US3063835A - Corrosion-resistant alloys - Google Patents

Corrosion-resistant alloys Download PDF

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US3063835A
US3063835A US821134A US82113459A US3063835A US 3063835 A US3063835 A US 3063835A US 821134 A US821134 A US 821134A US 82113459 A US82113459 A US 82113459A US 3063835 A US3063835 A US 3063835A
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percent
titanium
corrosion
alloys
alloy
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Stern Milton
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Union Carbide Corp
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Union Carbide Corp
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Priority to GB21160/60A priority patent/GB903679A/en
Priority to LU38827D priority patent/LU38827A1/xx
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium

Definitions

  • This invention relates to corrosion-resistant alloys and, particularly, to corrosion resistant alloys in which titanium or chromium is the predominant metal.
  • Titanium and many of its alloys, as well as chromium and many of its alloys are noted for excellent resistance to oxidizing corrosive media.
  • non-oxidizing corrosive media such as hydrochloric and sulfuric acid solutions
  • these metals and alloys exhibit little or no resistance. It would be most desirable to have available alloys capable of withstanding corrosive environments ranging from strongly oxidizing to weakly oxidizing or non-oxidizing.
  • An alloy of this type would have the widest utility. For example, such an alloy would be invaluable in chemical plant equipment.
  • Hydrochloric and sulfuric acids are prime examples of non-oxidizing corrosive media. These acids enter into many important commercial processes. They require storing and handling equipment which combine the desirable properties cited above. If a titanium alloy, for example, were to possess resistance to non-oxidizing acid solutions, in addition to its natural endowments of lightness, strength, and resistance to oxidizing acid solutions, it would be extremely useful in such applications.
  • titanium alloys specifically to resist attack by a strong non-oxidizing acid.
  • the corrosion resistance is derived in great measure from the molybdenum which is itself resistant to these acids, but the eitectiveness of the molybdenum does not become especially significant until amounts up to 20 percent are added.
  • One disadvantage of this alloy is that the tendency toward brittleness increases along with molybdenum content so that by the time 40 percent is reached, the alloy has become excessively brittle and difiicult to fabricate.
  • resistance to non-oxidizing acids is gained, the resistance to oxidizing acids is lost.
  • One widely used method for preventing corrosion is to add passivating inhibitors to the environment which, it is believed, operate by producing local action current to anodically polarize a metal into the passive potential region. It is not always desirable, however, to alter the composition of a solution to prevent corrosion of the equipment in which it is contained, particularly when the composition of the solution is critical or specific to some process. Such a means of preventing corrosion is limited to the particular case where the composition of the contained solution is not critical.
  • corosion resistance can be achieved in non-oxidizing environments by artificially anodically polarizing the base metal by applying an external current (which might be termed anodic protection as opposed to cathodic protection).
  • anodic protection as opposed to cathodic protection
  • the primary object of this invention to provide alloys of titanium and alloys of chromium which are resistant to the attack of oxidizing and non-oxidizing corrosive media.
  • a corrosion resistant alloy consisting essentially of from 0.005 to 5 percent by weight in the aggregate of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, rhenium, and alloys thereof, and the balance a metal selected from the group consisting of titanium, chromium, and alloys thereof wherein said selected metal is present in predominant amounts.
  • alloys of the invention have been prepared and tested. Dramatic improvements in corrosion rates were obtained and are set forth in the following table in comparison with pure titanium and various titanium alloys. In these tests, the samples were degreased, pickled, dried, and weighed. They were then immersed in boiling acid of composition and concentration as set forth, for one period of 24 hours duration, removed, washed, and weighed again. The corrosion rate was calculated and reported as mils penetration per year.
  • Table I indicates the results of noble metal additions to substantially pure titanium.
  • Table II provides the same information as to noble metal additions to binary and tertiary titanium base alloys. The percentages given in each case are percentages by weight of the total alloy.
  • FIGS. 1 and 2 demonstrate the eifectiveness of platinum and palladium in decreasing the rate of corrosion of titanium in hydrochloric and sulfuric acid, respectively.
  • the addition of 0.035 percent palladium is effective in reducing the corrosion rate of titaniumrexposed to 10.0 percent boiling HCl to the level of approximately 100 mils penetration per year, only 0.005 percent is necessary to reduce the rate to the same level when titanium is exposed to 3.0 percent boiling HCl.
  • the additive is used in amounts of 0.1 to 0.5 percent. With amounts below 0.1 percent noble metal addition, the desired improvement in corrosion resistance may not be needs. As cited previously, as little as.005 percent of noble metal addition to titanium may sufiice for low concentrations of acids. With amounts substantially in excess of about 2.0 per- 4 cent, no marked degree of improvement results.
  • the noble metals may be present in the alloy either singly or in any combination with each other.
  • the titanium-base alloys shown in Table II also exhibit improved corrosion resistance in non-oxidizing media when alloyed with one of the noble metals listed. It is seen from Table II that alloys containing at least about 80 percent by weight titanium are benefitted. Of especial significance is the titanium-molybdenum-noble metal alloy shown in Table II.
  • Some alloys of titanium and molybdenum are known to possess resistance to corrosive non-oxidizing media because of the resistance to such media naturally possessed by molybdenum.
  • the resistance to non-oxidizing media of a titanium-40 percent molybdenum alloy is much greater than the resistance of pure titanium in such media.
  • the increased resistance to non-oxidizing media poossessed by this alloy is acquired at the expense of the resistance to oxidizing media normally possessed by titanium.
  • With amounts of less than 40 percent molybdenum in titanium the resistance to non-oxidizing media is not as great. Below 15 percent molybdenum, a titanium molybdenum alloy shows little of this resistance to non-oxidizing media.
  • titanium-molybdenum alloys of one of the noble metals selected from the group ruthenium, rhodium, palladium, osmium, iridium, platinium, gold and rhenium a corrosion resistance alloy is obtained that is suitable for use in both oxidizing and non-oxidizing media.
  • the titaniumbase alloy should contain from about 8 percent to 20 percent by weight molybdenum, and may contain up to 5 percent by weight of one or more of the noble metals.
  • a preferred range of composition is from 8 to 20 percent molybdenum, from 0.05 to 2 percent palladium, and the balance titanium and incidental impurities. Any noble metal from the group listed above may beused; but because of economic considerations, it is preferred to use palladium.
  • an alloy may be prepared that consists of from 12 to 14 percent molybdenum, about 0.2 percent palladium, and the balance titanium and incidental impurities.
  • the alloys shown in Table V II include some high-molybdenum titanium-base alloys which show greatly improved resistance to non-oxidizing media, but do not exhibit the re'sistance'to oxidizing'media found in the alloys of this invention.
  • Table -III indicates the results of noble metal additions to substantially pure chromium.
  • Table IV provides the same information as to noble metal additions to binary and tertiary chromium-base alloys. The percentages given in each case are percentages by weight of the total alloy.
  • the 0.5 osmium addition while it decreases the rate drastically, is not as elfective as an equal amount of platinum. It will further be observed that, in general, additions of noble metal reduce the rate of corrosion of chromium in boiling non-oxidizing acids of concentrations as high as 60%.
  • the proportion of noble metal addition may be varied according to the anticipated use. Where contact with a more rigorous environment is anticipated, such as strong concentrations of acid, more noble metal is required. For best results in conditions where exposure to strong solutions is encountered, the additive is used in amounts of between 0.05 and 0.5%. With amounts below 0.05% noble metal addition, the desired improvement in corrosion resistance may not be suflicient to meet the particular needs. As little as 0.005% of noble metal addition may suflice for low concentration of acid, however. With amounts substantially in excess of about 5%, no marked degree of improvement results.
  • the noble metals may be present either singly or in combination with each other.
  • the alloys of the present invention may be prepared according to current metallurgical practice, although the invention is not limited by the method of preparation.
  • the ingredients may be in any commercially pure form since the invention is not limited to the degree of its constituents.
  • a corrosion-resistant alloy consisting essentially of from about 0.005 to about 5 percent by weight in the aggregate of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, and rhenium, and the balance titanium and incidental impurities.
  • a corrosion-resistant alloy consisting essentially of from about 0.05 to about 2 percent by weight in the aggregate of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, and rhenium, and the balance titanium and incidental impurities.
  • a corrosion-resistant alloy consisting essentially of about 0.05 percent by weight palladium, and the balance titanium and incidental impurities.
  • a corrosion-resistant alloy consisting essentially of about 0.05 percent by weight platinum, and the balance titanium and incidental impurities.
  • a corrosion resistant alloy consisting essentially of from about 8 to about 20 percent by weight molybdenum, from about 0.05 to about 2 percent by weight in the aggregate of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, and rhenium, and the balance titanium and incidental impurities.
  • a corrosion-resistant alloy consisting essentially of from about 8 to about 20 percent by weight molybdenum, from about 0.05 to about 2 percent by weight palladium, and the balance titanium and incidental impurities.
  • a corrosion-resistant alloy consisting essentially of from about 12 to 14 percent by weight molybdenum, about 0.2 palladium, and the balance titanium and incidental impurities.
  • a corrosion resistant alloy consisting essentially of about 0.2 percent by weight palladium, and the balance titanium and incidental impurities.
  • a corrosion-resistant alloy consisting essentially of from about 0.005 to about 5 percent by weight in the aggregate of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iriditun, platinum, and rhenium, and the balance substantially all a metallic material selected from the group consisting of titanium and alloys of titanium with at least one element selected from the group consisting of aluminum, vanadium, manganese, molybdenum, and carbon containing :at least about percent by weight titanium.
  • a corrosion-resistant alloy consisting essentially of from about 0.05 to about 2 percent by weight in the aggregate of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, and rhenium, and the balance substantially all a metallic material selected from the group consisting of titanium and alloys of titanium with at alloy containing consisting of 40 and the balance may also be made 7 7 least one element selected from the group consisting of FOREIGN PATIENTS aluminum, vanadinm, manganese, molybdenum, and car- 18 212 Great Britain July 9, 1914 bon containing at least about 80 per-gent by weight ti- M1913 +11; V tanium. 1

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US821134A 1959-06-18 1959-06-18 Corrosion-resistant alloys Expired - Lifetime US3063835A (en)

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GB21160/60A GB903679A (en) 1959-06-18 1960-06-16 Improvements in and relating to chromium base alloys
LU38827D LU38827A1 (en(2012)) 1959-06-18 1960-06-16

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111406A (en) * 1961-09-13 1963-11-19 Gen Dynamics Corp High temperature resistant titanium base alloys
US3131059A (en) * 1961-09-13 1964-04-28 Gen Dynamics Corp Chromium-titanium base alloys resistant to high temperatures
US3479161A (en) * 1966-02-01 1969-11-18 Gen Electric Co Ltd Oxidation resistant tungsten and molybdenum alloy bodies
US3713901A (en) * 1970-04-20 1973-01-30 Trw Inc Oxidation resistant refractory alloys
FR2213986A1 (en) * 1973-01-16 1974-08-09 Glazunov Sergei Titanium alloy for gas and steam turbine blades - contg. rhenium, aluminium, zirconium, tin, molybdenum, tungsten, silicon and chromium
US3880655A (en) * 1972-11-17 1975-04-29 Sergei Georgievich Glazunov Titanium base alloy
US4011075A (en) * 1971-07-16 1977-03-08 The Furukawa Electric Co., Ltd. Materials for tamping battery mix
FR2333050A1 (fr) * 1975-11-27 1977-06-24 Johnson Matthey Co Ltd Alliage de titane perfectionne
DE3541223A1 (de) * 1984-11-22 1986-05-28 Nippon Mining Co., Ltd., Tokio/Tokyo Korrosionsbestaendige titanbasislegierung
JPS63114931A (ja) * 1986-10-31 1988-05-19 Sumitomo Metal Ind Ltd 油井環境用チタン合金の耐食性改善方法
US5238647A (en) * 1990-12-26 1993-08-24 Nippon Mining And Metals Company Limited Titanium alloys with excellent corrosion resistance
US5316722A (en) * 1992-07-09 1994-05-31 Kabushiki Kaisha Kobe Seiko Sho Corrosion resistant Ti-Cr-Ni alloy containing a platinum group metal
US6334913B1 (en) 1998-12-28 2002-01-01 Kobe Steel, Ltd. Corrosion-resistant titanium alloy
US6409792B1 (en) 2000-11-06 2002-06-25 Rmi Titanium Company Process for melting and casting ruthenium-containing or iridium-containing titanium alloys
US6607846B1 (en) 2002-09-25 2003-08-19 Titanium Metals Corporation Titanium article having improved corrosion resistance
US20040058190A1 (en) * 2002-09-25 2004-03-25 Grauman James S. Fabricated titanium article having improved corrosion resistance
US20050021129A1 (en) * 2000-12-28 2005-01-27 Pelton Brian Lee Thermoelastic and superelastic Ni-Ti-W alloy
US20070212251A1 (en) * 2004-04-09 2007-09-13 Hiroaki Otsuka High Strength AlphaType Titanuim Alloy
RU2320745C1 (ru) * 2006-07-11 2008-03-27 Юлия Алексеевна Щепочкина Сплав на основе титана
EP1909348A4 (en) * 2005-07-28 2008-09-24 Kobe Steel Ltd MATERIAL FOR TITANIUM ELECTRODE
RU2346071C1 (ru) * 2007-05-29 2009-02-10 Юлия Алексеевна Щепочкина Сплав на основе титана
RU2426808C1 (ru) * 2010-04-29 2011-08-20 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") Сплав на основе титана
RU2451771C2 (ru) * 2010-08-27 2012-05-27 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" Фгуп "Цнии Км "Прометей" Способ формирования коррозионно-стойкого покрытия на изделиях из титановых сплавов
RU2619535C1 (ru) * 2016-07-12 2017-05-16 Юлия Алексеевна Щепочкина Сплав на основе титана

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE68908629T2 (de) * 1988-07-01 1994-03-24 Gen Electric Metallische Schutzschicht für Bauelemente aus hochtemperaturbeständigen Legierungen für Düsentriebwerke.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2247755A (en) * 1940-02-03 1941-07-01 Mallory & Co Inc P R Electric contact
US2659669A (en) * 1950-07-03 1953-11-17 Hi Loy Company Inc Composition and method for the production of alloys

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2247755A (en) * 1940-02-03 1941-07-01 Mallory & Co Inc P R Electric contact
US2659669A (en) * 1950-07-03 1953-11-17 Hi Loy Company Inc Composition and method for the production of alloys

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111406A (en) * 1961-09-13 1963-11-19 Gen Dynamics Corp High temperature resistant titanium base alloys
US3131059A (en) * 1961-09-13 1964-04-28 Gen Dynamics Corp Chromium-titanium base alloys resistant to high temperatures
US3479161A (en) * 1966-02-01 1969-11-18 Gen Electric Co Ltd Oxidation resistant tungsten and molybdenum alloy bodies
US3713901A (en) * 1970-04-20 1973-01-30 Trw Inc Oxidation resistant refractory alloys
US4011075A (en) * 1971-07-16 1977-03-08 The Furukawa Electric Co., Ltd. Materials for tamping battery mix
US3880655A (en) * 1972-11-17 1975-04-29 Sergei Georgievich Glazunov Titanium base alloy
FR2213986A1 (en) * 1973-01-16 1974-08-09 Glazunov Sergei Titanium alloy for gas and steam turbine blades - contg. rhenium, aluminium, zirconium, tin, molybdenum, tungsten, silicon and chromium
FR2333050A1 (fr) * 1975-11-27 1977-06-24 Johnson Matthey Co Ltd Alliage de titane perfectionne
US4139373A (en) * 1975-11-27 1979-02-13 Johnson, Matthey & Co., Limited Alloys of titanium
DE3541223A1 (de) * 1984-11-22 1986-05-28 Nippon Mining Co., Ltd., Tokio/Tokyo Korrosionsbestaendige titanbasislegierung
US4666666A (en) * 1984-11-22 1987-05-19 Nippon Mining Co., Ltd. Corrosion-resistant titanium-base alloy
GB2198144A (en) * 1986-10-31 1988-06-08 Sumitomo Metal Ind Method of improving the resistance of ti-based alloys to corrosion
US4859415A (en) * 1986-10-31 1989-08-22 Sumitomo Metal Industries, Ltd. Method of improving the resistance of Ti-based alloys to corrosion in deep-well environments
GB2198144B (en) * 1986-10-31 1991-06-26 Sumitomo Metal Ind Method of improving the resistance of ti-based alloys to corrosion
JPS63114931A (ja) * 1986-10-31 1988-05-19 Sumitomo Metal Ind Ltd 油井環境用チタン合金の耐食性改善方法
US5238647A (en) * 1990-12-26 1993-08-24 Nippon Mining And Metals Company Limited Titanium alloys with excellent corrosion resistance
US5316722A (en) * 1992-07-09 1994-05-31 Kabushiki Kaisha Kobe Seiko Sho Corrosion resistant Ti-Cr-Ni alloy containing a platinum group metal
DE19962585C2 (de) * 1998-12-28 2003-06-26 Kobe Steel Ltd Korrosionsbeständige Titanlegierung und daraus bestehende Komponenten
US6334913B1 (en) 1998-12-28 2002-01-01 Kobe Steel, Ltd. Corrosion-resistant titanium alloy
US6409792B1 (en) 2000-11-06 2002-06-25 Rmi Titanium Company Process for melting and casting ruthenium-containing or iridium-containing titanium alloys
WO2002042506A3 (en) * 2000-11-06 2003-03-13 Rmi Titanium Co Process for melting and casting ruthenium-containing or iridium-containing titanium alloys
US8974517B2 (en) 2000-12-28 2015-03-10 Abbott Cardiovascular Systems Inc. Thermoelastic and superelastic NI-TI-W alloy
US7658760B2 (en) 2000-12-28 2010-02-09 Abbott Cardiovascular Systems Inc. Thermoelastic and superelastic Ni-Ti-W alloy
US8702790B2 (en) 2000-12-28 2014-04-22 Abbott Cardiovascular Systems Inc. Thermoelastic and superelastic Ni—Ti—W alloy
US20050021129A1 (en) * 2000-12-28 2005-01-27 Pelton Brian Lee Thermoelastic and superelastic Ni-Ti-W alloy
US8382819B2 (en) 2000-12-28 2013-02-26 Abbot Cardiovascular Systems Inc. Thermoelastic and superelastic Ni-Ti-W alloy
US20040058190A1 (en) * 2002-09-25 2004-03-25 Grauman James S. Fabricated titanium article having improved corrosion resistance
EP1734153A3 (en) * 2002-09-25 2007-04-11 Titanium Metals Corporation Titanium article having improved corrosion resistance
US6607846B1 (en) 2002-09-25 2003-08-19 Titanium Metals Corporation Titanium article having improved corrosion resistance
EP1403399A3 (en) * 2002-09-25 2004-04-07 Titanium Metals Corporation Titanium article having improved corrosion resistance
US6849344B2 (en) * 2002-09-25 2005-02-01 Titanium Metals Corp. Fabricated titanium article having improved corrosion resistance
RU2336366C2 (ru) * 2002-09-25 2008-10-20 Титаниум Металс Корпорейшн Титановое изделие с повышенной коррозионной стойкостью
RU2336366C9 (ru) * 2002-09-25 2008-12-20 Титаниум Металс Корпорейшн Титановое изделие с повышенной коррозионной стойкостью
KR100721107B1 (ko) 2002-09-25 2007-05-22 티타늄 메탈스 코포레이션 내부식성을 가진 티탄 물품
RU2380459C2 (ru) * 2003-06-03 2010-01-27 Титаниум Металс Корпорейшн Титановое изделие с улучшенной коррозионной устойчивостью и способ улучшения коррозионной стойкости титанового изделия
US8562763B2 (en) * 2004-04-09 2013-10-22 Nippon Steel & Sumitomo Metal Corporation High strength α+β type titanuim alloy
US20070212251A1 (en) * 2004-04-09 2007-09-13 Hiroaki Otsuka High Strength AlphaType Titanuim Alloy
US20100119882A1 (en) * 2005-07-28 2010-05-13 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Titanium electrode material
US8137866B2 (en) 2005-07-28 2012-03-20 Kobe Steel, Ltd. Titanium material for fuel cell separator having low contact resistance
EP1909348A4 (en) * 2005-07-28 2008-09-24 Kobe Steel Ltd MATERIAL FOR TITANIUM ELECTRODE
RU2320745C1 (ru) * 2006-07-11 2008-03-27 Юлия Алексеевна Щепочкина Сплав на основе титана
RU2346071C1 (ru) * 2007-05-29 2009-02-10 Юлия Алексеевна Щепочкина Сплав на основе титана
RU2426808C1 (ru) * 2010-04-29 2011-08-20 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") Сплав на основе титана
RU2451771C2 (ru) * 2010-08-27 2012-05-27 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" Фгуп "Цнии Км "Прометей" Способ формирования коррозионно-стойкого покрытия на изделиях из титановых сплавов
RU2619535C1 (ru) * 2016-07-12 2017-05-16 Юлия Алексеевна Щепочкина Сплав на основе титана

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LU38827A1 (en(2012)) 1960-08-16

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