US3715299A - Electroplating apparatus including means to disturb the boundary layer adjacent a moving electrode - Google Patents

Electroplating apparatus including means to disturb the boundary layer adjacent a moving electrode Download PDF

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US3715299A
US3715299A US00079827A US3715299DA US3715299A US 3715299 A US3715299 A US 3715299A US 00079827 A US00079827 A US 00079827A US 3715299D A US3715299D A US 3715299DA US 3715299 A US3715299 A US 3715299A
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solution
boundary layer
electrode
cathode
electrodes
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R Anderson
R Beyer
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FUTURE SYST Inc
FUTURE SYST INC US
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Assigned to HEYMAN, DR. KARL reassignment HEYMAN, DR. KARL CERTIFIED ORDER FILED IN UNITED STATES BANKRUPTCY COURT FOR THE NORTHERN DISTRICT OF CALIFORNIA CONFIRMING SALE OF SAID PATENTS TO ASSIGNEE. EFFECTIVE DATE: MARCH 24, 1986 Assignors: FUTURE SYSTEMS INC., BY: JEROME E. ROBERTSON, TRUSTEE IN BANKRUPTCY
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells

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  • Apparatus for transfer of mass e.g. metallic ions to or from a relatively stationary body from or into a mov- [52] 5355 ia/ ing fluid.
  • Means are included for continuously disturblm Cl ing the fluid about the surface of the body to discourage the establishment of a steady state boundary layer of the fluid.
  • PATENTEDFEB 6 I975 3,715,299 SHEET 3 0F 3 9o FIG. l0 z INVENTORS.
  • Electrodeposition structures heretofore available commonly include an anode, a cathode and means for circulating the solution intermediate and past the cathode and anode. A voltage difference is established across the electrodes such that the metal is attracted and deposited on the cathode and extracted from the solution. The collected metal may then be removed from the cathode. It has been found that the efficiency and success of transfer of the metal from the solution to the collecting electrode is dependent on the boundary layer of fluid established about the relative stationary body of the electrode.
  • Electrodeposition structures There are presently various electrodeposition structures available. Commonly, as the metal content is depleted the impedance and the current through the solution varies. Frequently, the potential value between the electrodes is controlled as the concentration of metal within the solution varies to effect certain separations. A common approach is to install a sensor cell to sense the metal concentration within the solution. The potential across the electrodes is controlled responsive to the sensor.
  • boundary layer of relatively motionless solution tends to form adjacent the cathode.
  • the metal ions within this layer commonly referred to as a boundary layer, are substantially depleted.
  • the boundary layer being relatively motionless retains its position and impedes the transfer of metal from the solution outside the layer to the surface of the collecting electrode.
  • the metal ions need be of sufficient velocity to penetrate said layer. To realize the higher velocity, increased electrical potential need be established across the electrodes.
  • Electrodeposition apparatus is widely used in the recovery of silver metal from silver bearing solutions such as that commonly used in photographical fixing baths.
  • the recovery of silver serves two key functions to recover silver for further use and to regenerate the fixer for further use.
  • prior art electrodeposition silver recovery systems it has been found that as the laminar flow of the silver bearing fixer (hypo) solution takes place about an electrode, the electrical current density must be controlled and varied as the silver concentration varies in order to prevent breakdown of thiosulfate ion which causes silver sulfide precipitation. As silver is depleted from the solution, the excess electrical energy is more readily available for alternate reactions to occur. The insoluable silver sulfide precipitate, in turn, renders the solution unsuitable for further use. Thus, to preserve the collected silver and the solution for further use it is necessary to avoid silver sulfiding. This requires control of the electrical energy relative to the silver metal concentration of the solution.
  • Another approach in the silver recovery art is to utilize a batch process.
  • a number of recovery units are tied in cascade array and the silver bearing solution is permitted to flow from one recovery unit to another.
  • the solution in each succeeding unit has less silver and each unit is operated at less current density relative to the preceding unit.
  • the silver concentration is diluted to the level of that particular unit and then transferred to the next succeeding unit. It has been found that with the batch process, the recovery of silver becomes more time consuming in succeeding units as the silver content is decreased and the current density decreased. Consequently, it becomes necessary to sacrifice either time or the degree of extraction of silver from the solution in the terminal unit.
  • Canadian Patent No. 491,453 describes apparatus for recovery of silver from hypo solution utilizing a stationary cylindrical cathode and a plurality of carbon anodes driven in a circular path coaxial with the cathode and radially spaced from the interior and exterior surfaces of the cathode.
  • the present invention relates to an improved apparatus for mass transfer and control of boundary layer.
  • the invention has proven to provide a significant improvement in electrodeposition apparatus for recovery of metals from metal bearing solutions.
  • the invention teaches structure for facilitating the transfer of solution about the face of the body moving relative to the solution e.g. a collecting electrode, and.
  • the stationary electrode carries a plurality of flexible tripper arms protruding towards the col lecting surface of the collecting electrode and terminating adjacent to the collecting electrode.
  • Means are included to transfer the solution intermediate the electrodes while the rotating electrode provides radial motion to the solution.
  • the tripper arms disturb and agitate the solution adjacent the collecting electrode thereby discouraging buildup of a boundary layer.
  • the exemplary embodiment may be further adapted such that the input portal of the apparatus for the solution is at a higher level than the output portal.
  • the solution flows from the input portal to the output portal by fluid displacement in an axial direction about at least one electrode while the rotating electrode simultaneously imparts radial motion.
  • the solution then exits at the lower level such that minimal mixing of the incoming solution with rejuvenated solution takes place.
  • FIG. 5 is a sectional view along the line 55 of FIG. 1 and theoretically illustrating the eddy current action of the solution about the cathode of FIG. 1 with boundary layer trippers;
  • FIG. 6 illustrates a partially sectioned plan view of an alternative embodiment of an electrodeposition apparatus incorporating two anodes and the principles of the present invention
  • FIG. 7 illustrates a sectional view taken along the line 7-7 of FIG. 6.
  • FIG. 8-10 schematically illustrate other embodiments of electrodeposition apparatus incorporating the teachings of the present invention.
  • the present invention has been found to be highly beneficial in apparatus for the recovery of silver from silver bearing solutions, such as fixative baths used in the photographic industry. Such solutions are commonly referred to as hypo or fixer.
  • silver is dispersed in a gelatin material in the form of silver halides-primarily silver bromide and silver chloride. The remainder of the silver halides are believed reduced to pure silver due to exposure of light.
  • the silver ion part of the silver halides is extracted as a complex with a thiosulfate ion in the hypo solution.
  • the hypo solution may, lose its effectiveness and utility for processing film.
  • the silver within the hypo is a valuable commodity. Accordingly, the removal and collection of the silver from the hypo is an important concept to permit reuse of the hypo solution in processing film and recovery of the silver for reuse of the metal itself.
  • FIG. 1 illustrates a silver recovery electrodeposition apparatus, referred to by the general reference character 1 and incorporating the teachings of the present invention.
  • the apparatus 1 includes a control panel-base support member 3 supporting about its top surface a retainer in the form of an enclosure 5 in which a volume of hypo or other silver bearing solution may be retained.
  • the enclosure has a removable top 7 and an integral bottom end wall 9.
  • the enclosure 5 including the walls 7 and 9 comprise a nonmetallic material compatible with the hypo solution. Such material may comprise a plastic, fiberglass, polyvinyl chloride, etc.
  • Extending through the bottom surface 9 within the center of the enclosure 5 is a fixed cylindrical shaft housing 11.
  • the housing 11 houses a cylindrical rotatable shaft 13.
  • the shaft 13 is comprised of an electrically conductive material and rotates about its axis within the housing 11 and the enclosure 5.
  • the exterior of the housing 11 carries a non-metallic coating compatible with the hypo, e.g. plastic, fiberglass, polyvinyl chloride, etc.
  • the housing 11 is sealed about the bottom surface 9 with an epoxy to prevent leakage.
  • an axialthrust bearing (not shown) to provide lateral and axial support and guidance to the shaft.
  • an electrically conductive coupling member 17 adapted to be secured to the shaft by means of a fastener 19 such that the coupling member 17 rotates responsive to the shaft 13.
  • a triangular shaped support member 21 comprised of a non-conductive material extends radially from the coupling member 17 and is secured to the shaft 13.
  • a plurality of three columns 23 are joined to the support member at the apexes and extend from said support member parallel to the rotating shaft 13.
  • a conducting strip 24 is secured to the top of the shaft 13 and extends laterally therefrom.
  • an impeller 25 adapted to urge axial flow of the solution.
  • the impeller 25 is supported above the surface of the bottom wall 9.
  • the impeller 25 is illustrated as carrying a plurality of openings 27 in the form of arcurate slots of substantially equivalent size relative to one another.
  • the impeller 25 carries an outer ridge 29 about the outside of the column members 23.
  • Engaging the exterior of the column members 23 and resting on the ridge 29 is a right circular cylinder cathode 31 referred to as the collecting electrode on which the silver is to be collected.
  • the cathode 31 is substantially coaxial with the shaft 13.
  • the cathode 31, which is comprised of an electrically conductive material, e.g. stainless steel, is secured to the strip 24. Accordingly, application of an electrical potential on the shaft 13 places the cathode 31 at a similar potential and rotation of the shaft 13 places the cathode 31 in simultaneous rotation within the enclosure 5.
  • anode 33 preferably comprised of a material having a high electrical conductivity and not subject to attack by the hypo solution, e.g. stainless steel.
  • the anode 31 is substantially coaxial with the cathode 31 and is positioned flush against the interior side walls of the enclosure 5.
  • the top of the anode 33 is preferably below the level of the top of the cathode 31.
  • the anode 33 is desirably spaced laterally from the cathode 31 such that the cross-sectional area of the enclosed spacing between the anode 33 and the exterior surface of the cathode 31 is substantially equal to the cross-sectional area intermediate the interior surface of the cathode and shaft housing 11.
  • This provides for substantially equal flow areas about the interior and exterior surfaces of the cathode.
  • Joined to the enclosure 5 about the top edge of the anode 33 is an outlet 34 permitting exit of the solution from the enclosure 5.
  • An inlet portal 35 is included to permit entering of solution about the interior of the cathode 31.
  • the drive shaft 13 extends through the bottom wall 9 of the enclosure 5. About the exposed end, is a drive means including a gear 36 engaging a drive gear 37 driven by an electric drive motor 39 within the interior of the support member 3.
  • the panel-base support member 3 may be designed to include an ammeter 41 to indicate the current through the solution intermediate the electrodes 31 and 33. Within the panelbase support there may be a suitable d.c. power source means (not shown) for applying a d.c. voltage between the cathode 31 and anode 33.
  • the panel-base member 3 may also include an on-off switch 43, a voltage regulator control 45 extending to the power source means (not shown) and a speed regulator 47 to control the speed of the motor 39 and the rotational velocity of the shaft 13 and the cathode 31.
  • a hypo solution may be retained within the enclosure 5 and enter within the interior of the cathode 31.
  • the solution may be contained if the portal 34 is closed or there may be a continuous flow of solution if the portals 34 and 35 are open.
  • the motor 39 drives the cathode 31 in a rotary motion and the hypo solution circulates about the interior and exterior of the cathode. As the cathode 31 rotates hypo is continuously drawn down about the interior of the cathode and upward between the cathode 31 and anode 33 area. At the same time, the rotating cathode imparts radial motion to the hypo.
  • the hypo As the hypo is circulated, silver is plated on the surface of the cathode reducing the content of the silver ions within the hypo. After a substantial amount of silver is collected on the cathode 31, the cover 7 is removed, the strip 24 is disengaged and the entire unitary cathode may be removed by sliding it off of the column members 23. After removal of the cathode 31, the collected silver may be removed by flexing the cathode. Also, the hypo is rejuvenated and may be reused in processing film.
  • the structure of FIG. 1 further carries a boundary layer tripper means including a plurality of arms in the form of flexible flaps 49 longitudinally engaged to and projecting from the exterior surface of the stationary anode 33.
  • the flaps 49 are evenly radially spaced apart about the anode. For example, in FIG. 1 the flaps 49 are spaced approximately l20 apart.
  • the flaps 49 extend longitudinally substantially end-to-end of the cathode 31 and terminate adjacent to the exterior collecting surface of the cathode 31 such that they extend substantially radially relative to said collecting surface.
  • the flaps 49 assume a concave shape and are comprised of an electrically non-conductive material compatible with the hypo solution so as not to be corroded or deteriorated to any substantial degree by the solution.
  • flaps 49 comprised of a saturated hydrocarbon elastomer material of approximately onesixteenth inch thickness have proven compatible. Such materials may include ethylene-propylene, rubber, neoprene rubber, n-butyl rubber, polyethylene, etc.
  • the flaps are flexible and pivot about the point of engagement with the anode.
  • the flaps terminate adjacent to the cathode surface within the area of the boundary layer.
  • the flaps 49 terminate to leave a space in the order of onefourth to three-eighths inch between the terminal end of the tabs and the cathode surface.
  • the drive means moves the cathode 31 relative to the flaps 49 by driving the cathode 31 about the axis of the shaft 13.
  • the flaps 49 serve to disturb the hypo solution adjacent the surface of the cathode 31 and discourage establishment of a relative motionless layer of solution adjacent said cathode surface.
  • the flaps 49 extend adjacent to the cathode within the area of this otherwise motionless layer.
  • the theoretical explanation of the function and results of the boundary layer trippers is believed to be as follows. Theoretically, in mass transfer through liquids, a relative motionless layer of solution tends to be formed adjacent to a relative stationary surface. The liquid outside the layer, referred to as the bulk flow area, flows at a net bulk velocity. With the structure of FIG. 1 the net velocity Vr of the liquid within the bulk is dependent upon the vectorial sum of the rotational velocity component and the axial velocity component.
  • the flow fluid is retarded at and near the surface of the cathode 31 by the laminar boundary layer.
  • the laminar boundary layer of solution tends to build up about the cathode surface and the depth d" of the layer is a function of the velocity of the fluid in the bulk relative to the velocity of the relative stationary surface. For example, assuming the system is initially static and starting at a given point, as the fluid is transferred axially across the relative axially stationary surface, the thickness of the layer increases along the cathode surface as illustrated by the line Yo in FIG. 4. Analyzing the boundary layer as consisting of an incompressible fluid, the pressure differential of the fluid within the layer of zone (a) relative to outside the layer of zone (b) is small (see FIG.
  • the line PQ represents the development of the boundary layer adjacent a given point on the cathode from start to steady state with the enclosure 5 containing a supply of hypo.
  • a profile will be set up corresponding to a vertical section in FIG. 4. This is designated as section 8-8.
  • the thickness d depends on the rotational velocity of the cathode or solid boundary.
  • the boundary layer at the cathode 31 is continually disturbed at the cathode surface. This is designated by the point P in FIG. 4 and with the moving solid boundary cathode 31 and the stagnant bulk fluid, steady state is never reached. Eddy currents are induced at point P adjacent to the surface of the rotating cathode 31. These intense eddy currents persist for a period of time and tend to dampen until the cathode has rotated around to another boundary layer tripper and the process is repeated. The induced eddy current phenomena adjacent to the surface of the cathode 31 thereby facilitates attraction to the cathode and transfer of fluid to the immediate adjacent surface of the cathode.
  • the eddy currents, at a given point on the cathode tend to persist at the surface for a substantial time period while the cathode rotates.
  • the eddy currents at said given point tend to dampen intermediate successive trippersand are rejuvenated when the next tripper 49 is encountered.
  • Said phenomena is illustrated schematically in FIG. illustrating a cross-sectional view of the structure of FIG. 1 taken along the line 5-5.
  • the boundary layer tripper flaps 49 tend to continuously disturb the solution'about the cathode surface.
  • the supply of hypo is circulated adjacent to the cathode allowing ready transfer of silver ions from the circulating supply to the cathode.
  • the electrical potential necessary to attract the silver ions to reach the cathode is substantially decreased thereby decreasing the necessary electrical power between the electrodes to realize electrodeposition.
  • the electrical potential is decreased the tendency of silver sulfide at the cathode for a given current is deminished.
  • the boundary layer tripper flaps 49 have been found to provide improved efficiency in electrodeposition in various ways. First, the boundary layer is decreased thereby facilitating transfer of silver ions from the bulk solution to the cathode surface. Second, the solution is circulated immediately adjacent to the cathode surface thereby facilitating transfer of the silver ions from the circulating solution to the cathode. Third, the continuous circulation has been found to virtually eliminate the tendency of sulfiding thus permitting increased current densities, even as the silver ion content decreases.
  • Embodiments of silver recovery units incorporating boundary layer tripper flaps 49 have been found to accommodate current densities in the order of 100 amperes per square foot of cathode surface area with hypo solutions of silver concentration in the order 0.1 troy ounces per gallon without detectable sulfiding of the silver.
  • the incorporation of the boundary layer trippers have been found to permit units similar to the unit 1, to perform similar to a batch process without the reaction times necessary in batch processes. With the unit 1 as the solution transfers axially, the concentration of succeeding increments of solution of axial movement have less silver concentration. At the same time, the high degree of agitation has been found to permit a uniform potential across the electrodes not withstanding the changing concentrations along the axial plane.
  • FIG. 6 illustrates a plan view of a further embodiment of a silver recovery unit incorporating the teachings of the present invention and referred to by the general reference character 60.
  • the unit 60 exteriorally is similar to the unit 1 of FIG. 1 such that elements common to those of the unit 1 carry the same reference with a prime designation.
  • the unit 60 is designed to incorporate a pair of stationary right circular cylinder anodes 62 and 64.
  • a rotatable right circular cylinder cathode 66 is positioned intermediate the anodes 62 and 64 such that each of the anodes is adjacent a collecting surface of the cathode 66.
  • the anode 62 carries a plurality of evenly spaced boundary layer tripper flaps 49 and the anode 64 carries a plurality of evenly spaced boundary layer tripper flaps 49".
  • the support member 21 is comprised of an electrically conductive material such that the cathode 66 is at the same electrical potential as the shaft 13.
  • FIG. 7 illustrates a cross-sectional segment of the structure 60 taken along the line 7-7.
  • Each of the anodes 62 and 64 carry a positive potential relative to the cathode 66 such that silver is plated on both exterior surfaces of the cathode 66 as illustrated by the layers of collected silver 68 and 70.
  • the boundary layer tripper flaps 49 and 49 simultaneously disturb the solution adjacent both exterior surfaces of the cathode to facilitate plating on both of said surfaces as the cathode is rotationally driven about the shaft 13.
  • the eddy currents are intensified at both surfaces of the cathode.
  • the plating on both surfaces of the cathode is desired to be uniform.
  • the spacing between the cathode and the anodes was critical for uniform plating.
  • the boundary layer trippers 49 and 49 aid in uniform plating because the electrical resistance at the surface of the cathode is decreased, due to decrease or elimination of the boundary layer. Consequently, the spacing between the cathode and anodes has been found not to be as critical as heretofore known.
  • FIG. 8 schematically illustrates a plan view of a further embodiment of an electrodeposition apparatus incorporating the teachings of the present invention and referred to by the general reference character 72.
  • the apparatus 72 includes a stationary right cylindrical anode 74 and a rotating right cylindrical cathode 75. Suspended intermediate thereof and adjacent the cathode are a plurality of arms in the form of stationary flexible tubes or rods 76. The rods 76 are positioned immediately adjacent to the surface of the cathode and function as the boundary layer trippers. There may also be included impeding vanes 78 to impede rotational flow of the solution and to agitate the solution. As the cathode rotates, the tubes or rods 76, which are stationary, create eddy currents adjacent to the cathode to discourage the establishment of a boundary layer.
  • FIG. 9 schematically illustrates a further embodiment of an electrodeposition apparatus incorporating the teachings of the present invention and referred to by the general reference character 82.
  • the apparatus 82 includes a stationary right cylindrical anode 84 and a stationary right cylindrical cathode 85.
  • a rotating member 87 supports a plurality of arms in the form of flexible, concave boundary layer trippers 88 similar to the flaps 49.
  • the flaps 88 are rotated coaxially about the area intermediate the anode 84 and cathode 85.
  • the flaps 88 terminate immediately adjacent to the surface of the cathode and functions to discourage the establishment of a boundary layer about the cathode 85.
  • FIG. 10 A further embodiment of electrodeposition apparatus incorporating the teachings of the present invention and referred to by the general reference character. 90 is illustrated in FIG. 10.
  • the apparatus 90 includes a drive shaft 92 supporting a plurality of disc cathodes 94.
  • a plurality of arms in the form of flexible members 96 protrude to within the area intermediate adjacent the discs 94.
  • the members 96 serve as boundary layer trippers to disturb the solution about said discs and discourage the establishment of boundary layers about the disc surfaces.
  • the members 96 are supported by a column 98.
  • An anode 100 is included.
  • the cathodes 94 are moved relative to the boundary layer trippers 96 by maintaining the trippers 96 stationary while the cathodes are rotated by the shaft 92.
  • Apparatus for the electrodeposition of a metal from a body of solution comprising:
  • a retainer for retaining a volume of a solution bearing a metal to be recovered
  • a first electrode member within the retainer and having a first collecting surface to receive and collect said metals
  • a second electrode member within the retainer and disposed in spaced apart relationship with said first electrode member, the space between said first collecting surface and second electrode defining a chamber for passage of a body of said solution;
  • boundary layer tripper means disposed within said chamber and stationary relative to said second electrode member, said boundary layer tripper means extending into said boundary layer of fluid for creating eddy currents of fluid within said boundary layer as said first electrode member is moved.
  • first and second electrodes are in the form of a right circular cylindrical body disposed in coaxial relationship, and wherein said boundary layer tripper means includes at least one elongated member having a longitudinal dimension extending substantially parallel with said first collecting surface.
  • boundary layer tripper means includes a plurality of arms positioned within said chamber, each of said arms having a longitudinally extending end, each of said arms positioned with its respective longitudinal dimension extending substantially parallel with said first collecting surface.
  • Apparatus for electrodeposition of a metal from a solution comprising, in combination:
  • a retainer for retaining a volume of solution bearing a metal to be recovered
  • first electrode member within the retainer and having a first collecting surface and a second collecting surface, said first and second collecting surfaces being positioned to be exposed to the solution within the retainer to receive and collect said metal;
  • first and second electrodes positioned relative to one another to permit said solution to circulate intermediate the first and second electrodes;
  • a third electrode member within the retainer and spaced from the second collecting surface of the first electrode with the first electrode positioned intermediate the second and third electrodes, the first and third electrodes positioned relative to one another to permit said solution to circulate intermediate the first and third electrodes;
  • electrical power means for establishing an electrical potential on the first and second electrodes relative to one another and on the first and third electrodes relative to one another;
  • boundary layer tripper means intermediate the first and second electrode members and intermediate the first and third electrode members for disturbing the solution adjacent the first and second collecting surfaces
  • the boundary layer tripper means including at least one arm positioned within the retainer intermediate the first and second electrodes and projecting toward said first collecting surface and at least one arm positioned within the retainer intermediate the first and third electrodes and projecting toward said second collecting surface;
  • the boundary layer tripper means includes a plurality of said arms with the second and third electrodes each being engaged to a plurality of arms, the arms engaged to the second electrode being substantially uniformally spaced relative to one another about the first collecting surface of the first electrode, and the arms engaged to the third electrode being substantially uniformally spaced relative to one another about the second collecting surface of the first electrode.
  • first, second and third electrode members are in the form of right circular cylinders coaxial about a common axis with the first electrode member positioned intermediate the second and third electrodes, the first electrode member being engaged to the drive means, the drive means being adapted to rotate the first electrode about said common axis;
  • the boundary layer tripper means includes a first set of boundary layer trippers and a second set of boundary layer trippers, said first set of boundary layer trippers being positioned intermediate the first and the second electrode members and adjacent said first collecting surface for disturbing the solution adjacent to said first collecting surface, and said second set of boundary layer trippers being positioned intermediate the first and the third electrode members and adjacent said second collecting surface for disturbing the solution adjacent to said second collecting surface, each of the first set and each of the second set of boundary layer tripper means extending substantially normal to said first and second collecting surfaces of the first electrode;

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Cited By (14)

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US3873434A (en) * 1971-08-23 1975-03-25 Arthur S King Corrosion control assembly
US3985634A (en) * 1975-01-27 1976-10-12 Larson Kay R Electrolytic silver recovery apparatus
US4028212A (en) * 1976-06-14 1977-06-07 Bowen Woodrow L Silver recovery apparatus
US4049507A (en) * 1974-09-18 1977-09-20 Sony Corporation Electrodepositing method
US4149954A (en) * 1977-08-23 1979-04-17 Ransbottom Terry L Metal recovery apparatus
US4169033A (en) * 1978-06-19 1979-09-25 Rkc Corporation Electroplating cell
US4302317A (en) * 1976-04-05 1981-11-24 Mock Karl J Means for recovering a precious metal from an electrolyte solution containing ions of said metal
US4302318A (en) * 1976-04-05 1981-11-24 Mock Karl J Means for recovering silver from photo chemicals
US5102522A (en) * 1990-12-10 1992-04-07 James Rivers Metal recovery apparatus
US5462649A (en) * 1994-01-10 1995-10-31 Electroplating Technologies, Inc. Method and apparatus for electrolytic plating
US20040222099A1 (en) * 1999-12-28 2004-11-11 Tetsuo Tanaka Method of producing metal ferrules, and device therefor
US20070289867A1 (en) * 2001-03-30 2007-12-20 Uri Cohen Apparatus for enhanced electrochemical deposition
US20100243462A1 (en) * 2002-11-05 2010-09-30 Uri Cohen Methods for Activating Openings for Jets Electroplating
CN108642298A (zh) * 2018-04-24 2018-10-12 山东建筑大学 一种光伏黑硅片生产线用废液回收方法

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FR2481716A1 (fr) * 1980-04-30 1981-11-06 Mock Karl Appareil pour recuperer l'argent des produits chimiques pour photographie

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US2536912A (en) * 1944-07-12 1951-01-02 Ibm Electrolysis etching device
US3477926A (en) * 1965-05-24 1969-11-11 Eastman Kodak Co Electrolytic process and apparatus for recovering metals
US3560366A (en) * 1968-04-12 1971-02-02 Oscar Fisher Ag-o-mat silver recovery unit

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US2536912A (en) * 1944-07-12 1951-01-02 Ibm Electrolysis etching device
US3477926A (en) * 1965-05-24 1969-11-11 Eastman Kodak Co Electrolytic process and apparatus for recovering metals
US3560366A (en) * 1968-04-12 1971-02-02 Oscar Fisher Ag-o-mat silver recovery unit

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873434A (en) * 1971-08-23 1975-03-25 Arthur S King Corrosion control assembly
US4049507A (en) * 1974-09-18 1977-09-20 Sony Corporation Electrodepositing method
US3985634A (en) * 1975-01-27 1976-10-12 Larson Kay R Electrolytic silver recovery apparatus
US4302317A (en) * 1976-04-05 1981-11-24 Mock Karl J Means for recovering a precious metal from an electrolyte solution containing ions of said metal
US4302318A (en) * 1976-04-05 1981-11-24 Mock Karl J Means for recovering silver from photo chemicals
US4028212A (en) * 1976-06-14 1977-06-07 Bowen Woodrow L Silver recovery apparatus
US4149954A (en) * 1977-08-23 1979-04-17 Ransbottom Terry L Metal recovery apparatus
US4169033A (en) * 1978-06-19 1979-09-25 Rkc Corporation Electroplating cell
US5102522A (en) * 1990-12-10 1992-04-07 James Rivers Metal recovery apparatus
US5462649A (en) * 1994-01-10 1995-10-31 Electroplating Technologies, Inc. Method and apparatus for electrolytic plating
US20040222099A1 (en) * 1999-12-28 2004-11-11 Tetsuo Tanaka Method of producing metal ferrules, and device therefor
US7090761B2 (en) * 1999-12-28 2006-08-15 Smk Corporation Method of producing metal ferrules, and device therefor
US20070289867A1 (en) * 2001-03-30 2007-12-20 Uri Cohen Apparatus for enhanced electrochemical deposition
US8349149B2 (en) * 2001-03-30 2013-01-08 Uri Cohen Apparatus for enhanced electrochemical deposition
US20100243462A1 (en) * 2002-11-05 2010-09-30 Uri Cohen Methods for Activating Openings for Jets Electroplating
US9911614B2 (en) 2002-11-05 2018-03-06 Uri Cohen Methods for activating openings for jets electroplating
CN108642298A (zh) * 2018-04-24 2018-10-12 山东建筑大学 一种光伏黑硅片生产线用废液回收方法
CN108642298B (zh) * 2018-04-24 2020-05-26 山东建筑大学 一种光伏黑硅片生产线用废液回收方法

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