CA2778865A1 - Alloys of the type fe3aita(ru) and use thereof as electrode material for the synthesis of sodium chlorate - Google Patents
Alloys of the type fe3aita(ru) and use thereof as electrode material for the synthesis of sodium chlorate Download PDFInfo
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- CA2778865A1 CA2778865A1 CA2778865A CA2778865A CA2778865A1 CA 2778865 A1 CA2778865 A1 CA 2778865A1 CA 2778865 A CA2778865 A CA 2778865A CA 2778865 A CA2778865 A CA 2778865A CA 2778865 A1 CA2778865 A1 CA 2778865A1
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- sodium chlorate
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000000956 alloy Substances 0.000 title claims abstract description 50
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- 239000007772 electrode material Substances 0.000 title claims abstract description 7
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 241000894007 species Species 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- 229910052741 iridium Inorganic materials 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- UJXVAJQDLVNWPS-UHFFFAOYSA-N [Al].[Al].[Al].[Fe] Chemical compound [Al].[Al].[Al].[Fe] UJXVAJQDLVNWPS-UHFFFAOYSA-N 0.000 claims description 5
- 229910021326 iron aluminide Inorganic materials 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 16
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000010587 phase diagram Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000000133 mechanosynthesis reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
- C25B1/265—Chlorates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23F—NON-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
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
- C23F13/14—Material for sacrificial anodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Prevention Of Electric Corrosion (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Disclosed is an alloy of the formula:
Fe3-x Al1+x M y T z Ta t wherein M represents at least one catalytic specie selected from the group consisting of Ru, Ir, Pd, Pt, Rh, Os, Re and Ag; T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, O, N, P, F, S, CI, Na and Ti; and Ta represents tantalum. Such an alloy can be used as an electrode material for the synthesis of sodium chlorate. It can also be used as a coating for protection against corrosion.
Fe3-x Al1+x M y T z Ta t wherein M represents at least one catalytic specie selected from the group consisting of Ru, Ir, Pd, Pt, Rh, Os, Re and Ag; T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, O, N, P, F, S, CI, Na and Ti; and Ta represents tantalum. Such an alloy can be used as an electrode material for the synthesis of sodium chlorate. It can also be used as a coating for protection against corrosion.
Description
Alloys of the Type Fe3AlTa(Ru) And Use Thereof as Electrode Material for the Synthesis of Sodium Chlorate FIELD OF INVENTION
The present invention relates to new catalytic alloys based on Fe, Al, Ta and catalytic species such as Ru.
The present invention also relates to the use of such catalytic alloys as electrode material for the synthesis of sodium chlorate.
TECHNOLOGICAL BACKGROUND
Nanocrystalline alloys of the formula 1-xMyTz wherein M represents at least one catalytic specie selected from the group consisting of Ru, Jr. Pd, Pt, Rh, Os, Re and Ag;
T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, 0, N, P, F. S, Cl and Na;
x is a number higher than -1 and smaller than or equal to +1 y is a number higher than 0 and smaller than or equal to +1 z is a number ranging between 0 and +1 have been disclosed recently as efficient cathodic materials for the synthesis of sodium chlorate (see CA 2,687,129 and the corresponding international application WO
2008/138148). These catalytic materials, when use as cathode for the eleetrosynthesis of sodium chlorate show very low cathodic overpotentials and they do not absorb hydrogen when the H2 evolution reaction takes place on their surfaces. These materials also show good corrosion resistance in the sodium chlorate electrolyte under typical industrial operating conditions (NaC103: 550g/1; NaCI: 110 g/1; NaCr207: 3g/I; NaCIO: 1 g/I; pH=
6.5 and temperatures around 70 C).
Although corrosion resistance of these Fe3A11+,MTz alloys is quite good at pH
6.5, it is not the case in acidic conditions. Standard industrial practises use acid wash from time to time to clean electrochemical cells and electrodes. To do so, MCI solutions at concentrations varying between 3% (¨ 1M) and 9% (¨ 3M) are often used. When the above mentioned alloys are put in contact with such concentrated acidic solutions, they can be severely damaged.
Indeed, the corrosion resistance of these new catalytic alloys in HC1 solutions at low pH is not so good.
SUMMARY OF THE INVENTION
To solve this problem, the inventors of record have search new formulations and have discover surprisingly that the addition of a small amount of Ta to these materials could make these new alloys not only highly resistant to corrosion in chlorate electrolyte but also in acidic (HC1) solutions without loosing any performance regarding the electrochemical synthesis of sodium chlorate.
Fe3A1(Ru) alloys are often single phase solid solutions usually prepared in a nanocrystalline form by mecanosynthesis. A powder mixture of ruthenium and iron aluminide is milled intensively for several hours until the Ru catalytic element enters and gets highly dispersed into the cubic crystalline structure of iron aluminide (Fe3A1). The nanocrystalline Fe3A1(Ru) alloy thus formed is highly active thanks to its high surface area and highly dispersed electrocatalytic element.
The present inventors have actually found by investigating various ternary phase diagrams that Ta (tantalum) which is known to be a good corrosion resistant element, is quite soluble in Fe-Al alloys. Therefore, Fe3A1(Ru)Tat with various Ta concentration "t" can be prepared as a single phase material by mechanosynthesis very easily and these new alloys show not only good electrocatalytic activity towards the electrosynthesis of sodium chlorate but also good corrosion resistance in the sodium chlorate electrolyte as well as in concentrated HC1 solutions.
Therefore, the first object of the present invention is an alloy characterized by the following formula:
Fe3_,A11+,MyT,Tat wherein:
M represents at least one catalytic specie selected from the group consisting of Ru, 1r, Pd, Pt, Rh, Os, Re and Ag;
T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu.
Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, 0, N, P, F, S, Cl, Na and Ti;
x is a number higher than -1 and smaller than or equal to +1 y is a number higher than 0 and smaller than or equal to +1 z is a number ranging between 0 and +I
and t is a number higher than 0 and smaller than or equal to +1, preferably lower than 0.4 and more preferably lower than or equal to 0.2 The alloy of the invention is preferably in a nanocrystalline state. If nanocrystalline, the crystallites are smaller than 100nm. The alloy is also preferably a single phase material with a cubic crystallographic structure but can also be multiphase depending on the x, y, z and t composition. Most of the time, these alloys are metastable. In other words, they decompose or transform into a different state when heated at high temperatures. But again, they can also be thermodynamically stable depending on the x, y, z and t composition.
A second object of the present invention is the use of such alloys as electrode material for the synthesis of sodium chlorate. In order to prepare an electrode of these alloys, several methods can be used. A preferred one is thermal spray such as the high velocity oxyfuel (HVOF) technique using the alloy in powder form as feedstock for the spray gun. If the method of preparation involves a rapid quenching process, the alloy can be prepared in a nanocrystalline state.
Even though, the preferred application of these new materials is sodium chlorate, several other electrochemical processes can take advantage of these alloys such as industrial and swimming pool water treatment.
Moreover, since the corrosion resistance of these new alloys is very good in various conditions, a third object of the present invention is the use of these alloys as coating for the protection against corrosion. If the targeted application is a coating for protection against corrosion. there may be no advantage of adding a large amount of expensive catalytic element to the alloy. In these cases, the molar content "y" can be chosen small to reduce costs. Moreover, it may be advantageous to add some Ti (titanium) to the alloy since Ti is also known for its good corrosion resistance and the inventors of the present invention found that Ti like Ta is quite soluble in iron-aluminium alloys.
The invention and its associated advantages will be better understood upon reading the following more detailed but not limitative description of preferred modes of achievement of it, made with reference to the enclosed drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows an equilibrium ternary phase diagram of the Fe, Al and Ta at 1000 C.
Fig. 2 shows pictures of a corrosion test in 5% HC1 solution for a sample containing Ta according to the invention (right end side) and a similar sample not containing Ta (left end side).
Fig. 3 represents the hydrogen released as a function of time during corrosion tests in a 5%
HC1 solution for samples according to the invention containing Ta with composition t of 0.1, 0.2, 0.3 and 0.4 and a similar sample not containing Ta.
Fig. 4 represents a figure similar to Fig. 3 where in addition to the previously presented results, the hydrogen released as a function of time is shown for a sample of the invention Fe3_,A.11+,MyTzTat containing both Nb (element T) and Ta with a respective molar content of z = 0.1 and t = 0.2.
Fig. 5 shows X-ray diffraction spectra of a mixture of a powder of the prior art Fe3_ ,A11,MyT, and a powder of Ta at an equivalent molar content of t = 0.2 as a function of milling time during a mecanosynthesis process.
Fig. 6 shows a picture of a ball milled powder of the invention containing Nb and Ta at a respective molar content of z = 0.1 and t = 0.2.
Fig. 7 a) and b) show pictures of a coating according to the invention made from the powder of Fig. 6 using a thermal spray technique at two different magnifications 120 and 5000x.
Fig. 8 show samples of coated electrodes after lhour immersion in 5% HC1 solution. The left end side is an electrode of the prior art while the right end side is an electrode according to the present invention containing Ta.
Fig. 9 shows cyclic voltametric curves (current ¨ voltage curves) in a chlorate solution taken at a rate of 5mV/sec at 20 C and pH=6.5 for a sample of the invention and a standard stainless steel 316 sample.
Fig. 10 shows an equilibrium ternary phase diagram of the Fe, Al and Ti at 1200 C.
Fig. 11 shows an electrochemical test in a standard chlorate solution using an electrode according to the invention containing Ta at a molar content oft = 0.1.
DETAILED DECRIPTION OF THE INVENTION
As it can be seen, Fig. 1 shows a ternary phase diagram of Fe, Al and Ta at 1000 C. Ta is quite soluble in FexAli_x alloys especially near the equiatomic composition (x = 0,5). By inserting Ta into the cubic FeAl alloy at high temperature, a single phase FeAlTat material can be prepared at room temperature using a rapid quenching process. If the Ta content is high, the single phase obtain at room temperature will most likely be metastable.
Fig. 2 represents a corrosion test of an alloy containing Ta according to the invention in comparison with a similar alloy not containing Ta. The samples are immerged in a 5% HC1 solution. On the left end part of the picture, we see for the alloy not containing Ta, a lot of hydrogen bubbles indicating severe corrosion in the acidic solution. On the contrary, for the alloy containing Ta in the picture on the right end side, very little bubble formation is observed indicating a much better corrosion resistance in the HC1 solution.
Fig. 3 represents corrosion tests similar to the ones of Fig. 2 showing the amount of hydrogen released during the test as a function of time. The sample of the prior art not containing Ta, Fe3Ali+,M,T, releases 11m1 of hydrogen in about 7,5min while the sample of the present invention Fe3_xA11+\M)TzTa0,2 containing Ta at a molar content of y= 0.2 releases only 3.9 ml in 340min. Fig. 3 also shows that, even with a small concentration of Ta of t = 0.1, significant improvement in the corrosion resistance of the alloy can be achieved.
This very large improvement in the corrosion resistance of the alloy of the prior art with very small additions of Ta was unexpected.
Fig. 4 represents corrosion tests similar to the ones of Fig. 3 where, in addition to the curves presented in Fig. 3, the results of a sample containing both Nb and Ta are presented. When Ta is added at a composition t = 0.2 to a sample of the prior art already containing Nb (Fe3_,A11+,M),T, where T is Nb at a molar content of z = 0.1) a synergetic effect takes place and a huge improvement in the corrosion resistance is achieved. The sample Fe3_,A11,,M),Nbo iTa0,2 released only 1,5m1 of hydrogen in 500min. This synergetic effect when both Nb and Ta are present in the alloy and which gives incredible improvement in the corrosion resistance of the alloy in HCI solution was also unexpected.
Fig. 5 shows X-ray diffraction spectra of a mixture of an alloy powder of the prior art with a powder of Ta at a molar content of t = 0.2 as a function of the milling time during a mecanosynthesis process. We see the characteristic X-ray peak of the iron aluminide powder (Fe3A1) cubic structure around 44 and a peak corresponding to Ta at about 38.4 . By increasing the milling time from 1 h to 12h, we observe that the intensity of the Ta peak decreases and vanishes after about 12h of milling. This indicates that all of the Ta has penetrated into the crystalline structure of iron aluminide to form a metastable solid solution.
Fig. 6 shows a scanning electron micrograph taken at a magnification of 2000x of a ball milled powder of the invention Fe3.,A11+,MyTzTat which comprises both Nb and Ta at a molar content of Nbo 1Ta0,2 (T is Nb, z = 0.1 and t = 0.2). The average particle size of this nanocrystalline powder is around 10 microns.
Fig. 7a) and b) represent scanning electron micrographs at 120x and 5000x magnification respectively of the surface of a coating according to the invention made by FIVOF thermal spray using the powder shown in Fig. 6. Thus, the material of the coating contains both Nb and Ta elements. This electrocatalytic coating is not only corrosion resistant in the chlorate electrolytic but also in hydrochloric acid solutions.
Fig. 8 represents images of electrodes after immersion in a 5% HC1 solution for one hour.
The left side is a picture of an electrode of the prior art (Fe3,Ali,õMyTz) while the right side shows a picture of an electrode of the present invention (Fe3_,,Ali+xMyTzTat).
The electrode of the prior art has been destroyed by the acid wash treatment. The catalytic coating has peeled off from the substrate. On the contrary. the electrode of the present invention shown on the right end side is intact and shows no damage.
Fig. 9 shows current versus voltage curves taken at a scan rate of 5mV/sec in a highly corrosive environment (chlorate solution at 20 C and pH=6.5) for a coating of the invention containing both Ta and Nb and a standard stainless steel 316 sample. The breakdown potentials on the anodic side (positive voltages) are almost the same for the two samples indicating that under these conditions, the coating material of the invention is a corrosion resistant material as good as stainless steel 316.
Fig. 10 represents a ternary phase diagram of Fe, Al and Ti at 1200 C. One can see that, on the Fe rich side of the Fe-Al system, Ti is quite soluble in the alloys.
Therefore, for applications as corrosion resistant coatings, it may be advantageous of adding not only Ta but also Ti to the alloys since Ti is known to be a good corrosion resistant element especially in chlorine environment. However, the addition of Ti is not recommended in applications as electrode for the hydrogen evolution reaction since Ti is known to form stable hydrides as discussed in CA 2,687,129 mentioned hereinabove.
Fig. 11 shows an electrochemical test conducted in a standard chlorate solution using a DSA
as anode and an electrode material of the invention as cathode. The material according to the invention contains Ta at a molar content of t = 0.1. The anodic and cathodic voltages are measured with respect to a Ag/AgC1 reference electrode. 1.3 volt has been substracted from the Anode-Cathode voltage difference in order to show the three traces on the same figure.
Open circuit (OC) events for durations of 30sec. lmin and 2min have been conducted during the test. Has it can be seen, the voltage of the cell remains stable in spite of these events.
The present invention relates to new catalytic alloys based on Fe, Al, Ta and catalytic species such as Ru.
The present invention also relates to the use of such catalytic alloys as electrode material for the synthesis of sodium chlorate.
TECHNOLOGICAL BACKGROUND
Nanocrystalline alloys of the formula 1-xMyTz wherein M represents at least one catalytic specie selected from the group consisting of Ru, Jr. Pd, Pt, Rh, Os, Re and Ag;
T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, 0, N, P, F. S, Cl and Na;
x is a number higher than -1 and smaller than or equal to +1 y is a number higher than 0 and smaller than or equal to +1 z is a number ranging between 0 and +1 have been disclosed recently as efficient cathodic materials for the synthesis of sodium chlorate (see CA 2,687,129 and the corresponding international application WO
2008/138148). These catalytic materials, when use as cathode for the eleetrosynthesis of sodium chlorate show very low cathodic overpotentials and they do not absorb hydrogen when the H2 evolution reaction takes place on their surfaces. These materials also show good corrosion resistance in the sodium chlorate electrolyte under typical industrial operating conditions (NaC103: 550g/1; NaCI: 110 g/1; NaCr207: 3g/I; NaCIO: 1 g/I; pH=
6.5 and temperatures around 70 C).
Although corrosion resistance of these Fe3A11+,MTz alloys is quite good at pH
6.5, it is not the case in acidic conditions. Standard industrial practises use acid wash from time to time to clean electrochemical cells and electrodes. To do so, MCI solutions at concentrations varying between 3% (¨ 1M) and 9% (¨ 3M) are often used. When the above mentioned alloys are put in contact with such concentrated acidic solutions, they can be severely damaged.
Indeed, the corrosion resistance of these new catalytic alloys in HC1 solutions at low pH is not so good.
SUMMARY OF THE INVENTION
To solve this problem, the inventors of record have search new formulations and have discover surprisingly that the addition of a small amount of Ta to these materials could make these new alloys not only highly resistant to corrosion in chlorate electrolyte but also in acidic (HC1) solutions without loosing any performance regarding the electrochemical synthesis of sodium chlorate.
Fe3A1(Ru) alloys are often single phase solid solutions usually prepared in a nanocrystalline form by mecanosynthesis. A powder mixture of ruthenium and iron aluminide is milled intensively for several hours until the Ru catalytic element enters and gets highly dispersed into the cubic crystalline structure of iron aluminide (Fe3A1). The nanocrystalline Fe3A1(Ru) alloy thus formed is highly active thanks to its high surface area and highly dispersed electrocatalytic element.
The present inventors have actually found by investigating various ternary phase diagrams that Ta (tantalum) which is known to be a good corrosion resistant element, is quite soluble in Fe-Al alloys. Therefore, Fe3A1(Ru)Tat with various Ta concentration "t" can be prepared as a single phase material by mechanosynthesis very easily and these new alloys show not only good electrocatalytic activity towards the electrosynthesis of sodium chlorate but also good corrosion resistance in the sodium chlorate electrolyte as well as in concentrated HC1 solutions.
Therefore, the first object of the present invention is an alloy characterized by the following formula:
Fe3_,A11+,MyT,Tat wherein:
M represents at least one catalytic specie selected from the group consisting of Ru, 1r, Pd, Pt, Rh, Os, Re and Ag;
T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu.
Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, 0, N, P, F, S, Cl, Na and Ti;
x is a number higher than -1 and smaller than or equal to +1 y is a number higher than 0 and smaller than or equal to +1 z is a number ranging between 0 and +I
and t is a number higher than 0 and smaller than or equal to +1, preferably lower than 0.4 and more preferably lower than or equal to 0.2 The alloy of the invention is preferably in a nanocrystalline state. If nanocrystalline, the crystallites are smaller than 100nm. The alloy is also preferably a single phase material with a cubic crystallographic structure but can also be multiphase depending on the x, y, z and t composition. Most of the time, these alloys are metastable. In other words, they decompose or transform into a different state when heated at high temperatures. But again, they can also be thermodynamically stable depending on the x, y, z and t composition.
A second object of the present invention is the use of such alloys as electrode material for the synthesis of sodium chlorate. In order to prepare an electrode of these alloys, several methods can be used. A preferred one is thermal spray such as the high velocity oxyfuel (HVOF) technique using the alloy in powder form as feedstock for the spray gun. If the method of preparation involves a rapid quenching process, the alloy can be prepared in a nanocrystalline state.
Even though, the preferred application of these new materials is sodium chlorate, several other electrochemical processes can take advantage of these alloys such as industrial and swimming pool water treatment.
Moreover, since the corrosion resistance of these new alloys is very good in various conditions, a third object of the present invention is the use of these alloys as coating for the protection against corrosion. If the targeted application is a coating for protection against corrosion. there may be no advantage of adding a large amount of expensive catalytic element to the alloy. In these cases, the molar content "y" can be chosen small to reduce costs. Moreover, it may be advantageous to add some Ti (titanium) to the alloy since Ti is also known for its good corrosion resistance and the inventors of the present invention found that Ti like Ta is quite soluble in iron-aluminium alloys.
The invention and its associated advantages will be better understood upon reading the following more detailed but not limitative description of preferred modes of achievement of it, made with reference to the enclosed drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows an equilibrium ternary phase diagram of the Fe, Al and Ta at 1000 C.
Fig. 2 shows pictures of a corrosion test in 5% HC1 solution for a sample containing Ta according to the invention (right end side) and a similar sample not containing Ta (left end side).
Fig. 3 represents the hydrogen released as a function of time during corrosion tests in a 5%
HC1 solution for samples according to the invention containing Ta with composition t of 0.1, 0.2, 0.3 and 0.4 and a similar sample not containing Ta.
Fig. 4 represents a figure similar to Fig. 3 where in addition to the previously presented results, the hydrogen released as a function of time is shown for a sample of the invention Fe3_,A.11+,MyTzTat containing both Nb (element T) and Ta with a respective molar content of z = 0.1 and t = 0.2.
Fig. 5 shows X-ray diffraction spectra of a mixture of a powder of the prior art Fe3_ ,A11,MyT, and a powder of Ta at an equivalent molar content of t = 0.2 as a function of milling time during a mecanosynthesis process.
Fig. 6 shows a picture of a ball milled powder of the invention containing Nb and Ta at a respective molar content of z = 0.1 and t = 0.2.
Fig. 7 a) and b) show pictures of a coating according to the invention made from the powder of Fig. 6 using a thermal spray technique at two different magnifications 120 and 5000x.
Fig. 8 show samples of coated electrodes after lhour immersion in 5% HC1 solution. The left end side is an electrode of the prior art while the right end side is an electrode according to the present invention containing Ta.
Fig. 9 shows cyclic voltametric curves (current ¨ voltage curves) in a chlorate solution taken at a rate of 5mV/sec at 20 C and pH=6.5 for a sample of the invention and a standard stainless steel 316 sample.
Fig. 10 shows an equilibrium ternary phase diagram of the Fe, Al and Ti at 1200 C.
Fig. 11 shows an electrochemical test in a standard chlorate solution using an electrode according to the invention containing Ta at a molar content oft = 0.1.
DETAILED DECRIPTION OF THE INVENTION
As it can be seen, Fig. 1 shows a ternary phase diagram of Fe, Al and Ta at 1000 C. Ta is quite soluble in FexAli_x alloys especially near the equiatomic composition (x = 0,5). By inserting Ta into the cubic FeAl alloy at high temperature, a single phase FeAlTat material can be prepared at room temperature using a rapid quenching process. If the Ta content is high, the single phase obtain at room temperature will most likely be metastable.
Fig. 2 represents a corrosion test of an alloy containing Ta according to the invention in comparison with a similar alloy not containing Ta. The samples are immerged in a 5% HC1 solution. On the left end part of the picture, we see for the alloy not containing Ta, a lot of hydrogen bubbles indicating severe corrosion in the acidic solution. On the contrary, for the alloy containing Ta in the picture on the right end side, very little bubble formation is observed indicating a much better corrosion resistance in the HC1 solution.
Fig. 3 represents corrosion tests similar to the ones of Fig. 2 showing the amount of hydrogen released during the test as a function of time. The sample of the prior art not containing Ta, Fe3Ali+,M,T, releases 11m1 of hydrogen in about 7,5min while the sample of the present invention Fe3_xA11+\M)TzTa0,2 containing Ta at a molar content of y= 0.2 releases only 3.9 ml in 340min. Fig. 3 also shows that, even with a small concentration of Ta of t = 0.1, significant improvement in the corrosion resistance of the alloy can be achieved.
This very large improvement in the corrosion resistance of the alloy of the prior art with very small additions of Ta was unexpected.
Fig. 4 represents corrosion tests similar to the ones of Fig. 3 where, in addition to the curves presented in Fig. 3, the results of a sample containing both Nb and Ta are presented. When Ta is added at a composition t = 0.2 to a sample of the prior art already containing Nb (Fe3_,A11+,M),T, where T is Nb at a molar content of z = 0.1) a synergetic effect takes place and a huge improvement in the corrosion resistance is achieved. The sample Fe3_,A11,,M),Nbo iTa0,2 released only 1,5m1 of hydrogen in 500min. This synergetic effect when both Nb and Ta are present in the alloy and which gives incredible improvement in the corrosion resistance of the alloy in HCI solution was also unexpected.
Fig. 5 shows X-ray diffraction spectra of a mixture of an alloy powder of the prior art with a powder of Ta at a molar content of t = 0.2 as a function of the milling time during a mecanosynthesis process. We see the characteristic X-ray peak of the iron aluminide powder (Fe3A1) cubic structure around 44 and a peak corresponding to Ta at about 38.4 . By increasing the milling time from 1 h to 12h, we observe that the intensity of the Ta peak decreases and vanishes after about 12h of milling. This indicates that all of the Ta has penetrated into the crystalline structure of iron aluminide to form a metastable solid solution.
Fig. 6 shows a scanning electron micrograph taken at a magnification of 2000x of a ball milled powder of the invention Fe3.,A11+,MyTzTat which comprises both Nb and Ta at a molar content of Nbo 1Ta0,2 (T is Nb, z = 0.1 and t = 0.2). The average particle size of this nanocrystalline powder is around 10 microns.
Fig. 7a) and b) represent scanning electron micrographs at 120x and 5000x magnification respectively of the surface of a coating according to the invention made by FIVOF thermal spray using the powder shown in Fig. 6. Thus, the material of the coating contains both Nb and Ta elements. This electrocatalytic coating is not only corrosion resistant in the chlorate electrolytic but also in hydrochloric acid solutions.
Fig. 8 represents images of electrodes after immersion in a 5% HC1 solution for one hour.
The left side is a picture of an electrode of the prior art (Fe3,Ali,õMyTz) while the right side shows a picture of an electrode of the present invention (Fe3_,,Ali+xMyTzTat).
The electrode of the prior art has been destroyed by the acid wash treatment. The catalytic coating has peeled off from the substrate. On the contrary. the electrode of the present invention shown on the right end side is intact and shows no damage.
Fig. 9 shows current versus voltage curves taken at a scan rate of 5mV/sec in a highly corrosive environment (chlorate solution at 20 C and pH=6.5) for a coating of the invention containing both Ta and Nb and a standard stainless steel 316 sample. The breakdown potentials on the anodic side (positive voltages) are almost the same for the two samples indicating that under these conditions, the coating material of the invention is a corrosion resistant material as good as stainless steel 316.
Fig. 10 represents a ternary phase diagram of Fe, Al and Ti at 1200 C. One can see that, on the Fe rich side of the Fe-Al system, Ti is quite soluble in the alloys.
Therefore, for applications as corrosion resistant coatings, it may be advantageous of adding not only Ta but also Ti to the alloys since Ti is known to be a good corrosion resistant element especially in chlorine environment. However, the addition of Ti is not recommended in applications as electrode for the hydrogen evolution reaction since Ti is known to form stable hydrides as discussed in CA 2,687,129 mentioned hereinabove.
Fig. 11 shows an electrochemical test conducted in a standard chlorate solution using a DSA
as anode and an electrode material of the invention as cathode. The material according to the invention contains Ta at a molar content of t = 0.1. The anodic and cathodic voltages are measured with respect to a Ag/AgC1 reference electrode. 1.3 volt has been substracted from the Anode-Cathode voltage difference in order to show the three traces on the same figure.
Open circuit (OC) events for durations of 30sec. lmin and 2min have been conducted during the test. Has it can be seen, the voltage of the cell remains stable in spite of these events.
Claims (10)
1. An alloy of the formula:
Fe3-x Al1+x M y T z Ta t wherein:
M represents at least one catalytic specie selected from the group consisting of Ru, Ir, Pd, Pt, Rh, Os, Re and Ag;
T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, O, N, P, F, S, Cl, Na and Ti;
x is a number higher than -1 and smaller than or equal to +1 y is a number higher than 0 and smaller than or equal to +1 z is a number ranging between 0 and +1 Ta represents tantalum and t is a number higher than 0 and smaller than or equal to +1.
Fe3-x Al1+x M y T z Ta t wherein:
M represents at least one catalytic specie selected from the group consisting of Ru, Ir, Pd, Pt, Rh, Os, Re and Ag;
T represents at least one element selected from the group consisting of Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y, Mn, Cd, Si, B, C, O, N, P, F, S, Cl, Na and Ti;
x is a number higher than -1 and smaller than or equal to +1 y is a number higher than 0 and smaller than or equal to +1 z is a number ranging between 0 and +1 Ta represents tantalum and t is a number higher than 0 and smaller than or equal to +1.
2. The alloy according to claim 1, characterized in that t is a number lower than 0.4.
3. The alloy according to claim 2, characterized in that t is a number lower or equal to 0.2.
4. The alloy according to any one of claims 1 to 3, characterized in that it is a material with a nanocrystalline structure.
5. The alloy according to any one of claims 1 to 4, characterized in that it is a material with a single phase metastable structure.
6. A method of fabrication of an alloy as claimed in any one of claims 1 to 5, in powder form, which consists of milling intensively a mixture of an iron aluminide powder with powders of the M, T and Ta species.
7. A coating of an alloy as claimed in any one of claims 1 to 5, which is prepared by using the powder according to claim 6 and a thermal spray technique to project the powder on a substrate thus producing a coated electrode or a corrosion resistant coating.
8. A corrosion resistant coating according to claim 7, characterized in that it is made of an alloy according to claim 1 containing Ti.
9. Use of an alloy according to any one of claims 1 to 5, as an electrode material for the synthesis of sodium chlorate.
10. Use of an alloy according to any one of claims 1 to 5, as a coating for protection against corrosion
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2778865A CA2778865A1 (en) | 2012-05-25 | 2012-05-25 | Alloys of the type fe3aita(ru) and use thereof as electrode material for the synthesis of sodium chlorate |
CA2873922A CA2873922A1 (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
CN201380027068.2A CN104471097A (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
BR112014029091A BR112014029091A2 (en) | 2012-05-25 | 2013-04-26 | fe3-xmytztat alloys, method of manufacture of the alloys, coating of said corrosion resistant alloy and use thereof. |
PCT/CA2013/050323 WO2013173916A1 (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
EP13793202.6A EP2855726A4 (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
US14/403,296 US20150096900A1 (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3aita(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CA2778865A CA2778865A1 (en) | 2012-05-25 | 2012-05-25 | Alloys of the type fe3aita(ru) and use thereof as electrode material for the synthesis of sodium chlorate |
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CA2778865A1 true CA2778865A1 (en) | 2013-11-25 |
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ID=49622968
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CA2778865A Abandoned CA2778865A1 (en) | 2012-05-25 | 2012-05-25 | Alloys of the type fe3aita(ru) and use thereof as electrode material for the synthesis of sodium chlorate |
CA2873922A Abandoned CA2873922A1 (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
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CA2873922A Abandoned CA2873922A1 (en) | 2012-05-25 | 2013-04-26 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
Country Status (6)
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US (1) | US20150096900A1 (en) |
EP (1) | EP2855726A4 (en) |
CN (1) | CN104471097A (en) |
BR (1) | BR112014029091A2 (en) |
CA (2) | CA2778865A1 (en) |
WO (1) | WO2013173916A1 (en) |
Cited By (1)
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CN103667892A (en) * | 2013-11-29 | 2014-03-26 | 国网河南省电力公司平顶山供电公司 | Ground grid alloy material resisting to acid soil corrosion and wearing |
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CA3016761A1 (en) | 2016-04-20 | 2017-10-26 | Arconic Inc. | Fcc materials of aluminum, cobalt, iron and nickel, and products made therefrom |
WO2017184778A1 (en) | 2016-04-20 | 2017-10-26 | Arconic Inc. | Fcc materials of aluminum, cobalt and nickel, and products made therefrom |
CN110090942B (en) * | 2019-06-06 | 2020-10-09 | 西安建筑科技大学 | Method for preparing Fe-Al-Ta multifunctional integrated material by Bridgman directional solidification technology |
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US3591483A (en) * | 1968-09-27 | 1971-07-06 | Diamond Shamrock Corp | Diaphragm-type electrolytic cells |
GB1355797A (en) * | 1970-05-15 | 1974-06-05 | Albright & Wilson | Electrodes for use in electrolytic cells |
GB1361602A (en) * | 1971-05-04 | 1974-07-30 | Albright & Wilson | Electrolysis of brine |
JPS5562146A (en) * | 1978-10-31 | 1980-05-10 | Hitachi Metals Ltd | Corrosion resistant, high permeability alloy |
US4447503A (en) * | 1980-05-01 | 1984-05-08 | Howmet Turbine Components Corporation | Superalloy coating composition with high temperature oxidation resistance |
US4405368A (en) * | 1981-05-07 | 1983-09-20 | Marko Materials, Inc. | Iron-aluminum alloys containing boron which have been processed by rapid solidification process and method |
JP2790451B2 (en) * | 1987-04-10 | 1998-08-27 | 松下電器産業株式会社 | Soft magnetic alloy film containing nitrogen |
US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
WO1992009714A1 (en) * | 1990-11-30 | 1992-06-11 | Mitsui Petrochemical Industries, Ltd. | Iron-base soft magnetic alloy |
US5620651A (en) * | 1994-12-29 | 1997-04-15 | Philip Morris Incorporated | Iron aluminide useful as electrical resistance heating elements |
CA2154428C (en) * | 1995-07-21 | 2005-03-22 | Robert Schulz | Ti, ru, fe and o alloys; use thereof for producing cathodes used for electrochemically synthesizing sodium chlorate |
DE19941228B4 (en) * | 1999-08-30 | 2009-12-31 | Alstom | Iron aluminide coating and its use |
CN1433486A (en) * | 2000-06-08 | 2003-07-30 | 表面工程设计产品公司 | Coating system for high temperature stainless steel |
CA2612881C (en) * | 2000-06-08 | 2012-09-18 | Bodycote Metallurgical Coatings Limited | Coating system for high temperature stainless steel |
CA2348145C (en) * | 2001-05-22 | 2005-04-12 | Surface Engineered Products Corporation | Protective system for high temperature metal alloys |
US6475642B1 (en) * | 2000-08-31 | 2002-11-05 | General Electric Company | Oxidation-resistant coatings, and related articles and processes |
US20020134468A1 (en) * | 2001-03-21 | 2002-09-26 | Reddy Budda V. | Aluminum containing iron-based alloys with enhanced ferromagnetic properties |
US6489043B1 (en) * | 2001-11-09 | 2002-12-03 | Chrysalis Technologies Incorporated | Iron aluminide fuel injector component |
CA2588906A1 (en) * | 2007-05-15 | 2008-11-15 | Hydro Quebec | Fe3al(ru) nanocrystalline alloys and use thereof in nanocrystalline form or not for the production of electrodes for the synthesis of sodium chlorate |
-
2012
- 2012-05-25 CA CA2778865A patent/CA2778865A1/en not_active Abandoned
-
2013
- 2013-04-26 WO PCT/CA2013/050323 patent/WO2013173916A1/en active Application Filing
- 2013-04-26 CN CN201380027068.2A patent/CN104471097A/en active Pending
- 2013-04-26 EP EP13793202.6A patent/EP2855726A4/en not_active Withdrawn
- 2013-04-26 BR BR112014029091A patent/BR112014029091A2/en not_active IP Right Cessation
- 2013-04-26 US US14/403,296 patent/US20150096900A1/en not_active Abandoned
- 2013-04-26 CA CA2873922A patent/CA2873922A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103667892A (en) * | 2013-11-29 | 2014-03-26 | 国网河南省电力公司平顶山供电公司 | Ground grid alloy material resisting to acid soil corrosion and wearing |
CN103667892B (en) * | 2013-11-29 | 2016-04-13 | 国家电网公司 | The ground net alloy material that a kind of acid resistance soil corrosion is wear-resisting |
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EP2855726A1 (en) | 2015-04-08 |
CA2873922A1 (en) | 2013-11-28 |
WO2013173916A1 (en) | 2013-11-28 |
EP2855726A4 (en) | 2016-03-30 |
BR112014029091A2 (en) | 2017-06-27 |
US20150096900A1 (en) | 2015-04-09 |
CN104471097A (en) | 2015-03-25 |
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