CA1235386A - Process for making raney nickel coated cathode, and product thereof - Google Patents

Process for making raney nickel coated cathode, and product thereof

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Publication number
CA1235386A
CA1235386A CA000433480A CA433480A CA1235386A CA 1235386 A CA1235386 A CA 1235386A CA 000433480 A CA000433480 A CA 000433480A CA 433480 A CA433480 A CA 433480A CA 1235386 A CA1235386 A CA 1235386A
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cathode
nickel
anode
compartment
coating
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French (fr)
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Homi C. Bhedwar
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052Electrodes comprising one or more electrocatalytic coatings on a substrate
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/32Alkaline compositions
    • C23F1/36Alkaline compositions for etching aluminium or alloys thereof
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

TITLE
PROCESS FOR MAKING RANEY NICKEL COATED
CATHODE, AND PRODUCT THEREOF
ABSTRACT OF THE DISCLOSURE
Raney-nickel coated cathodes are made by plasma spraying a nickel/aluminum composition containing 56 to 59% by wt. nickel onto an electrically conductive foraminous cathode substrate, and activating the coated substrate by leaching aluminum from the coating with caustic. The activated cathode is especially useful in chloroalkali processes, as it operates at low hydrogen overvoltage, and durable against stalling and flaking.

Description

I
TO TOE
PROCESS FOR MAKING RANGY NICKEL COATED
CATHODE AND PRODUCT THEREOF
BACKGROUND OF THE INVENTION
This invention relates to a process for making an improved low hydrogen overvoltage cathode of the Rangy nickel type for use in chloralkali electrolysis, and to the cathode so made.
Cathodes of the Rangy nickel type are known in the art, ego, U.S. 4,116,804, U.S. 4,169,025 and U.S. 4,251,344. However, Rangy nickel coated cathodes of the prior art, while initially exhibiting good performance characteristics, suffer certain defects. Such Rangy nickel coating on the cathode 15 substrate has been of low durability, i.e., easily mechanically damaged and lost even by, e.g., water lets. For example, when such a cathode is used in a diaphragm-type chloralkali cell wherein an asbestos diaphragm is deposited directly onto the cathode 20 surface, such diaphragm gradually loses its permeability dye to clogging of the pores, usually after about 9 to 15 months, and must be removed and replaced; removal is ordinarily accomplished by spraying with jets of water, and during such 25 spraying, the jets of water have caused loss of some of the Rangy nickel by flaking or spelling. When the replacement diaphragm is deposited and baked, ordinarily at 355C in air for 4 hours, some deactivation of the Rangy nickel coating by oxidation 30 occurs. This progressive spelling and deactivation of Rangy nickel after multiple washes and bakes is responsible for a progressive loss of the voltage benefit provided by the Rangy nickel, i.e., the operating voltage of the cathode progressively 35 increases and approaches the operating voltage of the AD-5271 cathode substrate.
2 or Accordingly, it is a principal object of this invention to provide an improved Rangy nickel coated cathode having a more durable Rangy nickel surface than those previously known, and a process for making same.
Other objects will appear hereinafter SUMMARY OF THE INVENTION
Briefly, according to the present invention, there is provided a process for making a durable, low-hydrogen-overvoltage cathode for chloralkali use which comprises applying a nickel/aluminum alloy composition containing 56 to 59 by weight of nickel onto a suitable cathode substrate by plasma spraying, followed by leaching with caustic to remove aluminum.
More specifically, there is provided in accordance with the invention a process for making a low-hydrogen-overvoltage cathode for a chloralkali cell which comprises (a) plasma spraying a coating of a nickel/aluminum alloy composition containing 56 to 59% by wt. nickel onto a pheromones substrate of iron, ferrous alloy, nickel or nickel alloy, and by leaching aluminum from said coating by contacting the article prepared in step (a) with a caustic solution There are also provided in accordance with the invention a Rangy nickel coated cathode made by said process, a chloralkali cell containing said cathode, and a process or electrolysis of an alkali metal chloride in said cell.
DETAILED DESCRIPTION OF THE INVENTION
.
In the present invention a selected nickel/aluminum alloy composition is applied to an electrically conductive cathode substrate by plasma spraying.

It is a requirement of the present invention that the ~ickel/aluminum alloy composition employed for deposition on the cathode substrate contain about 56 to 59~ by wt. nickel. Nickel/aluminum alloys in this composition range contain the interme~allic compound Noah as the predominant phase, but also contain minor amounts of Nil and Noah, the exact amounts of these varying with the specific overall composition. Preferably, the nickel/aluminum alloy composition contains 56.5 to 57.5~ by wt.
nickel, most preferably substantially 57~ by wt.
nickel.
The nickel/aluminum alloy is suitably employed in the form of particles or granules, preferably 36 to 90 microns (165 to 400 mesh) in size, more preferably 36 to 53 microns (270 to 400 mesh) in size.
The electrically conductive cathode substrate can have various configurations, e.g., I flat, tubular, fingers, etc., but in any case should be pheromones, e.g., woven wire screen, expanded sheet metal or punched sheet metal. Iron, ferrous alloys such as mild steel and stainless steel, nickel and nickel alloys are particularly suitable materials for this substrate.
It is another requirement of the present invention that the nickel/aluminum alloy composition be deposited on the cathode substrate with the use of plasma spraying, also termed plasma arc spraying.
Plasma spraying is a known technique for depositing metal particles onto a substrate. Briefly streams of a gas and the metal particles are separately fed to a spray nozzle torch), and there is an electrical power input to the gas stream which ionizes the gas;
recombination of the positive ions and electrons in the gas stream after mixing with the metal particles releases energy which heats and partially melts the metal particles, and the partially melted metal particles adhere to the substrate on contact with it. Various gases, including nitrogen and argon, are suitable gases for this purpose. Argon is a preferred gas The power input need only be sufficient to partially melt the metal particles, e.g. 20 to 30 kilowatts in apparatus of ordinary size.
In most cases it is preferred to coat the fabricated cathode component rather than to coat the pheromones sheet material used to fabricate the cathode, because welding and other assembly techniques are more easily accomplished with the substrate in the uncoated condition. Also, it is best to clean the surface of the substrate before coating, as by sandblasting, or blasting with other grit such as alumina.
The cathodes of this invention can be either one-side or two-side coated However if only one side is coated it is preferred to coat the side which will face the membrane or diaphragm in order tug obtain the maximum reduction in cell voltage Thickness of the nickel/aluminum alloy coating applied to the cathode substrate of about 13 to 508 microns (0.5 to 20 Melissa is suitable, and is preferably about 127 to 254 microns (5 to 10 miss).
Following deposition of the nickel/aluminum alloy composition on the substrate, the Rangy nickel surface is developed by contacting the coated article with any strong base such as a caustic 501ution so as to leach aluminum from the coating. The concentration of the caustic is not critical; aqueous caustic solution containing 5 to 15% by woo Noah is suitable for this purpose, and 5 hours to 1 day is adequate time for the leaching. A 10~ by wt. aqueous caustic solution for 16 hours is typical. Similarly the temperature for leaching is not critical;
temperatures from room temperature up to the boiling point of the caustic solution are suitable. For coatings of indicated thickness, about 70 to 90% of the aluminum will ordinarily be removed during such leaching; some aluminum appears to remain even after much longer leaching time, but is believed not to be deleterious to performance of the resulting cathode.
This leaching step is also referred to as activation, and can be carried out prior to or after assembly of the cell. The Rangy nickel cathode so made, if permitted to dry, heats up upon contact with air, due to the pyrophoric character of Rangy nickel.
The Rangy nickel coated cathode so made not only exhibits low hydrogen overvoltage, but the coating has improved durability against flaking and spelling, as is shown hereinbelow in Example 9 and Comparative Examples B, C and D. As shown therein, the nickel/aluminum alloy composition applied as the coating in the process of the present invention provides an activated Rangy nickel cathode surface which unexpectedly is much more resistant against spelling and flaking than those derived from alloys which contain 55% by wt. nickel or less, which spell at a commercially unacceptable rate. Also as shown therein, although all the compositions tested initially showed good reductions in hydrogen overvoltage, the improvement in hydrogen overvoltage unexpectedly was maintained at a higher level following wash/bake cycles in the case of the nickel/aluminum alloy composition applied as the coating in the process of the present invention than did those containing lesser (55~ by woo nickel arid lower) and greater (62% by wt. nickel) amounts of nickel.
The cathode made by the process herein can be used as the cathode in known types of electrochemical cells which comprise a cathode compartment, a cathode disposed within said cathode compartment, an anode compartment, an anode disposed within said anode compartment, and a separator disposed between the anode and cathode compartments.
It is especially useful in chloralkali cells of such description. The separator can be, e.g., a liquid permeable diaphragm; such diaphragm can be fabricated of, e.g., asbestos fibers or per fluorinated polymer fibers. The separator can alternatively be a membrane, e.g., of highly fluorinated or per fluorinated ion-exchange polymer; membrane of such polymer containing sulfonate and/or carboxylate groups is now well known in the chloralkali art, e.g., U.S. 4,192,725, U.S. 4,065,366 and 20 U.S. 4,178,218. As is now known in this art, such membrane cells can be operated in both narrow gap (1-3 mm spacing from anode to cathode) and zero gap (both electrodes in contact with the membrane) configurations.
In a chloralkali process for electrolysis of an alkali metal chloride such as sodium chloride in such a cell, an aqueous alkali metal chloride solution is introduced into the anode compartment, an electric current is passed through the cell an aqueous alkali metal hydroxide solution is removed from the cathode compartment and chlorine is removed from the anode compartment In a membrane cell, water (or dilute alkali metal hydroxide at startup) is generally introduced into the cathode compartment, and spent alkali metal chloride solution is removed from the anode compartment. In a diaphragm cell, all of the unrequited alkali metal chloride solution percolates through the diaphragm into the cathode compartment, and is removed along with the product caustic.
The present invention has numerous advantages when compared to the prior art. These include (1) high resistance to flaking, spelling and mechanical damage of the activated coating; (2) resistance to oxidizing atmospheres, such as heating in air, e.g., during baking of a diaphragm thereon;
(3) low hydrogen overvoltage compared to mild steel cathodes and No cathodes; (4) good tolerance to moderate amounts of contamination by iron overplaying; (5) a variety of substrates including mild steel, stainless steel and nickel can be used;
(6) low cost and convenient application to preconstructed cathode components; and (7) the substrate is rarely heated above 200C, so thaw warping is minimal.
To further illustrate the innovative aspects of the present invention, the following examples are provided.
In the examples, abbreviations are used as 25 follows:
PTFE refers to polytetrafluoroethylene;
TFE/EVE refers to a copolymer of tetrafluoro-ethylene and methyl perfluoro(4,7-dioxa-5-methyl-8-nonenoate);
TFE/PSEPVE refers to a copolymer of twitter-fluoroethylene and perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride);
EWE refers to equivalent weight.

EXAMPLES
Example 1 A commercial cathode screen made of 0.23 cm (0.092 inch) diameter steel wire spaced on 0042 cm centers (6 mesh) was sandblasted, and then plasma arc coated on one side with a 178-203 micron (7-8 mill thick coating of a nickel aluminize alloy whose composition was nominally 57% Nix q3~ Al, particle size range was 100~ smaller than 90 microns (i.e., through 165 mesh) to 30% smaller than 42 microns (i.e., through 325 Messiah Spraying conditions were:
Metco*Type 7 MY (TUB) Torch-707 Nozzle Metro IMP Dual Power Feeders Torch Gas - 2.1 m3/hr (75 ft3/hr~ nitrogen Volts - 60 Amperes - 425 Kilowatts - 27.3 No. of Passes - 5.
The screen surface was cooled with compressed air jets.
A sample portion of the screen was cut out, and a 7.62 cm (3 inch) diameter circular section cut from the sample. The circle was welded into a stainless steel cathode holder such that the coated side would face toward the anode in the subsequently assembled cell, leached in 10% caustic, and a PTFE
fiber-asbestos diaphragm (TAB Diamond Shamrock*
composition) was deposited on the Rangy nickel coated surface of the screen and baked. Performance of this cathode was as follows, with typical steel cathode performance given for comparison En. 1 Steel Current Density, amp/dm 18.3 18.3 Actual Current, amps 8.3 8.3 35 Cell Voltage, volts 2.85 3.10 Advantage vs. Steel, my 250 ---*denotes trade mark Exempt e 2 A cathode finger from a Diamond Shamrock MDC-55* cathode assembly was sprayed on one side with nickel aluminize of the same composition as in Example 1. before the finger was sprayed, it was decreased and sandblasted. Spraying conditions were:
Metro Type 7 MY (TUB) ~orch~707 Nozzle Metro 31~P Dual Power Feeders Torch Gas - 2.1 m3/hr ~75 ft3~hr) nitrogen Volts - 62 Amperes - 450 Kilowatts - 27.9 No. of Passes - 4.
The screen surface was cooled with an air blast.
A sample was cut from this screen, leached in 10% caustic, coated with a TAB diaphragm directly on the Rangy nickel coated surface, and tested in a 7.62 (3-inch) diameter diaphragm cell with the Rangy nickel coated surface facing the anode Performance of the coaxed sample at two different current densities was:
En. 2 Current Density, amp/dm 18.3 11 25 Actual Current, amps 8~3 5.0 Cell Voltage, volts 2.83 2.54 The advantage for the cathode of Example 2 vs. the steel cathode shown for comparison in Example 1 was 270 my.
Example 3 The fingers for three Diamond Shamrock MDC-55 cathode assemblies (cathode cans) were plasma sprayed with nickel aluminize of the same composition as in Example 1 under the conditions outlined under Example 2, only on the sides of the fingers which *denotes trade mark *I

~L~3~3~6 10 '' were subsequently coated with the diaphragm coating and which would face toward the anode. Each can was then leached for about 16 hours in cold 10% caustic solution. The cans were then washed, and a Diamond Shamrock TAB diaphragm deposited and baked on each.
Each can was assembled into a chloralkali cell and operated in a cell line. All the cans performed similarly. Performance compared to steel was:
En. 3 Steel 10 Current Density, amp/dm 11.3 11.3 Actual Current, kilo amps 62 62 Cell Voltage, volts 2.70 2.88 Advantage us steel, my 180 ---Example 4 Samples of Type 304 stainless steel screen of 0.18 cm (0.072 inch) diameter wire spaced on 0.4~
cm centers (6 mesh) were welded into stainless steel cathode rings and sprayed with a 0.015 cm (Molly) thick coating of nickel aluminize of the same composition as in Example 1, only on what side to which the diaphragm coating was subsequently applied and which would face toward the anode in the subsequently assembled cell The coating was leached with 10~ caustic. A TAB diaphragm was deposited and baked onto the screens and the cathode assembly operated in a 7.62 cm tthree-inch) cell. After initial operation, the diaphragms were removed, new diaphragms installed, and a second run made.
Data are:
En. 3 En. 4 Steel lo Cycle end Cycle Average "
Current Density, amp/dm 18.3 18.3 18.3 Actual Current, kilo amps OWE 8.3 8.3 Cell Voltage, volts 2.99 2.89 3.11 Advantage us steel, my 120 220 --3~3~
Example 5 - Preparation of a cathode for evaluation in a narrow gap membrane cell.
A cathode for a laboratory membrane cell was prepared by cutting out a 7.62 cm (3-inch) diameter disk of a flattened expanded metal having dimensions of 2.54 cm LID (long way diamond) x 0.635 cm SOD
(short way diamond) x 0.16 cm strand width x 0.12 cm thick of a type 200 nickel. A length of 0.635 cm nickel tubing was welded to the center of the disk to serve as a current conductor.
A coating of an alloy of 57~ 0.5% by wt.
No and 43% + 0.5% by wt. Al was applied to both sides of this cathode by plasma spraying. The alloy was in the form of a fine powder having a particle size of 15 42 to 110 microns (i.e., between 140 mesh and 325 mesh). Conditions of application were as follows.
Power - 40 V and 580 A (23.2 ow) Arc Gas - 2.63 m fur (93 CFH) argon at 3.448 x 105 Pa (50 psi) 10.16 cm (4 inch) TODD (torch to work piece distance) The coating thickness was 203 microns (8 miss) on both sides of the expanded metal. The coating was activated by immersing the cathode in a solution of 10% Noah at room temperature for 16 hours. The cathode was then water rinsed and kept wet until installed in a cell.
Example 6 - Performance of a two-side coated cathode for evaluation in a finite gap membrane cell.
The cathode of Example 5 was mounted in a small cell having an active area of 45 cm , together with a reinforced fluorinated ion exchange membrane and a dimensionally stable anode. The membrane comprised a 38 micron (1~5 mill layer of TFE/EVE having an equivalent weight of 1080, a 100 micron (4 mill layer of TFE/PSEPVE having an equivalent weight of 1100, a layer of fabric having both PTF~ filaments and polyethylene terephthalate filaments, and a 25 micron (1 mill layer of TFE/PSEPVE having an equivalent weight of 1100, and was treated with an aqueous bath containing 11% KOCH
and 30% dimethylsulfoxide to hydrolyze the functional groups to carboxylate and sulfonate groups. The membrane was mounted with the carboxylate side toward the cathode. The electrodes were positioned Jo that there was a 3 mm gap between them. The cell was constructed so that a hydraulic head corresponding to approximately 25.4 cm (10 inches) of water on the cat de side pressed the membrane against the anode.
The cell was operated at 90C with a current density of 31 Adam. A saturated solution of purified sodium chloride was fed to the acolyte chamber at such a rate as to maintain a concentration of 200 g/l Nail. Water was added to the catholyte chamber to maintain the concentration of caustic produced at 32 + I
After 7 days, the cell was performing at 96%
current efficiency and 3.17 volts. The performance remained unchanged after 110 days of operation.
Comparative Example A
Example 6 was repeated except that the cathode was made from uncoated mild steel expanded mesh. After 7 days, the cell was operating at 96.4%
current efficiency and 3.51 volts. This is 340 my higher than the activated cathode of Example 6.
Example 7 - Performance of a one-side coated cathode in a finite gap membrane cell.
Example 5 was repeated except that the coating was applied only to the one face of the 13 ii3~3~3 cathode which faced the membrane in the cell. This cathode was then installed and operated in a test cell under the same conditions as Example 6.
After 7 days, the cell was operating at 97.6% current efficiency and 3.20 volts. After 30 days, the cell voltage was 3.18 volts and remained unchanged after 110 days of operation. This it 330 my lower than the mild steel cathode of Comparative Example A.
0 Example 8 - Performance of a two-side coated cathode in a zero gap membrane cell.
A cathode prepared as per Example 5 was mounted in a small cell having an active area of 45 cm . The membrane comprised a 38 micron (1.5 mill layer of TFE/EVE having an equivalent weight of 1080 and a 100 micron (4 mill layer of TFE/PSEPVE having an equivalent weight of 1100, was coated on both sides with an inorganic nonconductive layer comprised of ZrO2 particles bonded with a solution in ethanol of a 950 equivalent weight copolymer of TFE/PSEPVE and dried, and was treated with KOCH as in En. 6 to hydrolyze the functional groups to carboxylate and sulfonate groups. A
dimensionally stable anode was used and the electrodes were positioned close together with the membrane between them such that there was no gap between the membrane and either electrode. The membrane was mounted with the carboxylate side toward the cathode. The cell was operated at 90C with a current density of 31 Adam . A saturated solution of purified sodium chloride was fed to the acolyte chamber at such a rate as to maintain the concentration at 200 g/l Nail. Water was added to the catholyte chamber to maintain the concentration of caustic produced at 32 1%.

3~3~
After 7 days, the cell was performing at 97.8% current efficiency and 3.09 volts.
Example 9 and Comparative Examples B, C and D
Samples of mild steel cathode screen made of 0,23 cm (0.092 inch) diameter wire spaced on 0.42 cm centers (6 mesh), cleaned by blasting with 700 micron (24 mesh alumina grit at 5.5 x 105 Pa (80 psi), were plasma sprayed at the following conditions:
Volts - 40 Amperes - 620 Power - 24.8 ow TODD (torch to workups distance -6.3-7.6 cm (205 - 3 inches) Arc gas - 2.63 m ho (93 CFH) argon at 3.45 x 105 Pa (50 Sue Four different nickel/aluminum alloy compositions were used, having nickel/aluminum weight ratios of 52/48 (En. B), 55/45 (Err C) 57/43 (En. 9) and 62/38 (En. D). All had particle sizes of 42-110 microns (140 to 325 mesh). The coating thickness applied was 152-178 microns (6-7 miss).
The plasma spray coated cathodes were activated by leaching successively in 2% aqueous caustic at 25C, 5% aqueous caustic at 25~C, 10~
aqueous caustic at 25C, and 10~ aqueous caustic at 80C, each stage being carried out until hydrogen evolution ceased before proceeding to the next stage.
Each cathode circular disk, 8.25 cm or 3.25 inches in diameter) was tested for performance in a small chloralkali cell as follows. The cell had anode and cathode compartments separated by a membrane of a per fluorinated ion exchange polymer having sulfonate groups; the area of membrane in use was circular, 3.5 cm in diameter. The anode was a 35 platinum screen. A reference standard calmly awry to electrode and the cathode to be tested were placed in the cathode compartment, with the calmly electrode as close as possible to, or in contact with, the cathode under test. The anode compartment was filled with a sodium chloride solution (2509 Nucleator of solution); the cathode compartment was filled with a sodium chloride/sodium hydroxide solution containing about 13% sodium hydroxide (3 liters of the above Nail solution, 1~5 liters water and 5859 Noah.
Electrolysis was carried out at a current density of 15.5 Adam at cay 90~C, until stable electrode potentials were attained. The difference in potential between the test cathode and reference calmly electrode was measured with a high impedance digital voltmeter at intervals throughout the electrolysis period. The performance was compared against an uncoated mild steel cathode, and the results given below are reported as the millivolts advantage for the coated cathode vs. mild steel.
Each test cathode was then subjected to a sequence of water spray at 1.03 x 107 Pa ~1500 psi) for 3 minutes on each side of the cathode to simulate the conditions of removal of a spent asbestos diaphragm and baking at 355C for 4 hours to simulate the baking a newly applied asbestos diaphragm, even though no asbestos was actually removed or deposited. The amount of Rangy nickel coating which spelled off during the water spraying was collected by filtration and weighed. The cell performance of the washed and baked cathode was again evaluated.
This sequence was carried out ten times for each test cathode. The results are summarized in Tables I and II.

Table 1 REDUCTION IN HYDROGEN
OVERVOLTAGE VS. MILD STEEL CATHODE
at 15 Adam (1 Asia (in millivolts) _.
5 Nickel aluminize coating composition (% by wt.) Number of En. B En. Rex. 9 En D
Wash/Bake Cycles 52/4855/45 57/43 _2/38 2 153 16~ 153 14~
3 153 150 14~ 141
4 143 1~6 146 136 17 Lo Table II
CUMULATE VIE COATING STALL
luring 1. 03 x 107 Pa tl500 psi) WATER JET SPRAY
(in milligrams) Nickel aluminize coating Q composition (% by we.) Number of En. Box. Rex. 9 En. D
Wash/Bake Seychelles 55/45 57/43 62/38 1 ~.76.1 4.4 0.7 2 12.913.1 11.9 8.3 3 13.614.7 16.~ 21.
4 45 22.2 25.5 25.8 45.827.3 25.5 2605 6 ~5.86307 32.6 28.2 7 48.263.7 32.6 28.2 8 54.269.2 32.7 29.2 9 77.091.2 36.3 29.9 8~.091.6 37.3 34.7 I~D~lSTRIAL APPLICABILITY
The present invention is useful whenever Rangy nickel coated electrodes are desired. It finds use especially in the chloralkali field where low hydrogen overvoltage cathodes are needed. The cathodes are more durable than those of the prior art, and have other advantages set forth above.

Claims (21)

  1. CLAIMS:
    l. Process for making a low-hydrogen-overvoltage cathode for a chloralkali cell which comprises (a) plasma spraying a coating of a nickel/aluminum alloy composition containing 56 to 59% by wt. nickel onto a foraminous substrate of iron, ferrous alloy, nickel or nickel alloy, and (b) leaching aluminum from said coating by contacting the article prepared in step (a) with a caustic solution.
  2. 2. The process of Claim l wherein said nickel/aluminum alloy composition used in step (a) is in the form of 36 to 90 micron particles.
  3. 3. the process of Claim 2 wherein the coating made in step (a) is 13 to 508 microns thick.
  4. 4. The process of Claim 3 wherein said nickel/aluminum alloy composition used in step (a) is in the form of 36 to 53 micron particles.
  5. 5. The process of Claim 4 wherein the coating made in step (a) is 127 to 254 microns thick.
  6. 6. The process of Claim 5 wherein said plasma spraying is carried out with an argon or nitrogen gas plasma generated with 20 to 30 kilowatts of power.
  7. 7. The process of Claim 5 wherein said step (b) is carried out for a time sufficient to remove about 70-90% by weight of the aluminum from said coating.
  8. 8. The process of Claim 5 wherein said caustic solution in step (b) is 5 to 15% by wt.
    aqueous NaOH, and said contacting is for a time of 5 hours to 1 day.
  9. 9. The process of any one of Claim l, Claim 3 and Claim 5 wherein said nickel/aluminum alloy com-position contains 56.5 to 57.5% by wt. nickel.
  10. 10. The process of any one of Claim 1, Claim 3 and Claim 5 wherein said nickel/aluminum alloy composition is substantially 57% by wt. nickel.
  11. 11. The cathode made by the process of any one of Claim 1, Claim 3 and Claim 5.
  12. 12. The cathode made by the process of any one of Claim 2, Claim 4 and Claim 6.
  13. 13. The cathode made by the process of Claim 7 or Claim 8.
  14. 14. The cathode made by the process of any one of Claim 1, Claim 3 and Claim 5 wherein said nickel/aluminum alloy composition contains 56.5 to 57.5% by wt. nickel.
  15. 15. The cathode made by the process of any one of Claim 1, Claim 3 and Claim 5 wherein said nickel/aluminum alloy composition is sub-stantially 57% by wt. nickel.
  16. 16. In a chloralkali cell comprising a cathode compartment, a cathode disposed within said cathode compartment, an anode compartment, an anode disposed within said anode compartment, and a separator disposed between said anode and cathode compartments, the improvement which com-prises said cathode being a cathode made by the process of Claim 1.
  17. 17. In a chloralkali cell comprising a cathode compartment, a cathode disposed within said cathode compartment, an anode compartment, an anode disposed within said anode compartment, and a separator disposed between said anode and cathode compartments, the improvement which com-prises said cathode being a cathode made by the process of Claim 3.
  18. 18. In a chloralkali cell comprising a cathode compartment, a cathode disposed within said cathode compartment, an anode compartment, an anode disposed within said anode compartment, and a separator disposed between said anode and cathode compartments, the improvement which com-prises said cathode being a cathode made by the process of Claim 5.
  19. 19. The chloralkali cell of any one of Claim 16, Claim 17 and Claim 18 wherein said separator is a liquid permeable diaphragm.
  20. 20. The chloralkali cell of any one of Claim 16, Claim 17 and Claim 18 wherein said diaphragm comprises asbestos fibers.
  21. 21. The chloralkali cell of any one of Claim 16, Claim 17 and Claim 18 wherein said separator is a membrane of highly fluorinated ion-exchange polymer.
CA000433480A 1982-07-30 1983-07-28 Process for making raney nickel coated cathode, and product thereof Expired CA1235386A (en)

Applications Claiming Priority (2)

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US40330682A 1982-07-30 1982-07-30
US403,306 1989-09-01

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JP (1) JPS5941486A (en)
KR (1) KR840005497A (en)
AU (1) AU559813B2 (en)
CA (1) CA1235386A (en)
IN (1) IN157836B (en)
NZ (1) NZ205086A (en)
ZA (1) ZA835530B (en)

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Publication number Priority date Publication date Assignee Title
US4555413A (en) * 1984-08-01 1985-11-26 Inco Alloys International, Inc. Process for preparing H2 evolution cathodes
JPS6487757A (en) * 1987-09-28 1989-03-31 Kanegafuchi Chemical Ind Production of low hydrogen overvoltage cathode
RU2110619C1 (en) * 1996-09-09 1998-05-10 Закрытое акционерное общество "Техно-ТМ" Electrode for electrochemical processes and method of manufacturing thereof
DE102005011047A1 (en) 2005-03-08 2006-09-14 Bayer Technology Services Gmbh Catalyst molded substance, obtained by thermally spraying a catalytically active metal and a catalytically inactive metal on a carrier and subsequently removing the inactive metal, useful as hydrogenation catalyst
GB0806855D0 (en) * 2008-04-16 2008-05-14 Secr Defence Pyrophoric material
ES2798874T3 (en) * 2017-09-21 2020-12-14 Hymeth Aps Procedure for preparing an electrocatalyst

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GB1172435A (en) * 1966-04-01 1969-11-26 Varta Ag Gas Diffusion Electrodes
US4024044A (en) * 1975-09-15 1977-05-17 Diamond Shamrock Corporation Electrolysis cathodes bearing a melt-sprayed and leached nickel or cobalt coating
US4116804A (en) * 1976-11-17 1978-09-26 E. I. Du Pont De Nemours And Company Catalytically active porous nickel electrodes

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ZA835530B (en) 1985-03-27
KR840005497A (en) 1984-11-14
NZ205086A (en) 1986-05-09
AU1738483A (en) 1984-02-02
EP0100659A1 (en) 1984-02-15
JPS5941486A (en) 1984-03-07
JPS6116424B2 (en) 1986-04-30
IN157836B (en) 1986-07-05
AU559813B2 (en) 1987-03-19

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