CN114910114B - In-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process - Google Patents
In-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process Download PDFInfo
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- CN114910114B CN114910114B CN202110169482.3A CN202110169482A CN114910114B CN 114910114 B CN114910114 B CN 114910114B CN 202110169482 A CN202110169482 A CN 202110169482A CN 114910114 B CN114910114 B CN 114910114B
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D21/00—Measuring or testing not otherwise provided for
- G01D21/02—Measuring two or more variables by means not covered by a single other subclass
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
- G05D27/00—Simultaneous control of variables covered by two or more of main groups G05D1/00 - G05D25/00
- G05D27/02—Simultaneous control of variables covered by two or more of main groups G05D1/00 - G05D25/00 characterised by the use of electric means
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Abstract
The application provides an online in-situ monitoring device for internal stress of a plating layer and pH of plating solution in an electroforming process, which comprises a measuring electroforming tank with a bottom plate, a cathode chamber, an anode chamber and a connecting channel, a real-time stress observation platform capable of capturing dynamic change of a cathode test piece, a pH measuring device capable of realizing real-time pH monitoring and a circulating liquid flow passage for communicating the measuring electroforming tank with an industrial production electroforming tank; the real-time stress observation platform is arranged at the side surface opposite to the cathode chamber, and the pH measuring device is communicated with the anode chamber through a pH real-time monitoring passage. According to the application, through improvement of the plating layer stress electroforming tank, the influence of edge effect can be eliminated to the greatest extent, and on-line in-situ monitoring of plating layer stress and plating solution pH can be realized by matching with the in-situ stress test platform and the liquid flow pipeline channel.
Description
Technical Field
The application belongs to the field of electroforming chemistry, and particularly relates to an online in-situ monitoring device for internal stress of a plating layer and pH of a plating solution in an industrial electroforming process.
Background
With the rapid development of the deep space exploration technology, pulsar navigation and astronomical observation technologies, the demand of people for high-efficiency and high-performance X-ray telescopes is increasing. At present, the lens of the X-ray telescope mainly adopts a Wolter-I type electroformed lens, and the main preparation process comprises the steps of aluminum mandrel processing, mandrel surface Ni-P alloy chemical plating, mandrel surface ultra-fine cutting and polishing, surface gold film sputtering, electroforming zero-stress nickel or nickel-cobalt alloy lens, lens and mandrel separation and the like. One of the difficulties is the high precision, low stress electroforming nickel cobalt lens technology.
After plating a layer of gold film on the surface of the ultra-smooth mandrel by magnetron sputtering, the ultra-smooth mandrel is required to be immersed into nickel or nickel cobalt electroplating solution for electroforming, and the electroformed lens is required to meet the requirements of low stress, high precision and high strength. If the stress of the electroformed layer (lens) is too large in the electroforming process, on one hand, the lens can be deformed, and the surface type precision can not meet the design requirement; on the other hand, too much stress on the lens can affect its mechanical properties. It is therefore important to control the stress of the electroformed layer (lens) during electroforming.
In conventional industrial electroforming stress control, a part of the electroforming solution is usually taken out of an industrial electroforming tank before electroforming, and stress test is performed, and the measured stress is not in-line stress. On one hand, the accuracy of stress control in the mode is poor, the industrial electroforming time is often more than 24 hours, and the stress test time is generally 1 hour, so that the stress test can only represent the stress condition of the industrial electroforming in the early stage, and the stress change of the industrial electroforming in the later stage can only be predicted empirically; on the other hand, because the electroforming liquid is analyzed after each electroforming is finished, the electroforming of the next mandrel can be performed after the waiting stress test result comes out; secondly, the flexibility of stress test is poor, and the method can not monitor the stress in the electroforming process in real time and correct the electroforming parameters in the electroforming process properly.
Meanwhile, the current common online stress test method is mainly a cathode bending method, in-situ observation is carried out on a cathode test piece through an auxiliary means, and stress calculation is carried out on observed data by applying a Stoney formula. However, in many methods, the effect of edge effects on cathode stress testing is not considered. In fact, during electroforming, the electric lines of force at the edges of the cathode test piece are denser, the current density is greater, and the measurement of the cathode stress is more affected, which is greater when the coating thickness is thicker, due to the influence of the edge effect.
In addition, the pH of the electroforming solution is constantly changing during the electroforming process. Generally, the buffer is contained in the electroforming solution, but the surface area of the cathode mandrel is large, and the hydrogen evolution reaction of the cathode consumes more hydrogen ions, so that the pH of the electroforming solution is raised. And during each electroforming, the surface area of the cathode mandrel is different, the adopted current density is different, and the speed of pH rise is also different. In order to maintain the pH of the electroforming solution unchanged, the pH of the electroforming solution needs to be monitored in real time during the electroforming process. However, the electric field in the electroforming solution affects the zero potential of the pH electrode, so that the measured value of the pH electrode fluctuates and deviates greatly, and therefore the pH electrode cannot be directly inserted into the electroforming solution for measurement, and the electroforming solution needs to be taken out and then the measurement is performed.
Disclosure of Invention
In view of the above, the application aims to provide an online in-situ monitoring device for the internal stress of a plating layer and the pH value of a plating solution in an electroforming process, which can eliminate the influence of an edge effect to the greatest extent and can realize online in-situ monitoring of the stress of the plating layer and the pH value of the plating solution by matching with an in-situ stress test platform and a liquid flow pipeline passage through improvement of a plating layer stress electroforming tank.
In order to achieve the above purpose, the technical scheme of the application is realized as follows:
an online in-situ monitoring device for internal stress of a plating layer and pH of plating solution in an electroforming process comprises a measuring electroforming tank with a bottom plate, a cathode chamber, an anode chamber and a connecting channel, a real-time stress observation platform capable of capturing dynamic changes of a cathode test piece, a pH measuring device capable of realizing real-time pH monitoring and a circulating liquid flow passage for communicating the measuring electroforming tank with an industrial production electroforming tank; the real-time stress observation platform is arranged at the side surface opposite to the cathode chamber, and the pH measuring device is communicated with the anode chamber through a pH real-time monitoring passage.
Further, the main body of the measuring electroforming tank is in a convex shape, wherein the small end of the convex shape is a cathode chamber, the large end of the convex shape is an anode chamber, the side surface of the cathode chamber is also connected with a fixed plate, and the real-time stress observation platform is arranged on the fixed plate; a concave socket is formed in the upper end face of the cathode chamber, a cathode clamp is matched at the concave socket, the cathode clamp comprises a short-side T-shaped plate and a long-side T-shaped plate with square through holes, and a cathode test piece is inserted into the concave socket and fixed with the two T-shaped plates in a sandwich manner; the side of the cathode chamber is provided with scales, and two ends of each scale are respectively provided with a long vertical line mark.
Further, a square groove and a step are formed in the connection part of the cathode chamber and the anode chamber on the bottom plate, the square groove is a fixed groove of the connecting channel, the step and the connecting channel form a bottom fixed groove of a long-side T-shaped plate, and a square ring fixing frame is further arranged on the inner side wall, far away from the cathode chamber, of the anode chamber and used for fixing the anode plate; the connecting channel is a square channel, and the square through hole of the square channel has the same shape as the cathode test piece; the cathode test piece substrate is a silicon wafer, and one side of the silicon wafer is deposited with a layer of gold film in a magnetron sputtering mode.
Further, the upper part of the long-side T-shaped plate is in a T shape, the shape and the size of the long-side T-shaped plate are consistent with those of the short-side T-shaped plate, the lower part of the long-side T-shaped plate is in a U shape, and the thickness of the lower part of the long-side T-shaped plate extends outwards to twice the thickness of the upper part; one side of the short-side T-shaped plate is stuck with a titanium plate, one side of the titanium plate extends out of the T-shaped plate, the cathode test piece is arranged on the long-side T-shaped plate, the square deposition area of the cathode test piece and the square through hole of the long-side T-shaped plate are in a superposition state, and the side edge of the cathode test piece is not contacted with the side wall of the square through hole of the long-side T-shaped plate.
Further, the real-time stress observation platform comprises a round light source, a lens, a CCD camera, an L-shaped connecting plate and a computer, wherein a round observation port is formed in the short side of the L-shaped connecting plate, an arc-shaped hole and a plurality of through holes are formed in the long side of the L-shaped connecting plate, the L-shaped connecting plate is adjusted and fixed on a fixed plate on the side face of the cathode chamber through the arc-shaped hole and the through holes, the lens is connected with the CCD camera and is arranged on the long side of the L-shaped plate, and the lens points to the round observation port; the circular light source is arranged on the outer side of the short side of the L-shaped connecting plate and is coaxially arranged with the circular observation port, and image data of the cathode test piece observed by the CCD camera is transmitted to the computer through a data line.
Further, the stress observation platform is positioned and calibrated through a long vertical line on the side surface of the cathode chamber; the image data observed by the stress observation platform is the displacement value of each point on the side edge of the lower half part of the cathode test piece; and the displacement value is subjected to software fitting to obtain a curvature value.
Further, the pH measuring device comprises an overflow joint, a pH electrode, a liquid storage overflow device and a first circulating pump, wherein the lower end of the liquid storage overflow device is a liquid inlet end, the middle end of the liquid storage overflow device is an overflow end, the upper end of the liquid storage overflow device is a pH measuring port, the pH electrode is inserted into the pH measuring port, the overflow end is provided with the overflow joint, the lower end of the liquid storage overflow device is communicated with the first circulating pump, and the first circulating pump is communicated with the anode chamber through a pH real-time monitoring passage.
Furthermore, three bottom through holes and three square grooves are formed in one side of the bottom plate of the electroplating bath, each bottom through hole corresponds to one square groove, the bottom through holes are communicated with the corresponding square groove, two upper through holes are formed in the side wall of the anode chamber, and the through holes are in sealing connection through silica gel plugs with different apertures;
the upper port of the anode chamber, which is close to the cathode, is connected with the bottom port of the bottom plate, which is close to the anode, and is connected with the industrial electroforming tank; the upper port of the anode chamber, which is close to the anode, is connected with the bottom opening of the bottom plate, which is close to the cathode, and the pH real-time monitoring passage; and a heating rod is inserted into the bottom opening in the middle of the bottom plate and is connected with the temperature controller.
Further, the pH real-time monitoring passage comprises a valve and a plurality of silica gel pipes, wherein a first screw thread pagoda joint of the valve is connected with a second screw thread pagoda joint of the pH measuring device through the silica gel pipes, and an overflow joint of the pH measuring device is connected with an upper through port, close to an anode, of the side wall of the anode chamber through a liquid inlet joint and the silica gel pipes, so that the pH real-time monitoring passage is formed.
Further, the circulation liquid flow path comprises a second valve, a second circulation pump and a plurality of silica gel pipes, a third screw thread pagoda joint of the second valve is connected with a fourth screw thread pagoda joint through the silica gel pipes, the fourth screw thread pagoda joint is connected with the water outlet end of the second circulation pump, the water inlet end of the second circulation pump is connected with a fifth screw thread pagoda joint, the fifth screw thread pagoda joint is connected with the industrial electroforming tank through the silica gel pipes, meanwhile, the industrial electroforming tank is connected with an overflow joint through the silica gel pipes, and the overflow joint is communicated with an upper port of the side wall of the anode chamber, which is close to the cathode, so that a circulation path for measuring electroforming liquid in the electroforming tank and the industrial electroforming tank is formed.
Compared with the prior art, the online in-situ monitoring device for the internal stress of the plating layer and the pH value of the plating solution in the electroforming process has the following advantages:
the device is used as a device for testing the in-situ stress and the pH in real time, can be matched with an automatic control system, automatically adjusts the current and the pH in the electroforming process through a controller and software according to the measured stress and pH, adjusts the technological parameters at any time, and stably controls the quality of products.
When the real-time in-situ stress and pH online measuring device is used, the second circulating pump pumps the electroforming liquid in the industrial electroforming tank into the measuring electroforming tank, and after the electroforming liquid in the measuring electroforming tank is full, the electroforming liquid flows into the industrial electroforming tank again from the overflow port, and the temperature control system in the measuring electroforming tank is used for auxiliary heating, so that the temperature in the measuring electroforming tank is consistent with the temperature in the industrial electroforming tank; simultaneously, the first circulating pump starts to work, and electroforming liquid in the measurement electroforming tank sequentially passes through the water inlet at the lower end of the liquid storage overflow device, the liquid storage cavity and the middle-end overflow port through the first circulating pump and returns to the measurement electroforming tank; the upper end opening of the liquid storage overflow device is a pH electrode socket and is used for measuring pH; after the whole testing device is in a stable state, assembling the cathode test piece and the cathode clamp in a sandwich mode, and inserting the cathode test piece and the cathode clamp into a concave socket at the upper end of the cathode chamber for fixing; and (3) switching on a power supply, observing the bending deformation condition of the cathode sheet at any time through a CCD camera on the side surface of the cathode, and calculating the in-situ stress through a computer.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a schematic diagram of a device for on-line in-situ monitoring of internal stress of a plating layer and pH of a plating solution in an electroforming process according to an embodiment of the application;
FIG. 2 is a schematic diagram of a structure of a measuring electroforming tank in an in-situ online monitoring device for internal stress of a plating layer and pH of a plating solution in an electroforming process according to an embodiment of the application;
FIG. 3 is a structural exploded view of an on-line in-situ monitoring device for internal stress of a plating layer and pH of a plating solution (excluding a pH measuring device) during electroforming according to an embodiment of the application;
fig. 4 is a structural exploded view of a pH measuring apparatus in an in-situ online monitoring apparatus for internal stress of a plating layer and pH of a plating solution during electroforming according to an embodiment of the application.
Reference numerals illustrate:
10-a measurement electroforming cell,
11-cathode chamber, 111-cathode test piece, 112-short side T-shaped plate, 113-long side T-shaped plate, 12-anode chamber, 121-anode plate, 13-connecting channel, 14-valve No. one, 141-first screw thread pagoda joint, 142-connecting valve, 144-through port silica gel plug No. one, 15-valve No. two, 151-third screw thread pagoda joint, 16-liquid inlet joint, 17-overflow joint, 171-through joint, 172-through port silica gel plug No. two, 18-fixed plate, 181-screw thread through hole; 101-concave sockets, 102-bottom ports I, 103-bottom ports II, 104-bottom ports III, 105-upper ports I, 106-upper ports II, 107-steps, 108-square grooves, 109-square ring fixing frames and 1010-bottom plates;
20-heating rod;
30-a pH measuring device, wherein the pH measuring device,
31-overflow joint, 32-second screw treasury joint, 33-pH electrode, 34-annular top cover, 35-liquid storage overflow device and 36-first circulating pump;
40-a second circulating pump, 41-a fifth screw-thread pagoda joint, 42-a fourth screw-thread pagoda joint;
50-a real-time stress observation platform,
51-annular light source, 52-L-shaped connecting plate, 521-arc hole, 522-through hole, 53-lens, 54-CCD camera.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
In addition, the industrial electroforming tank mentioned in the embodiments of the present application is generally specially designed according to its production task, while the present application focuses on measuring the electroforming tank, and there is no special requirement for the industrial electroforming tank, and is an existing structure, so the drawings do not give a schematic view of the industrial electroforming tank.
The application will be described in detail below with reference to the drawings in connection with embodiments.
As shown in fig. 1 to 4, an on-line in-situ monitoring device for internal stress of a plating layer and pH of a plating solution in an electroforming process comprises a measurement electroforming tank 10 having a bottom plate 1010, a cathode chamber 11, an anode chamber 12 and a connecting channel 13, a real-time stress observation platform 50 capable of capturing dynamic changes of a cathode test piece 111, a pH measuring device 30 capable of realizing real-time pH monitoring, and a circulating liquid flow path for communicating the measurement electroforming tank 10 with an industrial production electroforming tank; the real-time stress observation platform 50 is arranged at the side surface opposite to the cathode chamber 11, and the pH measuring device 30 is communicated with the anode chamber 12 through a pH real-time monitoring passage;
the main body of the measuring electroforming tank 10 is in a convex shape, wherein the small end of the convex shape is a cathode chamber 11, the large end of the convex shape is an anode chamber 12, the side surface of the cathode chamber 11 is also connected with a fixed plate 18, and the real-time stress observation platform 50 is arranged on the fixed plate 18; a concave jack 101 is formed on the upper end surface of the cathode chamber 11, a cathode clamp is matched at the concave jack 101, the cathode clamp comprises a short-side T-shaped plate 112 and a long-side T-shaped plate 113 with square through holes, and a cathode test piece 111 is inserted into the concave jack and fixed with the two T-shaped plates in a sandwich mode; the surface of the T-shaped plate with the titanium sheet is contacted with the conductive surface of the cathode sheet. The titanium sheet mainly acts as a lead, and current is connected and conducted with a cathode wire on a power supply through the titanium sheet which extends out of the T-shaped plate, and the connection position is positioned at the outer side of the electroforming tank, so that the corrosion of the cathode wire of the power supply can be effectively prevented; the cathode chamber 11 side has the scale, and has a long vertical line mark at the scale both ends respectively for the location and the measurement of industry CCD camera, and the position of scale flushes with cathode test piece lower extreme position, prevents that scale or cathode piece from surpassing the visual angle scope when the camera observes.
The material of the measuring electroforming tank 10 can be polyvinyl chloride, tetrafluoroethylene, organic glass and the like, preferably organic glass, which has high hardness, high corrosion resistance and easy adhesion; meanwhile, the organic glass has various colors and varieties, and can adapt to different requirements. Preferably, the cathode chamber 11 can be made of transparent organic glass, so that on one hand, the light transmission effect is good, and the observation is easy; on the other hand, the price is low and the processing is easy. Wherein the side wall of the cathode chamber can be made of organic glass with the thickness of 5mm and 10mm, preferably 5mm, and can have higher light transmittance under the condition of meeting the strength requirement. The selected materials can be processed by laser cutting, milling cutter cutting and wire cutting. Taking organic glass as an example, a processing mode of 'wire cutting' is preferable, and the organic glass processed by the wire cutting has higher precision. The molded plexiglas is bonded into the measurement electroforming bath 10 by a glue dedicated to the plexiglas.
One side of the bottom plate 1010 of the measuring electroforming tank 10 is provided with three bottom through holes and three corresponding square grooves, namely a first bottom through hole 102, a second bottom through hole 103 and a third bottom through hole 104, wherein the square grooves corresponding to the first bottom through hole 102 and the third bottom through hole 104 are short in distance, play a role in guiding electroforming liquid, and the square grooves corresponding to the second bottom through hole 103 are long in distance and serve as sockets of heating rods.
Two upper through holes are formed in the side wall of the anode chamber, and the through holes are connected in a sealing manner through silica gel plugs with different apertures;
the upper port of the anode chamber, which is close to the cathode, is connected with the bottom port of the bottom plate, which is close to the anode, and is connected with the industrial electroforming tank; the upper port of the anode chamber, which is close to the anode, is connected with the bottom opening of the bottom plate, which is close to the cathode, and the pH real-time monitoring passage; and a heating rod is inserted into a bottom through hole in the middle of the bottom plate and is connected with the temperature controller.
The bottom plate 1010 of the measuring electroforming tank 10 has a square groove 108 and a step 107, the square groove 108 is a fixing groove of the connecting channel 13, and the step 107 and the connecting channel 13 constitute a bottom fixing groove of the long-side T-shaped plate 113. The connecting channel 13 is a square channel, the length is more than 10cm, and the size and the shape of a square through hole of the connecting channel 13 are identical to those of a square cathode window of a long-side T-shaped plate. The function of the connecting channel 13 is mainly two: firstly, weakening the influence of edge effect on the cathode plate during electroforming; secondly, the disturbance of the electroforming liquid to the cathode test piece during circulation is reduced. The connecting channel is arranged in the square groove of the bottom plate, and the square channels with different square through holes are replaced, so that the connecting channel can be suitable for cathode test pieces with different sizes. The channels correspond to the cathode test pieces, and can be applied in a larger range.
The bottom plate 1010 of the measuring electroforming cell 10 has a fixing plate 18 for fixing the real-time stress observation platform 50, and the fixing plate 18 has a plurality of screw through holes 181 spaced apart by 20mm corresponding to the through holes 522 and the arc holes 521 in the connection plate 52.
The measurement electroforming tank 10 includes a cathode chamber 11 having a concave socket 101 at the upper end thereof, which is symmetrical and serves as a fixing tank for the upper ends of a short-side T-shaped plate 112 and a long-side T-shaped plate 113.
The side wall of the anode chamber 12 included in the measuring electroforming tank 10 is provided with a first upper through hole 105 and a second upper through hole 106, wherein the second upper through hole 106 acts as an overflow port, and the first upper through hole 105 acts as a liquid inlet; the measurement electroforming tank 10 includes an anode chamber having a square ring holder 109 for fixing the anode plate 121.
Valve number one 14 links to each other with the bottom through hole one 102 of bottom plate 1010, valve number one 14 comprises through hole silica gel plug one 144, a connecting valve 142 and two first screw thread pagoda connects 141, and the through hole silica gel plug one 144 rotatory stopper is gone into bottom through hole one 102, and the pagoda end of one of them first screw thread pagoda connects links to each other with the through hole of through hole silica gel plug one 144, and the screw thread end links to each other with the one end of connecting valve 142, and the other end of connecting valve 142 links to each other with another first screw thread pagoda connects 141 screw thread end, and valve number one 14 and bottom through hole one 102 are connected and are accomplished. The bottom port two 103 of the bottom plate 1010 is connected with the heating rod 20, and the bottom port three 104 of the bottom plate 1010 is connected with the valve two 15 in the same way as the valve one 14.
The second upper port 106 of the anode chamber 12 is connected with the overflow joint 17, the overflow joint 17 consists of a second through-hole silica gel plug 172 and a straight-through joint 171, the second through-hole silica gel plug 172 is rotationally plugged into the second upper port 106, and the straight-through joint 171 is rotationally plugged into the second through-hole silica gel plug 172, so that the connection is completed. The upper port one 105 of the anode chamber 12 is connected to the inlet connection 16 in a manner consistent with the overflow connection 17. The square ring holder 109 of the anode chamber 12 is used for mounting the anode plate 121.
The cathode test piece 111 is a strip-shaped silicon oxide wafer with the thickness of 0.01mm, one surface of the silicon wafer is deposited with a 50nm gold film by a magnetron sputtering mode, and the cathode test piece is divided into an upper diversion area and a lower square deposition area by using insulating glue with the width of 2cm as a dividing line. Facing the anode during electroforming, is a deposition surface for metal ions. According to the characteristics of the silicon oxide wafer, the back surface of the cathode wafer is not conductive, and the whole deposition process is single-sided electroplating; the long side T-shaped plate 113 has an upper portion in a "T" shape, the upper portion has a shape and size identical to those of the short side T-shaped plate 112, a lower portion in a "u" shape, and the thickness of the lower portion of the long side T-shaped plate extends outwardly to twice the thickness of the upper portion. One side of the short-side T-shaped plate 112 is stuck with a titanium plate, one side of the titanium plate extends out of the T-shaped plate for 1cm, and the rest parts are overlapped; the cathode test piece 111 is arranged on the long-side T-shaped plate 113, so that the square deposition area of the cathode test piece 111 is in a superposition state with the square through hole of the long-side T-shaped plate 113, but the side edge of the cathode test piece 111 is not contacted with the side wall of the square through hole of the long-side T-shaped plate 113; the size of the periphery of a rectangular cathode window extending from the lower part of the long-side T-shaped plate is slightly larger than that of a cathode test piece, and the exceeding value is about 0.1-0.2mm, so as to reduce the edge effect generated during electroforming as much as possible.
The bottom of the long-side T-shaped plate 113 is inserted into a square groove formed by the step 107 and the connecting channel 13, the upper part of the long-side T-shaped plate 113 is overlapped with the concave insertion opening 101, and the thickness of the upper part of the long-side T-shaped plate 113 is half of the width of the concave groove; the short-side T-shaped plate 112 is adhered with a titanium plate, is inserted into the concave groove 101 and is tightly clamped with the long-side T-shaped plate 113, so that the fixing effect is achieved, and meanwhile, the conduction path is formed by contacting the surface of the short-side T-shaped plate 112 with the titanium plate with the surface of the cathode test piece 111 with the gold film.
The real-time stress observation platform 50 comprises an L-shaped connecting plate 52, a light source 51, a lens 53 and a CCD camera 54, wherein a short plate of the L-shaped connecting plate 52 is provided with a round through hole with a diameter slightly wider than that of the lens, and the light source 51 is arranged on the outer side of the short plate; the lens 53 is connected to the CCD camera 54 and is fixed to the long plate of the L-shaped connection plate 52, and the L-shaped connection plate 52 has an arc-shaped hole 521 and a through-hole 522 corresponding to the screw-threaded through-hole 181 of the fixed plate 18. The image observed by the CCD camera 54 is transmitted to a computer through a data line, after the vision measurement software locates and calibrates two vertical lines passing through the side surface of the cathode chamber, the displacement of the lower part of the cathode test piece 111 at each position of 2mm interval is measured in real time and data are stored, then the average curvature R is obtained through data fitting, and the stress value is obtained by substituting R into Stoney formula;
during fixing, a through hole 522 on the L-shaped connecting plate 52 and a threaded through hole 181 on the fixing plate 18 are firstly selected to be fixed by using M8 screws, then according to practical conditions, the angle of the lens is adjusted by taking the fixed point as the center of a circle, and finally the lens is fixed with the connecting plate 18 by using M8 screws through an arc hole 521.
The pH measuring device 30 comprises a second screw thread pagoda joint 32, a first circulating pump 36, a liquid storage overflow device 35, an overflow joint 31 and an annular top cover 34, wherein the second screw thread pagoda joint 32 is connected with the water inlet end of the first circulating pump 36, the water outlet end of the first circulating pump 36 is connected with the lower end of the liquid storage overflow device 35, the upper end of the first circulating pump is connected with the annular top cover 34, a through hole of the annular top cover 34 is used for inserting a pH electrode 33, and the middle end of the liquid storage overflow device 35 is connected with the overflow joint 31. In operation, electroforming liquid sequentially passes through the second screw pagoda joint 32, the first circulating pump 36 and the lower end of the liquid storage overflow device 35 to enter the accommodating cavity of the liquid storage overflow device 35, and after the electroforming liquid is stored to be full of the accommodating cavity, the electroforming liquid flows out through the overflow joint 31. During electroforming, the zero value of the pH meter is affected by the electric field, so that the direct insertion of the pH electrode into the electroforming tank causes fluctuation and deviation of the measurement result. The water inlet end of the first circulating pump is connected with the opening of the bottom plate close to the anode end, and the water outlet end is connected with the lower end of the liquid storage overflow device; the middle end of the liquid storage overflow device is an overflow port, the first circulating pump pumps the electroforming liquid into the liquid storage overflow device to reach the position of a water outlet, and the electroforming liquid flows out, so that the liquid level is stable; the upper end is provided with a pH meter socket, and the pH meter is inserted to obtain a numerical value.
The first screw thread pagoda joint 141 of the first valve 14 is connected with the second screw thread pagoda joint 32 of the pH measuring device 30 through a silicone tube, the overflow joint 31 of the pH measuring device 30 is connected with the upper port I105 of the side wall of the anode chamber 12 through a liquid inlet joint 16 and a silicone tube, and a pH measuring liquid flow path is formed; the third screw thread pagoda joint 151 of the second valve 15 is connected with the fourth screw thread pagoda joint 42 through a silicone tube, the fourth screw thread pagoda joint 42 is connected with the water outlet end of the second circulating pump 40, the water inlet end of the second circulating pump 40 is connected with the fifth screw thread pagoda joint 41, and then is connected with the industrial electroforming tank through the silicone tube, meanwhile, the industrial electroforming tank is also connected with the overflow joint 17, and the overflow joint 17 is communicated with the second upper port 106, thus forming a circulating passage for measuring electroforming liquid in the electroforming tank and the industrial electroforming tank.
The heating rod 20 is connected with a temperature controller, so that the temperature of the electroforming tank can be controlled; an auxiliary temperature control system is added because the temperature of the measuring cell is low due to heat dissipation when the electroforming solution is introduced from the industrial electroforming cell into the measuring cell 10. The heating rod 20 is connected to a temperature controller, which measures the temperature of the electroforming solution by a temperature probe, and controls the on/off of the heating rod 20 to control the temperature. The real-time stress observation platform 50 is connected with a computer and can observe and analyze the bending stress of the cathode test piece 111 on line; the titanium sheet with the length of 1cm extending out of the side surface of the short-side T-shaped plate 112 is connected with the positive electrode of the power supply; the anode plate 121 is connected to the positive electrode of the power supply.
The working process of the monitoring device of the application is as follows: after the plating solution in the industrial electroforming tank is heated to a preset temperature, a second circulating pump 40 is opened to guide the electroforming solution into the measuring electroforming tank 10, after the plating solution fills the measuring electroforming tank 10, the plating solution starts to flow into the industrial plating tank from an overflow joint 17, and at the moment, a second valve 15 is adjusted to enable the plating solution to flow in a laminar flow mode in a proper flow manner;
because the heating rod 20 is connected with the temperature controller, when the flow of the plating solution is stable, the power supply of the temperature controller is turned on to perform auxiliary temperature control. The power supply and the connecting valve 142 of the first circulating pump 36 of the pH measuring device 30 are opened, the plating solution starts to be stored in the liquid storage overflow device 35, and after the plating solution reaches a certain capacity, the plating solution flows out of the overflow joint 31; adjusting the connecting valve 142 to achieve a proper flow rate of the plating solution; the pH meter 33 is inserted into the upper end of the liquid storage overflow device 35 through the annular top cover 34 to start the real-time monitoring of the pH value;
since the flow guiding area above the cathode test piece 111 and the insulating tape serving as a dividing line are sandwiched between the short-side T-shaped plate 112 and the upper part of the long-side T-shaped plate 113, and the surface covered with the gold film is opposite to the surface of the short-side T-shaped plate to which the titanium sheet is adhered, the cathode current can be conducted; the deposition area below the cathode test piece 111 is embedded into the square through hole below the long-side T-shaped plate 113, the shape of the deposition area is the same as that of the square through hole, and the size of the deposition area is slightly smaller than that of the square through hole, and the deposition area and the square through hole are basically overlapped but are not contacted, so that the edge effect of the cathode test piece is reduced to the greatest extent under the condition that the cathode test piece can be freely bent; the bottom surfaces of the assembled cathode test piece 111, the short-side T-shaped plate 112 and the long-side T-shaped plate 113 are embedded into a square groove formed by the step 107 and the connecting channel 13, the upper part of the square groove is inserted into the concave groove 101 of the cathode chamber 11, and the whole cathode is installed;
the side of the cathode chamber 11 is provided with scales, and two ends of the cathode chamber are respectively provided with a vertical red line; the light source 51, the lens 53, the CCD camera 54 and the connecting plate 52 form an integrated stress observation platform 50; the CCD camera 54 is arranged opposite to the surface of the cathode chamber 11 with scales, and the CCD camera and the cathode chamber are vertically arranged by adjusting the connecting plate 52. The computer performs the calibration of the physical size and the image size through the scale and the red line of the fixed distance on the side surface of the cathode chamber before the measurement; measuring horizontal distances from the left-end vertical red line and the right-end vertical red line to the cathode test piece 111 respectively during measurement; a measurement point was set every 2mm in the lower half of the cathode test piece 111, and the real-time change in bending curvature of the cathode test piece was obtained by fitting the data. Finally, a real-time change curve of the coating stress is obtained through a Stoney formula. It should be noted that the stress measured before electroforming needs to be zeroed.
In this embodiment, the specific processing manner of the data observed by the stress observation platform is as follows:
step 1: fitting the obtained data by software to obtain the bending curvature R of the cathode.
Step 2: and obtaining the thickness Hf of the electroformed layer at each moment by a conversion formula of the electric quantity and the thickness.
Formula I: :
in the formula I, C represents the electric quantity of electroforming at each moment; m represents the molar mass of the deposited metal; n represents the valence state of the deposited metal; f represents Faraday constant; ρ represents the density of the deposited metal; s represents the area of the cathode test piece.
Step 3: substituting the obtained curvature R and electroformed layer thickness Hf into Stoney formula to obtain stress value.
Formula II:
formula II is Stoney formula, wherein E s 、V s The elastic modulus and poisson ratio of the silicon wafer are; h s Is the thickness of the silicon wafer.
In the embodiment, the power supply is a battery performance test system, and different steps can be set so as to adjust the electroforming process; the electroformed anode 121 employs the same anode as the industrial electroformed tank.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (6)
1. An online in-situ monitoring device for internal stress of a plating layer and pH of plating solution in an electroforming process is characterized in that: comprises a measuring electroforming tank with a bottom plate, a cathode chamber, an anode chamber and a connecting channel; a real-time stress observation platform capable of capturing dynamic changes of the cathode test piece, a pH measuring device capable of realizing real-time pH monitoring and a circulating liquid flow passage for communicating the measuring electroforming tank with the industrial production electroforming tank; the real-time stress observation platform is arranged at the side surface opposite to the cathode chamber, and the pH measuring device is communicated with the anode chamber through a pH real-time monitoring passage;
the real-time stress observation platform comprises a round light source, a lens, a CCD camera, an L-shaped connecting plate and a computer; a round observation port is arranged on the short side of the L-shaped connecting plate, an arc-shaped hole and a plurality of through holes are arranged on the long side of the L-shaped connecting plate, the L-shaped connecting plate is fixed on a fixed plate on the side surface of the cathode chamber through one arc-shaped hole and a plurality of through holes, the lens is connected with the CCD camera and is arranged on the long side of the L-shaped plate, and the lens points to the round observation port; the circular light source is arranged on the outer side of the short side of the L-shaped connecting plate and is coaxially arranged with the circular observation port, and image data of the cathode test piece observed by the CCD camera is transmitted to the computer through a data line;
the pH measuring device comprises an overflow joint, a pH electrode, a liquid storage overflow device and a first circulating pump, wherein the lower end of the liquid storage overflow device is a liquid inlet end, the middle end of the liquid storage overflow device is an overflow end, the upper end of the liquid storage overflow device is a pH measuring port, the pH electrode is inserted into the pH measuring port, the overflow end is provided with the overflow joint, the lower end of the liquid storage overflow device is communicated with the first circulating pump, and the first circulating pump is communicated with the anode chamber;
three bottom through holes and three square grooves are formed in one side of a bottom plate of the electroplating bath, each bottom through hole corresponds to one square groove, the bottom through holes are communicated with the corresponding square groove, two upper through holes are formed in the side wall of the anode chamber, and the through holes are connected in a sealing mode through silica gel plugs with different apertures;
the upper port of the anode chamber, which is close to the cathode, is connected with the bottom port of the bottom plate, which is close to the anode, and is connected with the industrial electroforming tank; the upper port of the anode chamber, which is close to the anode, is connected with the bottom opening of the bottom plate, which is close to the cathode, and the pH real-time monitoring passage; a heating rod is inserted into a bottom through hole in the middle of the bottom plate, and the heating rod is connected with a temperature controller;
the circulating liquid flow passage comprises a second valve, a second circulating pump and a plurality of silica gel pipes, a third screw thread pagoda joint of the second valve is connected with a fourth screw thread pagoda joint through the silica gel pipes, the fourth screw thread pagoda joint is connected with the water outlet end of the second circulating pump, the water inlet end of the second circulating pump is connected with a fifth screw thread pagoda joint, and the fifth screw thread pagoda joint is connected with the industrial electroforming tank through the silica gel pipes; meanwhile, the industrial electroforming tank is connected with the overflow joint through the silicone tube, and the overflow joint is communicated with the upper port of the side wall of the anode chamber, which is close to the cathode, so that a circulation passage for measuring electroforming liquid in the electroforming tank and the industrial electroforming tank is formed.
2. The on-line in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process according to claim 1, wherein: the main body of the measuring electroforming tank is in a convex shape, wherein the small end of the convex shape is a cathode chamber, the large end of the convex shape is an anode chamber, the side surface of the cathode chamber is also connected with a fixed plate, and the real-time stress observation platform is arranged on the fixed plate; a concave socket is formed in the upper end face of the cathode chamber, a cathode clamp is matched at the concave socket, the cathode clamp comprises a short-side T-shaped plate and a long-side T-shaped plate with square through holes, and a cathode test piece is inserted into the concave socket and fixed with the two T-shaped plates in a sandwich manner; the side of the cathode chamber is provided with scales, and two ends of each scale are respectively provided with a long vertical line mark.
3. An on-line in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process according to claim 2, wherein: a square groove and a step are formed in the connection part of the cathode chamber and the anode chamber on the bottom plate, the square groove is a fixed groove of the connecting channel, the step and the connecting channel form a bottom fixed groove of a long-side T-shaped plate, and a square ring fixing frame is further arranged on the inner side wall of the anode chamber far from the cathode chamber and used for fixing the anode plate; the connecting channel is a square channel, and the square through hole of the square channel has the same shape as the cathode test piece; the cathode test piece substrate is a silicon wafer, and one side of the silicon wafer is deposited with a layer of gold film in a magnetron sputtering mode.
4. An in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process according to claim 3, wherein: the upper part of the long-side T-shaped plate is in a T shape, the shape and the size of the long-side T-shaped plate are consistent with those of the short-side T-shaped plate, the lower part of the long-side T-shaped plate is in a U shape, and the thickness of the lower part of the long-side T-shaped plate extends outwards to twice the thickness of the upper part; one side of the short-side T-shaped plate is stuck with a titanium sheet, and one side of the titanium sheet extends out of the T-shaped plate; the cathode test piece is arranged on the long-side T-shaped plate, the square deposition area of the cathode test piece is in a superposition state with the square through hole of the long-side T-shaped plate, and the side edge of the cathode test piece is not contacted with the side wall of the square through hole of the long-side T-shaped plate.
5. The on-line in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process according to claim 1, wherein: the stress observation platform is positioned and calibrated through a long vertical line on the side surface of the cathode chamber; the image data observed by the stress observation platform is the displacement value of each point on the side edge of the lower half part of the cathode test piece; and the displacement value is subjected to software fitting to obtain a curvature value.
6. The on-line in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process according to claim 1, wherein: the pH real-time monitoring passage comprises a valve and a plurality of silica gel pipes, wherein a first screw thread pagoda joint of the valve is connected with a second screw thread pagoda joint of the pH measuring device through the silica gel pipe, and an overflow joint of the pH measuring device is connected with an upper port of the side wall of the anode chamber, which is close to the anode, through a liquid inlet joint and the silica gel pipe, so that the pH real-time monitoring passage is formed.
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| CN1651884A (en) * | 2004-02-03 | 2005-08-10 | 株式会社山本镀金试验器 | Electrode cartridge and a system for measuring internal stress of an electroplated film |
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