator;The stir speed (S.S.) of mechanical agitator is 200~500rpm;DC source is defeated The electric current density gone out is 1~13 A/dm2, preferably electric current density is 7A/dm2
5. electro-deposition completion of processing post processing: after electro-deposition completion of processing, by post processing, i.e. obtains desired properties and shape Parts.
Further scheme is: above-mentioned step 1. in, the uniform copper layer of about 10 μ m-thick on the plated surface of cathode base;On The step stated 3. in, the binary system electroplate liquid containing surface additive and electro-deposition slow releasing agent is nickel salt solution or copper salt solution; Surface additive is the additive being made up of dodecyl compounds and ether compound;Above-mentioned nickel salt or copper salt solution Concentration is 300~500g/L;The concentration of surface additive is 0.1~2g/L;Electro-deposition slow releasing agent is concentration 30g/L~60g/L Boric acid, bath pH values controls 2~6.
Further scheme is: a diameter of 5mm of the lower cylinder body of above-mentioned matrix;Under the lower cylinder body of matrix End is provided with angle of inclination and controls in the inclined-plane upwards of 60 ° concane gap or be provided with the periphery of the bottom indent lower circle away from matrix The arc concave shape breach of the outer peripheral face 1mm of trunk portion;Above-mentioned electrode is the insoluble Pt silk of diameter 1-2mm.
Further scheme also has: above-mentioned X is the square of the hollow of stainless steel to movable block and Y-direction movable block Body part;And Y-direction movable block be smaller in size than the X size to movable block.
The present invention has positive effect: (1) is of the present invention based on supercritical fluid 3D electro-deposition processing unit (plant), It can be effectively improved electrodeposition rate, improve deposition quality, prepared by electro-deposition complicated, smart at three dimensions in use Close metallic element, and electro-deposition techniques application can be widened.(2) in the supercritical electro-deposition system of the present invention, metal from The mass transfer performances of son is several ten times larger even hundreds of times than in conventional electrodeposition system.This high mass transfer rate can supplement rapidly The metal ion of cathode surface, significantly reduces concentration polarization, it is possible to enter by the electric current density higher than conventional electrodeposition Row electro-deposition, thus the problem overcoming the long processing time that tradition electro-deposition method exists.Supercritical fluid has pole simultaneously Good compatibility, can effectively absorb the hydrogen that cathode surface produces, it is to avoid defect occur in deposition cell surface and inside.(3) originally Invention can carry out 3D electro-deposition incessantly on non-smooth base part surface.(4) present invention can be according to being deposited zero Part shape need, by digitized programming set mobile anode and the motion track of swap cathode assembly and processing interval time Long, effectively control the accuracy of form and position and the sedimentary quality of deposition layer, it is not necessary to the negative electrode master mold that tradition electroforming is complicated.(5) originally The electro-deposition of invention is moved the electrode of anode and is equivalent to a point, under the constraint of the glass basis of mobile anode, and diverse location Time, the electric field intensity in corresponding region, cathode base surface and electric current density are all intimate equal, thus improve cathode base table The Electric Field Distribution in face, improves deposition layer quality.
Accompanying drawing explanation
Fig. 1 is structural representation based on supercritical fluid 3D electro-deposition processing unit (plant) of the present invention;
Fig. 2 is the planar structure schematic diagram of the swap cathode assembly in Fig. 1;
Fig. 3 is a kind of structural representation of the mobile anode in Fig. 1, and it is the section view of the axis upward and downward along mobile anode Figure;
Fig. 4 is the another kind of structural representation of the mobile anode in Fig. 1, and it is the section view of the axis upward and downward along mobile anode Figure.
Reference in above-mentioned accompanying drawing is as follows:
Dioxide bottle 1;
High-pressure pump 2;
CNC controller 3;
Reactor 4, body 41, air inlet 41-1, leakage fluid dram 41-2, heat coil 41-3, mechanical agitator 42;
Mobile anode assemblies 5, Z-direction linear electric motors 51, driving leading screw 52, anode connecting rod 53, mobile anode 54, matrix 54-1, Electrode 54-2, concane gap 54-3 in inclined-plane, arc concave shape breach 54-4;
Swap cathode assembly 6, X is to linear electric motors 61, X direction guiding rail 62, and X is to movable block 63, Y-direction linear electric motors 64, Y-direction guide rail 65, Y-direction movable block 66, fixture 67;
Cathode base 7;
DC source 8.
Detailed description of the invention
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings.
(embodiment 1)
The present embodiment when travel direction describes, with Fig. 1 left and right directions for X to, with Fig. 1 towards the back side in direction as Y-direction, to scheme The upward and downward of 1 is Z-direction.
Seeing Fig. 1 to Fig. 4, the method based on supercritical fluid 3D electro-deposition process component of the present embodiment, by based on super Critical fluids 3D electro-deposition processing unit (plant) is implemented, and this device is mainly by dioxide bottle 1, high-pressure pump 2, CNC controller 3, anti- Device 4, mobile anode assemblies 5, swap cathode assembly 6, DC source 8 and cathode base 7 is answered to form.
Dioxide bottle 1 prepares the CO of supercritical fluid for storage2Gas;To anti-when high-pressure pump 2 is used for needing Answer and device 4 is taken out pressure CO2Gas.
CNC controller 3 is the control controller of existing Numeric Control Technology, and digital control implement 3 adds man-hour for electro-deposition, controls to move Dynamic anode assemblies 5 and swap cathode assembly 6 move according to track set in advance.
Reactor 4 is mainly made up of body 41 and mechanical agitator 42.Body 41 is provided with air inlet 41-1, leakage fluid dram 41-2 and heating coil 41-3.Air inlet 41-1 is for inputting CO by high-pressure pump 22Gas;Leakage fluid dram 41-2 will be for using After supercritical fluid electroforming solution import in gas-liquid separator, carbon dioxide and the electroforming solution of separation return respectively Receive in retracting device and recycle;Heating coil 41-3 temperature of supercritical fluid electroforming solution in controlling reactor 4. Mechanical agitator 42 is arranged in body 41;Mechanical agitator 42 uses level to work to intermittent stirring mode, and stir speed (S.S.) is 200~500rpm, to improve the uniformity during electroforming and concordance.
Mobile anode assemblies 5 is mainly by Z-direction linear electric motors 51, driving leading screw 52, anode connecting rod 53 and mobile anode 54 Composition.
Z-direction linear electric motors 51 are fixedly mounted on the top of the body 41 of reactor 4;Drive leading screw 52 and Z-direction linear electric motors 51 are in transmission connection;Anode connecting rod 53 is fixing with driving leading screw 52 to be connected.The material driving leading screw 52 is rustless steel, in inside Sky, drives leading screw 52 to be built-in with the elastic conduction coil being insulated from, for movement anode 54 is connected power supply.Anode connecting rod 53 for built-in copper framework and carry out outward insulation, the body of rod part of engineering plastics acidproof, high voltage bearing;Drive the elasticity that leading screw 52 is built-in One end of conductive coil is electrically connected with mobile anode 54 by the built-in copper framework of anode connecting rod 53;Drive leading screw 52 built-in The other end of elastic conduction coil be connected with the positive electrical of DC source 8.All junctions all carry out close with high-pressure seal ring Envelope.
Seeing Fig. 3 and Fig. 4, mobile anode 54 is made up of matrix 54-1 and electrode 54-2.The material of matrix 54-1 is glass, Matrix 54-1 is integrally made up of upper cylinder body and lower cylinder body, and the diameter of the upper cylinder body of matrix 54-1 is less than lower cylinder The diameter of body, the upper cylinder body of matrix 54-1 is connected with anode connecting rod 53;The lower cylinder body of matrix 54-1 straight Footpath is about 5mm;The lower cylinder body of matrix 54-1 has 2 kinds of structures, and a kind of is the lower end of lower cylinder body at matrix 54-1 It is provided with concane gap 54-3 in inclined-plane upwards;Angle of inclination controls at about 60 °;Another kind is provided with arc concave shape breach 54- 4, the circumference of bottom indent is away from insulating glass external boundary about 1mm.Electrode 54-2 is insoluble Pt silk, a diameter of 1-2mm, electricity Pole 54-2 is arranged in matrix 54-1 and is positioned on the axial line of matrix 54-1.Concane gap 54-3 or arc concave shape in inclined-plane is set The purpose of breach 54-4 is to contribute to the concentration of electric field line, can well control deposition region, to carry in electrodeposition process High current efficiency and cast layer quality.
The mobile anode 54 of mobile anode assemblies 5 by Z-direction linear electric motors 51 by driving leading screw 52 and anode connecting rod 53 Transmission, can pump in the body 41 of reactor 4.
Still seeing Fig. 2, swap cathode assembly 6 is the most straight to movable block 63, Y-direction to linear electric motors 61, X direction guiding rail 62, X by X Line motor 64, Y-direction guide rail 65, Y-direction movable block 66 and fixture 67 form.
X is fixedly mounted on the body 41 of reactor 4 to linear electric motors 61;It is provided with 2 before and after X direction guiding rail 62 points;Guide X Rail 62 is fixedly mounted on the lower surface in the body 41 of reactor 4;X is square to the hollow that movable block 63 is stainless steel Body part.X is arranged on X direction guiding rail 62 to movable block 63 and can rely on X direction guiding rail about 62 under the driving of linear electric motors 61 at X To linear slide.
Y-direction linear electric motors 64 are fixedly mounted on X on the upper surface of movable block 63;About 65 points of Y-direction guide rail is provided with 2;Y Direction guiding rail 65 is fixedly mounted on X, and on the upper surface of movable block 63 and Y-direction guide rail 65 is vertically arranged with X direction guiding rail 62;But do not exist In same plane.Y-direction movable block 66 be smaller in size than X to movable block 63;Y-direction movable block 66 is the side of the hollow of stainless steel Body part;One layer of acidproof, high pressure resistant and insulation engineering plastics of high rigidity it are coated with on the upper surface of Y-direction movable block 66.Y-direction is moved Motion block 66 is sliding to straight line before and after being arranged on Y-direction guide rail 65 and can relying on Y-direction guide rail 65 under the driving of Y-direction linear electric motors 64 Dynamic.
The material of fixture 67 is acidproof, high pressure resistant and the insulation engineering plastics of high rigidity.Fixture 67 is arranged on Y-direction movable block On the upper surface of 66.Fixture 67 clamps the cathode base 7 as part to be processed in time using.During work, cathode base 7 with The negative electricity of DC source 8 connects.
All gap locations of swap cathode assembly 6 all seal with high-pressure seal ring.
The X of swap cathode assembly 6 is to linear electric motors 61 and Y-direction linear electric motors 64 and the Z-direction straight line of mobile anode assemblies 5 The operation of motor 51 is controlled by CNC controller 3.
The present embodiment based on supercritical fluid 3D electro-deposition processing unit (plant), it adds for accurate, complex three-dimensional parts The processing method of work, illustrates as a example by Ni-based electroplate liquid and stainless steel cathode matrix 7, and its processing method mainly includes following Step:
1. cathode base 7 chemical plating in advance processes: the plated surface last layer at cathode base 7 is prone to carry out the metal of electro-deposition, This metal may select fine copper or pure nickel, in the present embodiment, it is preferred to use on the plated surface of cathode base 7, about 10 μ m-thick is uniform Layers of copper;
2. cathode base is installed: cathode base 7 is fixed on the upper of Y-direction movable block 66 by the fixture 67 of swap cathode assembly 6 On end face;The upward and downward position of the mobile anode 54 of regulation so that it is do not interference with swap cathode assembly 6.
3. supercritical fluid is prepared: add in the reactor 4 and stir under nickel salt solution, boric acid and additive, ultrasound environments Mix 60 minutes so that it is be sufficiently mixed;Boric acid, as electro-deposition slow releasing agent, is optionally added, the concentration of boric acid be 30g/L~ 60g/L.Nickel salt solution is the solution of sulfur acid nickel and Nickel dichloride.;Wherein nickel sulfate consumption is 300~400g/L, Nickel dichloride. consumption It is 30~50g/L;Additive is made up of dodecyl compounds and ether compound, wherein dodecyl compounds consumption Being 0.1~2g/L, ether compound consumption is 0.1~1g/L.In the present embodiment, additive preferably employs sodium lauryl sulphate With Polyethylene Glycol trimethyl nonyl ethers.The concentration of each material is preferably: nickel sulfate 300g/L, Nickel dichloride. 35g/L, boric acid 40g/L, Sodium lauryl sulphate 0.2g/L, Polyethylene Glycol trimethyl nonyl ethers 0.8g/L.
Start high-pressure pump 2, carbon dioxide is passed through from dioxide bottle 1 air inlet of the body 41 of reactor 4 41-1 takes out in the body 41 being pressed onto reactor 4;Control pressure is 8 ~ 20MPa;Make alternating current by heating coil 41-3 simultaneously Heat under the effect of electromagnetic induction, by the control to the size of the current intensity of alternating current, temperature is controlled 35~70 DEG C, in the present embodiment preferably 50 DEG C, under above-mentioned pressure and temperature, it is stirred by mechanical agitator 42 and is formed Supercritical fluid ternary electro-deposition system.
In the present embodiment, carbon dioxide pressure in the body 41 of airtight reactor 4 is 13MPa;Machinery stirs The stir speed (S.S.) mixing device 42 is 200~500rpm;Preferably employing mechanical agitation speed in the present embodiment is 400rmp.Mechanical agitation Device 42 works to horizontal intermittent stirring mode about using.
4. electro-deposition processing: switch on power, under CNC controller 3 adopts the control of existing Numeric Control Technology, mobile anode 54 and swap cathode assembly 6 by predetermined orbiting motion;Upper relative to the cathode base 7 as cathode body of mobile anode 54 Lower mobile maximum single direction stroke is 5cm;Use timing electro-deposition mode to control cathode and anode to move;The electro-deposition course of processing is by many Individual processing interval is in series, and each processing interval is divided into deposition interval and cutter lifting is interval;Move anode 54 and negative electrode base simultaneously Body 7 discharges, and forms the electric field of relative constancy;Nickel ion in solution deposits to the surface of cathode base 7 under electric field action;Electricity Sedimentation time is 2~5 hours, and the interval duration of deposition is about 30min, and cutter lifting interval is 2min;In cutter lifting interval, swap cathode Assembly 6 is static.In the present embodiment, preferred electrodeposition time is 3 hours, deposition process interval 28min, cutter lifting interval duration 2min.
The electric current density of DC source 8 output is 1~13 A/dm2;Preferably employing electric current density in the present embodiment is 7A/ dm2
5. electro-deposition completion of processing post processing: after electro-deposition completion of processing, by the leakage fluid dram on the body 41 of reactor 4 Supercritical fluid electroforming solution is imported in gas-liquid separator by 41-2, and carbon dioxide and the electroforming solution of separation are separately recovered Recycle in retracting device.
6. cathode base post processing: taken out from reactor 4 by cathode base 7, is air-dried by washing and is done by pickling Only, the dense structure, the crystal grain that i.e. obtain combining closely with the rustless steel of cathode base 7 are tiny, surfacing, excellent performance and shape The preferable precision metal of shape, fine parts.
Above example is the explanation of the detailed description of the invention to the present invention, rather than limitation of the present invention, relevant technology The technical staff in field is without departing from the spirit and scope of the present invention, it is also possible to makes various conversion and change and obtains To the technical scheme of corresponding equivalent, the technical scheme of the most all equivalents all should be included into the patent protection model of the present invention Enclose.

Claims (1)

1. a method based on supercritical fluid 3D electro-deposition process component, it is characterised in that: by based on supercritical fluid 3D electro-deposition processing unit (plant) is implemented, and described supercritical fluid 3D electro-deposition processing unit (plant) includes dioxide bottle (1), high pressure Pump (2), CNC controller (3), reactor (4), mobile anode assemblies (5), swap cathode assembly (6), DC source (8) and work Cathode base (7) for processed parts;Described reactor (4) includes body (41) and mechanical agitator (42);Body (41) air inlet (41-1), leakage fluid dram (41-2) and heating coil (41-3) it are provided with;Described dioxide bottle (1) and height Carbon dioxide is provided to reactor (4) when press pump (2) is used for using;Described mobile anode assemblies (5) includes Z-direction straight line Motor (51), driving leading screw (52), anode connecting rod (53) and mobile anode (54);Z-direction linear electric motors (51) are fixedly mounted on The top of the body (41) of reactor (4);Leading screw (52) is driven to be in transmission connection with Z-direction linear electric motors (51);Anode connecting rod (53) with drive that leading screw (52) is fixing to be connected;Leading screw (52) is driven to be built-in with the elastic conduction coil being insulated from;Mobile anode (54) fixing with anode connecting rod (53) it is connected;Mobile anode (54) is by anode connecting rod (53) and drives leading screw (52) built-in The positive pole of elastic conduction coil external direct current power supply (8);The mobile anode (54) of mobile anode assemblies (5) is by Z-direction straight-line electric Machine (51), can be the most past in the body (41) of reactor (4) by driving leading screw (52) and the transmission of anode connecting rod (53) Multiple motion;
Described swap cathode assembly (6) includes that X is straight to movable block (63), Y-direction to linear electric motors (61), X direction guiding rail (62), X Line motor (64), Y-direction guide rail (65), Y-direction movable block (66) and fixture (67);X is fixedly mounted on reaction to linear electric motors (61) On the body (41) of device (4);X direction guiding rail (62) point is front and back provided with 2;X direction guiding rail (62) is fixedly mounted on the basis of reactor (4) On lower surface in body (41);X is arranged on X direction guiding rail (62) and in the X driving to linear electric motors (61) to movable block (63) Under can rely on X direction guiding rail (62) left and right to linear slide;
Y-direction linear electric motors (64) are fixedly mounted on X on the upper surface of movable block (63);Y-direction guide rail (65) point left and right is provided with 2 Root;Y-direction guide rail (65) is fixedly mounted on X, and on the upper surface of movable block (63) and Y-direction guide rail (65) is vertical with X direction guiding rail (62) Arrange;Insulation engineering plastics it are coated with on the upper surface of Y-direction movable block 66;Y-direction movable block (66) is arranged on Y-direction guide rail (65) And Y-direction guide rail (65) can be relied under the driving of Y-direction linear electric motors (64) front and back to linear slide;
The material of fixture (67) is acidproof, high pressure resistant and the insulation engineering plastics of high rigidity;Fixture (67) is arranged on Y-direction movable block (66), on upper surface, cathode base (7) when being used for using, is clamped;During use, cathode base (7) is negative with DC source (8) Pole electrically connects;
The X of swap cathode assembly (6) is to linear electric motors (61) and Y-direction linear electric motors (64) and the Z-direction of mobile anode assemblies (5) The operation of linear electric motors (51) is controlled by CNC controller (3);
The material of described driving leading screw (52) is rustless steel, inner hollow;Anode connecting rod (53) be built-in copper framework and Outer shoe insulation, the body of rod part of engineering plastics acidproof, high voltage bearing;Described driving leading screw (52) and the company of anode connecting rod (53) The place of connecing and anode connecting rod (53) all seal with high-pressure seal ring with the junction moving anode (54);
Described mobile anode (54) includes matrix (54-1) and electrode (54-2);The material of matrix (54-1) is glass, matrix (54-1) being integrally made up of upper cylinder body and lower cylinder body, the diameter of the upper cylinder body of matrix (54-1) is less than lower cylinder The diameter of body, the upper cylinder body of matrix (54-1) is fixing with anode connecting rod (53) to be connected;Electrode (54-2) is arranged on base Body (54-1) is interior and is positioned on the axial line of matrix (54-1);
The method of process component, comprises the following steps:
1. cathode base chemical plating in advance processes: easy at the plated surface last layer of the cathode base (7) as processed parts In the metal carrying out electro-deposition;
2. cathode base is installed: cathode base (7) is fixed on Y-direction movable block by the fixture (67) of swap cathode assembly (6) (66) on upper surface;The upward and downward position of the mobile anode (54) of regulation so that it is do not interference with swap cathode assembly (6);
3. prepare supercritical fluid: add in reactor (4) configured containing surface additive and the two of electro-deposition slow releasing agent Unit's system plating solution;After airtight, in reactor (4), be passed through carbon dioxide, control temperature in reactor (4) 35~ 70 DEG C, pressure in the range of 8~20MPa, form ternary electro-deposition system with supercritical carbon dioxide emulsion as carrier;
4. electro-deposition processing: switch on power, sets electro-deposition parameter and the position of mobile anode (54) opposing cathode matrix (7); Electro-deposition is carried out with in cathode base (7) under the control of CNC controller (3) and the stirring auxiliary of mechanical agitator (42) Outer surface obtain required deposition layer;CNC controller (3) controls mobile anode (54) and swap cathode assembly (6) by setting Fixed orbiting motion;Mobile anode (54) moves up and down maximum unidirectional row relative to the cathode base (7) as cathode body Journey is 5cm;The electro-deposition course of processing is in series by multiple processing intervals, and each processing interval is divided into deposition interval and cutter lifting district Between;Electrodeposition time is 2~5 hours, and the interval duration of each deposition controls to be 30min, and cutter lifting interval duration controls as 2min;Lift In cutter interval, swap cathode assembly (6) is static;
During described electro-deposition interval, the bottom of mobile anode (54) controls as 1cm with the spacing of cathode base (7);
Mechanical agitator (42) left and right is to horizontal intermittent stirring;The stir speed (S.S.) of mechanical agitator (42) is 200~500rpm;Directly The electric current density that stream power supply (8) exports is 1~13 A/dm2
5. electro-deposition completion of processing post processing: after electro-deposition completion of processing, by post processing, i.e. obtains desired properties and shape Parts.
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