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WO2004106559A2 - Procede permettant d'ameliorer la resistance a la corrosion des metaux - Google Patents

Procede permettant d'ameliorer la resistance a la corrosion des metaux Download PDF

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Publication number
WO2004106559A2
WO2004106559A2 PCT/GB2004/002232 GB2004002232W WO2004106559A2 WO 2004106559 A2 WO2004106559 A2 WO 2004106559A2 GB 2004002232 W GB2004002232 W GB 2004002232W WO 2004106559 A2 WO2004106559 A2 WO 2004106559A2
Authority
WO
WIPO (PCT)
Prior art keywords
metal
process according
corrosion resistance
cryogenic treatment
piping
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.)
Ceased
Application number
PCT/GB2004/002232
Other languages
English (en)
Other versions
WO2004106559A3 (fr
Inventor
Timothy Craig Garrison
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.)
Avecia Ltd
Avecia Inc
Original Assignee
Avecia Ltd
Avecia Inc
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 Avecia Ltd, Avecia Inc filed Critical Avecia Ltd
Priority to EP04734559A priority Critical patent/EP1639143A2/fr
Priority to JP2006530534A priority patent/JP2007503528A/ja
Publication of WO2004106559A2 publication Critical patent/WO2004106559A2/fr
Publication of WO2004106559A3 publication Critical patent/WO2004106559A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/04—Hardening by cooling below 0 degrees Celsius
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/001—Heat treatment of ferrous alloys containing Ni

Definitions

  • the present invention concerns a process for improving the corrosion resistance of metals, particularly steels, and especially high Ni alloys.
  • Cryogenic tempering either shallow or deep, but especially the latter, has attracted much attention recently as a means of increasing the life of cutting tools, especially those made from tool steels.
  • cryogenic treatment can improve the corrosion resistance of metals.
  • a process for improving the corrosion resistance of a metal comprising subjecting said metal to a cryogenic treatment.
  • Metals which can be subjected to the process according to the present invention include steels, especially stainless steels, such as for example austenitic stainless steels, including high nickel stainless steels, such as those available under the trade name INCOLOY, and duplex stainless steels.
  • High nickel stainless steels commonly comprise at least 5% w/w Ni, typically at least 8% w/w Ni, and may comprise from 25-30 % w/w Ni.
  • the process is particularly suited to the treatment of high nickel alloys, for example alloys containing at least 50% w/w nickel, and especially to those alloys of the type commercially available under the trade names HASTELLOY, MONEL and INCONEL.
  • the cryogenic treatment of the present invention commonly follows the procedures known in the art for the cryogenic tempering of tool steels, and generally comprises cooling the metal to substantially sub-ambient temperatures, and returning the metal to ambient temperature.
  • the cooling may be carried out rapidly, by for example immersion of the metal in a liquid of selected temperature.
  • this may induce undesirable transformations in the metal as a result of thermal shock.
  • it is preferred that the temperature of the metal is reduced in a controlled fashion to avoid thermal shock.
  • the metal may be maintained at the selected sub-ambient temperature for a period, which may range from several, such as 5 to 30 minutes, to many hours, for example 36-48 hours, depending for example on the temperature, the nature of the metal and the size and volume of the metal.
  • cryogenic treatment effects cryogenic stress relief of the metal, reducing the occurrence of stress cracks, and hence improving the corrosion resistance of the metal.
  • the process may employ shallow cryogenic treatment, for example where the sub- ambient temperature employed is in the range of from -60°C to -90°C.
  • shallow cryogenic treatment typically comprise cooling the metal by exposure to vapours from boiling liquid nitrogen.
  • the process employs deep cryogenic treatment, where the temperature employed is less than -90°C, preferably less than -130°C, and most preferably less than -155°C.
  • the temperature employed is in the range of from -180°C to -195°C, and most advantageously from about -185°C to about -190°C.
  • Such processes typically comprise cooling the metal by exposure to the vapours from boiling liquid nitrogen.
  • the metal is typically enclosed in a vented vessel which is injected with liquid nitrogen. It will be recognised that by feeding liquid nitrogen into the vessel at a controlled rate, the temperature in the vessel is reduced as the liquid nitrogen evaporates upon entry into the vessel, and thereby the metal sample is cooled.
  • the vessel is typically insulated to improve the cooling efficiency.
  • the rate of cooling employed can be selected at the convenience of the user, but in many embodiments is controlled to be in the range of from about 0.2°C/minute to about 2°C/minute, such as from 0.5°C/minute to 1 °C/minute.
  • the metal can be returned to ambient temperature. This may comprise active heating of the metal, or may comprise allowing the temperature of the vessel, and hence the metal, to increase to return to ambient temperature. In many embodiments, the temperature is increases at a rate of from 0.5°C to 10°C per minute, such as from 2°C to 7°C per minute, and preferably at about 5°C per minute.
  • the metal is preferably subjected to a heat treatment, for example mar-tempering employing conventional mar-tempering methodology.
  • the mar-tempering which comprises a cycle of heating and cooling, often repeated several, for example from 2 to 3, times, may be conducted after the metal has been stored at ambient temperature for a period, or may follow immediately the process by which the metal is returned to ambient temperature.
  • the mar- tempering comprises heating the metal to about 120°C to 175°C, preferably about 150°C, followed by cooling to ambient temperature.
  • the process according to the present invention comprises mar-tempering the metal by heating from sub-ambient temperature, preferably about -185°C to -190°C, to about 140°C to 160°C at a rate of from 2 to 7°C, preferably about 5°C, per minute.
  • the cryogenic treatment process can be carried out in commercially available apparatus known for the cryogenic tempering of tool steels. Such apparatus may additionally comprise the facility to effect mar-tempering.
  • the process according to the present invention is especially suited for improving the corrosion resistance of metals employed in the manufacture of filters, heaters, coolers, exchangers, piping, mechanical process equipment and the like.
  • the process may be applied to the metal prior to its fabrication of a given article of commerce, but is preferably applied to the fabricated article.
  • the process is particularly suited to improving the corrosion resistance of metals subjected to chloride corrosion. Examples of particular articles of commerce include especially heat exchanger tubes, cooler tubes, process piping, especially chemical process piping, filters, pumps, reactor vessels and storage tanks.
  • a metal having a given corrosion resistance or an article made from such a metal, can be selected to have the corrosion resistance improved, wherein the corrosion resistance is improved by treating the metal cryogenically, preferably the metal being subjected to a deep cryogenic treatment.
  • Hastelloy C276 Schedule 40 pipe was subjected to cryogenic treatment by cooling to -187°C by exposure to liquid nitrogen vapour in a thermally insulated container. Cooling was effected at the rate of 1 °C per minute and the pipes maintained at -187°C for 10 hours. The pipes were then allowed to warm to ambient temperature, and then subjected to mar-tempering by heating to 150°C, and allowing to cool to ambient temperature. The mar-tempering process employed 3 heating/cooling cycles.
  • the pipes were incorporated as heater elements in a reactor vessel employed to heat a benzene and phosphorus trichloride reaction mixture to a reaction temperature of 650°C.
  • the pipes so treated were observed to have a useful life which was at least 8 times longer than the corresponding non-cryogenically treated pipes prepared from the same grade of Hastelloy exposed to the same use conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

La présente invention concerne un procédé qui permet d'améliorer la résistance à la corrosion des métaux, en particulier des aciers et des alliages à haute teneur en nickel. Le procédé consiste à soumettre des pièces métalliques à un ou plusieurs traitements cryogéniques, facultativement suivis par un ou plusieurs traitements thermiques. Le traitement cryogénique s'effectue de préférence à des températures comprises entre -90 °C et -195 °C, et de préférence encore entre -180 °C et -195 °C. Le traitement thermique s'effectue de préférence à des températures comprises entre l20 °C et 175 °C. Le procédé de l'invention peut être utilisé dans le traitement de pièces et de composants métalliques. L'invention se rapporte également à des tubes d'échangeurs de chaleur, des tubes de refroidisseurs, des conduites, en particulier des conduites de traitement chimique, des pompes, des cuves à réaction et des réservoirs de stockage produits selon ce procédé.
PCT/GB2004/002232 2003-05-27 2004-05-24 Procede permettant d'ameliorer la resistance a la corrosion des metaux Ceased WO2004106559A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP04734559A EP1639143A2 (fr) 2003-05-27 2004-05-24 Procede permettant d'ameliorer la resistance a la corrosion des metaux
JP2006530534A JP2007503528A (ja) 2003-05-27 2004-05-24 金属の耐食性を改良する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47318903P 2003-05-27 2003-05-27
US60/473189 2003-05-27

Publications (2)

Publication Number Publication Date
WO2004106559A2 true WO2004106559A2 (fr) 2004-12-09
WO2004106559A3 WO2004106559A3 (fr) 2005-03-24

Family

ID=33490571

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2004/002232 Ceased WO2004106559A2 (fr) 2003-05-27 2004-05-24 Procede permettant d'ameliorer la resistance a la corrosion des metaux

Country Status (4)

Country Link
EP (1) EP1639143A2 (fr)
JP (1) JP2007503528A (fr)
CN (1) CN1795278A (fr)
WO (1) WO2004106559A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887558A1 (fr) * 2005-06-28 2006-12-29 Aubert & Duval Soc Par Actions Composition d'acier inoxydable martensitique, procede de fabrication d'une piece mecanique a partir de cet acier et piece ainsi obtenue
ITUA20165254A1 (it) * 2016-06-28 2017-12-28 Antonino Rinella Materiali metallici criotemprati, dotati di un'elevata capacita' di assorbire energia di deformazione elastica, destinati alla costruzione di armature di protezione per pneumatici resistenti alle perforazioni e alle lacerazioni.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891477A (en) * 1971-09-09 1975-06-24 Mangrove Enterprise Inc Material treatment by cryogenic cooling
US4739622A (en) * 1987-07-27 1988-04-26 Cryogenics International, Inc. Apparatus and method for the deep cryogenic treatment of materials
US5761974A (en) * 1996-07-22 1998-06-09 Board Of Regents Of The University Of Nebraska System and method for machining heat resistant materials
US5875636A (en) * 1997-10-01 1999-03-02 Nu-Bit, Inc. Process for the cryogenic treatment of metal containing materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887558A1 (fr) * 2005-06-28 2006-12-29 Aubert & Duval Soc Par Actions Composition d'acier inoxydable martensitique, procede de fabrication d'une piece mecanique a partir de cet acier et piece ainsi obtenue
WO2007003748A1 (fr) * 2005-06-28 2007-01-11 Aubert & Duval Composition d'acier inoxydable martensitique, procede de fabrication d'une piece mecanique a partir de cet acier et piece ainsi obtenue
US8097098B2 (en) 2005-06-28 2012-01-17 Aubert & Duval Martensitic stainless steel composition, method for making a mechanical part from said steel and resulting part
ITUA20165254A1 (it) * 2016-06-28 2017-12-28 Antonino Rinella Materiali metallici criotemprati, dotati di un'elevata capacita' di assorbire energia di deformazione elastica, destinati alla costruzione di armature di protezione per pneumatici resistenti alle perforazioni e alle lacerazioni.

Also Published As

Publication number Publication date
JP2007503528A (ja) 2007-02-22
CN1795278A (zh) 2006-06-28
EP1639143A2 (fr) 2006-03-29
WO2004106559A3 (fr) 2005-03-24

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