WO2006084919A1 - Acier inoxydable austenitique - Google Patents

Acier inoxydable austenitique Download PDF

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Publication number
WO2006084919A1
WO2006084919A1 PCT/EP2006/050923 EP2006050923W WO2006084919A1 WO 2006084919 A1 WO2006084919 A1 WO 2006084919A1 EP 2006050923 W EP2006050923 W EP 2006050923W WO 2006084919 A1 WO2006084919 A1 WO 2006084919A1
Authority
WO
WIPO (PCT)
Prior art keywords
stainless steel
austenitic stainless
steel
wires
steel according
Prior art date
Application number
PCT/EP2006/050923
Other languages
English (en)
Inventor
Mario Cusolito
Marco Valsecchi
Pedro M. Corcuera Amurzia
Original Assignee
Rodacciai Spa
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 Rodacciai Spa filed Critical Rodacciai Spa
Priority to AU2006212194A priority Critical patent/AU2006212194B2/en
Priority to EP06708260A priority patent/EP1851351B1/fr
Priority to US11/815,303 priority patent/US20080206088A1/en
Priority to ES06708260T priority patent/ES2390678T3/es
Priority to CA002597750A priority patent/CA2597750A1/fr
Publication of WO2006084919A1 publication Critical patent/WO2006084919A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

Definitions

  • the present invention relates to a new austenitic stainless steel with a low nickel content which has special characteristics in terms of corrosion resistance in given environments , deformability and suitability for work-hardening .
  • the steel according to the present invention is characterized by the following chemical composition :
  • a very important characteristic of the new steel is the small amount of nickel it contains : it is in fact well known that the price of this element is unstable, with a continuous tendency to increase, resulting in continuous variations in the costs of the articles produced with materials which contain this element .
  • Austenitic stainless steel is an iron and carbon alloy containing various other elements , the main ones of which are chromium and nickel . The combination of these elements gives the steel a basic property of corrosion resistance owing to the formation of a protective surface film which is due to the presence of a chromium content of at least 1.11% and whose qualities are improved by the presence of nickel and other elements .
  • Other typical properties of austenitic stainless steels are the very low magnetic permeability (non-magnetic property) , heat resistance, cold deformability and suitability for work-hardening . Owing to these properties , austenitic stainless steels are used in a very wide range of applications .
  • the most well known and widely used type of austenitic stainless steel contains about 18% chromium 10% nickel and has always been referred to as 18/10 steel .
  • this steel has been called X5CrNil8-10 and has been attributed the steel number 1.4301.
  • this steel is called 304.
  • the percentage by weight chemical composition envisaged for this steel by the European standard is as follows :
  • the maximum sulphur content coincides with that of basic steel, so that in fact this is not another steel, but only a variation of the same type 1.4301 obtained by dividing the analytical range permitted by sulphur .
  • Sulphur has the capacity to weaken the metallic matrix and therefore improve the machinability during the swarf removal operations .
  • sulphur even though present in limited amounts , modifies the corrosion resistance .
  • This micro-resulphurised variant is cited here because below it will often be used for comparison with the type 1.4301 steel and with the steel of this invention .
  • 1.4301 steel has extremely broad technological and corrosion properties such it has been become very widely established in the engineering sector as a structural material as well as in the environmental sector : it is in fact widely employed in the transportation, architecture and the domestic sectors , being used at high temperatures and in corrosive environments .
  • the type 1.4301 is the most well known, widespread and researched in the sector of austenitic stainless steels and therefore is used as a reference type for comparing the characteristics of other austenitic stainless steels .
  • the type 1.4307 - X2CrNil8-9 (AISI 304L in the US standards ) is a steel similar to the preceding one, but with a limited carbon content which improves the intergranular corrosion resistance .
  • the chemical composition of type 1.4307 steel is as follows :
  • the type 1.4306 - X2CrNil9 -11 is a further low- carbon variant with a greater content of nickel which is added in order to improve the cold deformability and the corrosion resistance .
  • the chemical composition of this type is as follows :
  • the type 1.4567 - X3CrNiCul8-9-4 is a version with the addition of copper in large amounts for the purpose of improving the cold deformability : it is used for those particular cold-pressed products where the preceding types are unable to withstand the extreme deformation, such as , for example, hexagonal socket head screws .
  • the chemical composition is as follows :
  • the main characteristics of an austenitic stainless steel are its corrosion resistance, nonmagnetic nature, cold-deformability and suitability for work-hardening . These characteristics are obtained by modifying various factors , including the chemical composition : in addition to chromium and nickel, the other secondary elements have an important effect .
  • the effect of chromium referred to as "alphagenic” , tends to stabilize the ferritic phase of the materials (alpha phase) : other elements , such as silicon and molybdenum, behave in the same manner as chromium, although to a lesser degree .
  • nickel which is a "gammagenic" element, and therefore has a stabilizing effect on the austenitic phase (gamma phase) : various elements such as carbon, nitrogen, copper and manganese behave in the same manner as nickel .
  • austenitic stainless steels with low nickel contents have been researched: some of these, which are more widely used and have been known for some time, are included in various standards and used because of their specific characteristics . Others have been recently developed with the aim of obtaining some of the basic characteristics of austenitic stainless steel . In fact, by suitably increasing the content of the less costly "gammagenic" elements (nitrogen, copper and manganese) , it is possible to obtain an austenitic stainless steel which is equally stable, but has a low percentage content of nickel (and therefore a price which is less dependent on the fluctuations of the cost of nickel) and with one or more technological properties the same as those of normal conventional austenitic steels with a higher nickel content . Austenitic steels with a low nickel content are for example described in EP593158 , EP694626, EP896072 , EP969113 e WO 00/26428.
  • the subj ect of the present invention is a steel having a nickel content which is markedly lower than that of basic steel type 1.4301 (AISI 304 ) and which, with suitable balancing of the other elements , has many- properties similar to the corresponding properties of basic steel type 1.4301 (AISI 304 ) ; it has the composition shown below :
  • the steel according to the present invention may be obtained by means of the conventional processes for the preparation of austenitic stainless steels , such as those for example described in "ASM Specialty Handbook - Stainless Steels” edited by "The Material Information Society” - USA. Preferably it has the composition indicated below :
  • the sulphur is less than 0.005 % .
  • the nickel is higher than 4.0 % .
  • the carbon is about 0.055 %
  • the manganese is about 7.50 %
  • the silicon is about 0.52 %
  • the sulphur is about 0.003 %
  • the phosphorus is about 0.032 %
  • the chromium is about 17.0 %
  • the nickel is about 4.0 %
  • the molybdenum is about 0.19 %
  • the copper is about 2.0 % and/or the nitrogen is about 0.17 % .
  • the sLccl according to the present invention presents a higher resistance to "stress corrosion cracki ng" (al so ca l l ed “del ayed corrosi on”) than the s teels commonly known in the art and, in particular, than those disclosed by WO 00/26428 , EP896072 or EP969113 ,
  • Such a hi gher resi stance can be expl ai ned through Lhc selected nickel range of between 3.5 and 4.5% by weight, as for instance subsequently demonstrated by J .
  • This improved resistance to "stress corrosion cracki ng" makes the steel of the present i nventi on particularly suitable for the manufacture of wires having a "deep drawing ratio" and which could be exposed to aggressive envi ronments a s for i nstance wires for agricultural use, electric household appliances , bicycle spokes ; wires for laundry drying frames ; wi res for a rchitecture, for meshwork and for hooks used on slate roofs .
  • the drawing of the rolls is performed by means of successive passes through the tools (drawing dies ) which deform the product, gradually decreasing its cross-section .
  • the reference stainless steel 1.4301 (AISI 304 ) is able to withstand drawing reductions of up to 88% . Beyond these values the work-hardening is such that the material breaks and is no longer capable of being deformed.
  • the stainless steel according to this invention under identical conditions , is able to withstand drawing with reductions in the cross-section in the region of 92-94% . This data is very important for detailed work where small diameters of the drawn wire are required, with the result that a certain amount of annealing during the reduction cycles may be dispensed with .
  • Table 1 shows the tensile strength and elongation at break values of the steel according to the invention for various degrees of reduction during drawing, compared with two reference steels : steel type 1.4307 with a low carbon content (about 0.02%) and steel type 1.4301 with a slightly higher carbon content (0.04%) .
  • Figure 1 shows in graph form the tensile strength values as a function of the drawing reduction for these steels
  • Figure 2 shows the same type of comparative graph relating this time to the percentage elongation at break value .
  • the work-hardening is due to the partial and progressive transformation of part of the austenite into martensite, which is the hardest component of steel .
  • a metallographic study was carried out on samples taken from materials in the annealed and work- hardened state, these revealing both the deformation of the grain, with elongation in the drawing direction, and the austenite-martensite transformation .
  • Figure 3 shows a longitudinal metallographic cross-section through the product in an ultra work- hardened state of the wire obtained with the new steel, in which the work-hardening lines due to the martensitic transformation are clearly visible .
  • Figure 4 shows the same type of cross-section carried out on a sample of the reference steel type 1.4301 (AISI 304 ) .
  • the relative magnetic permeability measures the ratio between the magnetic permeability of a material ⁇ and that of a vacuum ⁇ 0 .
  • the magnetic permeability of a material ⁇ (measured in Henry/metre [H/m] ) is defined by the ratio between the magnetic induction value B and the value of the magnetizing force H .
  • the magnetic permeability of a material basically measures the ferromagnetism, i . e . the property of a steel to react with a magnetic field of given value .
  • austenite is practically non-magnetic ( ⁇ r ⁇ l , 2 )
  • An austenitic steel in the solubilized state, and hence with a totally austenitic structure, is completely non-magnetic : when it is subj ected to a magnetic field, for example that of a magnet, it does not react .
  • An austenitic steel in the work-hardened state for example after undergoing drawing reductions , is increasingly more magnetic depending on the percentage of austenite transformed into martensite (basically dependent on the drawing reduction and the chemical composition) .
  • the magnetic permeability in a stainless steel assumes particular importance both in the case of more complex applications (e . g . solenoid valve bodies , where the part must not be influenced by the magnetic field of excitation of the valve) , but also for more straightforward applications , where recognition of the material is simply carried out by means of a magnet, as in the case of laundry drying frames sold at markets or in supermarkets : if the wire of the laundry drying rack is not attracted by the magnet, it is recognised as being austenitic stainless steel and is much more highly valued than the corresponding wire made of ferritic stainless steel or even galvanized iron, which are both highly ferromagnetic .
  • the possibility of obtaining drawn wires with high work-hardening values (required by the product itself in order to withstand the load of wet laundry) , without any significant variation in the magnetic permeability, results in the invention being particularly suitable for this type of use .
  • Socket-head cap screws (DIN 912 M5 x 12 ) : for this type of product normally a steel type 304Cu is used, with the addition of 3-4% Cu in order to improve the deformability.
  • the characteristics of the screws produced were determined by means of tensile tests carried out in accordance with the standard UNI EN ISO 3506 part 1 edition February 2000 and HV 500 microhardness tests .
  • the results of the tensile test are shown in Table
  • Figure 6 shows the microhardness values determined at various points in the longitudinal section of the screws DIN 933 M5 x 25 produced.
  • Figure 7 shows the microhardness values detected at various points of the cross-section of screws DIN 912 M5 x 12.
  • the comparisons have been made, as always , with screws made of normal steel type 1.4301 (AISI 304 ) .
  • the screws made with the steel according to the present study had a higher tensile strength of about 70 MPa in the case of hexagonal head screws and 95 MPa in the case of socket head screws : this greater difference is due to the very poor work-hardening property of the 304Cu steel used for the comparison .
  • the hardness values are about 100 HV points higher in the case of the steel according to the invention .
  • Corrosion-resistance tests were carried out using samples obtained by means of machine-tool processing of solubilized wire rod.
  • the new steel in fact has a performance perfectly in keeping with that of the reference types and only in the nitric acid test is the corrosion value slightly higher than that of the type 1.4307 micro-resulphurised steel .
  • both the steels used for comparison had an extremely low carbon content (type 1.4307 corresponds to the type AISI 304L, Low Carbon) : the new steel is therefore not affected, all other conditions being equal, by the C content which is higher than in the basic comparison steels .
  • Corrosion tests were carried out, in different work-hardening conditions , on some samples of drawn wire and drawn + solution annealed wire made from the new steel and, by way of comparison, various other qualities of stainless steel .
  • Table 4 lists the types of materials which underwent this type of test, their diameters and the associated working conditions .
  • Table 5 instead lists the tests which these samples underwent and the reference standards .
  • the behaviour of the new steel and the 1.4301 steel is instead greatly influenced by the degree of work-hardening : as known from the literature, the best corrosion resistance is obtained with the material in the solution annealed state, while it is worsened by work-hardening . It was noted, however, that the behaviour of the steel considered in this study is midway between the type 1.4301 and the type 14016.
  • test pieces After attack, all the test pieces were able to be bent through 180 ° without any signs of cracking or flaking on the surface subj ect to tensile stress .
  • the corrosion tests carried out were particularly numerous and covered all the possible ranges of applications such that it was possible to determine the characteristics of the new material with a wide series of tests .
  • the rapid hot tensile tests were carried out at a decidedly high temperature ( 900 0 C) compared to the operating temperatures normally permitted.
  • the results show that the new steel has a behaviour very similar to that of the normal reference steel, type 1.4301 , while only the type with a higher carbon content (1.4310 ) has a slightly higher hot strength, even though it as of the same order of magnitude .
  • the basic stainless steel 1.4301 (AISI 304 ) is resistant for fairly long periods in a high temperature oxidising environment : in particular the most common uses for this material are those which envisage stays in air up to about 500 0 C .
  • the new steel was also tested for its resistance to temperatures higher than room temperature by means of air heating tests inside a muffle furnace . The results can be seen in Figure 10.
  • the resistance was evaluated by measuring the depth of surface oxidation, i . e . the loss of diameter as a result of oxidation . It is possible to note that the new steel behaves in a manner perfectly similar to that of the of the various types with a high nickel content up to a temperature of higher than 800 0 C . As mentioned, the temperatures commonly used for normal austenitic steels (belonging to the family of 1.4301 steel) are about 500 0 C, while for higher temperatures refractory alloys (with high nickel contents ) or superalloys (nickel based alloys , not belonging to the family of steels ) are used. The new steel is therefore perfectly utilisable at the same temperatures at which the basic type is used since there is no variation in its characteristics .
  • the new stainless steel according to the present invention with a low nickel content possesses technical characteristics similar or comparable to those of steel type 1.4301.
  • the main advantage of this new steel from the commercial point of view is its lesser dependency on the nickel market and therefore its greater stability from a price point of view . From the technical point of view, the main advantage is the extremely high suitability for drawing which allows a large reduction during drawing and a small number of intermediate annealing operations .
  • the new material is particularly suitable as a substitute for traditional types of steel in certain specific applications

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

L’invention concerne un nouvel acier inoxydable austénitique ayant la composition en poids suivante : 0,03 % < carbone < 0,07 %, 7,0 % < manganèse < 8,5 %, 0,3 % < silicium < 0,7 %, soufre < 0,030 %, phosphore < 0,045 %, 16,5 % < chrome < 18,0 %, 3,5 % < nickel < 4,5 %, 0,1 % < molybdène < 0,5 %, 1,0 % < cuivre < 3,0 %, 0,1 % < azote < 0,3 %, la différence étant constituée de fer et d’impuretés courantes de procédé. L'acier obtenu ainsi possède une combinaison optimale de propriétés de résistance à la corrosion, d’aptitude au formage et d’écrouissage, qui le rendent approprié en tant que produit de remplacement d’un acier classique de type 1.4301 dans diverses applications spécifiques.
PCT/EP2006/050923 2005-02-14 2006-02-14 Acier inoxydable austenitique WO2006084919A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU2006212194A AU2006212194B2 (en) 2005-02-14 2006-02-14 Austenitic stainless steel
EP06708260A EP1851351B1 (fr) 2005-02-14 2006-02-14 Acier inoxidable austénitique
US11/815,303 US20080206088A1 (en) 2005-02-14 2006-02-14 Austenitic Stainless Steel
ES06708260T ES2390678T3 (es) 2005-02-14 2006-02-14 Acero inoxidable austenítico
CA002597750A CA2597750A1 (fr) 2005-02-14 2006-02-14 Acier inoxydable austenitique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05425070.9 2005-02-14
EP05425070A EP1690957A1 (fr) 2005-02-14 2005-02-14 Acier inoxidable austénitique

Publications (1)

Publication Number Publication Date
WO2006084919A1 true WO2006084919A1 (fr) 2006-08-17

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Family Applications (1)

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PCT/EP2006/050923 WO2006084919A1 (fr) 2005-02-14 2006-02-14 Acier inoxydable austenitique

Country Status (7)

Country Link
US (1) US20080206088A1 (fr)
EP (2) EP1690957A1 (fr)
AU (1) AU2006212194B2 (fr)
CA (1) CA2597750A1 (fr)
ES (1) ES2390678T3 (fr)
WO (1) WO2006084919A1 (fr)
ZA (1) ZA200705778B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8540933B2 (en) 2009-01-30 2013-09-24 Sandvik Intellectual Property Ab Stainless austenitic low Ni steel alloy

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US20080067276A1 (en) * 2006-04-04 2008-03-20 Trw Automotive Gmbh Force limiter for a belt retractor and method for manufacturing such a force limiter
WO2008049535A2 (fr) * 2006-10-24 2008-05-02 Khs Ag Remplisseuse
CN100503871C (zh) * 2007-08-15 2009-06-24 金雹峰 一种铁合金
US8313691B2 (en) 2007-11-29 2012-11-20 Ati Properties, Inc. Lean austenitic stainless steel
DK2245202T3 (da) 2007-12-20 2011-12-19 Ati Properties Inc Austenitisk rustfrit stål med lavt nikkelindhold indeholdende stabiliserende grundstoffer
US8337749B2 (en) 2007-12-20 2012-12-25 Ati Properties, Inc. Lean austenitic stainless steel
EP2229463B1 (fr) 2007-12-20 2017-09-06 ATI Properties LLC Acier inoxydable austénitique pauvre résistant à la corrosion
DE102008040545A1 (de) * 2008-07-18 2010-01-21 Robert Bosch Gmbh Metallisches Verbundbauteil, insbesondere für ein elektromagnetisches Ventil
FR2938563B1 (fr) * 2008-11-14 2013-02-01 Tournus Equipement Lave-mains
US8182963B2 (en) * 2009-07-10 2012-05-22 GM Global Technology Operations LLC Low-cost manganese-stabilized austenitic stainless steel alloys, bipolar plates comprising the alloys, and fuel cell systems comprising the bipolar plates
CN102337481B (zh) * 2010-07-20 2013-11-13 宝山钢铁股份有限公司 一种耐蚀性优良的含钼节镍奥氏体不锈钢及其制造方法
CN102605291A (zh) * 2012-03-27 2012-07-25 宝山钢铁股份有限公司 一种加工性能优良的节镍奥氏体不锈钢冷轧板及其制造方法
UA111115C2 (uk) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. Рентабельна феритна нержавіюча сталь
EP3360641A1 (fr) * 2017-02-09 2018-08-15 Oerlikon Schweisstechnik GmbH Flux de soudage aggloméré et procédé de soudage à l'arc submergé d'acier inoxydable austénitique en utilisant ce flux

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EP0694626A1 (fr) * 1994-07-26 1996-01-31 Acerinox S.A. Acier inoxydable austénitique à basse teneur en nickel
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WO2000026428A1 (fr) * 1998-11-02 2000-05-11 Crs Holdings, Inc. Acier inoxydable austenitique cr-mn-ni-cu
US6274084B1 (en) * 1998-07-02 2001-08-14 Ugine Sa Corrosion-resistant low-nickel austenitic stainless steel
GB2359095A (en) * 2000-02-14 2001-08-15 Jindal Strips Ltd Stainless steel

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US4568387A (en) * 1984-07-03 1986-02-04 Allegheny Ludlum Steel Corporation Austenitic stainless steel for low temperature service
EP0593158A1 (fr) * 1992-10-13 1994-04-20 Allegheny Ludlum Corporation Acier austénitique inoxydable du type chrome-nickel-manganèse et contenant en plus de cuivre et de l'azote
EP0694626A1 (fr) * 1994-07-26 1996-01-31 Acerinox S.A. Acier inoxydable austénitique à basse teneur en nickel
ES2142756A1 (es) * 1998-04-22 2000-04-16 Acerinox Sa Acero inoxidable austenitico con bajo contenido en niquel.
US6274084B1 (en) * 1998-07-02 2001-08-14 Ugine Sa Corrosion-resistant low-nickel austenitic stainless steel
WO2000026428A1 (fr) * 1998-11-02 2000-05-11 Crs Holdings, Inc. Acier inoxydable austenitique cr-mn-ni-cu
GB2359095A (en) * 2000-02-14 2001-08-15 Jindal Strips Ltd Stainless steel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8540933B2 (en) 2009-01-30 2013-09-24 Sandvik Intellectual Property Ab Stainless austenitic low Ni steel alloy

Also Published As

Publication number Publication date
US20080206088A1 (en) 2008-08-28
EP1690957A1 (fr) 2006-08-16
ZA200705778B (en) 2008-11-26
EP1851351B1 (fr) 2012-08-15
CA2597750A1 (fr) 2006-08-17
EP1851351A1 (fr) 2007-11-07
ES2390678T3 (es) 2012-11-15
AU2006212194A1 (en) 2006-08-17
AU2006212194B2 (en) 2010-09-09

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