US3844906A - Dynamic bath control process - Google Patents

Dynamic bath control process Download PDF

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Publication number
US3844906A
US3844906A US00362592A US36259273A US3844906A US 3844906 A US3844906 A US 3844906A US 00362592 A US00362592 A US 00362592A US 36259273 A US36259273 A US 36259273A US 3844906 A US3844906 A US 3844906A
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solution
nickel
electroforming
mandrel
belt
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R Bailey
D Kreckel
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Xerox Corp
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Xerox Corp
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Priority to GB2126173A priority Critical patent/GB1421818A/en
Priority to NL7306365.A priority patent/NL162694C/xx
Priority to BE130863A priority patent/BE799236A/xx
Priority to FR7316539A priority patent/FR2183944B1/fr
Priority to DE2323103A priority patent/DE2323103C3/de
Application filed by Xerox Corp filed Critical Xerox Corp
Priority to US00362592A priority patent/US3844906A/en
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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
    • C25D1/00—Electroforming
    • C25D1/10—Moulds; Masks; Masterforms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/02—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • 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
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/13—Purification and treatment of electroplating baths and plating wastes

Definitions

  • Tufariello ABSTRACT said solution onto a support mandrel and thereafter recovering said nickel belt by cooling said nickel coated mandrel effecting a parting of the nickel belt from the mandrel due to different respective coefficients of thermal expansion comprising: establishing an electroforming zone comprising a nickel anode and a cathode comprising said support mandrel, said anode and cathode being separated by said nickel sulfamate solution maintained at a temperature of about 140 to 160 F and having a current density therein ranging from about 200 to about 500 ampslft imparting sufficient agitation to said solution to continuously expose said cathode to fresh solution; maintaining said solution within said zone at a stable equilibrium composition:
  • This invention relates to a continuous nickel electroforming process. More particularly this invention relates to a process for maintaining steady state conditions in a dynamic nickel sulfamate electroforming bath which, in turn, enables the obtainment of a continuous, high output, nickel electroforming process.
  • This process is useful for the fabrication'of endless nickel belts which serve as supports for electrically photosensitive image retention surfaces employed in electrostatographic reproduction apparatus
  • an image is reproduced by initially establishing an electrostatic latent image on an image retention surface.
  • the image retention surface typically comprises a layer of electrically photosensitive material such as vitreous selenium formed on an electrically conductive substrate.
  • the electrostatic latent image can be developed by contacting the surface with a developer material which comprises, for example, a pigmented, electroscopic, thermoplastic resin.
  • This developer material adheres to the photosensitive surface in image configuration and can be subsequently transferred to a record medium such as a web or sheet of paper to which it is then fixed.
  • the photosensitive material is generally deposited on a conductive substrate generally comprising a cylindrically shaped body or drum.
  • an endless belt support body for use with an electrostatographic reproduction apparatus should, in addition to being electrically conductive and flexible, be seamless in order to avoid the necessity for indexing the operation of the machine to inhibit image formation at a seam of the belt.
  • An endless, seamless belt suitable for use in an electrostatographic apparatus must exhibit relatively high tensile strength to withstand the stresses imposed thereon during use and to avoid yielding under such conditions causing slack in the system which gives rise to vibrations and improper tracking. It has been found that for a belt of about 5 mils thickness, for example, the tensile strength must be at least about 90,000 psi for proper operation. Of course, as the thickness of the belt decreases, the tensile strength thereof must increase commensurately. Also, the belt must be sufficiently ductile to easily flex over rolls used to effect rotation of the belt without destroying the substrate due to the stresses encountered in flexing, rotation and translational motion of the belt. Moreover, there must be sufficient ductility to enable flexing without destroying the integrity of the photosensitive surface. Ductility in the belt (as measured by elongation) of from about 3 to 12 percent has been found suitable.
  • surface characteristic requirements must also be met.
  • Surface flaws such as pitting, nodular spotting, and other localized surface defects, such as arise from replication of the mandrel surface or suspended particulate materials, must be kept to a minimum because the effect thereof is manifested in poor ultimate copy quality.
  • any observable pit or any nodular spot having a diameter of about 10 mils or greater in the belt is sufficient to result in rejection of that belt.
  • An electrically conductive, flexible, seamless belt for use in an electrostatographic apparatus can be fabricated by an electroforming process wherein a metal from which the belt is to be fabricated is electrodeposited on a cylindrically shaped form or mandrel which is suspended in an electrolytic bath.
  • the materials from which the mandrel and the electroformed band are fabricated are selected to exhibit differing coefficients of thermal expansion for facilitating removal of the band from the mandrel upon cooling of the assembly.
  • the mandrel comprises a core cylinder formed of aluminum which is overcoated with a thin layer of chromium and is supported and rotated in a bath of nickel sulfamate.
  • a thin, flexible, seamless band of nickel is electroformed by this arrangement.
  • a diametric parting gap i.e., the gap formed by the difference between the average inside electroformed belt diameter and the average mandrel diameter at the parting temperature, must be at least about 8 mils and preferably at least about 10 to l 1 mils for reliable and rapid separation of the belt from the mandrel. For example, at a parting gap of about 6 mils, high incidents of both belt and mandrel damage are encountered due to inability to effect separation of the belt from the mandrel.
  • the parting gap is dependent upon the macrostress in the belt, the difference in linear coefficients of thermal expansion between the electroformed nickel and the mandrel material and the difference between the plating and parting temperatures, in the following manner:
  • parting gap AT (a a D S.D/E, 0.008 in.
  • D is the diameter of the mandrel (inches) at plating temperature
  • S is the internal stress in the belt (psi) and E is Youngs modulus for nickel
  • AT is the difference between the plating temperature and the parting temperature and a, a, is the difference in linear coefficients of thermal expansion between the mandrel material (M) and the electroformed nickel (Ni).
  • the nickel sulfamate electroforming bath is in a dynamic state with many different and sometimes competing reactions occurring. Needless to say, when fabricating belts for highly exacting specifications, it is critical to maintain uniform, steady state conditions within the electroforming bath despite the dynamic nature of the system.
  • 1t is still another object of this invention to provide endless, seamless, ductile nickel belts exhibiting relatively high tensile strength, and controlled surface roughness at high production rates.
  • the present invention provides a process for maintaining a continous and stable aqueous nickel sulfamate electroforming'solution adapted to form a relatively thin, flexible endless nickel belt by electrolytically depositing nickel from said solution onto a support mandrel and thereafter recovering said nickel belt by cooling said nickel coated mandrel effecting a parting of the nickel belt from the mandrel due to different respective coefficients of thermal expansion comprisl istablishing an electroforming zone comprising a nickel anode and a cathode comprising said support mandrel, said anode and cathode being separated by said nickel sulfamate solution maintained at a temperature of from about 140 to 160 F. and having a current density therein ranging from about 200 to 500 amps/ft";
  • the aqueous nickel sulfamate solution is maintained at a temperature of from about F. to about F. within the electroforming zone and the current density therein ranges from about 250 to 350 amps/ft and most preferably, the current density is about 300 amps/ft?
  • the aqueous nickel sulfamate solution is preferably maintained at a stable equilibrium composition within the electroforming zone comprising:
  • a relatively thin, ductile, electrically conductive seamless nickel belt is electroformed by preheating an electrically conductive mandrel, such as a mandrel having an aluminum core and a polished defect free chromium coating, at a preheating station 10.
  • Preheating is effected by contacting the mandrel with a nickel sulfamate solution at about 150 F. for a sufficient period of time to bring the mandrel to about 150 F.
  • Preheating in this manner allows the mandrel to expand to the dimensions desired in the electroforming zone 12 and enables the electroforming operation to begin as soon as the mandrel is placed in the electroforming zone 12. Thereafter, the mandrel is transported from preheating station to an electroforming zone 12.
  • the electroforming zone 12 comprises at least one cell containing an upstanding electrically conductive rotatable spindle which is centrally located within the cell and a concentrically located container spaced therefrom which contains donor metallic nickel.
  • the cell is filled with the nickel sulfamate electroforming solution.
  • the mandrel is positioned on the upstanding electrically conductive rotatable spindle and is rotated thereon.
  • a DC potential is applied between the rotating mandrel cathode and the donor metallic nickel anode for a sufficient period of time to effect electrodeposition of nickel on the mandrel to a predetermined thickness.
  • the mandrel and the nickel belt formed thereon are transferred to a nickel sulfamate solution recovery zone 14.
  • the belt-containing mandrel is transferred to a cooling zone 16 containing water maintained at about 60-75 F. or cooler for cooling the mandrel and the electroformed belt, whereby the belt, which exhibits a different coefficient of thermal expansion than the mandrel, can be readily separated from the mandrel.
  • the mandrel and belt are passed to a parting and cleaning station 18 at which the belt is removed from the mandrel, sprayed with water and subsequently passed to a drier (not shown). The mandrel is sprayed with water and checked for cleanliness before being recycled to preheat station 10 to commence another electroforming cycle.
  • the electroforming process described hereinabove is adpated for continuous, high production operation. Key factors in the success of such an operation are the composition of the electroformingsolution, the uniformity of the composition, and the stability thereof during long term continuous operation.
  • the process of the present invention enables a continuous, steady state operation to be maintained with resultant high productivity of nickel belts exhibiting a high degree of uniformity with relatively few rejects.
  • the relatively thin, ductile electrically conductive seamless nickel belts formed in the present invention must have a relatively high tensile strength of from about 90,000 to about 130,000 psi, yet have a ductility of between about 3 to 12 percent.
  • the electroformed belt in order for the process to operate on a continuous basis, must have an internal stress of r .000 055 psi to permit rapid parting of the belt from the mandrel.
  • the belt is very thin, typically exhibiting a thickness of about 0.005 inches.
  • the surface roughness exhibited by the belt ranges from about 10 to 80 microinches, RMS and preferably, exhibits a surface roughness of from about 30 to.50 microinches, RMS.
  • the current densities employed in the present invention range from about 200 to 500 amps/ft preferably, the current density is about 250-350 amps/ft and most preferably about 300 amps/ft.
  • current concentrations for economic operation can range from about 5 to 15 amps/gal.
  • a flow rate of about 15 gal/min of solution has been found sufficient to effect proper temperature control.
  • the combined effect of mandrel rotation and solution impingement assures uniformity of composition and temperature of the electroforming solution within the electroforming cell.
  • the nickel sulfamate solution is maintained at an equilibrium composition within the electroforming zone comprising:
  • metal halides in conventional nickel sulfamate electroforming solutions because they are known to contribute to tensile stress.
  • a metal halide generally a nickel halide such as nickel chloride, nickel bromide or nickel fluoride and preferably, nickel chloride
  • nickel chloride a metal halide
  • the inclusion of sufficient nickel halide to avoid anode polarization as evidenced by gradually increasing pH was found, however, to impart sufficient tensile stress to the electroformed belts to significantly interfere with the parting of the belt from the mandrel.
  • halide concentrations are also required in order to substantially eliminate anode polarization. Since the inclusion of halide is generally undesirable because of accompanying increases in tensile stress, a minimum of halide consistent with reduction of anode polarization is desired. It has been found in a preferred embodiment of the present invention that under steady state conditions, the minimum effective chloride concentration is obtained by maintaining a constant weight ratio of chloride (NiCl .6- H O) to total nickel of 0.12 i 0.02. When this ratio is exceeded, an increase in tensile stress in the belt is obtained.
  • the stress reducing agent must be added to the electroforming solution in proportion to the amount of nickel electrolytically deposited from said solution.
  • this can be accomplished by continuously charging to said solution from about 1.3 to 1.6 X 10 moles of a stress reducing agent per mole of nickel electrolytically deposited from said solution.
  • the addition of a stress reducing agent often is associated with the generation of organic degradation products which interfere with the electroforming process and may require periodic shut down for purification purposes.
  • Suitable stress reductin agents are sodium sulfobenzimide (saccharin), 2-methylbenzenesulfonamide, benzene sulfomate,
  • Saccharin has long been known as being effective in reducing the stress in electrodeposits (as well as grain refining). in the present invention, it has been found possible to use saccharin effectively at extremely low concentrations. Furthermore, a principal degradation product of saccharin, 2-methy1benzenesulfonamide (2- MBSA), has been found nearly as effective as saccharin itself in controlling stress. Still further, saccharin and 2-MBSA together form a system which tends to mask or minimize the effects of temporary, independent fluctuations in the levels of either component.
  • the levels of each are best controlled by continuously adding saccharin at the rate per mole of Ni plated set'forth hereinabove and allowing the levels to tend toward their steady state concentrations.
  • the steady state concentrations will be determined by apparent first order reaction rates, as will the rate of approach to steady state.
  • the steady state concentration of each component is a function of current density, temperature, agitation and current concentration. At steady state, however, the effects of the two components will be independent of concentration and will only be a function of addition rate.
  • the weight ratio of Z-MBSA/saccharin at steady state in the electroforming solution ranges from about 2:1 to about 3:1.
  • the pH of the electroforming solution is also important with respect to both yield and the physical properties of the nickel belt.
  • the pH for successful continuous operation can range from about 3.8 to 4.1. At a pH greater than about 4.1, surface flaws such as gas pitting increase. Also internal stress increases and interferes with parting of the electroformed belt from the mandrel. At a pH less than about 3.9, the metallic surface of the mandrel can become activated, especially when a chromium plated mandrel is employed, thereby causing the metal electroform to adhere to the chromium plating and thus seriously interfere with the operation of the process. Low pH also results in lower tensile strengths ini the final belt which increases the incidence of mechanical damage because of the weaker nature of the belt.
  • the pH level can be maintained by addition of an acid such as sulfamic acid, when necessary.
  • the pH can be essentially maintained within the range set forth above by maintaining a steady state concentration of buffering agent in the solution, generally boric acid (H 80 within the range of 5.0 to 5.4 oz/gal. It has been found that as the boric acid concentration goes below about 5.0, pH control is lost and an increase in surface flaws is observable. lf the boric acid concentration exceeds 5.4, there is sufficient boric acid present to result in precipitation thereof in any localized cold spots, thereby interfering with the process.
  • buffering agent generally boric acid (H 80 within the range of 5.0 to 5.4 oz/gal.
  • the surface tension of the solution can range from about 33 to about 37 dynes/cm in order to assure a high rate of production with minimum rejects because of surface flaws. It has been found that the surface tension of the solution can be maintained within this range by maintaining a steady state concentration of an anionic surfactant such as sodium lauryl sulfate, Duponol 80, a sodium alcohol sulfate, Petrowet R, a sodium hydrocarbon sulfonate (said latter two surfactants being available from E. l.
  • an anionic surfactant such as sodium lauryl sulfate, Duponol 80, a sodium alcohol sulfate, Petrowet R, a sodium hydrocarbon sulfonate
  • du Pont de Nemours & Co., 1nc.), and the like ranging from to 0.014 oz/gal within the solution, and preferably, by maintaining a steady state concentration of from 0 to 0.007 oz/gal of surfactant therein.
  • the amount of surfactant required will vary with the quality of water used. It is considered preferably to employ deionized water throughout the process of this invention.
  • the surfactant can be added continuously or periodically to sump 22 via line 34 to maintain the desired surfactant concentration in the electroforming solution.
  • the drive means provides a low resistance conductive element for conducting as relatively high amperage electrical current between the mandrel and a power supply.
  • the cell during the electroplating process, is adapted to draw, for example, a peak current of about 3,000 amperes DC at a potential of about 18 volts. In this manner, the mandrel effectively comprises the cathode of the cell.
  • An anode electrode for the electrolytic cell comprises an annular shaped basket containing metallic nickel which replenishes the nickel electrodeposited out of solution.
  • the nickel used for the anode comprises sulfur depolarized nickel. Suitable sulfur depolarized nickel is available under the tradenames SD Electrolytic Nickel and S Nickel Rounds from International Nickel Company.
  • the nickel may be in any suitable form or configuration. Typical forms include buttons, chips, squares and strips.
  • the basket is supported within the cell by an annular shaped basket support member which also supports an electroforming solution distributor manifold or sparger which is adapted to introduce the electroforming solution to the cell and effect agitation thereof.
  • a relatively high amperage current path with the basket is provided through a contact terminal which is attached to a current supply bus bar.
  • the nickel sulfamate electroforming solution is continuously circulated through a closed solution treating loop as shown in the drawings.
  • This loop comprises a series of processing stations which maintain a steady state composition of the solution, regulate the temperature of the solution and remove any impurities therefrom, thereby assuring the required conditions within the electroforming cell 12.
  • the electroforming cell 12 contains one wall thereof which is shorter than the others and acts as a weir over which the electroforming solution continuously overflows into a trough as recirculating solution is continuously pumped into the cell via the solution distributor manifold or sparger along the bottom of the cell.
  • the solution flows from the electroforming cell 12 via a trough to an electropurification zone 20 and a solution sump 22.
  • the solution is then pumped to a filtration zone 24 and to a heat exchange station 26 and is then recycled in purified condition at a desired temperature and composition to the electroplating cell 12 whereupon admixture with the solution contained therein, the steady state conditions set forth above are maintained on a continuous and stable basis.
  • the electrolytic purification station 20 is provided for removing dissolved metallic impurities from the nickel sulfamate solution prior to filtering.
  • a metal plate of steel or preferably, stainless steel, can be mounted in station 20 to function as the cathode electrode.
  • Anodes can be provided by a pluralityof anode baskets which comprise tubular shaped metallic bodies, preferably titanium, each having a fabric anode bag.
  • a DC potential is applied between the cathodes and the anodes of the purification station from a DC source.
  • the electropurification station 20 includes a wall thereof which extends coextensively with a wall of the solution sump zone 22 and functions as a weir.
  • the electroforming solution flows from electropurification zone 20 into the solution sump zone 22 via this weir.
  • the quantity of electroforming solution circulated within the closed loop described herein is maintained relatively constant. Replenishment of solution which is carried away by the mandrel when removed from the electroforming cell and water which is lost through evaporation is provided.
  • the solution can be replenished by the automatic addition of de-ionized water from a source 28 and/or by recycling solution from the nickel rinse zone 14 to sump 22 via line 30.
  • Sensors can be positioned in sump 22 adapted for automatically signaling a low level of solution therein and causing the operation of pumps which pump de-ionized water and- /or rinse solution to sump 22.
  • a pH meter can be positioned in sump 22 for sensing the pH of the solution and for effecting the addition of an acid such as sulfamic acid when necessary to maintain essentially constant pH.
  • the continuous addition of stress reducing agents as described hereinabove can be effected at sump 22 via line 32.
  • control of the surface tension of the solution can be maintained by continuous addition of surfactant to the sump via line 34. In this manner, all component additions or make up are made at the sump 22 thereby enabling maintenance of a homogeneous solution at a steady state equilibrium composition within the electroforming cell 12.
  • the solution which has been electrolytically purified can contain undissolved micron sized solids and sludge from the anodic dissolution of the nickel which must be removed prior to return to the electroforming cell 12.
  • This solution is pumped from the sump tank 22 to a filter station 24 which removes essentially all of the undissolved solids from the solution.
  • the temperature of the electroforming solution must be maintained within a desired range in order to provide a desired surface smoothness and uniformity in the electroformed belt.
  • the electroforming solution which flows from the cell is raised in temperature due to the flow of relatively large currents therein and accompanying generation of heat in the electroforming cell.
  • Means are provided at the heat exchanging station 26 for cooling the electroforming solution to a lower temperature.
  • the heat exchanger can be of conventional design and receives a coolant such as chilled water from a cooling or refrigerating system (not shown).
  • the electroplating solution which is cooled in the heat exchanger means can be successively pumped to a second heat exchanger which provides for increasing the temperature of the cooled solution to within relatively close limits of the desired temperature.
  • the second heat exchanger can be steam heated by steam derived from a steam generator (not illustrated).
  • the first cooling heat exchanger can, for example, cool the relatively warm solution from a temperature of 150 F. or above to a temperature of about 140 f.
  • the second warming heat exchanger will heat the solution to a temperature of 140 F. plus or minus 2 F.
  • the heat exchange station 26 is provided for heating the solution to the operating temperatuers on startup of the system and upon the addition of replenishment solution to the system.
  • the efflux from the heat exchange station 26 is pumped to the electroforming cell 12 where, upon admixture with the solution present within the cell, steady state conditions of both composition and temperature are maintained on a continuous basis.
  • Table 1 summarizes the data obtained in Examples 1-14.
  • the data summarized in Table 1 was collected under continuous and sustained operating conditions in which dynamic equilibrium was established in the manner set forth hereinabove.
  • the data represents average values for runs of 1 to 3 months duration in which the process operated continuously 7 hours per day. Data was not taken until after days of such operation since such period of time is normally required to assure the establishment of dynamic equilibrium as evidenced by uniformity of product and process conditions.
  • the runs were no longer than a week in duration.
  • Example Mandrel Core Ni oz/gal NiCl '6H O oz/gal Plating Temp. (F) T AT (T -T Parting Gap (in.) at T (Parting Temp.) Saccharin Concentration Mg/L Wt. Ratio Z-MBSA Saccharin Mole Ratio Saccharin Ni Surface Roughness (micr0inches.RMS) Belts Rejectable for Surface Flaws lnternal Stress. psi Tensile Strength. psi Elongation (71 in 2 in.) Coatability of Se on Electroform Remarks Example Mandrel Core Ni oz/gal NiCl '6H-,O oz/gal Plating Temp. (F) T AT T Parting Gap (in.) at
  • Example 1 14 the chromium surfaces of the 10 ness range of 10-12 microinches, RMS. l5
  • an electroforming zone comprising a sulfur depolarized nickel anode and a cathode comprising said support mandrel, said anode and cathode being separated by said nickel sulfamate solution maintained at a temperature of about to F. and having a current density therein ranging from about 200 to about 400 amps/ft imparting sufficient agitation to said solution to continuously expose said cathode to fresh solution;
  • a process for maintaining a continuous and stable aqueous nickel sulfamate electroforming solution adapted to form a relatively thin, ductile, seamless nickel belt by electrolytically depositing nickel from said solution onto a support mandrel and thereafter recovering said nickel belt by cooling said nickel coated mandrel effecting a parting of the nickel belt from the mandrel due to different respective coefficients of thermal expansion comprising:
  • an electroforming zone comprising a sulfur depolarized nickel anode and a cathode com- 17 prising said support mandrel, said anode and cathode being separate by said nickel sulfamate solution maintained at a temperature of about 150 to 160F. and having a current density therein ranging from about 250 to about 350 amps/ft imparting sufficient agitation to said solution to continuously expose said cathode to fresh solution; maintaining said solution within said zone at a stable equilibrium composition comprising:
  • the stress reducing agent is a mixture of sodium sulfobenzimide and Z-methylbenzenesulfonamide.
  • the nickel belt exhibits an internal stress of a surface roughness of from about 30 to 50 microinches, RMS, a tensile strength ranging from about 90,000 to 130,000 psi and a ductility of from about 3 to 12 percent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Photoreceptors In Electrophotography (AREA)
US00362592A 1972-05-08 1973-05-21 Dynamic bath control process Expired - Lifetime US3844906A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
GB2126173A GB1421818A (en) 1972-05-08 1973-05-04 Nickel electroforming process
NL7306365.A NL162694C (nl) 1972-05-08 1973-05-07 Werkwijze voor het elektrolytisch neerslaan van nikkel op een roterende doorn.
BE130863A BE799236A (fr) 1972-05-08 1973-05-08 Procede de reglage de bain dynamique,
FR7316539A FR2183944B1 (enrdf_load_stackoverflow) 1972-05-08 1973-05-08
DE2323103A DE2323103C3 (de) 1972-05-08 1973-05-08 Verfahren zum Stabilhalten eines galvanischen Nickelsulfamatbades für die Bandherstellung
US00362592A US3844906A (en) 1972-05-08 1973-05-21 Dynamic bath control process

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US25104572A 1972-05-08 1972-05-08
US00362592A US3844906A (en) 1972-05-08 1973-05-21 Dynamic bath control process

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US (1) US3844906A (enrdf_load_stackoverflow)
BE (1) BE799236A (enrdf_load_stackoverflow)
DE (1) DE2323103C3 (enrdf_load_stackoverflow)
FR (1) FR2183944B1 (enrdf_load_stackoverflow)
GB (1) GB1421818A (enrdf_load_stackoverflow)
NL (1) NL162694C (enrdf_load_stackoverflow)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963587A (en) * 1975-05-19 1976-06-15 Xerox Corporation Process for electroforming nickel foils
US4501646A (en) * 1984-06-25 1985-02-26 Xerox Corporation Electroforming process
US4557993A (en) * 1984-08-03 1985-12-10 Xerox Corporation Process for preparing an electrophotographic imaging member with NiO interlayer
US4678691A (en) * 1985-10-24 1987-07-07 Xerox Corporation Electroforming process and product
US4747992A (en) * 1986-03-24 1988-05-31 Sypula Donald S Process for fabricating a belt
DE3741421A1 (de) * 1986-12-08 1988-06-09 Xerox Corp Galvanoformungs-verfahren und galvanoformungs-vorrichtung
US4902386A (en) * 1989-08-02 1990-02-20 Xerox Corporation Electroforming mandrel and method of fabricating and using same
US5049243A (en) * 1990-12-24 1991-09-17 Xerox Corporation Electroforming process for multi-layer endless metal belt assembly
US5049242A (en) * 1990-12-24 1991-09-17 Xerox Corporation Endless metal belt assembly with controlled parameters
US5069758A (en) * 1991-01-28 1991-12-03 Xerox Corporation Process for suppressing the plywood effect in photosensitive imaging members
US5127885A (en) * 1990-12-24 1992-07-07 Xerox Corporation Endless metal belt with strengthened edges
US5131893A (en) * 1990-12-24 1992-07-21 Xerox Corporation Endless metal belt assembly with minimized contact friction
US5152723A (en) * 1990-12-24 1992-10-06 Xerox Corporation Endless metal belt assembly with hardened belt surfaces
US5215853A (en) * 1991-12-23 1993-06-01 Xerox Corporation Photosensitive imaging member and process for making same
US5221458A (en) * 1990-12-24 1993-06-22 Xerox Corporation Electroforming process for endless metal belt assembly with belts that are increasingly compressively stressed
US5230787A (en) * 1991-12-30 1993-07-27 Xerox Corporation Spring and process for making a spring for a fluid bearing by electroforming
US5472587A (en) * 1994-02-25 1995-12-05 Xerox Corporation Brushless electroforming apparatus
US5480528A (en) * 1994-02-25 1996-01-02 Xerox Corporation Brushless electrodeposition apparatus
US5524342A (en) * 1994-05-27 1996-06-11 Xerox Corporation Methods for shrinking nickel articles
US5543028A (en) * 1994-11-23 1996-08-06 Xerox Corporation Electroforming semi-step carousel, and process for using the same
US5652648A (en) * 1993-12-09 1997-07-29 Xerox Corporation Negative wrap back up roll adjacent the transfer nip
US5709586A (en) * 1995-05-08 1998-01-20 Xerox Corporation Honed mandrel
US5807472A (en) * 1997-01-13 1998-09-15 Xerox Corporation Parting fixture for removal of a substrate from a mandrel
US5853556A (en) * 1996-03-14 1998-12-29 Enthone-Omi, Inc. Use of hydroxy carboxylic acids as ductilizers for electroplating nickel-tungsten alloys
US5863394A (en) * 1996-10-02 1999-01-26 Xerox Corporation Apparatus for electrodeposition
CN1042150C (zh) * 1994-04-25 1999-02-17 北京有色金属研究总院 电解法生产镍箔的工艺方法
US6376088B1 (en) 1999-11-24 2002-04-23 Xerox Corporation Non-magnetic photoreceptor substrate and method of making a non-magnetic photoreceptor substrate
US6454978B1 (en) 2000-06-16 2002-09-24 Avery Dennison Corporation Process for making fuel cell plates
US20050025893A1 (en) * 2003-07-31 2005-02-03 Smith Clifford L. Composite tool coating system
WO2005031043A1 (de) * 2003-09-29 2005-04-07 Siemens Aktiengesellschaft Verfahren und herstellungsanlage zum herstellen eines schichtartigen bauteils
US20070063521A1 (en) * 2004-12-03 2007-03-22 Lancashire Christopher L Method and apparatus for plating automotive bumpers
US20200208287A1 (en) * 2016-09-19 2020-07-02 University Of Central Florida Research Foundation, Inc. Production of nanoporous films

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS585997B2 (ja) 1979-01-25 1983-02-02 株式会社井上ジャパックス研究所 電鋳装置

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US2287122A (en) * 1940-08-03 1942-06-23 Edward O Norris Inc Process of producing endless foraminous sheet-metal bands
US3186932A (en) * 1962-12-10 1965-06-01 Audio Matrix Inc Apparatus for forming phonograph record masters, mothers, and stampers
US3476657A (en) * 1967-03-28 1969-11-04 Friden Inc Method of forming a font belt
US3649509A (en) * 1969-07-08 1972-03-14 Buckbee Mears Co Electrodeposition systems

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DE1250712B (de) * 1963-05-22 1967-09-21 International Nickel Limited, London Galvanisches Nickelsulfamatbad und Verfahren zum Abscheiden von Nickeluberzugen
US3505177A (en) * 1966-05-31 1970-04-07 Xerox Corp Electroforming process
JPS528774B1 (enrdf_load_stackoverflow) * 1970-01-30 1977-03-11

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Publication number Priority date Publication date Assignee Title
US2287122A (en) * 1940-08-03 1942-06-23 Edward O Norris Inc Process of producing endless foraminous sheet-metal bands
US3186932A (en) * 1962-12-10 1965-06-01 Audio Matrix Inc Apparatus for forming phonograph record masters, mothers, and stampers
US3476657A (en) * 1967-03-28 1969-11-04 Friden Inc Method of forming a font belt
US3649509A (en) * 1969-07-08 1972-03-14 Buckbee Mears Co Electrodeposition systems

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963587A (en) * 1975-05-19 1976-06-15 Xerox Corporation Process for electroforming nickel foils
US4501646A (en) * 1984-06-25 1985-02-26 Xerox Corporation Electroforming process
JPS619591A (ja) * 1984-06-25 1986-01-17 ゼロツクス　コ−ポレ−シヨン 物品電気形成法
US4557993A (en) * 1984-08-03 1985-12-10 Xerox Corporation Process for preparing an electrophotographic imaging member with NiO interlayer
US4678691A (en) * 1985-10-24 1987-07-07 Xerox Corporation Electroforming process and product
US4747992A (en) * 1986-03-24 1988-05-31 Sypula Donald S Process for fabricating a belt
DE3741421A1 (de) * 1986-12-08 1988-06-09 Xerox Corp Galvanoformungs-verfahren und galvanoformungs-vorrichtung
US4781799A (en) * 1986-12-08 1988-11-01 Xerox Corporation Electroforming apparatus and process
DE3741421C2 (de) * 1986-12-08 2000-06-29 Xerox Corp Galvanoformungs-Verfahren
US4902386A (en) * 1989-08-02 1990-02-20 Xerox Corporation Electroforming mandrel and method of fabricating and using same
US5049242A (en) * 1990-12-24 1991-09-17 Xerox Corporation Endless metal belt assembly with controlled parameters
US5127885A (en) * 1990-12-24 1992-07-07 Xerox Corporation Endless metal belt with strengthened edges
US5131893A (en) * 1990-12-24 1992-07-21 Xerox Corporation Endless metal belt assembly with minimized contact friction
US5152723A (en) * 1990-12-24 1992-10-06 Xerox Corporation Endless metal belt assembly with hardened belt surfaces
US5221458A (en) * 1990-12-24 1993-06-22 Xerox Corporation Electroforming process for endless metal belt assembly with belts that are increasingly compressively stressed
US5049243A (en) * 1990-12-24 1991-09-17 Xerox Corporation Electroforming process for multi-layer endless metal belt assembly
US5069758A (en) * 1991-01-28 1991-12-03 Xerox Corporation Process for suppressing the plywood effect in photosensitive imaging members
US5215853A (en) * 1991-12-23 1993-06-01 Xerox Corporation Photosensitive imaging member and process for making same
US5230787A (en) * 1991-12-30 1993-07-27 Xerox Corporation Spring and process for making a spring for a fluid bearing by electroforming
US5652648A (en) * 1993-12-09 1997-07-29 Xerox Corporation Negative wrap back up roll adjacent the transfer nip
US5472587A (en) * 1994-02-25 1995-12-05 Xerox Corporation Brushless electroforming apparatus
US5480528A (en) * 1994-02-25 1996-01-02 Xerox Corporation Brushless electrodeposition apparatus
CN1042150C (zh) * 1994-04-25 1999-02-17 北京有色金属研究总院 电解法生产镍箔的工艺方法
US5524342A (en) * 1994-05-27 1996-06-11 Xerox Corporation Methods for shrinking nickel articles
US5543028A (en) * 1994-11-23 1996-08-06 Xerox Corporation Electroforming semi-step carousel, and process for using the same
US5709586A (en) * 1995-05-08 1998-01-20 Xerox Corporation Honed mandrel
US5853556A (en) * 1996-03-14 1998-12-29 Enthone-Omi, Inc. Use of hydroxy carboxylic acids as ductilizers for electroplating nickel-tungsten alloys
US5863394A (en) * 1996-10-02 1999-01-26 Xerox Corporation Apparatus for electrodeposition
US5807472A (en) * 1997-01-13 1998-09-15 Xerox Corporation Parting fixture for removal of a substrate from a mandrel
US6376088B1 (en) 1999-11-24 2002-04-23 Xerox Corporation Non-magnetic photoreceptor substrate and method of making a non-magnetic photoreceptor substrate
US6454978B1 (en) 2000-06-16 2002-09-24 Avery Dennison Corporation Process for making fuel cell plates
US20050025893A1 (en) * 2003-07-31 2005-02-03 Smith Clifford L. Composite tool coating system
WO2005031043A1 (de) * 2003-09-29 2005-04-07 Siemens Aktiengesellschaft Verfahren und herstellungsanlage zum herstellen eines schichtartigen bauteils
US20070035062A1 (en) * 2003-09-29 2007-02-15 Siemens Aktiengesellschaft Method and facility for the production of a layer-like part
US20070063521A1 (en) * 2004-12-03 2007-03-22 Lancashire Christopher L Method and apparatus for plating automotive bumpers
US20200208287A1 (en) * 2016-09-19 2020-07-02 University Of Central Florida Research Foundation, Inc. Production of nanoporous films
US11697885B2 (en) * 2016-09-19 2023-07-11 University Of Central Florida Research Foundation, Inc. Production of nanoporous films

Also Published As

Publication number Publication date
GB1421818A (en) 1976-01-21
DE2323103B2 (de) 1980-07-17
FR2183944A1 (enrdf_load_stackoverflow) 1973-12-21
NL162694B (nl) 1980-01-15
DE2323103A1 (de) 1973-11-22
BE799236A (fr) 1973-08-31
NL162694C (nl) 1980-06-16
NL7306365A (enrdf_load_stackoverflow) 1973-11-12
FR2183944B1 (enrdf_load_stackoverflow) 1976-06-11
DE2323103C3 (de) 1984-07-26

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