US2719797A - Platinizing tantalum - Google Patents
Platinizing tantalum Download PDFInfo
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- US2719797A US2719797A US163782A US16378250A US2719797A US 2719797 A US2719797 A US 2719797A US 163782 A US163782 A US 163782A US 16378250 A US16378250 A US 16378250A US 2719797 A US2719797 A US 2719797A
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- tantalum
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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
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J19/00—Details of vacuum tubes of the types covered by group H01J21/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2893/00—Discharge tubes and lamps
- H01J2893/0001—Electrodes and electrode systems suitable for discharge tubes or lamps
- H01J2893/0012—Constructional arrangements
- H01J2893/0019—Chemical composition and manufacture
- H01J2893/0022—Manufacture
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- 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
- Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
- Y10S205/917—Treatment of workpiece between coating steps
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- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9265—Special properties
- Y10S428/929—Electrical contact feature
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- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/934—Electrical process
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- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/936—Chemical deposition, e.g. electroless plating
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- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/94—Pressure bonding, e.g. explosive
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12819—Group VB metal-base component
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- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12875—Platinum group metal-base component
Definitions
- invention relates 'generallytoa'processfor coating tantalum and like metals with metals or. alloys of the platinum group and "is furthermore concerned withsimproved anodes manufactured according to this coating process.
- the invention also 'relates'to the application of 'theseimprovedanodes in certain electrochemical reactions anditrelates'p'articularlyto, a-process to produc'e"platinized tantalum for use as non-corrodingianodesin electrochemical'processes.
- a graphite anode undergoes "continual disintegration and must 'be “replaced from time to time *therby causing interruption of the electrochemical process which is a'costly-operation.
- it In the manufacture -of'chlor'ine bythe electrolysisofbrine, it 'is necessary to potifyfltheproduct from traces of carbon dioxide which result frorn the'oitidation of the 'graphiteanodes.
- 'Partic'leswhich dust (SE from'the graphite become deposited in the 'dia'phragr'ns which surround the electrodes thereby necessitating replacement of'the diaphragms along withthe electrodes.
- Electroplating .of a platinum metal .onto ,a tantalumibase results in a coating that ,may easily be stripped fromtheibase. Attempts to cover the tantalum strip with -a platinum metal foil and to holdthemetals together asby sweating, rolling or hammering, have proved to be unsatisfactory because the'platinum metal foil :is held '10 the tantalum only by mechanical .contact whichis not,su'fiicient topermit of its use as an :anode.
- the coats of platinum metal that have beenma'de by any of these processes are not truly "bonded to the tantalum, 'i. e. the tantalum is not platinizetl in'the sense thattheplatinum metal is united Withthetantalumbyatornic attraction forces asis obtainedby thisinvention.
- platinumimetalf as herein used, is meant the precious, metals ,in group MIII. .of sthe ,periodic .chart, excepting psmium, ,i. e. this .term includes ,the following metals: ruthenium, Platinum. 7 v "Broadly, the-processeof this,invention,involvesa-combination of successive treatments whereby-a thin.deposit of a platinum metal is made upon the surface ofza tantalum body and thereafter the platinum metal deposit istbondeditwthe' tantalum 'body by heating the whole' toa high temperature and under inert conditions!
- the thin deposit of a platinum metal may be applied'accordin-g to thisinvention in one: of several :difierent ways, such as .byelectroplating or by .the chemicalidecomposition of ,.a platinum metal compound 'applied on:thesurface .of the tantalum. It .should ,be :clearly understood that the thin ⁇ deposits .madeaccording totany-of these processes are. not ,firrn deposits until they have been 5 subsequently bonded in. thermannertdescribedlater in: thisqspecification.
- ;columbium may Lbemused instead ,of-.,tantalum.
- ralloys, inCllldlng5Sil1- tered products of these metals may'be;used,;i.-e'. alloys of the metals themselves as well as with the addition of other metals which do -not change the inertness of the :alloy.
- the etching may also be accomplished electrolytically in hydrofluoric acid using lead or silver as the cathode material.
- the cleaned and roughened tantalum is then dipped into or otherwise coated with a solution of, e. g. chloroplatinic acid (HzPtCls), which has been dissolved in a suitable volatile solvent.
- HzPtCls chloroplatinic acid
- the tantalum After dipping the tantalum into this solution, the excess solution is removed and the solvent is evaporated otf at a relatively slow temperature.
- the coated tantalum is then heated above the decomposition temperature (approximately 250 C.) of the chloroplatinic acid whereby a thin coat of platinum is left upon the tantalum surface, all other products of the decomposition being volatile.
- the platinum coating resulting from the above treatment amounts to approximately 0.00034 gram/cm.
- tantalum and columbium may be coated with other metals of the platinum metal group by using one of the following chemical compounds ruthenium nitroso bromide (RuNOBrsnHzO) palladium di-n-butylamine nitrite (Pd (C4H NH2) 2 (N02) 2) and iridium chloride acid H2IrCls6H20) Electroplating Another method for depositing the thin coat of a platinum metal upon the tantalum base is by electrolysis. After the tantalum base has been roughened as by etching in a manner as explained above, it is placed in the cathode position in a plating bath. A plating bath having the following compositon has been found to be suitable:
- Tantalum strips which have been platinized according to the above described chemical decomposition or electroplating procedures are placed into acold furnace.
- the furnace is evacuated to about l0- mm. of mercury and is then heated to a temperature below the lowest melting point of the metals involved and high enough to cause the metals to become bonded as required by this invention.
- any inert atmosphere such as helium, neon, argon, and the like may be substituted. These gases do not chemically combine with the tantalumas does oxygen, for example, and by the term inert conditions 'a's used in this specification and in the claims is meant such surroundings which are inert with respect to tantalum, such as a vacuum or a noble-gas atmosphere.
- a platinum layer on a tantalum strip which has not been subjected to the bonding treatment of this invention will upon being immersed in aqnal regia become completely dissolved.
- aqua regia will not completely dissolve the platinum layer and the weight of the bonded strip after it has been immersed in aqua regia is greater than the weight of its original tantalum constituent, thus indicating that the bonding treatment causes the platinum and tantalum metals to interdiffuse and become alloyed in such a composition that the alloy is not attacked by hot aqua regia.
- Tantalum strips which were platinized by the above described chemical decomposition procedure were heated in vacuum at 1200" C. and 1400 C. Platinizing according to this procedure produces layers of only up to 0.03 mm. in thickness per application. The layers thus deposited were not attacked by hot aqua regia, however, when these strips were tested as anodes in cells for. the production of chlorine and chlorates the current ceased to flow and the strips became corroded with a coherent tarnish layer. This corrosion of the anode indicates that the tantalum metal has diffused through the thin platinum layer to the outside surface of the platinum film where the tantalum becomes oxidized and stops the flow of current through the cell.
- platinized tantalum strips are bonded at temperatures of less than 800 C., the platinum metal layer is easily dissolved by aqua regia and the platinum films flake off from the tantalum base when the stripsare' used as anodes, thus indicating that substantially no alloying of the platinum andtantalum metals occurs when there is insufficient heating.
- tantalum base in such a manner that the outside layer of the platinum metal film will consist of substantially pure platinum whereas the inside layer of the film will be firmly bonded to the tantalum base by the formation of a thin layer of platinum-tantalum alloy.
- a tantalum strip which has been platinized in such a desired manner will behave like an ordinary platinum electrode, the apparently vulnerable zone of platinum-tantalum alloy being protected from contact with the electrolyte solution in thecell .by the outer layer of unalloyed platinum. To insure that the outer layer remains unalloyed during the heat treatment by which tantalum and platinum become bonded, a heavier platinum metal coat is required than in the alloy anodes described above.
- a heavy deposit of platinum metal may be applied to the tantalum base by electroplating in the manner described above; however, if such heavy deposit exceeds approximately 1 mu. in thickness, it cannot be successfully bonded. Apparently, during the electroplating process, stresses are generated in the platinum film cans ing blisters "to form which dofn'ot beco'me eoherently zb'onded to the tantalu'm base "when ith'e coated :metal is subsequently heated. I
- aiprimar'y coat which does "not exceed l'mu. in thickness.
- a ise'cond coat of any desired thickness such as for example 25 -'mu., may' be electroplated upon ithe "surface of 'the thin primary coat.
- iit-ha s been foundpOssible, for example, to platinize a tantalum rod of 6.7 millimeters diameter with a platinum film o'f25 microns in thickness, and, "thereafter, .to fdrawioutthe coated and bonded rod .to a diameter of .67 millimeter'without any danger of splitting the platinum Tfilmifrom the tantalum base.
- Iliis-rod a'fter'being reduced lin-diameter behaves like a-.puret platinum ano'de thus indicating that-the platinum-tantalum alloy whichis formed at the interface-of the film and-thebase does not extend lto the outside-surface of the film, and that the outer surface layer of the film comprises substantially pure .platinum. tAlso,-there isno'ilakingtotf o'f the platinum filmeven after 'long and continued use of the rod as an .anodezin a .chlorineor chlorate production cell thus indicating that :platinum film-is-firmly bonded to the tantalum base.
- the secondary coat may be applied in severalseparate layers andbetween the periods of the deposition of these several layers, the metals may be subjected to a bonding treatment. It is preferred that the primary coat be not more than 5% of the thickness of the secondary coat or the combined layers which may comprise the secondary coat It has been furthermore observed that the original surface film of the tantalum body that is not removed by the cleaning and roughening process, becomes diffused throughout the interior of the tantalum mass during the subsequent heating treatments whereby pure tantalum metal becomes joined by atomic attraction forces with the platinum deposit.
- the inner core of the tantalum base may consist of copper, silver, or other like metal.
- a tantalum tube which has been platinized on its outer surface according to the method of this invention may be slipped over a tightly fitting copper rod and the composite rod may then be swaged and drawn to any desired thickness.
- a composite rod as an anode in the electrolytic production of chlorine, chlorates, and percompounds, it is necessary that the tantalum covering ltrave iuobpenings tltrough Mitten the core may he attacked.
- 'A method of coating a base formed of material selected from the group consisting of tantalum, columbium and alloys of these metals platinum metal comprising the sequential manufacturing steps of depositing a primary coat of platinum metal on said base heating the coated base under inert conditions at an elevated temperature within the range of about 800 C. to about 1400 C. the melting point of said metals to alloy the adjacent surfaces of said metals, electroplating a second coat of platinum metal on said primary coat, and heating the coated mass at an elevated temperature below the melting point of said metals and within the range of about 800 C. to about 1400 C. to form coatings of pure Pt interspersed with interlayers of an alloy of Pt with the base metal.
- a method of producing an anode for use in electrochemical processes by providing an adherent coating of platinum metal on a base of tantalum which comprises the sequential manufacturing steps of cleaning and roughening the surface of the tantalum, depositing a thin first coat of platinum metal on the tantalum base, bonding said coat to said base by heating said metals in an inert atmosphere at a temperature above about 800 C. but
- said second coat comprises a plurality of separate deposited layers and the base and deposited layers are subjected to the step of heating under inert conditions below the each separate layer deposit, the thickness of said first layer being less than about 5 percent of the thickness of said second coat.
- step of depositing the layer of platinum is accomplished by washing said base metal with a solvent, cleaning and roughening said base metal as by etching, coating said cleaned base metal with a solution comprising a soluble compound of the platinum metal and a volatile solvent, evaporating the solvent from the liquid, and heating the coated base metal above the decomposition temperature of the soluble compound to decompose said compound and to volatilize the products of decomposition excepting the platinum metal.
- the primary coat is deposited by washing said base metal with a solvent, cleaning and roughening said base metal by etching, coating said cleaned base metal with a solution comprising a soluble' compound of the platinum metal and a volatile solvent, evaporating the solvent from the liquid, and heating the coated base metal above the decompo sition temperature of the soluble compound to decompose said compound and to volatilize the products of decomposition excepting the platinum metal.
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Description
United States PatentO $719,797 iPLAEUINIZING Edgar F. Rosenblatt, Montclair, and ilohann G. 1Cdhn, East 'Orange, 'N. J ,ass'ignors to "Baker & Co., Inc Newark, N. "J., 'a corporation of New 'Jersey No Drawing. :ApplicationMay '28, "1950.,
QSeriaLNo. 163,782
'13 Claims. (01. 117-65) "invention relates 'generallytoa'processfor coating tantalum and like metals with metals or. alloys of the platinum group and "is furthermore concerned withsimproved anodes manufactured according to this coating process. The inventionalso 'relates'to the application of 'theseimprovedanodes in certain electrochemical reactions anditrelates'p'articularlyto, a-process to produc'e"platinized tantalum for use as non-corrodingianodesin electrochemical'processes. t
In electrochemical processes, such as "the electrolysis of 'chlorides and the, production 'ofpercompounds, the proper selection of material from which to manufacture 'the elec'tr'odes is a'matter of prime'importance. In these processes, it is conventional to 'use electrodes of iron, steel, 'etc. in the cathode position; howeverfthere, are only 'a few ltnown materials "that may "constitute the'an'o'des, *becati'se' most materials while in the anode position are susceptible to intense 'corros'ion. If 1onlythefcheniical "characteristics of -'a materi'al were to be "considered in-'the 'selection 'of 'asuitableanodic material, the metals of "the platinum group would be the universal choice because "they arehighly'resistant to corrosion; however, the high cost ofthcse precious'metals prohibitstheir extended'commercial use. Substitute materials'have, :therefore, been resorted to, whenever possible, the primary anodic matei'ialemployed industrially beingthat-of graphite 1 Many disadvantages accompany 'the use o'f graphite as an anodic material. A graphite anode undergoes "continual disintegration and must 'be "replaced from time to time *therby causing interruption of the electrochemical process which is a'costly-operation. In the manufacture -of'chlor'ine bythe electrolysisofbrine, it 'is necessary to puiifyfltheproduct from traces of carbon dioxide which result frorn the'oitidation of the 'graphiteanodes. 'Partic'leswhich dust (SE from'the graphite become deposited in the 'dia'phragr'ns which surround the electrodes thereby necessitating replacement of'the diaphragms along withthe electrodes. Theseditficul'ties are not-encountered when anodes of'the platinum metals are used. -Alsothe 'overvoltage "characteristics "forclilorine discharge are more favorable with platinum metal anodes than with 'graphite anodes.
here-has -been a continualsearch for"a*m aterial which =hasthe desirable anodic-characteristics of'thepl'atinum metalsf'but-not their prohibitive costs. It-h a's 1ong-been considered that'tantalum would makeqan ideal anodic material because "of its remarkable chemical inertness. Tantalum is -not attacked by chlorine, hydrt'ic lilori'c acid, 'nitri'cacid,or aqua-regia. Then, too-its cost is veryf low as compared'withthe cost' of the platinum metals, How- -ever,'when atantalum electrode is used as {an anode, the flow of electric"current through the cell quicklyfstops. This phenomenon is'caused bythe formation of what'rnay be referred V to as an anodicifilm comprising "a layer of oXide which decreases "the material. 7
In order to prevent the formation of this film, attempts have been made 'to-"coat a tantalum base with platinum electric conductivity -'6f "the .metal. It. has 'beensuggested .that coating .with a platinum metal be accomplished by such .methods as electrolysis, hammering, welding, rolling, and-the like; however, none of these methods have been found .to lbe,.-satisfactory. They do not produce a coat of platinum metal .which adheres with sufficient tenacity to the tantalum baserthat the coated tantalum metal will'be commercially suiteddior .use as an anodein electrochemical,processes. Electroplating .of a platinum metal .onto ,a tantalumibase results in a coating that ,may easily be stripped fromtheibase. Attempts to cover the tantalum strip with -a platinum metal foil and to holdthemetals together asby sweating, rolling or hammering, have proved to be unsatisfactory because the'platinum metal foil :is held '10 the tantalum only by mechanical .contact whichis not,su'fiicient topermit of its use as an :anode. The coats of platinum metal that have beenma'de by any of these processes are not truly "bonded to the tantalum, 'i. e. the tantalum is not platinizetl in'the sense thattheplatinum metal is united Withthetantalumbyatornic attraction forces asis obtainedby thisinvention.
it is, therefore, 'one object of :this invention .to provide a thin, firmlyadherent, practically inseparable coat of .one or several of the platinum metals onto a base OfLtantalum or like metal. It is a further object of the invention 'to achieve =t'his result in a simple and-economical manner. Anotherobject 'of'this invention is'to'manu'facture a composite metal stoekhavingabodily newarrangement 'between tantalum and'platinummetals. It is a further object of this invention to improve. certain.electrochemical processes by using the improvedelectrodes of this'invention. Further objectsiandwariouszadvantages of this invention will become apparentifrom a considerationzofzthis specification and'the appended claims.
By the term platinumimetalf as herein used, is meant the precious, metals ,in group MIII. .of sthe ,periodic .chart, excepting psmium, ,i. e. this .term includes ,the following metals: ruthenium, Platinum. 7 v "Broadly, the-processeof this,invention,involvesa-combination of successive treatments whereby-a thin.deposit of a platinum metal is made upon the surface ofza tantalum body and thereafter the platinum metal deposit istbondeditwthe' tantalum 'body by heating the whole' toa high temperature and under inert conditions! The thin deposit of a platinum metal may be applied'accordin-g to thisinvention in one: of several :difierent ways, such as .byelectroplating or by .the chemicalidecomposition of ,.a platinum metal compound 'applied on:thesurface .of the tantalum. It .should ,be :clearly understood that the thin {deposits .madeaccording totany-of these processes are. not ,firrn deposits until they have been 5 subsequently bonded in. thermannertdescribedlater in: thisqspecification.
For the ,purpose ofthis invention, ;columbium,=may Lbemused instead ,of-.,tantalum. Also,ralloys, inCllldlng5Sil1- tered products of these metals, may'be;used,;i.-e'. alloys of the metals themselves as well as with the addition of other metals which do -not change the inertness of the :alloy. -At*the present -:time, :tan'talum is :preferre'd1over .use of =colurnbium :because 5 the :cost :of ;columbium is much-greater than'the cost of :tantalum' It;is intended also that the term "itantalunf as .used herein be mot limited to ,thechemically npure :metal 'but that vit include other marketable form 'which contains small and, there'- tfore, harmless \traces of impurities, such :as carbon, I iron, =etc. v i
. a Chemicaldecompasition As statedmbovegone"methodofapplyingathin coat =of a platinum metal is-by decomposing a metal compound on the suffaceofthe tantalum. 'To accomplishthis treat mentkthe tantalum Fbase is pre'ferablvwashed -as with -rhodiuin, palladium, iridium and n Q carbon tetrachloride and acetone. The surface of the tantalum metal is then cleaned and roughened to an extent depending upon the amount of coverage that is desired. This roughening may be accomplished by rubbing the metal with emory papers, by sand blasting, or by chemically etching with hydrofluoric acid. The etching may also be accomplished electrolytically in hydrofluoric acid using lead or silver as the cathode material. The cleaned and roughened tantalum is then dipped into or otherwise coated with a solution of, e. g. chloroplatinic acid (HzPtCls), which has been dissolved in a suitable volatile solvent. It has been found that one gram of chloroplatinic acid dissolved in a solution containing 15 ml. isopropyl alcohol and 15 ml. ethyl acetoacetate produces a uniform platinum coating. The more important constituent of this solvent is the ethyl acetoacetate since solutions having a higher concentration of this constituent give better results than do those having a greater proportion of the alcohol. After dipping the tantalum into this solution, the excess solution is removed and the solvent is evaporated otf at a relatively slow temperature. The coated tantalum is then heated above the decomposition temperature (approximately 250 C.) of the chloroplatinic acid whereby a thin coat of platinum is left upon the tantalum surface, all other products of the decomposition being volatile. The platinum coating resulting from the above treatment amounts to approximately 0.00034 gram/cm. In like manner, tantalum and columbium may be coated with other metals of the platinum metal group by using one of the following chemical compounds ruthenium nitroso bromide (RuNOBrsnHzO) palladium di-n-butylamine nitrite (Pd (C4H NH2) 2 (N02) 2) and iridium chloride acid H2IrCls6H20) Electroplating Another method for depositing the thin coat of a platinum metal upon the tantalum base is by electrolysis. After the tantalum base has been roughened as by etching in a manner as explained above, it is placed in the cathode position in a plating bath. A plating bath having the following compositon has been found to be suitable:
20 g. Pt(NH3)2(N02)2 commercially known as P-salt 100 g. ammonium nitrate 1 liter of ammonia Bonding Following the deposition of the thin platinum metal coating, the coated tantalum is subjected to the bonding treatment of this invention. An example of the manner in which this treatment is carried out follows:
Tantalum strips which have been platinized according to the above described chemical decomposition or electroplating procedures are placed into acold furnace. The furnace is evacuated to about l0- mm. of mercury and is then heated to a temperature below the lowest melting point of the metals involved and high enough to cause the metals to become bonded as required by this invention.
800 c. to 1400" 0. have been found suitable, the 0p- Temperatures ranging from approximately timum temperature being about 1000" C. After the bonding temperature has been maintained for approximately 15 minutes, the heating is discontinued, and when the temperature in the furnace has substantially dropped the evacuation is stopped and the coated tantalum is removed. Instead of treating the metal in a vacuum, it has been found that any inert atmosphere such as helium, neon, argon, and the like may be substituted. These gases do not chemically combine with the tantalumas does oxygen, for example, and by the term inert conditions 'a's used in this specification and in the claims is meant such surroundings which are inert with respect to tantalum, such as a vacuum or a noble-gas atmosphere.
A platinum layer on a tantalum strip which has not been subjected to the bonding treatment of this invention will upon being immersed in aqnal regia become completely dissolved. When, however, such a coated strip is bonded in the manner described above, aqua regia will not completely dissolve the platinum layer and the weight of the bonded strip after it has been immersed in aqua regia is greater than the weight of its original tantalum constituent, thus indicating that the bonding treatment causes the platinum and tantalum metals to interdiffuse and become alloyed in such a composition that the alloy is not attacked by hot aqua regia.
Tantalum strips which were platinized by the above described chemical decomposition procedure were heated in vacuum at 1200" C. and 1400 C. Platinizing according to this procedure produces layers of only up to 0.03 mm. in thickness per application. The layers thus deposited were not attacked by hot aqua regia, however, when these strips were tested as anodes in cells for. the production of chlorine and chlorates the current ceased to flow and the strips became corroded with a coherent tarnish layer. This corrosion of the anode indicates that the tantalum metal has diffused through the thin platinum layer to the outside surface of the platinum film where the tantalum becomes oxidized and stops the flow of current through the cell. If platinized tantalum strips are bonded at temperatures of less than 800 C., the platinum metal layer is easily dissolved by aqua regia and the platinum films flake off from the tantalum base when the stripsare' used as anodes, thus indicating that substantially no alloying of the platinum andtantalum metals occurs when there is insufficient heating.
It is desirable, therefore, to coat the tantalum base in such a manner that the outside layer of the platinum metal film will consist of substantially pure platinum whereas the inside layer of the film will be firmly bonded to the tantalum base by the formation of a thin layer of platinum-tantalum alloy. A tantalum strip which has been platinized in such a desired manner will behave like an ordinary platinum electrode, the apparently vulnerable zone of platinum-tantalum alloy being protected from contact with the electrolyte solution in thecell .by the outer layer of unalloyed platinum. To insure that the outer layer remains unalloyed during the heat treatment by which tantalum and platinum become bonded, a heavier platinum metal coat is required than in the alloy anodes described above. Also from a commercial standpoint, it is advantageous to apply a relatively thick platinum metal coat on a thick tantalum base and, thereafter, roll or otherwise draw out the thick coated bar to obtain the desired reduced strips having a top layer of unalloyed platinum metal. Such a procedure permits of more case in the handling of the metal composites and enables using smaller processing equipment having obvious economical advantages as well as reducingthe losses incurred during the etching treatment.
A heavy deposit of platinum metal may be applied to the tantalum base by electroplating in the manner described above; however, if such heavy deposit exceeds approximately 1 mu. in thickness, it cannot be successfully bonded. Apparently, during the electroplating process, stresses are generated in the platinum film cans ing blisters "to form which dofn'ot beco'me eoherently zb'onded to the tantalu'm base "when ith'e coated :metal is subsequently heated. I
-In practicing this "invention, it 'is, therefore, desirable to apply aiprimar'y coat which does "not exceed l'mu. in thickness. Following the bonding o'f the primary coat to the tantalum base in the manner as lreieina'liove described, a ise'cond coat of any desired thickness, such as for example 25 -'mu., may' be electroplated upon ithe "surface of 'the thin primary coat. The blistering =which oc- -'cu'rs"as stated -'abovewhen a thick platinum metal deposit is electroplated direetl-y upon a tantalum base, does not occurwhen the second ='coat-is deposited.
Following such a procedure, iit-ha s been foundpOssible, for example, to platinize a tantalum rod of 6.7 millimeters diameter with a platinum film o'f25 microns in thickness, and, "thereafter, .to fdrawioutthe coated and bonded rod .to a diameter of .67 millimeter'without any danger of splitting the platinum Tfilmifrom the tantalum base. Iliis-rod a'fter'being reduced lin-diameter behaves like a-.puret platinum ano'de thus indicating that-the platinum-tantalum alloy whichis formed at the interface-of the film and-thebase does not extend lto the outside-surface of the film, and that the outer surface layer of the film comprises substantially pure .platinum. tAlso,-there isno'ilakingtotf o'f the platinum filmeven after 'long and continued use of the rod as an .anodezin a .chlorineor chlorate production cell thus indicating that :platinum film-is-firmly bonded to the tantalum base. 7 The secondary coat may be applied in severalseparate layers andbetween the periods of the deposition of these several layers, the metals may be subjected to a bonding treatment. It is preferred that the primary coat be not more than 5% of the thickness of the secondary coat or the combined layers which may comprise the secondary coat It has been furthermore observed that the original surface film of the tantalum body that is not removed by the cleaning and roughening process, becomes diffused throughout the interior of the tantalum mass during the subsequent heating treatments whereby pure tantalum metal becomes joined by atomic attraction forces with the platinum deposit. When, however, no precautions are taken to prevent the formation of the surface film during the heating treatments, the film becomes considerable and is not completely dissolved into the tantalum mass, thus preventing the platinum deposit from joining directly to the pure tantalum. Also, it is noted that the diffusion of this surface film into the tantalum mass causes the development of permanent hardness of the tantalum, and when relatively large amounts of oxygen or nitrogen are absorbed in the metal, the tantalum becomes brittle. This brittleness is especially pronounced in the case where very thin strips of tantalum are used. By depositing platinum metals and bonding them to tantalum according to the process of this invention, these undesirable results are eliminated.
Examination with a microscope of the platinum metal films of this invention reveals that they have a rough or wavy profile, the indentations of which develop into pores when the coated sheets are reduced to small thicknesses. Although these pores expose the tantalum to the development of an anodic film, the coated tantalum spots are not affected when the composite metal is used as an anode. Also, the thin platinum outer layer prevents the alloy layer from being attacked.
The inner core of the tantalum base may consist of copper, silver, or other like metal. For example, a tantalum tube which has been platinized on its outer surface according to the method of this invention may be slipped over a tightly fitting copper rod and the composite rod may then be swaged and drawn to any desired thickness. When using such a composite rod as an anode in the electrolytic production of chlorine, chlorates, and percompounds, it is necessary that the tantalum covering ltrave iuobpenings tltrough Mitten the core may he attacked. aFro'm the a'bo've :Hescriptio'n, it=will be seen that we have disclosed :a process by which platinum :metals may be successfully a'nil firrnly bonded to taritalu'm metals, and that tantalum :whi'ch has' lteen platini'zed according =to :the manner itau'ght-fherein :m'ay be used as an an'ode in eleetr'ohemical processes, mud-especially in the fproduction of: chlorine; chlorates, andper-ompounds. The examples wh'ich ltav'e been-included in this spe'eification .have ibeen given by' way of illustration 'oril'yand t-tot by way of restriction or limitation. We -desire to have tit aundersto'od that wedo not' intend to "limit ourslves to ithe particular details tiesc'ribed i'e'xcept z'as #dfined -in the claims." I I 11. 'A rn'ethod of providinga'nadherenteoatifig of platinum metal on a base ot' material or the group consist- :ing of itantalum a'n'ti eolumbiu'm, eom'pris'ing the sequenftial .Imanufacturingsteps of dep'ositing a tliin cdntinuous llayer rof :platinum metal -"on' sai'd "b'ase "and-he'atin'g isaid filayer rand said base 'in' proximlty therto under inert conditions at an elevated temperature blowtliefmelt- -ing "pointiof said platinum metaban'd said base (material zandtwithinithei'ran'gemf about 800' cs'to about 1400 C. to inter-diffuse .L-said' ;metals :at '!the ibounda'ry thei'e'of, wherebyssaid platinum metal {layer becomes attended to :said material omits router surface and :is 'z'separate'd from the base by an interlayer of an alloy of lth'e platinum .withthe basmmetal A ,7
2. 'A method of coating a base formed of material selected from the group consisting of tantalum, columbium and alloys of these metals platinum metal comprising the sequential manufacturing steps of depositing a primary coat of platinum metal on said base heating the coated base under inert conditions at an elevated temperature within the range of about 800 C. to about 1400 C. the melting point of said metals to alloy the adjacent surfaces of said metals, electroplating a second coat of platinum metal on said primary coat, and heating the coated mass at an elevated temperature below the melting point of said metals and within the range of about 800 C. to about 1400 C. to form coatings of pure Pt interspersed with interlayers of an alloy of Pt with the base metal.
3. The method according to claim 2 wherein said second coat comprises a plurality of separate deposited layers and the composite metal is subjected to the step of heating-under inert conditions below the melting point of said metals and within the range of about 800 C. to about 1400" C. to alloy the adjacent surfaces of said metals between the steps of applying each separate layer deposit.
4. The method according to claim 2 wherein the thickness of the primary coat is not more than 5 percent of the thickness of the second coat.
5. A method of producing an anode for use in electrochemical processes by providing an adherent coating of platinum metal on a base of tantalum which comprises the sequential manufacturing steps of cleaning and roughening the surface of the tantalum, depositing a thin first coat of platinum metal on the tantalum base, bonding said coat to said base by heating said metals in an inert atmosphere at a temperature above about 800 C. but
below about 1400 C. whereby the remaining film migrates into the metals and the adjacent surfaces of said layer and said base are alloyed and said metals are joined together by atomic attraction forces, electroplating a second coat of platinum metal upon said first coat, heating the metals to an elevated temperature within the range of about 800 C. to about 1400 C., and reducing the thickness of the bonded metals.
6. The method according to claim 5 wherein the cleaning step is performed by etching the tantalum with hydrofluoric acid, the inert atmosphere being a vacuum, and the bonding temperature being about 1000" C.
, .7. The methodaccording to claim 5 wherein said second coat comprises a plurality of separate deposited layers and the base and deposited layers are subjected to the step of heating under inert conditions below the each separate layer deposit, the thickness of said first layer being less than about 5 percent of the thickness of said second coat.
8. The method according to claim 1 wherein the step of depositing the layer of platinum is accomplished by washing said base metal with a solvent, cleaning and roughening said base metal as by etching, coating said cleaned base metal with a solution comprising a soluble compound of the platinum metal and a volatile solvent, evaporating the solvent from the liquid, and heating the coated base metal above the decomposition temperature of the soluble compound to decompose said compound and to volatilize the products of decomposition excepting the platinum metal.
9. The method of claim 8 wherein the soluble compound is chloroplatinio acid and the solvent is a mixture of ,isopropyl alcohol and ethyl acetoacetate.
10. The method according to claim 1 wherein the step of depositing the layer of platinum is accomplished by electrolysis.
11. The method of claim 2 wherein the primary coat is deposited by washing said base metal with a solvent, cleaning and roughening said base metal by etching, coating said cleaned base metal with a solution comprising a soluble' compound of the platinum metal and a volatile solvent, evaporating the solvent from the liquid, and heating the coated base metal above the decompo sition temperature of the soluble compound to decompose said compound and to volatilize the products of decomposition excepting the platinum metal.
12. The method of claim 11 wherein the soluble compound is chloroplatinic acid and the solvent is a mixture of isopropyl alcohol and ethyl acetoacetate.
13. The method of claim 2 wherein the primary coat is deposited by electrolysis.
References Cited in the file of this patent UNITED STATES PATENTS 1,465,553 Kirk Aug. 21, 1923 2,114,161 Antisell Apr. 12,1938 2,226,720 Hansell Dec. 31, 1940 2,282,097 Taylor May 5, 1942 2,303,497 Reeve Dec. 1, 1942 2,370,242 Hensel Feb. 27, 1945 2,375,154 Volterra May 1, 1 945 2,401,040 Becker May 28, 1946 2,417,459 Eitel Mar. 18, 1947 2,418,460 Buehler Apr. 8', 1947 2,492,204 Van Gilder Dec. 27, 1949 2,497,109 Williams Feb. 14, 1950 2,539,096 Miller Jan. 23, 1951
Claims (1)
1. A METHOD OF PROVIDING AN ADHERENT COATING OF PLATINUM METAL ON A BASE OF MATERIAL OF THE GROUP CONSISTING OF TANTALUM AND COLUBIUM, COMPRISING THE SEQUENTIAL MANUFACTURING STEPS OF DEPOSITING A THIN CONTINUOUS LAYER OF PLATINUM METAL ON SAID BASE AND HEATING SAID LAYER AND SAID BASE IN PROXIMITY THERETO UNDER INERT CONDITIONS AT AN ELEVATED TEMPERATURE BELOW THE MELTING POINT OF SAID PLATINUM METAL AND SAID BASE MATERIAL AND WITHIN THE RANGE OF ABOUT 800* C. TO ABOUT 1400* C. TO INTER-DIFFUSE SAID METALS AT THE BOUNDARY THEROF, WHEREBY SAID PLATINUM METAL LAYER BECOMES BONDED TO SAID MATERIAL ON ITS OUTER SURFACE AND IS SEPARATED FROM THE BASE BY AN INTERLAYER OF AN ALLOY OF THE PLATINUM WITH THE BASE METAL.
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US163782A US2719797A (en) | 1950-05-23 | 1950-05-23 | Platinizing tantalum |
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US163782A US2719797A (en) | 1950-05-23 | 1950-05-23 | Platinizing tantalum |
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US2719797A true US2719797A (en) | 1955-10-04 |
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Cited By (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2761207A (en) * | 1955-03-16 | 1956-09-04 | Baker & Co Inc | Method of making a composite metal rod |
US2844868A (en) * | 1954-06-01 | 1958-07-29 | Sylvania Electric Prod | Method of joining refractory metals |
US2987453A (en) * | 1959-04-14 | 1961-06-06 | Harshaw Chem Corp | Method of electrodepositing chromium |
US2998359A (en) * | 1958-11-25 | 1961-08-29 | Engelhard Ind Inc | Method for preparing anodes for cathodic protection systems |
US3010891A (en) * | 1959-04-15 | 1961-11-28 | Engelhard Ind Inc | Trailing anode for cathodic protection systems |
US3065534A (en) * | 1955-03-30 | 1962-11-27 | Itt | Method of joining a semiconductor to a conductor |
US3066042A (en) * | 1959-11-27 | 1962-11-27 | Engelhard Ind Inc | Method of coating metal |
US3081252A (en) * | 1959-09-30 | 1963-03-12 | Chemionics Engineering Lab Inc | Pipe plug anode |
US3083451A (en) * | 1959-09-21 | 1963-04-02 | Ass Elect Ind Manchester Ltd | Beryllium brazing |
US3085949A (en) * | 1959-04-17 | 1963-04-16 | Ici Ltd | Surface treatment of titanium or titanium base alloy |
US3096272A (en) * | 1957-10-24 | 1963-07-02 | Amalgamated Curacao Patents Co | Noble metal coated titanium electrode and method of making and using it |
US3102086A (en) * | 1957-07-26 | 1963-08-27 | Ici Ltd | Method of improving the corrosion resistance of titanium metals |
US3103484A (en) * | 1959-10-10 | 1963-09-10 | Anodes for electrolytic chlorine | |
US3107422A (en) * | 1961-05-16 | 1963-10-22 | Bendix Corp | Rhodium diffusion process for bonding and sealing of metallic parts |
US3117023A (en) * | 1962-01-03 | 1964-01-07 | Ionics | Method of making a non-corroding electrode |
US3118828A (en) * | 1957-07-17 | 1964-01-21 | Ici Ltd | Electrode structure with titanium alloy base |
US3132928A (en) * | 1962-02-26 | 1964-05-12 | Donald D Crooks | Simultaneous brazing and corrosion protecting refractory metals |
US3133872A (en) * | 1959-03-10 | 1964-05-19 | Chemionics Engineering Lab Inc | Anode for electrochemical applications |
US3177131A (en) * | 1959-04-27 | 1965-04-06 | Ici Ltd | Method for the production of platinum coated titanium anodes |
US3207680A (en) * | 1962-05-03 | 1965-09-21 | Elizabeth L Macnamara | Method of electrodepositing iridium |
US3220938A (en) * | 1961-03-09 | 1965-11-30 | Bell Telephone Labor Inc | Oxide underlay for printed circuit components |
US3222270A (en) * | 1958-03-18 | 1965-12-07 | Ici Ltd | Multi-electrolytic cells |
US3223609A (en) * | 1961-10-30 | 1965-12-14 | Beckman Instruments Inc | Hygrometer |
US3236756A (en) * | 1957-04-09 | 1966-02-22 | Amalgamated Curacao Patents Co | Electrolysis with precious metalcoated titanium anode |
US3309292A (en) * | 1964-02-28 | 1967-03-14 | Richard L Andrews | Method for obtaining thick adherent coatings of platinum metals on refractory metals |
US3313721A (en) * | 1958-12-31 | 1967-04-11 | Englehard Ind Inc | Dish-shaped anode |
US3391446A (en) * | 1965-08-30 | 1968-07-09 | Atomic Energy Commission Usa | Aluminum brazing |
US3414439A (en) * | 1967-03-13 | 1968-12-03 | Engelhard Ind Inc | Fuel cell and process of using with ruthenium-tantalum alloy catalyst |
US3461058A (en) * | 1966-06-07 | 1969-08-12 | Engelhard Ind Inc | Method of producing a composite electrode |
US3475224A (en) * | 1967-01-03 | 1969-10-28 | Engelhard Ind Inc | Fuel cell having catalytic fuel electrode |
US3478415A (en) * | 1965-08-27 | 1969-11-18 | Johnson Matthey Co Ltd | Bonding of metals or alloys |
US3487536A (en) * | 1966-02-24 | 1970-01-06 | Teledyne Inc | Method of forming a high temperature ceramic-to-metal seal |
US3497425A (en) * | 1964-07-20 | 1970-02-24 | Imp Metal Ind Kynoch Ltd | Electrodes and methods of making same |
US3497426A (en) * | 1964-07-02 | 1970-02-24 | Nippon Carbide Kogyo Kk | Manufacture of electrode |
US3505180A (en) * | 1963-09-20 | 1970-04-07 | Energy Conversion Ltd | Method of making a thin gas diffusion membrane |
US3544285A (en) * | 1966-11-16 | 1970-12-01 | Imp Metal Ind Kynoch Ltd | Oxidation-resistant coatings |
US3617101A (en) * | 1969-06-13 | 1971-11-02 | Engelhard Min & Chem | Reference electrode for cathodic protection systems |
US3630768A (en) * | 1966-06-28 | 1971-12-28 | Electronor Corp | Chemical deposition formation of anodes |
US3950240A (en) * | 1975-05-05 | 1976-04-13 | Hooker Chemicals & Plastics Corporation | Anode for electrolytic processes |
US3954590A (en) * | 1972-08-18 | 1976-05-04 | E. I. Du Pont De Nemours And Company | Iridium thin ribbon electrodes for electrochemical cells |
US3974058A (en) * | 1974-09-16 | 1976-08-10 | Basf Wyandotte Corporation | Ruthenium coated cathodes |
US4036601A (en) * | 1974-03-26 | 1977-07-19 | Gesellschaft Fur Kernforschung M.B.H. | Corrosion-resistant turbine blades and method for producing them |
JPS535863B1 (en) * | 1965-05-12 | 1978-03-02 | ||
US4240878A (en) * | 1979-11-02 | 1980-12-23 | Sybron Corporation | Method of forming a platinum layer on tantalum |
US4502936A (en) * | 1980-11-26 | 1985-03-05 | Imi Kynoch Limited | Electrode and electrolytic cell |
FR2576804A1 (en) * | 1985-02-07 | 1986-08-08 | Commissariat Energie Atomique | LIQUID-LIQUID EXCHANGE PULSED ANNULAR COLUMN ADAPTED TO THE SIMULTANEOUS REALIZATION OF ELECTROLYSIS |
EP0259966B1 (en) * | 1986-08-06 | 1992-09-09 | Engelhard Corporation | Platinum coated filaments of platinum and rhodium; method of preparation and use in ammonia oxidation |
US5234774A (en) * | 1989-02-28 | 1993-08-10 | Canon Kabushiki Kaisha | Non-single crystalline materials containing ir, ta and al |
US5780173A (en) * | 1995-09-06 | 1998-07-14 | General Motors Corporation | Durable platinum/polyimide sensing structures |
WO2002004355A1 (en) * | 2000-07-13 | 2002-01-17 | Environmental Focus Internation Bv (Efi) | Method and metals to produce an electrode anode to electrolyze liquid wastes |
US20030148884A1 (en) * | 2002-02-04 | 2003-08-07 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-permeable membrane and manufacturing method of the same |
US6689270B1 (en) * | 1997-09-05 | 2004-02-10 | Lynn Evert | Water treatment apparatus reducing hard water deposits in a conduit |
WO2006133709A2 (en) * | 2005-06-15 | 2006-12-21 | Danfoss A/S | A corrosion resistant object having an outer layer of a precious metal |
US7771352B2 (en) | 1997-03-04 | 2010-08-10 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US7783333B2 (en) | 2004-07-13 | 2010-08-24 | Dexcom, Inc. | Transcutaneous medical device with variable stiffness |
US7831287B2 (en) | 2006-10-04 | 2010-11-09 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
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US7885697B2 (en) | 2004-07-13 | 2011-02-08 | Dexcom, Inc. | Transcutaneous analyte sensor |
US7905833B2 (en) | 2004-07-13 | 2011-03-15 | Dexcom, Inc. | Transcutaneous analyte sensor |
US7920906B2 (en) | 2005-03-10 | 2011-04-05 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
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US8160671B2 (en) | 2003-12-05 | 2012-04-17 | Dexcom, Inc. | Calibration techniques for a continuous analyte sensor |
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1465553A (en) * | 1920-02-25 | 1923-08-21 | Martin Copeland Company | Solder-filled wire and method of manufacturing same |
US2114161A (en) * | 1935-12-04 | 1938-04-12 | Copperweld Steel Co | Electrolytic copper |
US2226720A (en) * | 1937-05-21 | 1940-12-31 | Rca Corp | Reduction of undesired emissions of electronic discharge devices |
US2282097A (en) * | 1940-03-29 | 1942-05-05 | Warren G Taylor | Nonemitting electrode structure |
US2303497A (en) * | 1938-10-27 | 1942-12-01 | Bell Telephone Labor Inc | Duplex metal body |
US2370242A (en) * | 1943-01-15 | 1945-02-27 | Mallory & Co Inc P R | Refractory metal composition |
US2375154A (en) * | 1943-10-07 | 1945-05-01 | Metals & Controls Corp | Electric furnace |
US2401040A (en) * | 1942-10-05 | 1946-05-28 | Eitel Mccullough Inc | Method of making electronic tubes |
US2417459A (en) * | 1945-05-21 | 1947-03-18 | Eitel Mccullough Inc | Electron tube and electrode for the same |
US2418460A (en) * | 1943-12-31 | 1947-04-08 | Bell Telephone Labor Inc | Resistor |
US2492204A (en) * | 1945-05-23 | 1949-12-27 | Russell D Van Gilder | Electrodeposition of gold on tantalum |
US2497109A (en) * | 1946-02-04 | 1950-02-14 | Eitel Mccullough Inc | Electrode for electron tubes |
US2539096A (en) * | 1949-09-19 | 1951-01-23 | Eitel Mccullough Inc | Electron tube and grid for the same |
-
1950
- 1950-05-23 US US163782A patent/US2719797A/en not_active Expired - Lifetime
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1465553A (en) * | 1920-02-25 | 1923-08-21 | Martin Copeland Company | Solder-filled wire and method of manufacturing same |
US2114161A (en) * | 1935-12-04 | 1938-04-12 | Copperweld Steel Co | Electrolytic copper |
US2226720A (en) * | 1937-05-21 | 1940-12-31 | Rca Corp | Reduction of undesired emissions of electronic discharge devices |
US2303497A (en) * | 1938-10-27 | 1942-12-01 | Bell Telephone Labor Inc | Duplex metal body |
US2282097A (en) * | 1940-03-29 | 1942-05-05 | Warren G Taylor | Nonemitting electrode structure |
US2401040A (en) * | 1942-10-05 | 1946-05-28 | Eitel Mccullough Inc | Method of making electronic tubes |
US2370242A (en) * | 1943-01-15 | 1945-02-27 | Mallory & Co Inc P R | Refractory metal composition |
US2375154A (en) * | 1943-10-07 | 1945-05-01 | Metals & Controls Corp | Electric furnace |
US2418460A (en) * | 1943-12-31 | 1947-04-08 | Bell Telephone Labor Inc | Resistor |
US2417459A (en) * | 1945-05-21 | 1947-03-18 | Eitel Mccullough Inc | Electron tube and electrode for the same |
US2492204A (en) * | 1945-05-23 | 1949-12-27 | Russell D Van Gilder | Electrodeposition of gold on tantalum |
US2497109A (en) * | 1946-02-04 | 1950-02-14 | Eitel Mccullough Inc | Electrode for electron tubes |
US2539096A (en) * | 1949-09-19 | 1951-01-23 | Eitel Mccullough Inc | Electron tube and grid for the same |
Cited By (286)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2844868A (en) * | 1954-06-01 | 1958-07-29 | Sylvania Electric Prod | Method of joining refractory metals |
US2761207A (en) * | 1955-03-16 | 1956-09-04 | Baker & Co Inc | Method of making a composite metal rod |
US3065534A (en) * | 1955-03-30 | 1962-11-27 | Itt | Method of joining a semiconductor to a conductor |
US3236756A (en) * | 1957-04-09 | 1966-02-22 | Amalgamated Curacao Patents Co | Electrolysis with precious metalcoated titanium anode |
DE1217345B (en) * | 1957-04-09 | 1966-05-26 | Amalgamated Curacao Patents Co | Process for the production of an anode for the electrolysis of electrolytes containing chlorine ions |
US3278404A (en) * | 1957-07-17 | 1966-10-11 | Ici Ltd | Method and apparatus for cathodic protection |
US3118828A (en) * | 1957-07-17 | 1964-01-21 | Ici Ltd | Electrode structure with titanium alloy base |
US3102086A (en) * | 1957-07-26 | 1963-08-27 | Ici Ltd | Method of improving the corrosion resistance of titanium metals |
US3096272A (en) * | 1957-10-24 | 1963-07-02 | Amalgamated Curacao Patents Co | Noble metal coated titanium electrode and method of making and using it |
US3222270A (en) * | 1958-03-18 | 1965-12-07 | Ici Ltd | Multi-electrolytic cells |
US2998359A (en) * | 1958-11-25 | 1961-08-29 | Engelhard Ind Inc | Method for preparing anodes for cathodic protection systems |
US3313721A (en) * | 1958-12-31 | 1967-04-11 | Englehard Ind Inc | Dish-shaped anode |
US3133872A (en) * | 1959-03-10 | 1964-05-19 | Chemionics Engineering Lab Inc | Anode for electrochemical applications |
US2987453A (en) * | 1959-04-14 | 1961-06-06 | Harshaw Chem Corp | Method of electrodepositing chromium |
US3010891A (en) * | 1959-04-15 | 1961-11-28 | Engelhard Ind Inc | Trailing anode for cathodic protection systems |
US3085949A (en) * | 1959-04-17 | 1963-04-16 | Ici Ltd | Surface treatment of titanium or titanium base alloy |
US3177131A (en) * | 1959-04-27 | 1965-04-06 | Ici Ltd | Method for the production of platinum coated titanium anodes |
US3083451A (en) * | 1959-09-21 | 1963-04-02 | Ass Elect Ind Manchester Ltd | Beryllium brazing |
US3081252A (en) * | 1959-09-30 | 1963-03-12 | Chemionics Engineering Lab Inc | Pipe plug anode |
US3103484A (en) * | 1959-10-10 | 1963-09-10 | Anodes for electrolytic chlorine | |
US3066042A (en) * | 1959-11-27 | 1962-11-27 | Engelhard Ind Inc | Method of coating metal |
US3220938A (en) * | 1961-03-09 | 1965-11-30 | Bell Telephone Labor Inc | Oxide underlay for printed circuit components |
US3107422A (en) * | 1961-05-16 | 1963-10-22 | Bendix Corp | Rhodium diffusion process for bonding and sealing of metallic parts |
US3223609A (en) * | 1961-10-30 | 1965-12-14 | Beckman Instruments Inc | Hygrometer |
US3117023A (en) * | 1962-01-03 | 1964-01-07 | Ionics | Method of making a non-corroding electrode |
US3132928A (en) * | 1962-02-26 | 1964-05-12 | Donald D Crooks | Simultaneous brazing and corrosion protecting refractory metals |
US3207680A (en) * | 1962-05-03 | 1965-09-21 | Elizabeth L Macnamara | Method of electrodepositing iridium |
US3505180A (en) * | 1963-09-20 | 1970-04-07 | Energy Conversion Ltd | Method of making a thin gas diffusion membrane |
US3309292A (en) * | 1964-02-28 | 1967-03-14 | Richard L Andrews | Method for obtaining thick adherent coatings of platinum metals on refractory metals |
US3497426A (en) * | 1964-07-02 | 1970-02-24 | Nippon Carbide Kogyo Kk | Manufacture of electrode |
US3497425A (en) * | 1964-07-20 | 1970-02-24 | Imp Metal Ind Kynoch Ltd | Electrodes and methods of making same |
JPS535863B1 (en) * | 1965-05-12 | 1978-03-02 | ||
US3478415A (en) * | 1965-08-27 | 1969-11-18 | Johnson Matthey Co Ltd | Bonding of metals or alloys |
US3391446A (en) * | 1965-08-30 | 1968-07-09 | Atomic Energy Commission Usa | Aluminum brazing |
US3487536A (en) * | 1966-02-24 | 1970-01-06 | Teledyne Inc | Method of forming a high temperature ceramic-to-metal seal |
US3461058A (en) * | 1966-06-07 | 1969-08-12 | Engelhard Ind Inc | Method of producing a composite electrode |
US3630768A (en) * | 1966-06-28 | 1971-12-28 | Electronor Corp | Chemical deposition formation of anodes |
US3544285A (en) * | 1966-11-16 | 1970-12-01 | Imp Metal Ind Kynoch Ltd | Oxidation-resistant coatings |
US3475224A (en) * | 1967-01-03 | 1969-10-28 | Engelhard Ind Inc | Fuel cell having catalytic fuel electrode |
US3414439A (en) * | 1967-03-13 | 1968-12-03 | Engelhard Ind Inc | Fuel cell and process of using with ruthenium-tantalum alloy catalyst |
US3617101A (en) * | 1969-06-13 | 1971-11-02 | Engelhard Min & Chem | Reference electrode for cathodic protection systems |
US3954590A (en) * | 1972-08-18 | 1976-05-04 | E. I. Du Pont De Nemours And Company | Iridium thin ribbon electrodes for electrochemical cells |
US4036601A (en) * | 1974-03-26 | 1977-07-19 | Gesellschaft Fur Kernforschung M.B.H. | Corrosion-resistant turbine blades and method for producing them |
US3974058A (en) * | 1974-09-16 | 1976-08-10 | Basf Wyandotte Corporation | Ruthenium coated cathodes |
US3950240A (en) * | 1975-05-05 | 1976-04-13 | Hooker Chemicals & Plastics Corporation | Anode for electrolytic processes |
US4240878A (en) * | 1979-11-02 | 1980-12-23 | Sybron Corporation | Method of forming a platinum layer on tantalum |
US4502936A (en) * | 1980-11-26 | 1985-03-05 | Imi Kynoch Limited | Electrode and electrolytic cell |
EP0193434A1 (en) * | 1985-02-07 | 1986-09-03 | Commissariat A L'energie Atomique | Pulsated annular liquid-liquid exchange column adapted to simultaneous electrolysis |
FR2576804A1 (en) * | 1985-02-07 | 1986-08-08 | Commissariat Energie Atomique | LIQUID-LIQUID EXCHANGE PULSED ANNULAR COLUMN ADAPTED TO THE SIMULTANEOUS REALIZATION OF ELECTROLYSIS |
EP0259966B1 (en) * | 1986-08-06 | 1992-09-09 | Engelhard Corporation | Platinum coated filaments of platinum and rhodium; method of preparation and use in ammonia oxidation |
US5234774A (en) * | 1989-02-28 | 1993-08-10 | Canon Kabushiki Kaisha | Non-single crystalline materials containing ir, ta and al |
US5780173A (en) * | 1995-09-06 | 1998-07-14 | General Motors Corporation | Durable platinum/polyimide sensing structures |
US9155496B2 (en) | 1997-03-04 | 2015-10-13 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US7771352B2 (en) | 1997-03-04 | 2010-08-10 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US7901354B2 (en) | 1997-03-04 | 2011-03-08 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US6689270B1 (en) * | 1997-09-05 | 2004-02-10 | Lynn Evert | Water treatment apparatus reducing hard water deposits in a conduit |
US8226558B2 (en) | 1998-04-30 | 2012-07-24 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8666469B2 (en) | 1998-04-30 | 2014-03-04 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8880137B2 (en) | 1998-04-30 | 2014-11-04 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8840553B2 (en) | 1998-04-30 | 2014-09-23 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8974386B2 (en) | 1998-04-30 | 2015-03-10 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9011331B2 (en) | 1998-04-30 | 2015-04-21 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8774887B2 (en) | 1998-04-30 | 2014-07-08 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8744545B2 (en) | 1998-04-30 | 2014-06-03 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8734346B2 (en) | 1998-04-30 | 2014-05-27 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8738109B2 (en) | 1998-04-30 | 2014-05-27 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8734348B2 (en) | 1998-04-30 | 2014-05-27 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US10478108B2 (en) | 1998-04-30 | 2019-11-19 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9014773B2 (en) | 1998-04-30 | 2015-04-21 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9042953B2 (en) | 1998-04-30 | 2015-05-26 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8688188B2 (en) | 1998-04-30 | 2014-04-01 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8672844B2 (en) | 1998-04-30 | 2014-03-18 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8670815B2 (en) | 1998-04-30 | 2014-03-11 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8660627B2 (en) | 1998-04-30 | 2014-02-25 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8162829B2 (en) | 1998-04-30 | 2012-04-24 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8175673B2 (en) | 1998-04-30 | 2012-05-08 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8177716B2 (en) | 1998-04-30 | 2012-05-15 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8224413B2 (en) | 1998-04-30 | 2012-07-17 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8649841B2 (en) | 1998-04-30 | 2014-02-11 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8226557B2 (en) | 1998-04-30 | 2012-07-24 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8226555B2 (en) | 1998-04-30 | 2012-07-24 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8231532B2 (en) | 1998-04-30 | 2012-07-31 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8641619B2 (en) | 1998-04-30 | 2014-02-04 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8235896B2 (en) | 1998-04-30 | 2012-08-07 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8622906B2 (en) | 1998-04-30 | 2014-01-07 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8255031B2 (en) | 1998-04-30 | 2012-08-28 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8260392B2 (en) | 1998-04-30 | 2012-09-04 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8265726B2 (en) | 1998-04-30 | 2012-09-11 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8275439B2 (en) | 1998-04-30 | 2012-09-25 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8273022B2 (en) | 1998-04-30 | 2012-09-25 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8617071B2 (en) | 1998-04-30 | 2013-12-31 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9066695B2 (en) | 1998-04-30 | 2015-06-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8287454B2 (en) | 1998-04-30 | 2012-10-16 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8306598B2 (en) | 1998-04-30 | 2012-11-06 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8612159B2 (en) | 1998-04-30 | 2013-12-17 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8346336B2 (en) | 1998-04-30 | 2013-01-01 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8346337B2 (en) | 1998-04-30 | 2013-01-01 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8353829B2 (en) | 1998-04-30 | 2013-01-15 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8357091B2 (en) | 1998-04-30 | 2013-01-22 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8366614B2 (en) | 1998-04-30 | 2013-02-05 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8372005B2 (en) | 1998-04-30 | 2013-02-12 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8380273B2 (en) | 1998-04-30 | 2013-02-19 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8391945B2 (en) | 1998-04-30 | 2013-03-05 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9066694B2 (en) | 1998-04-30 | 2015-06-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8409131B2 (en) | 1998-04-30 | 2013-04-02 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8597189B2 (en) | 1998-04-30 | 2013-12-03 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9066697B2 (en) | 1998-04-30 | 2015-06-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9072477B2 (en) | 1998-04-30 | 2015-07-07 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8465425B2 (en) | 1998-04-30 | 2013-06-18 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8473021B2 (en) | 1998-04-30 | 2013-06-25 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8480580B2 (en) | 1998-04-30 | 2013-07-09 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9326714B2 (en) | 1998-04-30 | 2016-05-03 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
WO2002004355A1 (en) * | 2000-07-13 | 2002-01-17 | Environmental Focus Internation Bv (Efi) | Method and metals to produce an electrode anode to electrolyze liquid wastes |
US9498159B2 (en) | 2001-01-02 | 2016-11-22 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8652043B2 (en) | 2001-01-02 | 2014-02-18 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9011332B2 (en) | 2001-01-02 | 2015-04-21 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8668645B2 (en) | 2001-01-02 | 2014-03-11 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9610034B2 (en) | 2001-01-02 | 2017-04-04 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9804114B2 (en) | 2001-07-27 | 2017-10-31 | Dexcom, Inc. | Sensor head for use with implantable devices |
US9328371B2 (en) | 2001-07-27 | 2016-05-03 | Dexcom, Inc. | Sensor head for use with implantable devices |
US8509871B2 (en) | 2001-07-27 | 2013-08-13 | Dexcom, Inc. | Sensor head for use with implantable devices |
US7049008B2 (en) * | 2002-02-04 | 2006-05-23 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-permeable membrane and manufacturing method of the same |
US20030148884A1 (en) * | 2002-02-04 | 2003-08-07 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-permeable membrane and manufacturing method of the same |
US8394021B2 (en) | 2003-08-01 | 2013-03-12 | Dexcom, Inc. | System and methods for processing analyte sensor data |
US8788006B2 (en) | 2003-08-01 | 2014-07-22 | Dexcom, Inc. | System and methods for processing analyte sensor data |
US8622905B2 (en) | 2003-08-01 | 2014-01-07 | Dexcom, Inc. | System and methods for processing analyte sensor data |
US8700117B2 (en) | 2003-08-01 | 2014-04-15 | Dexcom, Inc. | System and methods for processing analyte sensor data |
US8676287B2 (en) | 2003-08-01 | 2014-03-18 | Dexcom, Inc. | System and methods for processing analyte sensor data |
US8282550B2 (en) | 2003-11-19 | 2012-10-09 | Dexcom, Inc. | Integrated receiver for continuous analyte sensor |
US7927274B2 (en) | 2003-11-19 | 2011-04-19 | Dexcom, Inc. | Integrated receiver for continuous analyte sensor |
US11564602B2 (en) | 2003-11-19 | 2023-01-31 | Dexcom, Inc. | Integrated receiver for continuous analyte sensor |
US11020031B1 (en) | 2003-12-05 | 2021-06-01 | Dexcom, Inc. | Analyte sensor |
US8249684B2 (en) | 2003-12-05 | 2012-08-21 | Dexcom, Inc. | Calibration techniques for a continuous analyte sensor |
US8911369B2 (en) | 2003-12-05 | 2014-12-16 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US11633133B2 (en) | 2003-12-05 | 2023-04-25 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US9579053B2 (en) | 2003-12-05 | 2017-02-28 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US10299712B2 (en) | 2003-12-05 | 2019-05-28 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US8160671B2 (en) | 2003-12-05 | 2012-04-17 | Dexcom, Inc. | Calibration techniques for a continuous analyte sensor |
US8428678B2 (en) | 2003-12-05 | 2013-04-23 | Dexcom, Inc. | Calibration techniques for a continuous analyte sensor |
US8287453B2 (en) | 2003-12-05 | 2012-10-16 | Dexcom, Inc. | Analyte sensor |
US11000215B1 (en) | 2003-12-05 | 2021-05-11 | Dexcom, Inc. | Analyte sensor |
US8882741B2 (en) | 2004-02-26 | 2014-11-11 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US12102410B2 (en) | 2004-02-26 | 2024-10-01 | Dexcom, Inc | Integrated medicament delivery device for use with continuous analyte sensor |
US10966609B2 (en) | 2004-02-26 | 2021-04-06 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US9937293B2 (en) | 2004-02-26 | 2018-04-10 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US8721585B2 (en) | 2004-02-26 | 2014-05-13 | Dex Com, Inc. | Integrated delivery device for continuous glucose sensor |
US10278580B2 (en) | 2004-02-26 | 2019-05-07 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US11246990B2 (en) | 2004-02-26 | 2022-02-15 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US10835672B2 (en) | 2004-02-26 | 2020-11-17 | Dexcom, Inc. | Integrated insulin delivery system with continuous glucose sensor |
US9155843B2 (en) | 2004-02-26 | 2015-10-13 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US8926585B2 (en) | 2004-02-26 | 2015-01-06 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US8808228B2 (en) | 2004-02-26 | 2014-08-19 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US8920401B2 (en) | 2004-02-26 | 2014-12-30 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US12115357B2 (en) | 2004-02-26 | 2024-10-15 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US7976492B2 (en) | 2004-02-26 | 2011-07-12 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US9050413B2 (en) | 2004-02-26 | 2015-06-09 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
US10327638B2 (en) | 2004-05-03 | 2019-06-25 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8792955B2 (en) | 2004-05-03 | 2014-07-29 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9833143B2 (en) | 2004-05-03 | 2017-12-05 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10918315B2 (en) | 2004-07-13 | 2021-02-16 | Dexcom, Inc. | Analyte sensor |
US10709363B2 (en) | 2004-07-13 | 2020-07-14 | Dexcom, Inc. | Analyte sensor |
US8801611B2 (en) | 2004-07-13 | 2014-08-12 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8792953B2 (en) | 2004-07-13 | 2014-07-29 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8792954B2 (en) | 2004-07-13 | 2014-07-29 | Dexcom, Inc. | Transcutaneous analyte sensor |
US7783333B2 (en) | 2004-07-13 | 2010-08-24 | Dexcom, Inc. | Transcutaneous medical device with variable stiffness |
US8721545B2 (en) | 2004-07-13 | 2014-05-13 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8690775B2 (en) | 2004-07-13 | 2014-04-08 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9044199B2 (en) | 2004-07-13 | 2015-06-02 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8483791B2 (en) | 2004-07-13 | 2013-07-09 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9060742B2 (en) | 2004-07-13 | 2015-06-23 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8615282B2 (en) | 2004-07-13 | 2013-12-24 | Dexcom, Inc. | Analyte sensor |
US11064917B2 (en) | 2004-07-13 | 2021-07-20 | Dexcom, Inc. | Analyte sensor |
US11045120B2 (en) | 2004-07-13 | 2021-06-29 | Dexcom, Inc. | Analyte sensor |
US11026605B1 (en) | 2004-07-13 | 2021-06-08 | Dexcom, Inc. | Analyte sensor |
US7857760B2 (en) | 2004-07-13 | 2010-12-28 | Dexcom, Inc. | Analyte sensor |
US7885697B2 (en) | 2004-07-13 | 2011-02-08 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9078626B2 (en) | 2004-07-13 | 2015-07-14 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8565848B2 (en) | 2004-07-13 | 2013-10-22 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10993642B2 (en) | 2004-07-13 | 2021-05-04 | Dexcom, Inc. | Analyte sensor |
US10993641B2 (en) | 2004-07-13 | 2021-05-04 | Dexcom, Inc. | Analyte sensor |
US9247900B2 (en) | 2004-07-13 | 2016-02-02 | Dexcom, Inc. | Analyte sensor |
US10980452B2 (en) | 2004-07-13 | 2021-04-20 | Dexcom, Inc. | Analyte sensor |
US7899511B2 (en) | 2004-07-13 | 2011-03-01 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US10932700B2 (en) | 2004-07-13 | 2021-03-02 | Dexcom, Inc. | Analyte sensor |
US8515519B2 (en) | 2004-07-13 | 2013-08-20 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8812072B2 (en) | 2004-07-13 | 2014-08-19 | Dexcom, Inc. | Transcutaneous medical device with variable stiffness |
US10314525B2 (en) | 2004-07-13 | 2019-06-11 | Dexcom, Inc. | Analyte sensor |
US8663109B2 (en) | 2004-07-13 | 2014-03-04 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10918313B2 (en) | 2004-07-13 | 2021-02-16 | Dexcom, Inc. | Analyte sensor |
US8457708B2 (en) | 2004-07-13 | 2013-06-04 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10918314B2 (en) | 2004-07-13 | 2021-02-16 | Dexcom, Inc. | Analyte sensor |
US9610031B2 (en) | 2004-07-13 | 2017-04-04 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9668677B2 (en) | 2004-07-13 | 2017-06-06 | Dexcom, Inc. | Analyte sensor |
US7905833B2 (en) | 2004-07-13 | 2011-03-15 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10827956B2 (en) | 2004-07-13 | 2020-11-10 | Dexcom, Inc. | Analyte sensor |
US10813576B2 (en) | 2004-07-13 | 2020-10-27 | Dexcom, Inc. | Analyte sensor |
US9775543B2 (en) | 2004-07-13 | 2017-10-03 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9801572B2 (en) | 2004-07-13 | 2017-10-31 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8313434B2 (en) | 2004-07-13 | 2012-11-20 | Dexcom, Inc. | Analyte sensor inserter system |
US9814414B2 (en) | 2004-07-13 | 2017-11-14 | Dexcom, Inc. | Transcutaneous analyte sensor |
US11883164B2 (en) | 2004-07-13 | 2024-01-30 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10799159B2 (en) | 2004-07-13 | 2020-10-13 | Dexcom, Inc. | Analyte sensor |
US8231531B2 (en) | 2004-07-13 | 2012-07-31 | Dexcom, Inc. | Analyte sensor |
US9986942B2 (en) | 2004-07-13 | 2018-06-05 | Dexcom, Inc. | Analyte sensor |
US10022078B2 (en) | 2004-07-13 | 2018-07-17 | Dexcom, Inc. | Analyte sensor |
US10799158B2 (en) | 2004-07-13 | 2020-10-13 | Dexcom, Inc. | Analyte sensor |
US10722152B2 (en) | 2004-07-13 | 2020-07-28 | Dexcom, Inc. | Analyte sensor |
US9414777B2 (en) | 2004-07-13 | 2016-08-16 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10709362B2 (en) | 2004-07-13 | 2020-07-14 | Dexcom, Inc. | Analyte sensor |
US8886272B2 (en) | 2004-07-13 | 2014-11-11 | Dexcom, Inc. | Analyte sensor |
US10524703B2 (en) | 2004-07-13 | 2020-01-07 | Dexcom, Inc. | Transcutaneous analyte sensor |
US7949381B2 (en) | 2004-07-13 | 2011-05-24 | Dexcom, Inc. | Transcutaneous analyte sensor |
US7946984B2 (en) | 2004-07-13 | 2011-05-24 | Dexcom, Inc. | Transcutaneous analyte sensor |
US10610137B2 (en) | 2005-03-10 | 2020-04-07 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US9918668B2 (en) | 2005-03-10 | 2018-03-20 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US9220449B2 (en) | 2005-03-10 | 2015-12-29 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US11000213B2 (en) | 2005-03-10 | 2021-05-11 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US7920906B2 (en) | 2005-03-10 | 2011-04-05 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US9314196B2 (en) | 2005-03-10 | 2016-04-19 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US9078608B2 (en) | 2005-03-10 | 2015-07-14 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10610135B2 (en) | 2005-03-10 | 2020-04-07 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10925524B2 (en) | 2005-03-10 | 2021-02-23 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10610136B2 (en) | 2005-03-10 | 2020-04-07 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10617336B2 (en) | 2005-03-10 | 2020-04-14 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10918318B2 (en) | 2005-03-10 | 2021-02-16 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10918316B2 (en) | 2005-03-10 | 2021-02-16 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10709364B2 (en) | 2005-03-10 | 2020-07-14 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US8579816B2 (en) | 2005-03-10 | 2013-11-12 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10716498B2 (en) | 2005-03-10 | 2020-07-21 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10918317B2 (en) | 2005-03-10 | 2021-02-16 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10743801B2 (en) | 2005-03-10 | 2020-08-18 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US11051726B2 (en) | 2005-03-10 | 2021-07-06 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US8560037B2 (en) | 2005-03-10 | 2013-10-15 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10898114B2 (en) | 2005-03-10 | 2021-01-26 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10856787B2 (en) | 2005-03-10 | 2020-12-08 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US8611978B2 (en) | 2005-03-10 | 2013-12-17 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US20080274372A1 (en) * | 2005-06-15 | 2008-11-06 | Danfoss A/S | Corrosion Resistant Object Having an Outer Layer of a Precious Metal |
WO2006133709A2 (en) * | 2005-06-15 | 2006-12-21 | Danfoss A/S | A corrosion resistant object having an outer layer of a precious metal |
WO2006133709A3 (en) * | 2005-06-15 | 2007-10-04 | Danfoss As | A corrosion resistant object having an outer layer of a precious metal |
US10813577B2 (en) | 2005-06-21 | 2020-10-27 | Dexcom, Inc. | Analyte sensor |
US11399748B2 (en) | 2005-11-01 | 2022-08-02 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8920319B2 (en) | 2005-11-01 | 2014-12-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US10201301B2 (en) | 2005-11-01 | 2019-02-12 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9078607B2 (en) | 2005-11-01 | 2015-07-14 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US11103165B2 (en) | 2005-11-01 | 2021-08-31 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US10231654B2 (en) | 2005-11-01 | 2019-03-19 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9326716B2 (en) | 2005-11-01 | 2016-05-03 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US10952652B2 (en) | 2005-11-01 | 2021-03-23 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8915850B2 (en) | 2005-11-01 | 2014-12-23 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US11911151B1 (en) | 2005-11-01 | 2024-02-27 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US11363975B2 (en) | 2005-11-01 | 2022-06-21 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US11272867B2 (en) | 2005-11-01 | 2022-03-15 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9757061B2 (en) | 2006-01-17 | 2017-09-12 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US11596332B2 (en) | 2006-01-17 | 2023-03-07 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US11191458B2 (en) | 2006-01-17 | 2021-12-07 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US10265000B2 (en) | 2006-01-17 | 2019-04-23 | Dexcom, Inc. | Low oxygen in vivo analyte sensor |
US9724028B2 (en) | 2006-02-22 | 2017-08-08 | Dexcom, Inc. | Analyte sensor |
US8133178B2 (en) | 2006-02-22 | 2012-03-13 | Dexcom, Inc. | Analyte sensor |
US10349873B2 (en) | 2006-10-04 | 2019-07-16 | Dexcom, Inc. | Analyte sensor |
US8423114B2 (en) | 2006-10-04 | 2013-04-16 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US7831287B2 (en) | 2006-10-04 | 2010-11-09 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US9504413B2 (en) | 2006-10-04 | 2016-11-29 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US11382539B2 (en) | 2006-10-04 | 2022-07-12 | Dexcom, Inc. | Analyte sensor |
US10136844B2 (en) | 2006-10-04 | 2018-11-27 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US11399745B2 (en) | 2006-10-04 | 2022-08-02 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US9741139B2 (en) | 2007-06-08 | 2017-08-22 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US10403012B2 (en) | 2007-06-08 | 2019-09-03 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US8562558B2 (en) | 2007-06-08 | 2013-10-22 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US11373347B2 (en) | 2007-06-08 | 2022-06-28 | Dexcom, Inc. | Integrated medicament delivery device for use with continuous analyte sensor |
US11160926B1 (en) | 2007-10-09 | 2021-11-02 | Dexcom, Inc. | Pre-connected analyte sensors |
US10653835B2 (en) | 2007-10-09 | 2020-05-19 | Dexcom, Inc. | Integrated insulin delivery system with continuous glucose sensor |
US11744943B2 (en) | 2007-10-09 | 2023-09-05 | Dexcom, Inc. | Integrated insulin delivery system with continuous glucose sensor |
US9339222B2 (en) | 2008-09-19 | 2016-05-17 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
US8560039B2 (en) | 2008-09-19 | 2013-10-15 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
US10028684B2 (en) | 2008-09-19 | 2018-07-24 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
US11918354B2 (en) | 2008-09-19 | 2024-03-05 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
US10028683B2 (en) | 2008-09-19 | 2018-07-24 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
US10561352B2 (en) | 2008-09-19 | 2020-02-18 | Dexcom, Inc. | Particle-containing membrane and particulate electrode for analyte sensors |
US10980461B2 (en) | 2008-11-07 | 2021-04-20 | Dexcom, Inc. | Advanced analyte sensor calibration and error detection |
US11706876B2 (en) | 2017-10-24 | 2023-07-18 | Dexcom, Inc. | Pre-connected analyte sensors |
US11350862B2 (en) | 2017-10-24 | 2022-06-07 | Dexcom, Inc. | Pre-connected analyte sensors |
US11943876B2 (en) | 2017-10-24 | 2024-03-26 | Dexcom, Inc. | Pre-connected analyte sensors |
US11382540B2 (en) | 2017-10-24 | 2022-07-12 | Dexcom, Inc. | Pre-connected analyte sensors |
US11331022B2 (en) | 2017-10-24 | 2022-05-17 | Dexcom, Inc. | Pre-connected analyte sensors |
US12150250B2 (en) | 2017-10-24 | 2024-11-19 | Dexcom, Inc. | Pre-connected analyte sensors |
US12226617B2 (en) | 2021-12-20 | 2025-02-18 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
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