EP0026863A1 - Alliages métalliques vitreux résistant à la corrosion - Google Patents

Alliages métalliques vitreux résistant à la corrosion Download PDF

Info

Publication number
EP0026863A1
EP0026863A1 EP80105612A EP80105612A EP0026863A1 EP 0026863 A1 EP0026863 A1 EP 0026863A1 EP 80105612 A EP80105612 A EP 80105612A EP 80105612 A EP80105612 A EP 80105612A EP 0026863 A1 EP0026863 A1 EP 0026863A1
Authority
EP
European Patent Office
Prior art keywords
phosphorus
atom percent
alloys
glassy metal
metal alloys
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP80105612A
Other languages
German (de)
English (en)
Inventor
Sheldon Kavesh
Nicholas J. Decristofaro
Claude Henschel
Peter Sexton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
Allied Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allied Corp filed Critical Allied Corp
Publication of EP0026863A1 publication Critical patent/EP0026863A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent

Definitions

  • This invention relates to corrosion resistant glassy metal alloys.
  • the corrosion resistance of any given metal or alloy in a reducing medium is often sharply different from its corrosion resistance in an oxidizing medium, with some metals and alloys being more resistant to reducing media and others to oxidizing media. These differences in behavior are thought to be attributable to differences between the corrosion mechanism in a reducing medium and the corrosion mechanism in an oxidizing medium.
  • corrosive attack by a reducing acid is generally considered to involve attack on the metal by hydrogen ions, resulting in the oxidation of metal to soluble ions and release of hydrogen gas.
  • Metals of relatively high nobility, therefore, as indicated by their positions in the galvanic series are generally resistant to corrosion by reducing acid.
  • Attack by oxidizing media does not involve release of hydrogen but commonly results in the formation of metal oxides or other metallic compounds at the metal surface. Unlike the situation with reducing acids, a favorable position relative to hydrogen in the electromotive series provides no insurance that a metal will not be rapidly attacked by an oxidizing medium.
  • certain elements such as chromium, aluminum and silicon, form tough insoluble oxide films upon initial contact with an oxidizing medium, and such films serve as barriers against further reaction between the medium and the metal to prevent further corrosion from taking place.
  • Sulfuric acid solutions are not only very corrosive generally, but the nature of their corrosion properties varies markedly with both acid concentration and temperature. This variability relates at least in part to sulfuric acid's ambivalent assumption of both reducing and oxidizing properties as its concentration temperature and the nature and proportion of various contaminants are altered. As a consequence of this variability in its corrosive properties, few materials are available which are reasonably resistant to sulfuric acid solution over a wide range of concentrations and temperatures.
  • Corrosion resistant crystalline alloys are well known and are exemplified by stainless steels, for example.
  • Corrosion resistant glassy metal alloys are also well known, see, for example, U.S. Patent . 3,856,513, which discloses a corrosion resistant glassy metal alloy, Fe 40 Ni 38 P 14 B 6 Al 2 the subscripts are in atom percent), as being several orders of magnitude less reactive than stainless steels with concentrated hydrochloric acid.
  • Other prior art corrosion resistant glassy metal alloys include iron-nickel-chromium- phosphorus-carbon alloys. However, these alloys evidence stress corrosion cracking and thus are not suitable in many applications, even though their corrosion resistance is superior to many other glassy metal alloys.
  • a metal alloy that is substantially glassy and resistant to corrosion in acid media.
  • the glassy metal alloy consists essentially of from about 0 to 18 atom .percent nickel, from 7 to about 21 atom percent chromium, from 0 to about 8 atom percent molybdenum, from about 13 to 18 atom percent of at least one element selected from the group consisting of phosphorus, carbon and boron, other than phosphorus plus carbon, and the balance essentially iron with the proviso that the ratio of phosphorus to the sum of phosphorus, boron and carbon present is greater than or equal to 0.64.
  • Potentiostatic anodic polarization measurements are performed by immersing a metallic electrode in an electrolyte solution and varying its potential in a stepwise manner with a special feedback power supply (i.e.., a potentiostat). If the current corresponding to each potential is recorded, an anodic polarization curve can be constructed.
  • a typical curve for an active-passive alloy is shown in FIG. 1. Potential is ploted on the ordinate and the logarithm of the current density on the abscissa. The current density, which is equivalent to the alloy dissolution rate, at first increases with increasing potential (active region 10). At more noble (positive) potentials, the dissolution current density decreases and then remains at a low value (passive region 11).
  • the current maximum which occurs at the primary passive potential Epp is termed the critical anodic current density I c .
  • the passive region begins at the passive potential E p and is characterized by the passive current density Ip;
  • Potentiostatic anodic polarization curves may be viewed as plots of solution oxidizing power (E) versus corrosion rate (current density).
  • E solution oxidizing power
  • current density current density
  • the range of useful corrosion resistance can be estimated by noting the width of the passive region and the potential at which the transpassive region begins. Although actual anodic polarization curves sometimes deviate from the schematic illustration of FIG. 1, they can be compared on the same basis.
  • the corrosion resistant alloys of the invention consist essentially of from about 0 to 18 atom percent nickel, from 7 to about 21 atom percent chromium, from 0 to about 8 atom percent molybdenum, from about 13 to 18 atom percent of at least one element selected from the group consisting of phosphorus, carbon and boron, other than phosphorus plus carbon, and the balance essentially iron with the proviso that the ratio of phosphorus to the sum of phosphorus, carbon and boron is greater than or equal to 0.64.
  • Glassy metal alloys of the invention are formed by cooling a melt of the desired composition at a rate of at least about l05oc/sec.
  • a variety of rapid quenching techniques well known to the glassy metal alloy art, are available for producing glassy metal powders, wires, ribbon and sheet.
  • a particular composition is selected, powders or granules of the requisite elements in the desired portions are melted and homogenized, and the molten alloy is rapidly quenched on a chill surface, such as a rapidly rotating cylinder, or in a suitable fluid medium, such as water.
  • a metastable, homogeneous, ductile material is obtained.
  • the metastable material may be amorphous or glassy, in which case there is no long range order.
  • X-ray diffraction patterns of glassy metal alloys show only a diffuse halo, similar to that observed for inorganic oxide glasses.
  • the amorphous metal alloys are at least 50% amorphous, and preferably at least 80% amorphous, as measured by X-ray diffraction. However, a substantial degree of amorphousness approaching 100% amorphous is obtained by forming these amorphous metal alloys in a partial vacuum. Ductility and corrosion resistance are thereby improved, and such alloys possessing a substantial degree of amorphousness are accordingly preferred.
  • Polarization curves for all alloys were obtained in IN H 2 SO 4 at 22°C. Materials exhibiting interesting characteristics were studied in other environments such as IN H 2 SO 4 plus 5 percent NaCl, ION H 2 SO 4 , and 38 percent HC1. In addition, weight losses were determined in 6% FeCl 3 at 60°C for 20 hours.
  • Table I compares alloy performance in hydrogen-saturated 1N H 2 SO 4 . Included are prior art crystalline and glassy metal alloys, as well as glassy metal alloys having compositions outside the scope of the invention.
  • Table II compares weight loss of alloys in 6% FeCl 3 at 60°C for 20 hours. Again, prior art crystalline and glassy metal alloys having compositions outside the scope of the invention are included for comparison.
  • the glassy metal alloys of the invention evidence values less than 1x10 A/cm , with many values less than 10 A/cm 2 . Further, these alloys are stable in 6% Fe/Cl 3 . Alloys outside the invention are seen not to possess this combination of corrosion resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
EP80105612A 1979-10-09 1980-09-19 Alliages métalliques vitreux résistant à la corrosion Withdrawn EP0026863A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8319879A 1979-10-09 1979-10-09
US83198 1979-10-09

Publications (1)

Publication Number Publication Date
EP0026863A1 true EP0026863A1 (fr) 1981-04-15

Family

ID=22176805

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80105612A Withdrawn EP0026863A1 (fr) 1979-10-09 1980-09-19 Alliages métalliques vitreux résistant à la corrosion

Country Status (3)

Country Link
EP (1) EP0026863A1 (fr)
JP (1) JPS5662948A (fr)
CA (1) CA1164685A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207736A3 (fr) * 1985-06-27 1988-12-07 The Standard Oil Company Compositions d'alliages amorphes ferreux, résistant à la corrosion
CN115233118A (zh) * 2021-04-24 2022-10-25 江苏科晶智能科技股份有限公司 铁镍铬基合金、由其制造的合金箔材和制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856513A (en) * 1972-12-26 1974-12-24 Allied Chem Novel amorphous metals and amorphous metal articles
US3986867A (en) * 1974-01-12 1976-10-19 The Research Institute For Iron, Steel And Other Metals Of The Tohoku University Iron-chromium series amorphous alloys

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856513A (en) * 1972-12-26 1974-12-24 Allied Chem Novel amorphous metals and amorphous metal articles
US3986867A (en) * 1974-01-12 1976-10-19 The Research Institute For Iron, Steel And Other Metals Of The Tohoku University Iron-chromium series amorphous alloys

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207736A3 (fr) * 1985-06-27 1988-12-07 The Standard Oil Company Compositions d'alliages amorphes ferreux, résistant à la corrosion
CN115233118A (zh) * 2021-04-24 2022-10-25 江苏科晶智能科技股份有限公司 铁镍铬基合金、由其制造的合金箔材和制备方法
CN115233117A (zh) * 2021-04-24 2022-10-25 江苏科晶智能科技股份有限公司 铁基合金、由其制造的合金箔材和制备方法
CN115233118B (zh) * 2021-04-24 2023-03-10 江苏科晶智能科技股份有限公司 铁镍铬基合金、由其制造的合金箔材和制备方法

Also Published As

Publication number Publication date
CA1164685A (fr) 1984-04-03
JPS5662948A (en) 1981-05-29

Similar Documents

Publication Publication Date Title
Streicher Development of pitting resistant Fe-Cr-Mo alloys
Bond et al. Anodic polarization of austenitic stainless steels in chloride media
Horvath et al. Critical potentials for pitting corrosion of Ni, Cr‐Ni, Cr‐Fe, and related stainless steels
US4701226A (en) Corrosion resistant amorphous chromium-metalloid alloy compositions
DE69518354T2 (de) Rostfreier Duplex-Stahl mit hoher Korrosionsbeständigkeit
Naka et al. Change in corrosion behavior of amorphous Fe P C alloys by alloying with various metallic elements
US4810314A (en) Enhanced corrosion resistant amorphous metal alloy coatings
CA1211302A (fr) Alliage austenitique a l'epreuve de la corrosion
Bond Effects of molybdenum on the pitting potentials of ferritic stainless steels at various temperatures
Naka et al. Effect of addition of chromium and molybdenum on the corrosion behavior of amorphous Fe-20B, Co-20B and Ni-20B alloys
DE10194846T5 (de) Verfahren zur Oberflächenbehandlung eines rostfreien Stahlprodukts für eine Brennstoffzelle
JPS61210143A (ja) 高耐食アモルフアス合金
Rife et al. Corrosion of iron-, nickel-and cobalt-base metallic glasses containing boron and silicon metalloids
Ruf et al. Extremely high corrosion resistance in amorphous Cr–B alloys
CA1164685A (fr) Alliages metalliques vitrifies resistant a la corrosion
US4808371A (en) Exterior protective member made of austenitic stainless steel for a sheathing heater element
WO2024100802A1 (fr) Matériau de titane, composant de dispositif chimique et dispositif chimique
EP0314805B1 (fr) Alliage amorphe tres resistant a la corrosion
Hashimoto et al. Extremely corrosion-resistant bulk amorphous alloys
JPS582259B2 (ja) 硝酸および弗酸よりなる混酸に対してすぐれた耐食性を示す高クロム合金
JPS62199744A (ja) 耐すき間腐食性に優れたチタン合金
US3932174A (en) Chromium, molybdenum ferritic stainless steels
Oh et al. Microstructural Development in the Surface Region during Oxidation of Iron‐Manganese‐Nickel‐Silicon Alloys
Pierna et al. Fe (735.) Cu1. Nb3B9Si13. 5Cr (0,-5) Amorphous Alloys
Shibad et al. Behaviour of titanium and its alloys with hafnium in selected corrosive media

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB IT

17P Request for examination filed

Effective date: 19810921

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ALLIED CORPORATION

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19831031

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SEXTON, PETER

Inventor name: KAVESH, SHELDON

Inventor name: DECRISTOFARO, NICHOLAS J.

Inventor name: HENSCHEL, CLAUDE