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US3102086A - Method of improving the corrosion resistance of titanium metals - Google Patents

Method of improving the corrosion resistance of titanium metals Download PDF

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Publication number
US3102086A
US3102086A US749052A US74905258A US3102086A US 3102086 A US3102086 A US 3102086A US 749052 A US749052 A US 749052A US 74905258 A US74905258 A US 74905258A US 3102086 A US3102086 A US 3102086A
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United States
Prior art keywords
titanium
potential
group
corrosion
metals
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US749052A
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Cotton Joseph Bernard
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/005Anodic protection

Definitions

  • titanium has taken a prominent place as a structural metal because of its outstanding corrosion resistance to many electrolytes. There remain however some important electrolytes in which the corrosion rates of titanium and its alloys prohibit their use for handling such media, e.g. as storage tanks and other equipment.
  • carbon When carbon is the cathodic material, it may take the form of discrete particles embedded in the surface, each particle being capable of protecting a surrounding area many times its size.
  • the protection given appears to be of a permanent nature and any scratches or damage of a similar character to the surface of the metal become sealed over by a protective film. This is opposite to the effect normally produced by coating a metal with a more noble or cathodic metal.
  • the current passing to the titanium to reduce its rate of corrosion may be produced by the galvanic couple formed between the titanium and more noble material when contact is made therebetween.
  • the contact between the two parts may be direct, i.e. by the attachment of the more noble material to the titanium surface, or indirect, i.e. by means of a wire or other lead external to the electrolyte.
  • Electrical contact between the titanium and the more noble element may with advantage be effected by in corporating the element in the surface of the metal and for this purpose a number of methods are available.
  • 'For metals such as platinum, functioning as a cathode, attachment may be achieved by plating'or spot-welding or vacuum deposition or spraying techniques.
  • non-metallic materials such as carbon
  • deposition by decomposition of carbon monoxide orcarbon dioxide vapours, or coating with oil and subsequently carbonising may be carried out. Bonding the metal to pieces of graphite is also suitable.
  • a method which can be used for both metals and non-metals is to introduce the cathodic material as a small quantity of powder during the last with potential, there is a more or less rapid drop towards a condition in which the titanium is substantially completely passive. --In cases therefore in which the poto give the requisite protection will vary with the cir- 45 cumstanoes. Many cases, a potential of 1.0 volt positive to the standard calomel electrode will give virtually complete protection and, for most electrolytes, it will rarely be necessary to raise the potential to more than about 3 volts. The power costs of operating the present invention are small in relation to the saving of plant and materials that is effected thereby.
  • the invention has special application to the improvement of the corrosion resistance of titanium in nonoxidizing acids.
  • EXAMPLE 1 A titanium strip 5 ems. long x 1 cm. wide is electrically connected to a graphite cathode and immersed in 40% w./w. sulphuric acid at 60 C., the graphite being partly immersed therein.
  • the electrical connection is by way of an external wire spot-welded to the titanium at one end and secured 2Jl'.”ll'.S other end as a push fit in a small hole drilled in the graphite.
  • the corrosion of the titanium expressed in inches penetration per year is 0.0035 as compared with the value of 1.12. inches for an unprotected control sample immersed in the solution.
  • EXAMPLE 2 The procedure of the previous example is repeated employing in place of the graphite a smooth platinum electrode coated with platinum black. The corrosion rate of the titanium as compared with that of an uncoupled control sample is reduced by a factor of approximately one-third.
  • EXAMPLE 3 A large tank constructed from titanium sheet and maintained at a positive potential of 3.0 volts with respect to a graphite cathode is protected from corrosion by 40% W./w. sulphuric acid contained within the tank at a temperature of 60 C.
  • the arrangement employs a graphite cathode partly immersed in the sulphuric acid in the tank, the electrical cell so formed being connected with a continuously trickle-charged battery.
  • the power consumption is approximately 3 watts per thousand square feet of immersed titanium surface. Comparative tests carried out for a period of the order of 700 hours indicate that the corrosion rate of the titanium is 7x 10 inches per year as compared with 1 inch per year for an unprotected specimen of titanium.
  • the accompanying table shows the degree of protection afforded to titanium in other electrolytes.
  • a method of reducing corrosion as set forth in claim 1 including increasing the potential difference between said structure and said non-ferrous material sufficiently to maintain said protective film by means of a source of direct current electricity electrically connected between said structure and said non-ferrous material, the positive connection being to said structure.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Prevention Of Electric Corrosion (AREA)

Description

United States Patent assignor to Imperial Chemical Industries Limited, L'ondon, England, a corporation of Great Britain No Drawing. Filed July 17, 1958, Ser. No. 749,052 Claims priority, application Great Britain July 26, 1957 4 Claims. (Cl. 204147) This invention relates to a method of improving the corrosion resistance of titanium and titanium-base alloys.
It is well known that in chemical plant and other industrial applications the use of the morecommon structural metals is severely limited by the poor corrosion resistance of such metals to the generality of electrolytes. In the past therefore it has been the practice to protect such metals with a surface coating of a more corrosion resistant or more noble substance In the case of such coatings it has been emphasized that the coverage of the metal must be complete since the presence of pores or other discontinuities in the surface layer gives rise to the formation of galvanic couples and corrosion of th underlying metal results.
For some years now, titanium has taken a prominent place as a structural metal because of its outstanding corrosion resistance to many electrolytes. There remain however some important electrolytes in which the corrosion rates of titanium and its alloys prohibit their use for handling such media, e.g. as storage tanks and other equipment.
According to the present invention a method of reducing the rate of corrosion of a structure of titanium or a titanium-base alloy of comparable anodic polarization properties to titanium in contact with a liquid medium Patented Aug. 27, 1963 2 stages of rolling powderedmetal to sheet, precautions being taken to ensure even distribution over the surface.
When carbon is the cathodic material, it may take the form of discrete particles embedded in the surface, each particle being capable of protecting a surrounding area many times its size. The protection given appears to be of a permanent nature and any scratches or damage of a similar character to the surface of the metal become sealed over by a protective film. This is opposite to the effect normally produced by coating a metal with a more noble or cathodic metal.
It will of course be appreciated that the more noble material must be employed in a form of suitable electrochemical character. Since the passage of current in most cases will require the evolution of hydrogen at the more noble material, the surface of this material must have a comparatively low overvoltage. Platinum therefore may well be used in the formof a platinum black. Smooth platinum coated with platinized platinum is especially suitable.
The amount of galvanic current produced as abovementioned and therefore'the resulting potential assumed by the titanium will depend inter alia on the electrolyte and the temperature. Cases may'arise therefore where the potential produced in this way is not sufficiently positive to give the required degree of protection to the titanium. Whether the potential produced is sufilcient for the purpose in hand may readily be reduced 'by reference to the potential/corrosion rate graph which can be .plotted by experiments conducted with titanium specimens for the particular electrolyte and set of operatingconditions. This graph is believed to take generally the same form for many electrolytes and it is found that after an initial increase of corrosion rate corrosive thereto comprises electrically-connecting the tective against corrosion by the liquid medium. One
example of a titanium-base alloy which can be protected according to the invention is an alloy of titanium and Zirconium containing 5% by weight of the latter.
' According to one embodiment of the invention the current passing to the titanium to reduce its rate of corrosion may be produced by the galvanic couple formed between the titanium and more noble material when contact is made therebetween. In such a case the contact between the two parts may be direct, i.e. by the attachment of the more noble material to the titanium surface, or indirect, i.e. by means of a wire or other lead external to the electrolyte.
Electrical contact between the titanium and the more noble element may with advantage be effected by in corporating the element in the surface of the metal and for this purpose a number of methods are available. 'For metals such as platinum, functioning as a cathode, attachment may be achieved by plating'or spot-welding or vacuum deposition or spraying techniques. In the case of non-metallic materials such as carbon, deposition by decomposition of carbon monoxide orcarbon dioxide vapours, or coating with oil and subsequently carbonising may be carried out. Bonding the metal to pieces of graphite is also suitable. A method which can be used for both metals and non-metals is to introduce the cathodic material as a small quantity of powder during the last with potential, there is a more or less rapid drop towards a condition in which the titanium is substantially completely passive. --In cases therefore in which the poto give the requisite protection will vary with the cir- 45 cumstanoes. Many cases, a potential of 1.0 volt positive to the standard calomel electrode will give virtually complete protection and, for most electrolytes, it will rarely be necessary to raise the potential to more than about 3 volts. The power costs of operating the present invention are small in relation to the saving of plant and materials that is effected thereby.
The invention has special application to the improvement of the corrosion resistance of titanium in nonoxidizing acids.
The invention is illustrated further in the following examples.
EXAMPLE 1 A titanium strip 5 ems. long x 1 cm. wide is electrically connected to a graphite cathode and immersed in 40% w./w. sulphuric acid at 60 C., the graphite being partly immersed therein. The electrical connection is by way of an external wire spot-welded to the titanium at one end and secured 2Jl'."ll'.S other end as a push fit in a small hole drilled in the graphite. The corrosion of the titanium expressed in inches penetration per year is 0.0035 as compared with the value of 1.12. inches for an unprotected control sample immersed in the solution.
EXAMPLE 2 The procedure of the previous example is repeated employing in place of the graphite a smooth platinum electrode coated with platinum black. The corrosion rate of the titanium as compared with that of an uncoupled control sample is reduced by a factor of approximately one-third.
EXAMPLE 3 A large tank constructed from titanium sheet and maintained at a positive potential of 3.0 volts with respect to a graphite cathode is protected from corrosion by 40% W./w. sulphuric acid contained within the tank at a temperature of 60 C. The arrangement employs a graphite cathode partly immersed in the sulphuric acid in the tank, the electrical cell so formed being connected with a continuously trickle-charged battery. The power consumption is approximately 3 watts per thousand square feet of immersed titanium surface. Comparative tests carried out for a period of the order of 700 hours indicate that the corrosion rate of the titanium is 7x 10 inches per year as compared with 1 inch per year for an unprotected specimen of titanium.
The accompanying table shows the degree of protection afforded to titanium in other electrolytes.
Corrosion Rates of Titanium in Various Media, With and Without Applied Positive Potential We claim:
1. A method of reducing the rate of corrosion of a structure of a metal selected from the group consisting of titanium and titanium base alloys having anodic polarization properties comparable to those of titanium, said structure being in contact with a liquid medium corrosive thereto and comprising a member of the group consisting of sulphuric, phosphoric, hydrochloric, oxalic and formic acids, said method comprising immersing a conductive material selected from the group consisting of carbon and metals of the platinum group in said liquid at a point remote from said metal structure, and electrically-connecting said structure and said material so that direct current passes between the structure and said material and through the liquid medium to increase 4 the potential of the structure to a value at which a protective film is maintained on the surface of said structure by anodic polarization, said potential being not substantially in excess of the minimum value required to maintain said film on the surface of said structure.
2. A method of reducing the rate of corrosion of a structure of a metal selected from the group consisting of titanium and titanium base alloys having anodic polarization properties comparable to those of titanium, the structure being in contact with a liquid medium corrosive thereto and comprising a member of the group consisting of sulfuric, phosphoric, hydrochloric, oxalic and formic acids, said method comprising placing said structure in direct contact with a conductive material selected from the group consisting of carbon and metals of the platinum group, said conductive material also being in contact with said liquid medium, whereby the galvanic couple formed between said structure and said conductive material causes direct current to pass between them and through the medium to increase the potential of the structure to the galvanic cell potential at which a protective film is maintained on the surface of the structure in contact with the liquid medium by anodic polarization, said potential being not substantially in excess of the minimum value required to maintain said film on the surface of said structure.
3. A method of reducing corrosion as set forth in claim 1 including increasing the potential difference between said structure and said non-ferrous material sufficiently to maintain said protective film by means of a source of direct current electricity electrically connected between said structure and said non-ferrous material, the positive connection being to said structure.
4. A method of reducing corrosion as set forth in claim 3 in which the potential of said structure is from 1 to 5 volts positive to the standard calomel electrode.
References Cited in the file of this patent UNITED STATES PATENTS 1,077,920 Stevens Nov. 4, 1913 1,477,099 Baum Dec. 11, 1923 1,787,672 Davenport Ian. 6, 1931 2,719,797 Rosenblatt et a1. Oct. 4, 1955 2,795,541 Muller June 11, 1957 2,871,425 Burnham Jan. 27, 1959 FOREIGN PATENTS 774,598 Great Britain May 15, 1957 OTHER REFERENCES Cotton: Platinum Metals Review, vol. 2, No. 2, April 1958, pages -57.

Claims (1)

1. A METHOD OF REDUCING THE RATE OF CORROSION OF A STRUCTURE OF A METAL SELECTED FROM THE GROUP CONSISTING OF TITANIUM AND TITANIUM BASE ALLOYS HAVING ANODIC POLARIZATIN PROPERTIES COMPARABLE TO THOSE OF TITANIUM, SAID STRUCTURE BEING IN CONTACT WITH A LIQUD MEDIUM CORROSIVE THERETO AND COMPRISING A MEMBER OF THE GROUP CONSISTING OF SULPHURIC, PHOSPHORIC, HYDROCHLORIC, OXALIC AND FORMIC ACIDS, SAID METHOD COMPRISING IMMERSING A CONDUCTIVE MATERIAL SELECTED FROM THE GROUP CONSISTING OF CARBON AND METALS OF THE PLATINUM GROUP IN SAID LIQUID AT A POINT REMOTE FROM SAID METAL STRUCTURE, AND ELECTRICALLY-CONNECTING SAID STRUCTURE AND SAID MATERIAL SO THAT DIRECT CURRENT PASSES BETWEEN THE STRUCTURE AND SAID MATERIAL AND THROUGH THE LIQUID MEDIUM TO INCREASE THE POTENTIAL OF THE STRUCTURE TO A VALUE AT WHICH A PROTECTIVE FILM IS MAINTAINED ON THE SURFACE OF SAID STRUCTURE BY ANODIC POLARIZATION, SAID POTENTIAL BEING NOT SUBSTANTIALLY IN EXCESS OF THE MINIMUM VALUE REQUIRED TO MAINTAIN SAID FILM ON THE SURFACE OF SAID STRUCTURE.
US749052A 1957-07-26 1958-07-17 Method of improving the corrosion resistance of titanium metals Expired - Lifetime US3102086A (en)

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Application Number Priority Date Filing Date Title
GB23726/57A GB860968A (en) 1957-07-26 1957-07-26 Method of improving the corrosion resistance of titanium and titanium base alloys
GB3661957 1957-11-25
GB3775057 1957-12-04

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BE (1) BE569804A (en)
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DE (1) DE1250234B (en)
FR (1) FR1239322A (en)
GB (1) GB860968A (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265601A (en) * 1961-05-26 1966-08-09 Inst Francais Du Petrole Process for protecting metals against corrosion at elevated temperatures
US3412000A (en) * 1965-04-14 1968-11-19 M & T Chemicals Inc Cathodic protection of titanium surfaces
US3461058A (en) * 1966-06-07 1969-08-12 Engelhard Ind Inc Method of producing a composite electrode
US3876517A (en) * 1973-07-20 1975-04-08 Ppg Industries Inc Reduction of crevice corrosion in bipolar chlorine diaphragm cells by locating the cathode screen at the crevice and maintaining the titanium within the crevice anodic
US3972796A (en) * 1974-02-15 1976-08-03 Dipl.-Ing. Hanns Frohler Kg Electrolytic apparatus
US4048045A (en) * 1974-12-19 1977-09-13 Hooker Chemicals & Plastics Corporation Lengthening anode life in electrolytic cell having molded body
US4202751A (en) * 1977-11-28 1980-05-13 Kobe Steel, Ltd. Sacrificial anode and apparatus employing same for treating hot sea water
US4256556A (en) * 1978-11-24 1981-03-17 Diamond Shamrock Corporation Anodically polarized surface for biofouling and scale control
US4330376A (en) * 1979-03-05 1982-05-18 Atlantic Richfield Company Process for inhibiting titanium corrosion
US4627900A (en) * 1982-08-27 1986-12-09 Amax Inc. Electrochemical dissolution and control of nickel sulfide scale
WO2004108992A1 (en) * 2003-06-03 2004-12-16 Titanium Metals Corporation Fabricated titanium article having improved corrosion resistance
US20070266754A1 (en) * 2006-05-16 2007-11-22 Surface Technology Holdings, Ltd. Metallic article with improved fatigue performance and corrosion resistance and method for making the same
EP2348140A1 (en) * 2008-09-26 2011-07-27 Rozen, Andrei Evgenievich Multilayer material with enhanced corrosion resistance (variants) and methods for preparing same
US20110223443A1 (en) * 2010-03-15 2011-09-15 Scheel Jeremy E Metallic components for use in corrosive environments and method of manufacturing
RU2451771C2 (en) * 2010-08-27 2012-05-27 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" Фгуп "Цнии Км "Прометей" Method for corrosion-resistant covering application to titanium alloy hardware

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2627536C2 (en) * 1976-06-19 1978-06-08 Hoechst Ag, 6000 Frankfurt Process for the corrosion protection of cast iron in boiling concentrated sulfuric acid
FR2361477A1 (en) * 1976-08-12 1978-03-10 Moisa Vladimir Corrosion protection of plant in chemical and allied industries - where plant is alternately anodically polarised and short circuited
US6607846B1 (en) * 2002-09-25 2003-08-19 Titanium Metals Corporation Titanium article having improved corrosion resistance

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1077920A (en) * 1913-01-27 1913-11-04 Us Smelting Refining & Mining Company Electrode.
US1477099A (en) * 1922-07-07 1923-12-11 Firm Of Chem Fab Weissenstein Anode for forming percompounds
US1787672A (en) * 1928-06-04 1931-01-06 Westinghouse Lamp Co Method of treating thorium
US2719797A (en) * 1950-05-23 1955-10-04 Baker & Co Inc Platinizing tantalum
GB774598A (en) * 1954-10-15 1957-05-15 Ici Ltd Improvements relating to titanium or titanium base alloys
US2795541A (en) * 1951-12-22 1957-06-11 Degussa Electrolytic production of percompounds
US2871425A (en) * 1954-09-16 1959-01-27 Fansteel Metallurgical Corp Capacitor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1077920A (en) * 1913-01-27 1913-11-04 Us Smelting Refining & Mining Company Electrode.
US1477099A (en) * 1922-07-07 1923-12-11 Firm Of Chem Fab Weissenstein Anode for forming percompounds
US1787672A (en) * 1928-06-04 1931-01-06 Westinghouse Lamp Co Method of treating thorium
US2719797A (en) * 1950-05-23 1955-10-04 Baker & Co Inc Platinizing tantalum
US2795541A (en) * 1951-12-22 1957-06-11 Degussa Electrolytic production of percompounds
US2871425A (en) * 1954-09-16 1959-01-27 Fansteel Metallurgical Corp Capacitor
GB774598A (en) * 1954-10-15 1957-05-15 Ici Ltd Improvements relating to titanium or titanium base alloys

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265601A (en) * 1961-05-26 1966-08-09 Inst Francais Du Petrole Process for protecting metals against corrosion at elevated temperatures
US3412000A (en) * 1965-04-14 1968-11-19 M & T Chemicals Inc Cathodic protection of titanium surfaces
US3461058A (en) * 1966-06-07 1969-08-12 Engelhard Ind Inc Method of producing a composite electrode
US3876517A (en) * 1973-07-20 1975-04-08 Ppg Industries Inc Reduction of crevice corrosion in bipolar chlorine diaphragm cells by locating the cathode screen at the crevice and maintaining the titanium within the crevice anodic
US3972796A (en) * 1974-02-15 1976-08-03 Dipl.-Ing. Hanns Frohler Kg Electrolytic apparatus
US4048045A (en) * 1974-12-19 1977-09-13 Hooker Chemicals & Plastics Corporation Lengthening anode life in electrolytic cell having molded body
US4202751A (en) * 1977-11-28 1980-05-13 Kobe Steel, Ltd. Sacrificial anode and apparatus employing same for treating hot sea water
US4256556A (en) * 1978-11-24 1981-03-17 Diamond Shamrock Corporation Anodically polarized surface for biofouling and scale control
US4330376A (en) * 1979-03-05 1982-05-18 Atlantic Richfield Company Process for inhibiting titanium corrosion
US4627900A (en) * 1982-08-27 1986-12-09 Amax Inc. Electrochemical dissolution and control of nickel sulfide scale
WO2004108992A1 (en) * 2003-06-03 2004-12-16 Titanium Metals Corporation Fabricated titanium article having improved corrosion resistance
US20070266754A1 (en) * 2006-05-16 2007-11-22 Surface Technology Holdings, Ltd. Metallic article with improved fatigue performance and corrosion resistance and method for making the same
US7762113B2 (en) 2006-05-16 2010-07-27 Surface Technology Holdings, Ltd. Metallic article with improved fatigue performance and corrosion resistance and method for making the same
US20100248003A1 (en) * 2006-05-16 2010-09-30 Surface Technology Holdings, Ltd. Metallic article with improved fatigue performance and corrosion resistance
US8033152B2 (en) 2006-05-16 2011-10-11 Surface Technology Holdings, Ltd. Metallic article with improved fatigue performance and corrosion resistance
EP2348140A1 (en) * 2008-09-26 2011-07-27 Rozen, Andrei Evgenievich Multilayer material with enhanced corrosion resistance (variants) and methods for preparing same
EP2348140A4 (en) * 2008-09-26 2013-08-07 Rozen Andrei Evgenievich Multilayer material with enhanced corrosion resistance (variants) and methods for preparing same
US20110223443A1 (en) * 2010-03-15 2011-09-15 Scheel Jeremy E Metallic components for use in corrosive environments and method of manufacturing
RU2451771C2 (en) * 2010-08-27 2012-05-27 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" Фгуп "Цнии Км "Прометей" Method for corrosion-resistant covering application to titanium alloy hardware

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BE569804A (en)
FR1239322A (en) 1960-08-26
GB860968A (en) 1961-02-15
CH375583A (en) 1964-02-29
DE1250234B (en) 1967-09-14

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