CN112323111B - Method for electrolyzing continuous terminal - Google Patents
Method for electrolyzing continuous terminal Download PDFInfo
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- CN112323111B CN112323111B CN202011205560.2A CN202011205560A CN112323111B CN 112323111 B CN112323111 B CN 112323111B CN 202011205560 A CN202011205560 A CN 202011205560A CN 112323111 B CN112323111 B CN 112323111B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0621—In horizontal cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0671—Selective plating
- C25D7/0678—Selective plating using masks
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0692—Regulating the thickness of the coating
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- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to the technical field of electrolytic surface treatment, in particular to an electrolytic method of a continuous terminal, which comprises the steps of carrying out full shielding on one surface of a material belt through a first conveyor belt, carrying out partial shielding on the other surface of the material belt through a second conveyor belt, and carrying out processing treatment on a part of the material belt extending out of the outer periphery of the second conveyor belt so as to realize the purpose of local processing.
Description
Technical Field
The invention relates to the technical field of electrolytic surface treatment, in particular to an electrolytic method of a continuous terminal.
Background
The noble metal surface treatment technology has been rapidly developed since being popularized and applied in the electronic industry. Particularly, gold plating surface treatment technology and process, because gold plating has good corrosion resistance, good ductility, soldering tin property, electrical conductivity and thermal conductivity, stable chemical properties and strong tarnish resistance, various gold plating technologies and processes are widely used in smart phones, computers, precision electronics industries such as automobiles and aerospace, and general civil electronic products such as televisions and refrigerators, and also in the field of processing ornaments and the like.
In order to fully utilize precious metal resources such as gold, which are limited in nature, when performing precious metal surface electrolytic treatment on electronic products with various continuous metal terminals, only precious metals need to be precipitated on effective functional areas of the products. This requires that the noble metal electrolysis technology must satisfy: noble metals can be precipitated only on the local part of the electronic product. Based on the requirement of the special noble metal electrolysis technology, the research on the noble metal electrolysis technology, particularly the gold electrolysis technology, is unprecedentedly developed in the recent development history of the electrolytic treatment of the metal surface, and a lot of local electrolysis technologies are emerged.
As the local electrolytic technique of noble metal, there are an immersion method using depth control of surface treatment solution, a brush plating method using local area control, and particularly, in recent years, a noble metal electrolytic technique using various masking methods to perform local surface treatment with respect to the shape and characteristics of electrolytic products has been more widely developed and applied, and various local electrolytic methods and apparatuses of noble metal have been gradually formed.
Patent document 1 (U.S. patent No.3,723,283) provides a surface treatment system for the production and processing of continuous terminals of strip-like electronic components. The system is capable of continuously passing strip terminal material between two flexible strip-like spacers which are not motor driven but merely idle. The gaskets are provided with spray holes according to the requirements of product specifications, an electrolytic solution spray inlet pipe is arranged in one gasket, an electrolytic solution outlet pipe is arranged in the other gasket, so that the electrolytic solution is kept in contact with other parts, and the electrolytic solution is arranged between the strip-shaped terminal material to be electrolyzed and the separately arranged electrodes, thereby completing the local device which only electrolyzes the preset part of the terminal material, and the terminal material which is shielded by the gaskets is not subjected to surface electrolysis. Although, the spacer masking apparatus improves the electrolytic efficiency of the terminal product by spraying the electrolytic solution to the terminal material instead of the dipping method of the electrolytic solution; it is not suitable for the particular noble metal electrolytic solution of the present invention, i.e., the particular noble metal electrolytic solution cannot be subjected to the solution spraying method, but can be processed into a continuous end product only by immersion electrolysis. In addition, the flexible strip-shaped gasket is not driven by a motor in operation, and the stability and the uniformity of operation cannot be maintained in long-time continuous production, so that the product quality cannot be ensured to be uniform, and the production efficiency is reduced and the production cost is increased.
Patent document 2 (U.S. patent No.5,045,167) discloses a continuous plating apparatus including an endless carrier movable along a continuous path, a product plating zone provided along a first portion of the carrier path where a strip-like metal material is plated (spot plating) with a noble metal solution ejected from a plating head. At least one independently mounted plating nozzle on the annular carrier, including a storage tank for the plating solution, an anode disposed in the storage tank for positively charging the plating solution; and a shielded plating hole through which the plating solution is sprayed to the negatively charged strip-shaped metal material, thereby completing a continuous plating apparatus in which only a specified single surface of the strip-shaped metal material is partially plated and the shielded strip-shaped metal material is not plated.
Although, the continuous device of the invention can partially coat one side of the continuous metal strip to obtain the production processing coating product with the product specification; however, the equipment is complex to manufacture, and has the defects of high management difficulty, difficulty in operation, inspection, adjustment, maintenance and the like in daily production and equipment maintenance; further, the solution supply employs a spray method, which is not applicable to the specific noble metal electrolytic solution of the present invention, i.e., the specific noble metal electrolytic solution cannot be subjected to a method of spraying a solution.
An electrolytic processing method of a continuous terminal material described in patent document 3(CN108779567A) includes the steps of: the continuous terminal is divided into a waste material area (A), a contact area (B) and a non-contact area (C) which are distributed from the edge of the terminal material positioning hole to the central area in sequence. The scrap region (A) is subjected to a surface insulation treatment to lose the metallic property of the scrap region (A). And immersing the terminal material into a noble metal electrolytic solution to electrolytically process the terminal material, wherein the noble metal cannot be electrolytically deposited in the waste material area (A) subjected to the insulation treatment in the electrolytic processing process. The consumption of noble metal can be reduced, and the cost is reduced. However, this method is limited to the simultaneous electrolytic machining of both sides of the continuous terminal, and the requirement for the local electrolytic machining of one side cannot be satisfied.
Patent document 4(CN106329288A) discloses a terminal partial shielding method, in which a part of a terminal that does not require plating is treated with an insulating film; putting the terminal into a plating bath, and performing electrolytic machining on the surface of the terminal; subsequently, the insulating film on the electrolytically processed terminal is removed to obtain a plated terminal product. The invention has the advantages of high production efficiency of electrolytic machining and high qualification rate of product quality.
However, in this method, an adhesive tape is required as a consumable, and since an adhesive tape attaching step and an adhesive tape removing step are required, the cost is higher than the cost of plating on the entire surface of the plating material, and further, there may be a defect that the adhesive of the adhesive tape remains on the plating material after plating.
Patent document 5(CN207596984U) the present application discloses a terminal local continuous electroplating device, which is applied to the technical field of advanced manufacturing and automation, specifically to the technical field of surface treatment. The device places the electrolytic solution groove through imitative work piece physique setting, the inside two-layer current stabilizer that sets up of upper water seat for the plating solution tends to steadily with the work piece contact when arriving the work piece standing groove, the plating solution is steady with the work piece contact, improve electroplating quality, open the electrolytic solution groove of placing simultaneously, can realize the local selection electrolytic machining of continuity of work piece, improve production efficiency, the liquid level of electrolytic solution among the prior art is not stable enough, local electrolysis is regional inaccurate, thereby lead to electrolysis product quality to descend and the problem that product manufacturing cost rises.
However, in the electrolytic product produced and processed by the method, the direct current power supply is adopted for electrolytic production, so that the phenomenon of uneven thickness distribution of the electrolytic metal film exists, and the redundant noble metal electrolytically precipitated at the end part of the product cannot be saved.
Patent document 6 (japanese patent JP 1995-. A pair of mask members for masking a large number of needle-shaped workpieces from both sides so as to leave one surface of the tip portion, and performing electroplating to bring a plating solution into partial contact with one single surface of the tip portion exposed from the mask members. In the machining mechanism, one of the pair of mask members has a plurality of grooves into which the arc-shaped workpiece is fitted, and the other mask member has a plurality of projections into which the grooves are fitted. A pair of mask members are provided to sandwich the arc-shaped workpiece and the recess and projection, and to expose one surface of a tip portion of the arc-shaped workpiece to a feature of the other mask member.
However, the equipment is complex to manufacture, and has the defects of high management difficulty, difficulty in operation, inspection, adjustment, maintenance and the like in daily production and equipment maintenance.
Patent document 7 (japanese patent JP 3461832B2) provides an apparatus for electrolytically treating a continuous terminal material, which is in contact with an electrolytic solution, through an electrolytic processing zone of an apparatus, the apparatus for conveying being in contact with the electrolytic solution only within the defined zone. Masking means for masking the terminal material, conveying means having an endless chain being provided for aligning and positioning the terminal material with the masking means and masking the apparatus with a continuously moving electrically conductive treatment material, means for supplying the treatment material with an electrolyte to pass an electric current between the treatment material as one electrode and the treatment material as the other electrode. The apparatus can be used to selectively electrolytically treat a defined area of functionality.
However, this apparatus also has problems of complicated manufacture and difficulty in maintenance.
Patent document 8 (japanese patent JP 2018-165378A) provides a mask member in which a plurality of rows of openings are provided in a vertical direction, and when a plating solution is ejected and supplied from each opening in a lateral direction, when the plating solution ejected to the openings of the rows falls due to the action of gravity, it interferes with the ejection of the plating solution ejected from the top to the openings of the second and subsequent rows, so that a metal material is exposed at the openings and the plating solution is found to stay near the surface and metal ions are not sufficiently supplied. Therefore, by making the openings of the second and subsequent rows from the top have a structure that does not restrict the residual plating solution, scorch discoloration of the partial plating can be prevented and a good plating layer can be obtained in the partially plated region.
The electrolysis technology is widely applied to production and processing equipment and is suitable for application to single-side local electrolysis products. In most cases, the electrolytic processing method can be used in place of the ring carrier (documents 1, 2, 6, and 7) and the masking with a film (documents 4 and 5). However, the above method cannot be applied to a noble metal alloy solution that cannot be sprayed.
Non-patent literature, china material science and equipment, 2009, phase 1, pp75. a nitric acid exposure experimental method is provided for connector surface gold-plated products, concentrated nitric acid is placed in a closed container glass dryer, a test sample is placed above a nitric acid solution according to specified conditions, a cover is placed on the container to form a closed system, and the closed container is filled with evaporated nitrogen dioxide gas to evaluate the corrosion resistance of the products.
The various local electrolysis apparatuses described in patent documents 1 to 8 provide a surface treatment method for a continuous metal terminal having various complicated requirements for local surface electrolysis of a noble metal. However, the noble metal alloy electrolytic solution to be discussed in the present invention cannot be used in a spray method, but only limited to an immersion electrolysis method, and therefore, none of the electrolysis techniques provided in the above-mentioned documents 1 to 8 can obtain satisfactory results.
In addition, according to the metal precipitation principle of all local electrolytic treatment equipment, a precious metal solution is sprayed to the surface of a continuous metal terminal through a narrow slit to obtain an electrolytic treatment product, the spraying strength and the direction uniformity of the precious metal solution directly influence the distribution uniformity of electrolytic precious metals for precious metal surface treatment, the performance and the surface quality of precipitated metals, and great difficulty is brought to continuously keeping the spraying strength uniformity and the direction uniformity of the precious metal solution unchanged in the long-time continuous surface treatment production process. Therefore, the noble metal film thickness is not uniformly distributed, which results in the increase of the noble metal usage and the insufficient corrosion resistance of the surface of the electrolytic noble metal, and the like, and the development of more effective electrolytic method and electrolytic equipment is urgently needed.
The uneven noble metal film thickness distribution means that in the methods of patent documents 1 to 8 in which a continuous metal terminal material is partially electrolyzed using a masking tape, the electrolytic film thickness obtained at the interface between the non-charged electrolytic region of the terminal material and the electrolytic region of the terminal material (the portion near the masking tape) is low, and the electrolytic film thickness at the tip and corner of the terminal material is high.
For a noble metal alloy electrolytic solution that cannot use the spray method, obtaining a local electrolytic product is limited to a method of impregnating the noble metal electrolytic solution. Therefore, the methods described in patent documents 1 to 8 have the following problems:
1) for the noble metal alloy electrolytic solution which can not be subjected to surface electrolytic treatment by using a spraying method, the prior art can not meet the specification requirement of products; 2) the noble metal film thickness distribution is not uniform when the single-side electrolytic treatment is carried out on the continuous terminal material; 3) the corrosion resistance of the continuous terminal electrolytic noble metal product is insufficient; 4) during the electrolytic treatment of the local surface, the defects of leakage and the electrolytic precipitation of noble metals by the leakage exist.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides an electrolysis method of a continuous terminal and continuous terminal electrolysis equipment, aiming at solving the technical problems of complex structure, low efficiency, high maintenance cost and uneven noble metal film thickness distribution during surface treatment of a continuous terminal material of local electrolysis equipment in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: an electrolytic method of a continuous terminal, comprising a plurality of terminal partial electrolytic masking devices arranged side by side from front to back at intervals, the terminal partial electrolytic masking devices being used for surface treatment of a material, comprising a partial electrolytic masking jig, the partial electrolytic masking jig comprising: a first masking belt and a second masking belt, the second masking belt is arranged at one side of the first masking belt and consistent with the conveying direction of the first masking belt, a channel extending along the conveying direction is formed between the second masking belt and the first masking belt, the material penetrates through the channel, the length direction of the material is consistent with the conveying direction of the belts, the material is clamped between the first masking belt and the second masking belt, the orthographic projection of the material on the first masking belt is positioned in the first masking belt, the orthographic projection of the second masking belt on the material is positioned in the material, so that one part of the material is exposed out of the outer peripheral edge of the second masking belt, and the material passes through between the first masking belt and the second masking belt of each terminal local electrolysis masking device,
each terminal local electrolysis shielding device also comprises an electrolysis device, the local electrolysis shielding jig is arranged in the electrolysis device, a material penetrates through the front end and the rear end of the electrolysis device, an accommodating cavity filled with electroplating solution is limited in the electrolysis device, the material is positioned in the accommodating cavity, one part of the material extending out of the outer periphery of the second shielding belt is contacted with the electroplating solution, the electrolysis device is connected with a pulse reverse power supply,
the method for electrolyzing the continuous terminal comprises the following steps:
s1: clamping the material between a first masking belt and a second masking belt, so that the material moves forwards along the conveying direction of a channel, one surface of the material is completely shielded by the first masking belt and is not contacted with electroplating solution, the other surface of the material is partially shielded by the second masking belt, the exposed part of the other surface of the material is contacted with the electroplating solution, and a metal film is electroplated on the exposed part of the other surface of the material;
s2: the current which is output by the pulse reverse power supply and applied to the vicinity of the material is periodically changed;
when a forward pulse current is applied, a metal film is electrically analyzed on the material to present a pulse forward waveform; when the reverse pulse current after the periodic variation is applied, the metal film on the material is electrolytically stripped, and then a pulse reverse waveform is presented.
S3: the material passes between a first masking belt and a second masking belt of the multi-terminal local electrolytic masking device, and finally a uniform metal film is obtained on the other exposed part of the material.
According to the electrolysis method of the continuous terminal, one surface of the material belt is completely shielded through the first conveyor belt, the other surface of the material belt is partially shielded through the second masking belt, and a part of the material belt extending out of the outer periphery of the second masking belt can be processed to achieve the purpose of local processing. The continuous terminal electrolysis method applies pulse periodic reverse current to the local surface of the continuous terminal material for electrolysis, and adjusts and controls the electrolytic noble metal on the surface of the continuous terminal material into the required noble metal film with uniform thickness distribution and excellent corrosion resistance; the adjustment and control of the local surface of the continuous terminal material are realized by a transmission motor precision adjusting system, a tension control assembly between the material and the annular shielding belt, and local electrolysis equipment and a method for transmitting the annular shielding belt by an electric device; the quality qualification rate of the continuous terminal product is improved, the use amount of a large amount of noble metal is saved, and the production cost of the electrolytic noble metal is greatly reduced.
In the step S2, the time range of the forward pulse output by the pulse periodic reverse power supply is 5ms to 50ms, and the time range of the reverse pulse output by the pulse reverse power supply is 1ms to 20 ms.
Further, specifically, the width of the first masking belt is not less than the width of the material, and the width of the second masking belt is less than the width of the material.
Further, specifically, a first tension control assembly is arranged in the first masking belt, the first tension control assembly comprises a tension wheel and a first transmission wheel, the tension wheel and the first transmission wheel form a motion loop of the first masking belt, a second tension control assembly is arranged in the second masking belt, the second tension control assembly comprises a tension wheel and a second transmission wheel, and the tension wheel and the second transmission wheel form a motion loop of the second masking belt.
Further, specifically, the first driving wheel is connected with a second gear, the second driving wheel is connected with a third gear, the second gear is meshed with the third gear, the second gear is further meshed with a speed regulating gear, and the speed regulating gear is in transmission connection with a rotating shaft of the motor.
Further, specifically, the local electrolytic masking jig further comprises a belt guide rail, and the belt guide rail is in sliding connection with the first masking belt or the second masking belt and used for limiting the motion track of the corresponding first masking belt or the second masking belt.
Further, specifically, the local electrolysis masking jig further comprises an electrolysis device, the local electrolysis masking jig is arranged in the electrolysis device, the material penetrates through the electrolysis device, a containing cavity filled with electroplating solution is limited in the electrolysis device, the material is located in the containing cavity, one part of the material, extending out of the outer periphery of the second masking belt, is in contact with the electroplating solution, and the electrolysis device is connected with a pulse reverse power supply.
Further, specifically, an electrolytic anode plate is further arranged in the electrolysis device, the electrolytic anode plate faces the material and extends out of one part of the outer periphery of the second masking belt, the electrolytic anode plate is connected with an anode output joint of the pulse reverse power supply, a cathode conductive wheel is connected to the part, penetrating through the first masking belt and the second masking belt, of the material in the extension direction, and the cathode conductive wheel is connected with a cathode output joint of the pulse reverse power supply.
Further, specifically, the local electrolysis masking jig further comprises a substrate, the electrolysis device comprises an inner sub-groove with an opening, the substrate is fixedly erected in the inner sub-groove through a support, and the first masking belt and the second masking belt are located below the substrate.
Further, specifically, the electrolysis device further comprises a mother tank for containing electroplating solution, the mother tank and the inner and outer tanks are communicated with each other through a solution conveying pipeline, a solution conveying pump is arranged on the solution conveying pipeline, and a backflow pipeline is communicated between the mother tank and the inner and outer tanks.
Furthermore, in order to guarantee the material straight line conveying, the through-hole has been seted up at the both ends of interior subslot, and the material runs through the through-hole, and the subslot outside is close to through-hole department and is provided with the spacing tool that leads in pairs, and the material presss from both sides tightly between every to spacing tool that leads.
The electrolytic method for the continuous terminal has the advantages that one surface of the material belt is completely shielded through the first conveyor belt, the other surface of the material belt is partially shielded through the second masking belt, a part of the material belt extending out of the outer periphery of the second masking belt can be processed to achieve the purpose of local processing, the problem that the existing equipment cannot effectively process the local part of the single surface of the material belt is solved, and the electrolytic method for the continuous terminal has the advantages of being high in mechanization degree, simple in structure, simple and convenient to use, free of pollution, low in cost, high in efficiency and the like.
Because the position of the material close to the second masking belt has liquid flowing dead angles, the liquid fluidity is weak, and the obtained metal ions are few, the metal film on the position of the material close to the second masking belt is relatively thin, the position of the material far away from the second masking belt has strong liquid fluidity, the obtained metal ions are more, therefore, the metal film on the material far away from the second masking belt is relatively thick, so that the phenomenon of uneven plating thickness of the metal film occurs on the material, the pulse reverse power supply is arranged, so that when the surface of the material is a negative electrode, metal ions are separated out through electrolysis, a metal film is formed on the surface of the material, then, the material is converted into an anode by a pulse reverse power supply, and the metal film on the surface of the material is electrolytically stripped under the action of the anode, the ion stripping at the position of the film thickness is more, and the ion stripping at the position of the film thickness is less, so that the required noble metal film has uniform thickness distribution and excellent corrosion resistance; the adjustment and control of the local surface of the continuous terminal material are realized by a transmission motor precision adjusting system, a tension control assembly between the material and the annular shielding belt, and local electrolysis equipment and a method for transmitting the annular shielding belt by an electric device; the quality qualification rate of the continuous terminal product is improved, the use amount of a large amount of noble metal is saved, and the production cost of the electrolytic noble metal is greatly reduced.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic plan view of a continuous terminal electrolysis apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic enlarged plan view of a partial electrolytic masking device of an embodiment of the present invention;
FIG. 3 is a schematic perspective view of the front side of a partial electrolytic masking device according to an embodiment of the present invention;
FIG. 4 is a schematic perspective view of the reverse side of a partial electrolytic masking device according to an embodiment of the present invention;
FIG. 5 is a perspective view of an electrolytic masking jig according to an embodiment of the present invention;
FIG. 6 is a bottom view of an electrolytic masking tool according to an embodiment of the present invention;
FIG. 7 is a schematic perspective view of a motor power assembly of the electrolytic masking tool according to the embodiment of the present invention;
FIG. 8 is a schematic perspective view of a tensioner assembly of the electrolytic masking tool of the embodiment of the present invention;
FIG. 9 is a schematic diagram of the pulse reverse electrolysis pulse waveform and the electrolytic film thickness profile of an embodiment of the present invention;
FIG. 10 is a schematic illustration of an asymmetric AC waveform and an electrolyte film thickness profile of an embodiment of the present invention;
fig. 11 is a schematic plan view of a terminal of an embodiment of the present invention and an overlay of fig. 8 and 9;
FIG. 12 is a cross-sectional view of a terminal of example 1 of the present invention and comparative experiment 1;
fig. 13 is a schematic plan view of a terminal of embodiment 1 of the present invention;
FIG. 14 shows a terminal film thickness measuring point in example 1 of the present invention;
fig. 15 is a schematic plan view of a terminal according to embodiment 2 of the present invention;
FIG. 16 is an enlarged view of the noble metal electrolysis region, showing the thickness measurement point of the terminal film in example 2 of the present invention;
fig. 17 is a nitric acid exposure test result of the product of example 1 of the present invention in which the surface of the terminal is plated with gold, sample 1;
fig. 18 is a nitric acid exposure test result of the product of example 2 of the present invention in which the terminal surface is plated with gold, and a test result of sample 2;
fig. 19 is a nitric acid exposure test result of the product of example 3 of the present invention in which the terminal surface is plated with gold, sample 3;
FIG. 20 is a graph of corrosion rate results after nitric acid exposure experiments for inventive example samples 1, 2, and 3;
in the figure: a continuous terminal electrolysis apparatus 1000; a terminal local electrolytic shield device 510;
an electrolytic masking device 300; an outer sub-groove 310; an inner sub-groove 320; a first cathode conductive wheel 330a, a second cathode conductive wheel 330 b; the first electrolysis anode 340a and the second electrolysis anode 340 b; an inlet limiting and guiding jig 350a and an outlet limiting and guiding jig 350 b; a female slot 360; a solution delivery pump 370; a solution delivery conduit 380; a solution return line 390;
a pulsed reverse power supply 200; forward pulse current setting 210; reverse pulse current setting 220; forward pulse time setting 230; reverse pulse time setting 240; an anode output terminal 250; a cathode output terminal 260;
an electrolytic masking jig 100; a first masking belt 10; a second masking belt 20; a belt guide 21; material 30; a speed-adjusting gear 40; the second gear 41; a third gear 42; a first driving pulley 43; a second transmission wheel 44; a tension pulley 45; a bearing 46; screws 47; a nut 48;
a motor 50; a motor base 51; a coupling 52; a rotating shaft 53; a drive flange 54; a flange seat 55;
a speed reducer 60; a substrate 70; a bracket 80; a leveling foot 81.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention. Furthermore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
As shown in fig. 1 to 3, which are embodiments of the present invention, a continuous terminal electrolysis apparatus 1000 includes a plurality of terminal partial electrolysis shielding apparatuses 510, wherein the continuous terminal electrolysis method includes: a local electrolytic masking device 300 and a pulsed reverse power supply 200 (also called a pulsed reverse power supply or a pulsed reverse rectifier).
Specifically, the local electrolytic masking device comprises a sub-tank 310, an inner sub-tank 320, an electrolytic masking jig 100, a mother tank 360, an electrolytic solution delivery pump 370, a solution delivery pipe 380 and a solution return pipe 390.
As shown in fig. 5 and 6, the local electrolytic masking jig 100 includes: a first masking belt 10 and a second masking belt 20. Specifically, the second masking belt 20 is disposed on one side of the first masking belt 10 and is consistent with the conveying direction of the first masking belt 10, a channel extending along the conveying direction is formed between the second masking belt 20 and the first masking belt 10, a material 30 to be processed extending along the conveying direction of the channel penetrates through the channel, an orthographic projection of the material 30 on the first masking belt 10 is located in the first masking belt 10, an orthographic projection of the second masking belt 20 on the material 30 is located in the material 30, and a part of the material 30 is exposed out of the outer periphery of the second masking belt 20.
In other words, the local electrolytic masking jig 100 according to the embodiment of the present invention is mainly composed of the first masking belt 10 and the second masking belt 20, and the first masking belt 10 may be disposed on one side of the second masking belt 20 and spaced apart from and opposite to the same. Between the first masking belt 10 and the second masking belt 20 there is a channel in which, in use, an elongated strip-like material 30 to be processed can be placed. Because the conveying directions of the first masking belt 10 and the second masking belt 20 are consistent, under the action of the first masking belt 10 and the second masking belt 20, the material 30 clamped in the channel moves along the same conveying direction, the automation degree is high, uninterrupted processing production can be realized, the processing production efficiency is improved, and the cost is reduced.
In addition, the orthographic projection of the continuous terminal material 30 on the first masking belt 10 is positioned in the first masking belt 10, the orthographic projection of the second masking belt 20 on the material 30 is positioned in the material 30, a part of the material 30 is exposed out of the outer periphery of the second masking belt 20, that is, a masking surface is arranged on one side of the material 30 close to the first masking belt 10 in the horizontal direction, and a surface to be processed is arranged on one side of the material 30 close to the second masking belt 20 in the horizontal direction. The first masking belt 10 is required to completely mask the masking surface of the material 30, and the second masking belt 20 is required to partially mask the surface of the material 30 to be processed. For example, when the first masking belt 10 and the second masking belt 20 are conveyed in the horizontal direction, and the first masking belt 10, the second masking belt 20, and the continuous terminal material 30 are respectively extended in the vertical direction, the dimension of the first masking belt 10 in the width direction may be greater than or equal to the dimension of the masking face in the width direction.
It should be noted that the second masking belt 20 may have various dimensions in the width direction, but the relationship between the second masking belt 20 and the material 30 is required to satisfy the purpose of partially exposing the surface to be processed, so that the exposed surface to be processed can be partially processed. When the upper end of the second masking belt 20 is flush with the upper end of the surface to be processed, the width of the second masking belt 20 is smaller than the width of the surface to be processed. When the upper end of the second masking belt 20 is higher than the upper end of the surface to be processed, the lower end of the surface to be processed is exposed to the outer peripheral edge of the lower end of the second masking belt 20. When the lower end of the second masking belt 20 is flush with the lower end of the surface to be processed, the upper end of the surface to be processed is exposed out of the outer periphery of the upper end of the second masking belt 20. When the upper end or the lower end of the second masking belt 20 and the upper end or the lower end of the surface to be processed cannot be kept flat, the second masking belt 20 and the surface to be processed only need to have a partially overlapped surface, and the portion of the surface to be processed is not masked.
Therefore, according to the local electrolytic masking tool 100 of the embodiment of the invention, the first masking belt 10 fully masks the masking surface of the material 30, the second masking belt 20 partially masks the surface to be processed of the material 30, and a part of the material 30, which is exposed out of the outer periphery of the second masking belt 20, can be processed to achieve the purpose of local processing, so that the problem that the existing equipment cannot effectively process the local part of the material 30 is solved, and the local electrolytic masking tool 100 has the advantages of high degree of mechanization, simple structure, convenience in use, no pollution, low cost, high efficiency and the like.
According to one embodiment of the invention, the width of the first masking strip 10 is not less than the width of the continuous terminal material 30 and the width of the second masking strip 20 is less than the width of the material 30. That is, when the material 30 passes through the passage, the shielding surface of the material 30 is completely shielded by the first masking belt 10, and the surface to be processed of the material 30 is partially shielded by the second masking belt 20, so that the portion of the material 30 exposed to the outer peripheral edge of the second masking belt 20 can be partially processed.
In some embodiments of the present invention, two sides of the material 30 respectively abut against the first masking belt 10 and the second masking belt 20, so that the material 30 can be clamped, and not only can the tightness of the region of the material 30 that does not need to be processed be ensured, but also the material 30 can be prevented from shifting and falling off during the processing.
According to an embodiment of the present invention, the local electrolytic masking tool 100 further includes a tension control assembly connected to the first masking belt 10 and the second masking belt 20 respectively to control the first masking belt 10 and the second masking belt 20 to run synchronously while reducing the tension between the two belts and the material.
Optionally, the tension control assembly comprises: the transmission wheel, axis of rotation 53 and speed governing gear 40, the wheel that rotates links to each other with first masking belt 10 or second masking belt 20, and axis of rotation 53 links to each other with the transmission wheel, and speed governing gear 40 links to each other and adjusts the slew rate of transmission wheel through axis of rotation 53 with the transmission wheel, and then when regulation and control first masking belt 10 and second masking belt 20 carried out synchronous operation, reduces the tension between two belts and the material.
Preferably, the first masking belt 10 and the second masking belt 20 are endless masking belts, which have the advantages of easy processing, wide sources, low price, small occupied space, etc.
According to an embodiment of the present invention, the local electrolytic masking tool 100 further comprises a belt guide, which is slidably connected with the first masking belt 10 or the second masking belt 20 for defining a motion track of the corresponding first masking belt 10 or the second masking belt 20.
The assembling process and the assembling characteristics of the partial electrolytic masking jig 100 according to the embodiment of the present invention are described in detail below.
As shown in fig. 7 and 8, the speed reducer 60 and the motor 50 constitute a motor power component, and are mounted on the motor base 51. A hole is reserved in the middle of the motor base 51, and power is transmitted to the speed regulating gear 40 through the coupler 52, the motor rotating shaft 53 and the transmission flange 54.
The transmission flange 54 is installed on the flange seat 55, the speed regulating gear 40, the second gear 41 and the third gear 42 are meshed, the second gear 41 and the third gear 42 are respectively connected with the first transmission wheel 43 and the second transmission wheel 44, the first transmission wheel 43 is connected with the first masking belt 10, the second transmission wheel 44 is connected with the second masking belt 20, and the speed regulating gear 40 is connected with the transmission wheels through the rotating shaft 53 and adjusts the rotating speed of the transmission wheels to drive the transmission belts to run. The first driving pulley 43 and the three tension pulleys 45 constitute a movement circuit of the first masking belt 10.
The tension pulley 45 is matched with the bearing 46, fixed at one end of the tension pulley 45 by a screw 47, and fixed at the other end on the base plate 70 by a hexagon nut 48, and the second transmission wheel 44 and the three tension pulleys 45 form a movement loop of the second masking belt 20.
The lower surface of the base plate 70 is further provided with a belt guide rail 21, the belt guide rail 21 is slidably connected with the first masking belt 10 or the second masking belt 20 to define a motion track of the corresponding first masking belt 10 or the second masking belt 20, and the first masking belt 10 and the second masking belt 20 ensure that the material 30 is clamped and the masking effect is achieved through the belt guide rail 21 at a position contacting the material 30.
The following describes in detail the mating process and assembly features of the local electrolysis apparatus 500 according to an embodiment of the present invention.
As shown in fig. 3 and 4, the local electrolytic masking jig 100 of fig. 3 is set in the inner sub-tank 320, and the local electrolytic masking device 300 is assembled. On the contrary, the local electrolytic masking fixture 100 in fig. 4 can be simply disassembled from the inner sub-tank, and has the advantages of simple structure, easy assembly and disassembly, simple and convenient use, low equipment cost, high efficiency and the like.
As shown in fig. 1, the terminal partial electrolysis shielding apparatus 510 of the embodiment of the present invention includes: a local electrolytic masking device 300 and a pulsed reverse power supply 200. The specific matching and assembling steps are as follows:
the anode output end 250 of the pulse reverse power supply 200 is connected with the first electrolytic anode plate 340a and the second electrolytic anode plate 340b of the local electrolytic masking device 300 by special coaxial cables; the first electrolytic anode plate 340a and the second electrolytic anode plate 340b are located below the base 70 and are oppositely arranged, the first electrolytic anode plate 340a and the second electrolytic anode plate 340b are located at two sides of the material 30 and are not in contact with the material 30, and the cathode output end 260 of the pulse reverse power supply 200 is connected with the first cathode conductive wheel 330a and the first cathode conductive wheel 330b of the local masking electrolysis device 300 by using special coaxial cables. By the electrolysis process unit of the local masking electrolysis device 510, the continuous terminal material 30 can be subjected to local electrolysis masking production processing; according to the noble metal coating thickness specification of the continuous terminal material 30, the production and processing requirements can be met by selecting the terminal local electrolytic shielding device 510 with 3-9 units.
The material 30 may be an alloy composed of any one monomer selected from copper, nickel, cobalt, tungsten, molybdenum, chromium, and zinc, or any two or more selected from copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc; or iron and iron alloy thereof, and various stainless steel materials; all of the metal materials may be continuous strip material or continuous lead frame material. In addition, all the materials with metal foils attached to the surfaces can be subjected to the production and processing of local surface electrolysis by the manufacturing method and the manufacturing equipment; for example, various plastic film materials with metal films attached to one or both sides can be used to produce the desired localized electrolytic precious metal product.
The optional width range of the material 30 is 7 mm-80 mm, the preferred range is 8 mm-70 mm, and the more preferred range is 9 mm-55 mm; the material 30 may have a thickness within a range of 0.06mm to 0.30mm, preferably within a range of 0.07mm to 0.25mm, and more preferably within a range of 0.09mm to 0.20 mm.
The optional width range of the first masking belt 10 is 6 mm-100 mm; preferably in the range of 7mm to 90mm, more preferably in the range of 8mm to 80 mm; the thickness range of the masking belt can be selected from 0.6mm to 8 mm.
The optional width range of the second masking belt 20 is 6 mm-100 mm; preferably in the range of 6mm to 70mm, more preferably in the range of 6mm to 50 mm; the thickness range of the masking belt can be selected from 0.6mm to 8 mm.
The material 30 has a height selectable for the local surface electrolytic machining of the noble metal within a range of 0.5mm to 10mm, preferably within a range of 0.5mm to 7mm, and more preferably within a range of 0.5mm to 5 mm.
The method for setting the pulse forward and reverse current output by the pulse reverse power supply 200 specifically comprises the following steps:
(1) the pulse periodic forward current density of the electrolytic precious metal liquid medicine can be selected within 0.5A/dm2~10A/dm2The preferable range is 0.6A/dm2~7A/dm2The preferable range is 0.7A/dm2~5A/dm2(ii) a Optional range of pulse periodic reverse current density 5A/dm2~50A/dm2The preferred range is 7A/dm2~30A/dm2More preferably in the range of 9A/dm2~20A/dm2。
(2) The selectable range of the pulse periodic forward current output by the pulse periodic reverse power supply is 0.5A-20A, the preferred range is 0.5A-17A, and the preferred range is 0.5A-15A; the pulse periodic reverse current can be selected from a range of 5A to 100A, preferably from a range of 5A to 80A, and preferably from a range of 5A to 70A.
(3) The forward pulse time output by the pulse periodic reverse power supply can be selected within a range of 5 ms-50 ms, preferably within a range of 5 ms-40 ms, and more preferably within a range of 5 ms-30 ms; the reverse pulse time output by the pulse reverse power supply can be selected within a range of 1 ms-20 ms, preferably within a range of 1 ms-15 ms, and preferably within a range of 1 ms-10 ms.
(4) The setting of the output current by the pulsed periodic reverse power supply can be calculated according to the following formula: the output current A of the pulse periodic reverse power supply is equal to the current density A/dm of the electrolytic precious metal liquid medicine2X material surface area dm2;
The terminal local electrolysis shielding device 510 for regulating and controlling the local surface electrolysis continuous terminal product by the pulse periodic reverse electrolysis technology is composed of a pulse reverse power supply 200 and a local electrolysis shielding device 300.
The selectable number of the terminal local electrolysis shielding devices 510 is 3-9 units, preferably in the range of 3-7 units, and more preferably in the range of 3-5 units.
The output current of the selectable pulse periodic reverse power supply of each electrolysis process equipment unit is regulated and controlled to be different, the output pulse time of the selectable pulse periodic reverse power supply of each electrolysis process equipment unit is regulated and controlled to be different, the test scheme of the local surface electrolysis continuous terminal product is designed and the test result is optimized through various permutation and combination of the selected different set condition units, the optimal test method of the local surface electrolysis continuous terminal is optimized, and the local electrolysis equipment and the method of the continuous terminal product required by the production requirement of the continuous terminal product are obtained.
The amount of precious metal saved by the local electrolysis apparatus and method can be calculated according to the following formula:
noble metal saving quantity gram (G) ═ pulse periodic reverse wave (G) -asymmetric AC wave (G)
The method for electrolyzing the continuous terminal comprises the following steps:
s1: clamping the material 30 between the first masking belt 10 and the second masking belt 20, so that the material 30 moves forwards along the channel conveying direction, one surface of the material 30 is completely shielded by the first masking belt 10 and is not contacted with the electroplating solution, the other surface of the material 30 is partially shielded by the second masking belt 20, the exposed part of the other surface of the material 30 is contacted with the electroplating solution, and the metal film is electroplated on the exposed part of the other surface of the material 30;
s2: the current applied near the material 30 and output by the pulse reverse power supply 200 changes periodically;
when the forward pulse current is applied, a metal film is electrically analyzed on the material 30 to present a pulse forward waveform; when the reverse pulse current after the periodic variation is applied, the metal film on the material 30 is electrolytically peeled off, and a pulse reverse waveform is presented.
S3: the material 30 passes between the first masking belt 10 and the second masking belt 20 of the multi-terminal partial electrolytic masking apparatus, and finally a uniform metal film is obtained on the other side exposed portion of the material 30.
Thus, the terminal partial electrolysis shielding apparatus 510 according to the embodiment of the present invention has at least the following advantages:
(1) the power supply is provided, namely, the equipment can be operated, and the material can be continuously processed by locally masking the electrolytic noble metal while being conveyed.
(2) Can realize mechanical local processing, has no interference of human factors and has high electrolytic processing quality.
(3) The production process efficiency can be improved by increasing the number of the terminal partial electrolytic masking devices 510.
The terminal local electrolytic masking device 510 according to the embodiment of the invention comprises the local electrolytic masking jig 100 of any one of the above embodiments.
In the embodiment of the present invention, the partial electrolytic masking device 300 further includes an electrolytic inner sub-tank 320, the electrolytic inner sub-tank 320 defines therein a housing chamber filled with an electrolytic solution, the material 30 is located in the housing chamber and a portion of the material 30 exposed to the outer peripheral edge of the second masking belt 20 is in contact with the electrolytic solution. The mother tank 360 is filled with plating solution, the plating solution is transferred from the solution transfer pipe 380 to the inside and outside tanks 320 by the solution transfer pump, and the plating solution in the inside and outside tanks 320 can be returned to the mother tank 360 through the solution return pipe 390, so that the plating solution can be filled under the substrate 70 in the inside and outside tanks 320.
As shown in fig. 3, the inner sub-tank 320 is fixedly installed below the substrate 70 by 4 horizontal adjustment legs 81, the horizontal adjustment legs 81 are respectively installed at the bottom of the base plate 80, when the electrolysis is performed, a part of the material 30 exposed out of the outer periphery of the second masking belt 20 is in contact with the plating solution, that is, the masking surface of the material 30 is not in contact with the electrolytic solution, and the surface to be processed of the material 30 is in close contact with the electrolytic solution, so that the purpose of the partial surface electrolysis of the material 30 can be achieved, and it should be noted that, in the production process, the number of the terminal partial electrolysis masking devices 510 can be selected within the range of 3-9 units according to the required quality of the electrolysis product and the requirement of the noble metal film thickness.
Example 1 according to the invention:
(1) continuous terminal material (material 30): phosphor bronze material, terminal width 13mm, width 0.64mm, thickness 0.16 mm; nickel plating film thickness Min 2.0 μm on the continuous terminal material in advance, and terminal product film thickness measurement points: 1.7mm from the tip of the terminal and 0.32mm in the middle of the terminal width (fig. 13, 14).
(2) Specification of continuous terminal electrolytic product: one side and the side are partially required to be Rh/Ru with the lowest Min of 1.27 mu m; rhodium ruthenium can not be attached to the other side of the film; the thickness of the gold plating film is 0.03-0.05 μm, which is consistent with the Rh/Ru plating, and gold can not be attached to the other surface.
The specific manufacturing process of the continuous terminal product comprises the following steps:
a common roll-to-roll continuous terminal surface treatment production line is adopted, the continuous terminal material is introduced into an electrolytic degreasing tank through a discharging buffer machine to be cleaned to remove grease and the like on the surface of the metal material, and then the continuous terminal material enters an acid activation tank to be cleaned and activated to obtain a clean continuous terminal material (material 30).
Then, before the electrolytic treatment by the terminal partial electrolytic masking device 510, the pretreated continuous terminal material was subjected to a pre-Rh/Ru plating process to form a 0.1 μm Rh/Ru alloy on the nickel layer of the continuous terminal material.
Then, in the electrolysis method of the first continuous terminal, the left side and the right side of the continuous terminal material are provided with a first electrolysis anode plate 340a and a second electrolysis anode plate 340b, and the first electrolysis anode plate 340a and the second electrolysis anode plate 340b are connected with the anode output 250 of the pulse reverse power supply 200; the cathode conductive wheel I330 a at the inlet and the cathode conductive wheel II 330b at the outlet are connected with the cathode output of the pulse reverse power supply 260; a guiding jig 350a is arranged at the inlet and a guiding jig 350b is arranged at the outlet; on the other hand, as shown in fig. 4, the continuous terminal material enters the masking electrolysis jig, one side of the continuous terminal material is contacted with the first masking belt 10 and is completely shielded, and the other side of the continuous terminal material is contacted with the second masking belt 20 and is also shielded except for the exposed area needing electrolysis; in addition, a masking belt guide rail 21 is further disposed on the base plate 70, the masking belt guide rail 21 is slidably connected with the first masking belt 10 or the second masking belt 20 for defining a motion track of the corresponding first masking belt 10 or the second masking belt 20, and the first masking belt 10 and the second masking belt 20 ensure clamping of the material 30 and achieve a masking effect through the masking belt guide rail 21 at a position contacting the material 30.
Similarly, the electrolytic method of the second continuous terminal to the electrolytic method of the seventh continuous terminal are connected in the same manner as the electrolytic method of the first continuous terminal. The details are shown in fig. 1 and 2.
The plating layer specification Min of the continuous terminal material is 1.27 μm, so the continuous terminal material belongs to a product with high film thickness. The pre-rhodium ruthenium plating section plates 0.1 μm, so subsequently it is necessary to plate Rh/Ru with Min 1.17 μm. Preferably 7 units of the masking electrolysis equipment are used for local masking electrolysis treatment; setting the total limit of the local plating Rh/Ru manufactured by seven pulse reverse power supplies to be 21 equal parts, wherein each equal part is 0.051-0.057 mu m; for example, in the experimental condition No.1, 15 parts of pulse reverse power source are used, the Rh/Ru film thickness range required to be achieved after treatment is 0.835-0.907 μm, and 1 part of each of the 2 nd to 6 th pulse reverse power sources are used, and after treatment by each pulse reverse power source, the Rh/Ru film thickness range on the surface of the material is 0.055-0.060 μm (see Table 1 for details).
Table 17 units of the allocation limit of the pulse reverse power supply for the film thickness of the plating surface: mum of
The running speed of the continuous terminal masking electrolysis equipment manufacturing production line is preferably 3.5 m/min; when the condition No.7 in the table 1 is adopted by 7 pulse reverse power supplies, the film thickness range of Rh/Ru subjected to 7 times of electrolysis is 0.167-0.181 micrometers, namely the conditions of forward and reverse pulse current and forward and reverse pulse time set by the 7 pulse reverse power supplies are the same, the film thickness and density difference from the lowest layer to the surface layer are small, and the surface characteristics of the continuous terminal material are uniform and consistent.
When the condition No.1 is adopted, the pulse reverse power supply needs to set larger forward pulse current and longer forward pulse time, the set value of the reverse pulse current needs to be small, and the set value of the reverse pulse time needs to be shorter; the obtained electrolytic Rh/Ru has high roughness and poor density; setting conditions of the six pulse reverse power supplies are smaller forward pulse current and longer forward pulse time compared with the condition No.7, and setting values of the reverse pulse current are slightly larger than the condition No.7, and the reverse pulse time is much shorter than the condition No. 7; therefore, the obtained film thickness reaches the product specification, and the surface compactness is better compared with the condition No. 7.
When the conditions No.2 to No.6 are adopted, the surface film thickness of the continuous terminal material meets the requirement, and the compactness range is between the conditions No.1 and No. 7.
When the condition No.13 is adopted, the six pulse reverse power supplies need to set smaller forward pulse current and longer forward pulse time, and set larger reverse pulse current and shorter reverse pulse time; the obtained Rh/Ru coating has thin film thickness and good density. The last pulse reverse power supply is set with a large forward pulse current and a long forward pulse time, and with a large reverse pulse current and a short reverse pulse time, the resulting surface film thickness reaches the product specification and is slightly less dense than the surface of condition No. 7.
When the conditions No.8 to No.12 are adopted, the film thickness of the continuous terminal material is required, and the compactness is between the conditions No.7 and No. 13.
After the obtained Rh/Ru continuous terminal material is fully washed, a local masking electrolysis device 600 is used for electrolysis to obtain a final product of Au 0.10 mu m meeting the product specification requirement.
The most preferable condition in this example is No.5 by the above comparative experiment.
According to another comparative example of the invention:
the test conditions were the same as in example 1 except that seven types of asymmetric ac rectifiers were used instead of the pulse reverse power source. The Rh/Ru film thickness at the product measuring point is not less than 1.27 mu m and meets the product specification.
As shown in FIGS. 9 and 10, the noble metal film thickness distributions obtained when electrolysis was carried out with a pulse periodic reverse wave and a generally used asymmetric alternating current wave were completely different. Electrolyzing and precipitating metal on the surface of the continuous terminal material by using a pulse reverse power supply through the applied forward pulse wave, automatically switching to reverse pulse wave to electrolyze and strip the metal on the surface of the continuous terminal material after the set forward pulse time is over, wherein the reverse pulse wave current is preferably used for stripping a region with higher current density on the surface of the terminal, such as the front end part or the corner part of the terminal; similarly, after the reverse pulse time is over, the current wave is automatically switched to the forward pulse current wave, and the result of the cyclic and reciprocating periodic electrolysis achieves the result that the metal film thickness is uniformly distributed (figure 9). On the other hand, in the conventional asymmetric ac power supply, only the electrolytic deposition is performed on the surface of the continuous terminal in the electrolytic process, and the film thickness at the tip or corner of the terminal is increased more than that in the flat region as the electrolytic deposition accumulates when the measurement point of the flat portion meets the specification (fig. 10).
As can be seen from fig. 9 and 10, the amount of noble metal electrolytically deposited by the asymmetric ac power supply is much larger than that by the pulse periodic reverse wave power supply, based on the specification of the measurement point of the flat portion. The saved precious metal usage can be solved from:
saving precious metal (%) (asymmetric alternating current wave-pulse periodic reverse wave)/asymmetric alternating current wave.
Example 2 according to the invention:
(1) continuous terminal material: phosphor bronze material, terminal width 15mm, width 0.64mm, thickness 0.16 mm; nickel plating film thickness Min 2.0 μm on the continuous terminal material in advance, and terminal product film thickness measurement points: 2mm from the tip of the terminal and 0.32mm in the middle of the terminal width (fig. 15 and 16).
Table 2: 9 units of allocation credit for the film thickness of the plating surface manufactured by the pulse reverse power supply: mum of
(2) Specification of continuous terminal electrolytic product: the lowest Min 1.52 mu m palladium nickel is required for the single side and the side part; the other side can not be attached with palladium nickel; the thickness of the gold plating film is 0.03 to 0.05 μm, which is consistent with the Pd/Ni plating, and gold cannot be attached to the other surface.
The specific manufacturing process of the continuous terminal product comprises the following steps:
the continuous terminal material is introduced into an electrolytic degreasing tank through a discharging buffer machine to be cleaned to remove grease and the like on the surface of the metal material, and then enters an acid activation tank to be cleaned and activated to obtain the clean continuous terminal material.
Then, before the electrolytic treatment by the masking electrolytic device, the pretreated continuous terminal material is subjected to a Pd/Ni pre-plating process to form a 0.1 μm Pd/Ni alloy on the nickel layer of the continuous terminal material.
Then, in the electrolysis method of the first continuous terminal, the left side and the right side of the continuous terminal material are provided with a first electrolysis anode plate 340a and a second electrolysis anode plate 340b, and the first electrolysis anode plate 340a and the second electrolysis anode plate 340b are connected with the anode output 250 of the pulse reverse power supply 200; the cathode conductive I330 a at the inlet and the cathode conductive II 330b at the outlet are connected with the cathode output of the pulse reverse power supply 260; a guiding jig 350a is arranged at the inlet and a guiding jig 350b is arranged at the outlet; on the other hand, as shown in fig. 4, the continuous terminal material enters the electrolytic masking jig, one side of which is in contact with the first masking belt 10 and is completely masked, and the other side of which is in contact with the second masking belt 20 and is also masked except for the exposed area needing electrolysis; in addition, a masking belt guide rail 21 is further disposed on the base plate 70, the masking belt guide rail 21 is slidably connected with the first masking belt 10 or the second masking belt 20 for defining a motion track of the corresponding first masking belt 10 or the second masking belt 20, and the first masking belt 10 and the second masking belt 20 ensure clamping of the material 30 and achieve a masking effect through the masking belt guide rail 21 at a position contacting the material 30.
Similarly, the electrolytic method of the second continuous terminal to the electrolytic method of the seventh continuous terminal are connected in the same manner as the electrolytic method of the first continuous terminal. The details are shown in fig. 1 and 2.
The electrolytic film thickness of the continuous terminal is Min 1.52 μm, which is a high-film-thickness product. The electrolytic film thickness of the palladium-nickel pre-plating section is 0.1 μm, so that Pd/Ni with Min of 1.42 μm needs to be electrolyzed subsequently. Preferably 9 units of local electrolysis equipment to perform local masking electrolysis treatment; setting the total amount of the local plating Pd/Ni manufactured by the nine pulse reverse power supplies 510 to 590 as 27 equal parts, wherein each equal part is 0.052-0.056 μm; for example, under the experimental conditions No.1, 17 parts of pulse reverse power source, 0.894-0.957 μm of Pd/Ni film thickness required to be achieved after treatment, and 1 part of each of 8 pulse reverse power sources, the Pd/Ni film thickness on the surface of the material after treatment with each pulse reverse power source should be 0.052-0.056 μm (see Table 2 for details).
The running speed of the continuous terminal electrolysis manufacturing production line is preferably 3.0 m/min; when the condition No.8 in Table 1 is adopted by the 9 pulse reverse power supplies, the Pd/Ni film thickness ranges from 0.157 to 0.168 mu m in 9 times of electrolysis, namely the forward and reverse pulse current and the forward and reverse pulse time conditions set by the 9 pulse reverse power supplies are the same, the film thickness and density difference from the lowest layer to the surface layer are small, and the surface characteristics of the continuous terminal material are uniform and consistent.
When the condition No.1 is adopted, the 17 equal parts of the second pulse reverse power supply need to set larger forward pulse current and longer forward pulse time, the set value of the reverse pulse current needs to be small, and the set value of the reverse pulse time needs to be shorter; the obtained electrolytic Pd/Ni film is thick and has slightly poor density; setting relatively small forward pulse current and long forward pulse time in 3 equal parts of a pulse reverse power supply, and setting the reverse pulse current to be small; the setting conditions of 1 equal part of each of the seven subsequent pulse reverse power supplies are smaller forward pulse current and longer forward pulse time compared with the condition No.8, the setting value of the reverse pulse current is slightly larger than the condition No.8, and the reverse pulse time is much shorter than the condition No. 8; therefore, the obtained film thickness reaches the product specification, and the surface compactness is better than that of the condition No. 8.
When the conditions from No.2 to No.7 are adopted, the surface film thickness of the lead frame material meets the requirement, and the compactness range is between the conditions from No.1 to No. 8.
When the condition No.15 is adopted, the seven pulse reverse power supplies need to set smaller forward pulse current and longer forward pulse time, and set larger reverse pulse current and shorter reverse pulse time; the obtained Pd/Ni plating layer has thinner film thickness and good density; the subsequent pulse reverse power supply adopts the same condition as No.8 to obtain a surface with better relative density; the last pulse reverse power supply is set with a larger forward pulse current and a longer forward pulse time, and a larger reverse pulse current and a shorter reverse pulse time, so that the obtained surface film thickness reaches the product specification and is slightly poorer in surface compactness compared with the condition No. 8.
When the conditions No.8 to No.14 are adopted, the film thickness of the continuous terminal material reaches the requirement, and the compactness is between the conditions No.9 and No. 15.
After the obtained Pd/Ni continuous terminal material is fully washed, the obtained Pd/Ni continuous terminal material is electrolyzed by using a local electrolysis masking device 600 to obtain a final product of Au 0.10 mu m meeting the specification requirement of the product.
The most preferable condition in this example is No.6 by the above comparative experiment.
Example 3 according to the invention:
(1) continuous terminal material: phosphor bronze material, terminal width 13mm, width 0.64mm, thickness 0.16 mm; nickel plating film thickness Min 2.0 μm on the continuous terminal material in advance, and terminal product film thickness measurement points: 1.7mm from the tip of the terminal and 0.32mm in the middle of the terminal width (fig. 13 and 14).
(2) Specification of continuous terminal electrolytic product: the lowest Min 0.38 mu m palladium nickel is required for the single side and the side part; the other side can not be attached with palladium nickel; the thickness of the gold plating film is not less than 0.76 μm, which is consistent with Pd/Ni plating, and gold cannot be attached to the other surface.
The specific manufacturing process of the continuous terminal product comprises the following steps:
the continuous terminal material is introduced into an electrolytic degreasing tank through a discharging buffer machine to be cleaned to remove grease and the like on the surface of the metal material, and then enters an acid activation tank to be cleaned and activated to obtain the clean continuous terminal material.
Then, as shown in FIG. 15, before the electrolytic treatment using the masking electrolytic device 510, the pretreated continuous terminal material is subjected to a Pd/Ni pre-plating process 500 to form a 0.1 μm Pd/Ni alloy on the nickel layer of the continuous terminal material.
Subsequently, in the first masked electrolytic device 510, anode plates 340a and 340b provided on the left and right sides of the continuous terminal material are connected to the anode output 250 of the pulse reverse power supply 200; the cathode conductor 330a at the inlet and the cathode conductor 330b at the outlet are connected to the cathode output of the pulsed reverse power supply 260; a guiding jig 350a is arranged at the inlet and a guiding jig 350b is arranged at the outlet; on the other hand, as shown in fig. 4, the continuous terminal material enters the masking electrolysis jig, one side of the continuous terminal material is contacted with the first masking belt 10 and is completely shielded, and the other side of the continuous terminal material is contacted with the second masking belt 20 and is also shielded except for the exposed area needing electrolysis; in addition, a masking belt guide rail 21 is further disposed on the base plate 70, the masking belt guide rail 21 is slidably connected with the first masking belt 10 or the second masking belt 20 to define a motion track of the corresponding first masking belt 10 or the second masking belt 20, and the first masking belt 10 and the second masking belt 20 ensure clamping of the material 30 and achieve a masking effect through the masking belt guide rail 21 at a position contacting the material 30.
Likewise, the masked electrolytic device 520 is connected to the masked electrolytic device 600 in the same manner as the first partially masked electrolytic device 510. Details are shown in fig. 2 and 17.
Specification Min 0.38 μm of continuous terminal material. The running speed of the continuous terminal material masking electrolysis equipment manufacturing production line is preferably 3.0 m/min; the palladium-nickel pre-plating is plated with 0.08 μm, and then Pd/Ni with Min 0.30 μm needs to be plated. Preferably 3 units of the masking electrolysis equipment are used for local masking electrolysis treatment; setting the total amount of Pd/Ni plated locally in three pulse reverse power sources 510-530 to be 3 equal parts, each equal part is plated with 0.10 μm on average; the optimum conditions for the pulse reverse power supply were as in example 2.
After the palladium-nickel continuous terminal material is fully washed by pure water, common asymmetric alternating current is set to be pre-plated with gold of 0.08 mu m by using a masking electrolysis device 540, Au of Min 0.68 mu m needs to be plated subsequently, and 6 pulse reverse power supplies are adopted to form the masking electrolysis devices 550-600; the final product of 0.76 μm Au meeting the specification requirement of the product was obtained by performing electrolysis under the optimum conditions of the pulse reverse power supply in example 1.
An example of a corrosion resistance test of a continuous end product according to the present invention:
the corrosion resistance test sample used the same terminal material as shown in fig. 13.
Sample 1: ni, 2.0 μm, Rh/Ru, 1.27 μm, Au, 0.03-0.05 μm; prepared as in No.5 of example 1.
Sample 2: ni, 2.0 μm, Pd/Ni, 1.52 μm, Au, 0.03-0.05 μm; prepared as in No.6 of example 2.
Sample 3: 2.0 μm of Ni, 0.38 μm of Pd/Ni and 0.76 μm of Au; prepared according to the best conditions of example 3.
Nitric acid exposure test: performing a nitric acid exposure experiment on the product with the gold-plated connector surface according to a non-reference method and evaluating the corrosion resistance of the product; the test time was 2 hours.
The results of the experiments are shown in fig. 17 to 20, and the corrosion resistance was judged from the results of the degree of corrosion of the sample.
[ Corrosion resistance test of continuous terminal product ]
The corrosion resistance test sample used the same terminal material as shown in fig. 13.
Sample 1: ni, 2.0 μm, Rh/Ru, 1.27 μm, Au, 0.03-0.05 μm; prepared as in No.5 of example 1.
Sample 2: ni, 2.0 μm, Pd/Ni, 1.52 μm, Au, 0.03-0.05 μm; prepared as in No.6 of example 2.
Sample 3: 2.0 μm of Ni, 0.38 μm of Pd/Ni and 0.76 μm of Au; prepared according to the best conditions of example 3.
Nitric acid exposure test: according to a nitric acid exposure experimental method of a product with the gold-plated connector surface, the corrosion resistance of the product is evaluated according to a non-reference method; the test time was 2 hours.
As shown in fig. 17 to 19, sample 1 is hardly corroded and has excellent corrosion resistance; Rh/Ru alloys play a very important role. Both sample 2 and sample 3 have different degrees of corrosion, and the corrosion resistance of the Pd/Ni alloy is greatly different from that of the Rh/Ru alloy.
As shown in fig. 20, the percentage of the corroded area after the test is counted by a small grid test method, and the corrosion rate of the sample 1 is only 0.03%; the corrosion rate of sample 2 having the same gold film thickness as that of sample 1 was 11.13%; the corrosion rate of the thick gold sample 3 is 2.03 percent, compared with the corrosion rate of the thin gold sample 1, the corrosion resistance of the thick gold is far inferior to that of the thin gold sample, and the basis of the corrosion rate is that the Rh/Ru alloy coating electrolytically precipitated by adopting the pulse periodic reverse electrolysis technology has very excellent corrosion resistance.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. An electrolytic method for a continuous terminal, characterized in that: including a plurality of preceding backward terminal local electrolysis shielding apparatus that set up side by side interval, terminal local electrolysis shielding apparatus for carry out surface treatment to material (30), terminal local electrolysis shielding apparatus includes local electrolysis masking tool (100), local electrolysis masking tool (100) include: a first masking belt (10) and a second masking belt (20), the second masking belt (20) being disposed on one side of the first masking belt (10) and corresponding to a transport direction of the first masking belt (10), a passage extending in the transport direction being formed between the second masking belt (20) and the first masking belt (10), the material (30) passing through the passage, a length direction of the material (30) corresponding to the transport direction of the belt, the material (30) being clamped between the first masking belt (10) and the second masking belt (20), an orthographic projection of the material (30) on the first masking belt (10) being located within the first masking belt (10), an orthographic projection of the second masking belt (20) on the material (30) being located within the material (30) such that a portion of the material (30) is exposed to an outer peripheral edge of the second masking belt (20), the material (30) being locally electrolytically shielded from each terminal by the first masking belt (10) and the second masking belt (20), the material (30) (20) The air flow passes through the air inlet pipe and the air outlet pipe,
each terminal local electrolysis shielding device further comprises an electrolysis device (500), the local electrolysis shielding jig (100) is arranged in the electrolysis device (500), a material (30) penetrates through the front end and the rear end of the electrolysis device (500), an accommodating cavity filled with electroplating solution is defined in the electrolysis device (500), the material (30) is positioned in the accommodating cavity, one part of the material (30) extending out of the outer periphery of the second shielding belt (20) is in contact with the electroplating solution, the electrolysis device (500) is connected with a pulse reverse power supply (200),
the method for electrolyzing the continuous terminal comprises the following steps:
s1: clamping the material (30) between the first masking belt (10) and the second masking belt (20) to enable the material (30) to move forwards along the channel conveying direction, completely shielding one surface of the material (30) by the first masking belt (10) and not contacting with electroplating solution, partially shielding the other surface of the material (30) by the second masking belt (20), contacting the exposed part of the other surface of the material (30) with the electroplating solution, and electroplating a metal film on the exposed part of the other surface of the material (30);
s2: the current which is output by the pulse reverse power supply (200) and is applied to the vicinity of the material (30) is periodically changed;
when a forward pulse current is applied, a metal film is analyzed on the material (30) to present a pulse forward waveform; when the reverse pulse current after the periodic variation is applied to the metal film on the material (30), the metal film is electrolytically stripped, and then the pulse reverse waveform is presented;
s3: the material (30) passes between a first masking belt (10) and a second masking belt (20) of the multi-terminal partial electrolytic masking device, and finally a uniform metal film is obtained on the other exposed part of the material (30).
2. The electrolytic method of continuous termination according to claim 1, wherein: in the step S2, the time range of the forward pulse output by the pulse periodic reverse power supply is 5ms to 50ms, and the time range of the reverse pulse output by the pulse reverse power supply is 1ms to 20 ms.
3. The electrolytic method of continuous termination according to claim 1, wherein: the width of the first masking belt (10) is not less than the width of the material (30), and the width of the second masking belt (20) is less than the width of the material (30).
4. The electrolytic method of continuous termination according to claim 1, wherein: a first tension control assembly is arranged in the first masking belt (10), the first tension control assembly comprises a tension wheel (45) and a first driving wheel (43), the tension wheel (45) and the first driving wheel (43) form a motion loop of the first masking belt (10),
and a second tension control assembly is arranged in the second masking belt (20), the second tension control assembly comprises a tension wheel (45) and a second transmission wheel (44), and the tension wheel (45) and the second transmission wheel (44) form a movement loop of the second masking belt (20).
5. The electrolytic method of continuous termination according to claim 4, wherein: the first transmission wheel (43) is connected with a second gear (41), the second transmission wheel (44) is connected with a third gear (42), the second gear (41) is meshed with the third gear (42), the second gear (41) is further meshed with a speed regulating gear (40), and the speed regulating gear (40) is in transmission connection with a rotating shaft (53) of the motor (50).
6. The electrolytic method of continuous termination according to claim 5, wherein: the device also comprises a belt guide rail (21), wherein the belt guide rail (21) is in sliding connection with the first masking belt (10) or the second masking belt (20) and used for limiting the motion track of the corresponding first masking belt (10) or the second masking belt (20).
7. The electrolytic method of continuous termination according to claim 6, wherein: still be provided with the electrolysis anode plate in electrolytic device (500), the electrolysis anode plate orientation material (30) stretch out the partly of the outer peripheral edges of second masking belt (20), the electrolysis anode plate is connected with positive pole output connector (250) of pulse reverse power supply (200), is connected with the electrically conductive wheel of negative pole on the part that material (30) extension degree direction wore out first masking belt (10) and second masking belt (20), and the electrically conductive wheel of negative pole is connected with negative pole output connector (260) of pulse reverse power supply (200).
8. The electrolytic method of continuous termination according to claim 7, wherein: the local electrolysis masking jig (100) further comprises a substrate (70), the electrolysis device (500) comprises an inner sub-groove (320) with an opening, the substrate (70) is fixedly erected in the inner sub-groove (320) through a support (80), and the first masking belt (10) and the second masking belt (20) are located below the substrate (70).
9. The electrolytic method of continuous termination according to claim 8, wherein: the electrolytic device (500) further comprises a mother tank (360) for containing electroplating solution, the mother tank (360) and the inner and outer tanks (320) are communicated with each other through a solution conveying pipeline (380), a solution conveying pump (370) is arranged on the solution conveying pipeline (380), and a solution return pipeline (390) is further communicated between the mother tank (360) and the inner and outer tanks (320).
10. The electrolytic method of continuous termination according to claim 8, wherein: through holes are formed in two ends of the inner sub groove (320), the material (30) penetrates through the through holes, paired limiting guide jigs are arranged at the positions, close to the through holes, of the outer portion of the inner sub groove (320), and the material (30) is clamped between each pair of limiting guide jigs.
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