US2443599A - Electroplating method employing pulsating current of adjustable wave form - Google Patents

Electroplating method employing pulsating current of adjustable wave form Download PDF

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US2443599A
US2443599A US441694A US44169442A US2443599A US 2443599 A US2443599 A US 2443599A US 441694 A US441694 A US 441694A US 44169442 A US44169442 A US 44169442A US 2443599 A US2443599 A US 2443599A
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plating
voltage
direct current
alternating current
bath
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Allan E Chester
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Poor and Co
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Poor and Co
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Priority to GB35113/47A priority patent/GB647799A/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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • Y10S204/08—AC plus DC
    • 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
    • Y10S204/09—Wave forms

Definitions

  • my invention relates to plating in still tanks while .at the same timeobtaining .high platinglspeeds greaterthan the speeds now obtainable using semi-mechanical plating processes which physically and yprogressivelymove the work, or obtainable using dynamic or projection plating processes which move the work 'and the bath relative to each other at'comparatively high speeds.
  • An object of my invention is to produce bright adherent metallic deposits of good quality at high electro-plating rates.
  • Another object of my invention is to employ :pulsating .direct'currcnt in 'electro-plating to in- ;crease"1the possible plating rate and-t0, have the instantaneous'value :oi-the pulsating applied voltgiven direct current voltage to produce a desired :plating'result.
  • Yet another-object of my invention is-to prorvidea method of. plating zinc which can efiec- .tively use zinc oxide containing impurities and known as secondary zinc, which iscommercially .zaviailable readily at a comparatively low price,
  • Rig; 1 shows a. circuit for combining an alterhating-current voltage of adjustablev magnitude .an'd a direct current plating voltage, and applyingthe combined resultant to the plating work,
  • the source supplying the alternating current being connected in series with the plating generator.
  • Fig. 2 shows a circuit similar to that of Fig. 1
  • FIG. 3 shows anotherform of circuit for .com- Joining the Jdirec't. current ,output of a, plating '10 .generator with -an .al-ternatiugcunrent. ,vo'ltage component obtained from the. secondary of a transformer in whose primary. circuit is connected in series an adjustable reactor having in its magnetic circuit a separatev leg wound wit-h a winding supplied with. direct current ofxadjustable magnitude, for adjustingthe saturation of the magnetic circuit of the reactor and thereby adjusting the secondary voltage ofthetrans'former.
  • Fig. 4 shows a circuit for combining the direct current output of. a plating genenator'withjthe alternating current voltage component obtained from the secondary of a, shell type transformer having a third legwhich, may be adjustably saturated by a direct cur-rent winding.
  • Fig. 5 shows another circuitfor combining an alternating current component with the direct current output of a plating generator, the altern-ating current voltage being connected in parallel with the plating generator, and suitable reactors being inserted in series respectively between the generator and the work, and the alternating current source and thework.
  • Fig. 6 shows a, circuit arrangement wherein a plating tank is provided with a plurality of pairs of electrodes, and unv-arying direct current voltage .is applied to certain pairs of electrodes, and an alternating voltage is applied to certain other pairs of electrodes, so that currents flow in the tank having both direct and alternating current components.
  • the prior art has used various devices in the effort to break up the hydrogen envelope, including the lifting of the work out of the bath, the useof stirring rods, and the use of wetting agents on the work.
  • rectifiers for electro-plating has been proposed primarily to avoid the high cost of plating generators, and the rectifiers and associated filters were accordingly designed, so far as possible, to duplicate the performance of the plating generator, that is, to give either a substantially unvarying direct current voltage, or at least to approach thereto, so far as that was possible.
  • Another reason for trying to use rectifiers notwithstanding their inherent shortcomings, has been to avoid the rotating parts and commutator troubles met with in plating generators.
  • One practical objection to rectifiers is their prohibitively high costs for the heavy currents involved in plating.
  • the purpose of adding the organic addition agents which have been applied to the bath has been in the first place to reduce the crystal size of the plated metal and to produce a bright plate, and in the second place to increase the cathode efliciency, that is, the ratio between the actual rate of deposition and the electro-chemically theoretically possible rate of deposition, expressed in amperes per square foot.
  • I superpose alternating current and direct current components to obtain a pulsating direct current, and make adjustment of their respective magnitudes to get optimum relative proportions of the alternating current and direct current components for the size and geography of the tank, that is, the positions and distance apart of the electrodes and the work, the kind of work, and other structural features involved.
  • I vary the magnitude of the alternating current component applied to the direct current voltage of a given magnitude, in such a way that the instantaneous value of the voltage is at all times positive.
  • the current is at all times uni-directional. I find that if this condition is not maintained, and the direction of the current is allowed to reverse during parts of the cycle, slimes are formed and are plated as colloids, causing a smudgy deposit.
  • My method will produce improved deposits of a variety of metals from baths of numerous different compositions, but for best results I prefer to add to the bath a small quantity of a difficultly soluble organic salt as an addition agent.
  • My process can be used in plating various different metals, in particular it has been found especially well adapted for metals that plate well from an alkaline cyanide bath, which usually has good throwing power.
  • myprocess can also be used for plating from other ordinarily used baths including an acid bath such as an acid sulphate zinc bath.
  • My method may be applied to existing installations including a standard plating generator by connecting a source of alternating current voltage of suitable characteristics into the direct current plating circuit.
  • One method of varying the magnitude of the alternating current component is to employ two transformers with the primary of the second transformer connected to a variable tap on the secondary of the first transformer. This arrangement, however, involves excessive expense and is likely to spark badly even if pigtails are provided on the primary.
  • Fig. 1 there is shown a circuit for controlling and applying a pulsating voltage of desired wave form with desired magnitude of alternating current component to the ordinary two electrodes of a conventional plating tank.
  • the plating tank is shown at I, with the electrodes 2, 2.
  • a standard plating generator 3 is connected through variable resistor 4 to one of the electrodes 2, and a storage battery 5 is floated across the generator.
  • the secondary winding 6 of a transformer I is connected in series with the generator and the electrodes.
  • the secondary winding 6 of transformer 1 usually consists of some three or four turns.
  • the primary 8 of transformer I is supplied from supply terminals l0, ID, with alternating current-of standard commercial voltage and frequency, such as 230 volts, single phase, 60 cycle, and a, movable core variable inductor 9 is connected in series with the supply circuit.
  • alternating current-of standard commercial voltage and frequency such as 230 volts, single phase, 60 cycle
  • a, movable core variable inductor 9 is connected in series with the supply circuit.
  • Fig. 2 I have shown a circuit generally similar to that of Fig. 1, wherein, however, a condenser H is connected across the terminals of plating generator 3, instead of floating the secondary battery 5 of Fig. 1 thereacross. This arrangement is found preferable under some conditions.
  • Fig. 3 I have shown an arrangement wherein the primary circuit of transformer 1 has connected in series therein an adjustable realctor I2 consisting of a shell type frame with three legs, having the windings l3 and M on the two outer legs connected in series between a supply terminal and a terminal of primary 8, and having an auxiliary saturating winding l5 on the middle leg of the shell frame, which is connected to a source It of direct current voltage of adjustable magnitude, for the purpose of controllably adjusting the saturation of the magnetic circuit of the shell frame, and thereby controllably adjusting the magnitude of the alternating current component of the voltage delivered by secondary windin 6.
  • This adjustable reactor with variable direct current, for saturation affords a very convenient and rugged means for adjusting the magnitude of the alternating current component in the platin circuit.
  • Another way of varying the magnitude of the alternating current component in the plating circuit is to employ a circuit generally similar to that of Fig. 1 with a single phase transformer, and to apply on one of the legs of the transformer frame an auxiliary direct current winding, and to adjust the magnitude of the current flowing therethrough for controllably saturating the magnetic circuit of the transformer and thereby adjusting its output voltage.
  • a shell type transformer frame having three legs.
  • Such an arrangement is shown in Fig. 4, wherein secondary winding 19 of transformer i8 is connected in the plating circuit, and primary winding 20 is connected to supply terminals l0, (0.
  • On the middle leg of the transformer frame there is connected an auxiliary direct current winding 2
  • variable resistor 23 By adjusting variable resistor 23, the magnitude of the saturating direct current passing through auxiliary winding 2
  • Fig. 1-4 I have shown circuit arrangements wherein the source of alternating current has been connected in series with the source of direct current constituted by the plating generator.
  • alternating current component is conveniently the secondary winding of a transformer 29, having primary winding 3
  • This parallel circuit arrangement may in some cases be found desirable to avoid any possible feed-back, but such feed-back seldom presents any problem.
  • the arrangement of Fig. 5 usually involves a more expensive type of tank construction than do the arrangements of Figs. 1-4.
  • Fig. 6 Such an arrangement is shown in Fig. 6, wherein there are positioned within plating tank 49, a plurality of pairs of direct-current electrodes, 34, 35, 35, 31, 38, 3-9, and also a plurality of pairs of alternating current electrodes 40, 4
  • Objects to be plated'constituting the work may constitute the cathodes of the direct current electrodes.
  • The'direct current electrodes are connected to a plating generator 44.
  • the alternating currentelectrodes are connected to the secondary winding 41 of transformer 45, whose primary 48 is supplied from a commercial source of alternating current through a variable inductor 48.
  • I usually ground the anode to avoid the possibility of having a comparatively high primary voltage such as 230 volts to ground.
  • the alternating current voltage may be capacitatively coupled to the plating circuit if special requirements exist, but this is usually more expensive than the method which I have described in detail for applying the alternating current to the plating circuit.
  • rectifiers For supplying the alternating current component for my method, it would also be possible to use one or more rectifiers, as of the selenium or copper type, but for the type of load involved in electro-plating employing my method, these have been found to give unsatisfactory and poor performance including poor voltage regulation and to involve comparatively high costs. Furthermore, rectifiers do not conveniently provide for a variable adjustment of the magnitude of the alternating current component of the pulsating voltage which is necessary to obtain the full benefit of my process.
  • the transformer reactors, 'wiring, meters, resistors, and protective devices may be conveniently mounted on a frame as a panel unit.
  • circuits 1 provide adjusting means for varying the magnitude of the alternating current component which is combined with the direct current voltage component.
  • I adjust the value of the alternating current voltage com-ponent in such a manner that the lowest instantaneous value of voltage representing the algebraic sum of the constant direct current potential and the greatest negative value of the alternating. current voltage wave at its negative peak is positive but reduced to such a value that polarization at the cathode is practically nonexisting, and no hydrogen bubbles are maintained on the cathode at the instant of the low peak.
  • This condition will generally occur for baths such as an alkaline cyanide zinc bath, to which it is usual in conventional plating to apply a direct current voltage of about three volts. between 0.5 and 1.5 volts for the valley" instantaneous value in using my method.
  • a satisfactory lowest instantaneous voltage is in many cases about 0.9 ,volt.
  • the minimum instantaneous val1ey" voltage will be 6-5.09 or 0.91 volt.
  • the adjustments are made to provide a pulsating voltage whose minimum instantaneous valley value has been selected as an optimum value, determined according to the shape and dimensions of the tank and of the work.
  • the area of the work constituting the cathode is an important factor, since with the anode area being fixed, the cathode area determines the anode-cathode ratio.
  • the unvarying direct current component which I employ may be permitted to go as high as 24 volts, while still keeping the minimum instantaneous value of the pulsating current produced down to from 0.5 to 1.5 volts, by supplying an alternating current component of suitably large magnitude.
  • lauric alcohol sulfonate lauric sulfonate
  • the lauric sulfonate assists materially in retaining the glucona'te in suspension.
  • the lauric sulfonate may be considered to be a wetting. suspending and floccul-ating agent, reducing the surface tension and producing better deposits, by reason of its being occluded in the plate at the cathode. As a practical matter it is necessary for the bath to contain some agent capable of retaining the gluconate in suspension.
  • the quantities of the several ingredients as mentioned for the preferred bath may be varied within tolerances of approximately plus or minus 20% without serious impairment of the results obtained.
  • the bath is originally prepared according to the formula above given, it may be expected that its composition will vary considerably after it has been used in active piating work for a number of weeks, varying in concentration perhaps as much as but it will continue to give satisfactory plating results. Plating with this bath is ordinarily conducted at ordinary room temperatures.
  • the calcium gluconate acts chemically in the following manner:
  • the acid ion oxidizes at the anode, due to the presence of nascent oxygen. This generates saccharic acid, which, in turn, reacts with the excess sodium carbonate to produce the insoluble calcium carbonate, and return the acid ion to the anode for regeneration as a saccharate.
  • the calcium gluconate acts as a control agent for controlling the action and performance of the described bath when employed with the pulsating current method which I have described.
  • My method including my preferred pulsating voltage and my preferred electrolyte, produces extremely rapid and clean adherent deposits in a manner not heretofore attained in the art.
  • the bath is kept free from sludge and the deposits are brlgh
  • the apparatus is simple and rugged, and the application of the method does not involve difficult adjustments.
  • the method of obtaining napid clean deposition which consists in applying to the cathode with respect to the anode a pulsating direct current voltage whose instantaneous value is always positive, said pulsating voltage having an unvarying direct current component and further having a sinusoidal alternating current component, the lowest instantaneous value of the said pulsating voltage at the negative alternating peak being between 0.5 volts and 1.5 volts, said direct current component having a voltage not substantially higher than 24 volts and said alternating current component having a frequency within the range of from about 25 to 60 cycles, inclusive.
  • the method of obtaining rapid clean deposition which consists in applying to the cathode with respect to the anode a pulsating direct current voltage whose instantaneous value is always positive, said pulsating voltage having an unvarying direct current com nent and [further having a sinusoidal alternating current component, the instantaneous peak value of the alternating component considered separately being at least half of the value of the unvarying direct current component and the lowest instantaneous value of the said pulsating voltage at the negative alternating peak being between 0.5 and 1.5 volt, said direct current component having a voltage not substantially higher than 24 volts and said alternating current component having a frequency within the range of from about 25 to 60 cycles, inclusive.
  • the method of obtaining rapid deposition which consists in applying to the cathode with respect to the anode a pulsating direct current voltage whose instantaneous value is always positive, the lowest instantaneous value of said pulsating voltage at the negative alternating peak being between 0.5 volt and 1.5 volts, said direct current component having a voltage not substantially higher than 24 volts and said alternating current component having a frequency within the range of from about 25 to 60 cycles, inclusive.
  • the method of electrodeposition which comprises electnodepositing stantaneous value of the voltage of which is always positive, said pulsating current having a direct current voltage component and an alternating current voltage component, the lowest instantaneous value of the said pulsating voltage at the negative peak being between 0.5 volt and 1.5 volts, said direct current component having a voltage not substantially higher than 24 volts, said alternating current component, when considered separately, having an instantaneous peak value of substantially at least half of the value of the direct current component, and said alternating current component having a frequency within the range of from about 25 to 60 cycles, inclusive.
  • the step which comprises electrodepositing zinc from an aqueous alkaline cyanid-zinc plating bath with a pulsating current voltage in sine wave form, the instantaneous value of which is always positive, said pulsating voltage having a direct current component and an altemating current component, the lowest instantaneous value of the said pulsating voltage at the negative peak being between 0.5 volt and 1.5 volts, said direct current 11 component having a. voltage not substantially higher than 24 volts andsaidalternating current component having a frequency within the range of 'from about 25 to 60 cycles,inclusive.
  • the step which comprises electrodepositing zinc from an aqueous acidzinc plating bath with a pulsating current voltage in sine wave form, the instantaneous value of which is always positive, said pulsating voltage having a direct current component and an alternating current component, the lowest instantaneous value of the said pulsating voltage at the negative peak being between 0.5 volt and 1.5 volts, said direct current component having a voltage not substantially higher than 24 volts and-said alternatingcurrent component having a frequency within the range-of from about 25 to 60 cycleainclusive.
  • the step which comprises electrodepositing copper from. an aqueous alkaline copper plating bath witha pule sating current solution in sine wave form, the instantaneous value of which is always positive, said pulsating voltage having a direct current component and an alternating current component, the lowest instantaneous value of the said pulsating voltage at the negative peak being be- 12 tween 0.5 volt and 1.5 volts, said direct current component having a voltage. notsubstantially higher than 24 volts and said alternating current component having a frequency within the range of from about 25 to cycles, inclusive.

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US441694A US2443599A (en) 1942-05-04 1942-05-04 Electroplating method employing pulsating current of adjustable wave form
GB35113/47A GB647799A (en) 1942-05-04 1947-12-31 Electroplating method employing pulsating current

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2515192A (en) * 1944-09-27 1950-07-18 Poor & Co Method of electroplating
US2548867A (en) * 1945-04-14 1951-04-17 Poor & Co Electroplating metals
US2606147A (en) * 1944-09-27 1952-08-05 Poor & Co Electrodeposition of arsenic
US2619454A (en) * 1945-08-30 1952-11-25 Brush Dev Co Method of manufacturing a magnetic recording medium by electrodeposition
US2651610A (en) * 1950-07-17 1953-09-08 Poor & Co Method of electroplating zinc
US2651609A (en) * 1950-07-17 1953-09-08 Poor & Co Method of electroplating copper
US2935454A (en) * 1953-05-01 1960-05-03 Tokumoto Shin-Ichi Method of the electrodeposition of titanium metal
US3269933A (en) * 1961-03-17 1966-08-30 American Mach & Foundry Electrodialysis apparatus for desalinization of fluids having automatic current control means
US3276976A (en) * 1962-02-13 1966-10-04 Air Prod & Chem Method of making a fuel cell electrode
US3418222A (en) * 1966-02-28 1968-12-24 Murdock Inc Aluminum anodizing method
US3669856A (en) * 1968-06-21 1972-06-13 Ove Christopher Gedde Process for the production of colored protective coatings on articles of aluminum or aluminum alloys
US3716464A (en) * 1969-12-30 1973-02-13 Ibm Method for electrodepositing of alloy film of a given composition from a given solution
US3959088A (en) * 1975-03-19 1976-05-25 The United States Of America As Represented By The Secretary Of The Army Method and apparatus for generating high amperage pulses from an A-C power source
US4038158A (en) * 1975-10-22 1977-07-26 E. I. Du Pont De Nemours And Company Electrochemical generation of field desorption emitters
US4290868A (en) * 1980-04-07 1981-09-22 Mack Michael H Iron plumbing corrosion minimizing method
US4515671A (en) * 1983-01-24 1985-05-07 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US5039381A (en) * 1989-05-25 1991-08-13 Mullarkey Edward J Method of electroplating a precious metal on a semiconductor device, integrated circuit or the like
WO2000020662A1 (en) * 1998-10-05 2000-04-13 Semitool, Inc. Submicron metallization using electrochemical deposition
US20020022363A1 (en) * 1998-02-04 2002-02-21 Thomas L. Ritzdorf Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US20020074233A1 (en) * 1998-02-04 2002-06-20 Semitool, Inc. Method and apparatus for low temperature annealing of metallization micro-structures in the production of a microelectronic device
US20040023494A1 (en) * 1998-03-13 2004-02-05 Semitool, Inc. Selective treatment of microelectronic workpiece surfaces

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB715525A (en) * 1951-06-19 1954-09-15 British Dielectric Res Ltd Improvements in or relating to electrolytic capacitors
US4092226A (en) * 1974-12-11 1978-05-30 Nikolaus Laing Process for the treatment of metal surfaces by electro-deposition of metal coatings at high current densities

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US1388874A (en) * 1920-02-18 1921-08-30 Ralph D Mershon Forming dielectric films
DE464709C (de) * 1928-08-23 Tech Beratungsstelle G M B H Verfahren zur elektrolytischen Vorbehandlung von Gegenstaenden, die einen metallischen UEberzug erhalten sollen
US1755479A (en) * 1924-04-28 1930-04-22 Jones W Bart Ett Method of and means for cyclic current control
US1918605A (en) * 1928-01-09 1933-07-18 Parker Rust Proof Co Chromium plating
GB414939A (en) * 1933-11-22 1934-08-16 Max Schlotter Improved process for electro-deposition of chromium
US2063760A (en) * 1931-09-10 1936-12-08 Schulein Joseph Bath for and process of electrodeposition of metal

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE464709C (de) * 1928-08-23 Tech Beratungsstelle G M B H Verfahren zur elektrolytischen Vorbehandlung von Gegenstaenden, die einen metallischen UEberzug erhalten sollen
US1388874A (en) * 1920-02-18 1921-08-30 Ralph D Mershon Forming dielectric films
US1755479A (en) * 1924-04-28 1930-04-22 Jones W Bart Ett Method of and means for cyclic current control
US1918605A (en) * 1928-01-09 1933-07-18 Parker Rust Proof Co Chromium plating
US2063760A (en) * 1931-09-10 1936-12-08 Schulein Joseph Bath for and process of electrodeposition of metal
GB414939A (en) * 1933-11-22 1934-08-16 Max Schlotter Improved process for electro-deposition of chromium

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2515192A (en) * 1944-09-27 1950-07-18 Poor & Co Method of electroplating
US2606147A (en) * 1944-09-27 1952-08-05 Poor & Co Electrodeposition of arsenic
US2548867A (en) * 1945-04-14 1951-04-17 Poor & Co Electroplating metals
US2619454A (en) * 1945-08-30 1952-11-25 Brush Dev Co Method of manufacturing a magnetic recording medium by electrodeposition
US2651610A (en) * 1950-07-17 1953-09-08 Poor & Co Method of electroplating zinc
US2651609A (en) * 1950-07-17 1953-09-08 Poor & Co Method of electroplating copper
US2935454A (en) * 1953-05-01 1960-05-03 Tokumoto Shin-Ichi Method of the electrodeposition of titanium metal
US3269933A (en) * 1961-03-17 1966-08-30 American Mach & Foundry Electrodialysis apparatus for desalinization of fluids having automatic current control means
US3276976A (en) * 1962-02-13 1966-10-04 Air Prod & Chem Method of making a fuel cell electrode
US3418222A (en) * 1966-02-28 1968-12-24 Murdock Inc Aluminum anodizing method
US3669856A (en) * 1968-06-21 1972-06-13 Ove Christopher Gedde Process for the production of colored protective coatings on articles of aluminum or aluminum alloys
US3716464A (en) * 1969-12-30 1973-02-13 Ibm Method for electrodepositing of alloy film of a given composition from a given solution
US3959088A (en) * 1975-03-19 1976-05-25 The United States Of America As Represented By The Secretary Of The Army Method and apparatus for generating high amperage pulses from an A-C power source
US4038158A (en) * 1975-10-22 1977-07-26 E. I. Du Pont De Nemours And Company Electrochemical generation of field desorption emitters
US4290868A (en) * 1980-04-07 1981-09-22 Mack Michael H Iron plumbing corrosion minimizing method
US4515671A (en) * 1983-01-24 1985-05-07 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US5039381A (en) * 1989-05-25 1991-08-13 Mullarkey Edward J Method of electroplating a precious metal on a semiconductor device, integrated circuit or the like
US7001471B2 (en) 1998-02-04 2006-02-21 Semitool, Inc. Method and apparatus for low-temperature annealing of metallization microstructures in the production of a microelectronic device
US20020022363A1 (en) * 1998-02-04 2002-02-21 Thomas L. Ritzdorf Method for filling recessed micro-structures with metallization in the production of a microelectronic device
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