EP0457658B1 - Stainless steel for use in native water environments - Google Patents
Stainless steel for use in native water environments Download PDFInfo
- Publication number
- EP0457658B1 EP0457658B1 EP91401215A EP91401215A EP0457658B1 EP 0457658 B1 EP0457658 B1 EP 0457658B1 EP 91401215 A EP91401215 A EP 91401215A EP 91401215 A EP91401215 A EP 91401215A EP 0457658 B1 EP0457658 B1 EP 0457658B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stainless steel
- tin
- equal
- nickel
- water environments
- 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.)
- Expired - Lifetime
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 10
- 239000010935 stainless steel Substances 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000013535 sea water Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000003416 augmentation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005258 corrosion kinetic Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
Definitions
- the present invention relates to stainless steel for use in natural aquatic environments: fresh water, brackish water and marine environments.
- FR-A-2 591 612 discloses an austenitic stainless steel comprising at least one additional element chosen from tin, germanium and antimony at a total content ranging from more than 0.02% by weight to 1 % in weight.
- This steel comprises by weight: 10 to 28% nickel, 1 to 3% molybdenum, 8 to 18% chromium, up to 0.12% carbon, up to 2% manganese, up to 1% silicon, 0 to 0.03% sulfur, 0 to 0.2% phosphorus, 0 to 0.65% titanium, 0 to 0.008% boron, more than 0.02 to 1 % in total of at least one element chosen from tin, germanium and antimony, the remainder consisting of iron and accidental impurities.
- the object of the present invention is to remedy these drawbacks by combating the harmful effects of the biological veil, by introducing into the steel elements "poisons" for the living organisms constituting this veil.
- the electrochemical measurements and the biofilm analyzes carried out within the framework of the present invention show that, in marine environment, the effect of the colonization of the surface on the electrochemical phenomena is not due to the haze which forms during the first stages of colonization, but is essentially linked to the change in the composition of the biological veil which occurs after ten days of immersion of stainless steel.
- tin at a content of between 0.5 and 4% by mass in a stainless steel containing in particular chromium and nickel significantly reduces the harmful effect of the biological veil.
- tin is due to a fungicidal action which delays and limits the formation of the biological veil which is the main responsible for the aggressiveness of sea water.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
- Prevention Of Electric Corrosion (AREA)
Description
La présente invention concerne un acier inoxydable pour une utilisation en milieux aquatiques naturels : eaux douces, saumâtres et milieux marins.The present invention relates to stainless steel for use in natural aquatic environments: fresh water, brackish water and marine environments.
On sait que l'eau de mer "vivante" est un milieu particulièrement agressif pour Les aciers inoxydables qui peuvent y subir des corrosions sévères par piqûre ou par crevasse.We know that "living" seawater is a particularly aggressive medium for stainless steels which can undergo severe corrosion by puncture or crevice.
Cette agressivité est beaucoup plus forte que celle de l'eau de mer "morte" ou synthetique. Des phénomènes électrochimiques spécifiques expliquent L'agressivité particulière de l'eau de mer "vivante".This aggressiveness is much stronger than that of "dead" or synthetic sea water. Specific electrochemical phenomena explain the particular aggressiveness of "living" seawater.
En effet, ces phénomènes qui sont liés à la formation et au développement d'un voile biologique à la surface des matériaux immergés en eau de mer, se traduisent dans tous les cas par une montée initiale du potentiel électrochimique des aciers inoxydables, qui peut atteindre des valeurs élevées selon la nuance de l'acier, ce qui suffit le plus souvent à expliquer l'amorçage de la corrosion localisée.Indeed, these phenomena which are linked to the formation and development of a biological veil on the surface of materials submerged in seawater, are in all cases reflected by an initial rise in the electrochemical potential of stainless steels, which can reach high values depending on the grade of steel, which is most often enough to explain the initiation of localized corrosion.
Jusqu'à présent, pour lutter contre l'effet spécifique du voile biologique sur la corrosion des aciers inoxydables, soit on augmente leur teneur en élément d'alliage, notamment le chrome et le molybdéne, ce qui s'avère très couteux, ou soit on traite l'eau de mer par chloration, ce qui, d'une part, n'est possible que pour des circuits fermés ou avec de faibles débits, et d'autre part, s'avère dangereux car un surdosage conduit à des montées de potentiels néfastes.Up to now, to combat the specific effect of the biological veil on the corrosion of stainless steels, either their content of alloying element, in particular chromium and molybdenum, is increased, which turns out to be very expensive, or either seawater is treated by chlorination, which, on the one hand, is only possible for closed circuits or with low flow rates, and on the other hand, is dangerous because an overdose leads to climbs harmful potentials.
On connaît dans le brevet FR-A-2 591 612 un acier inoxydable austénitique comprenant au moins un élément additionnel choisi parmi l'étain, le germanium et l'antimoine à une teneur totale allant de plus de 0,02% en poids à 1% en poids.FR-A-2 591 612 discloses an austenitic stainless steel comprising at least one additional element chosen from tin, germanium and antimony at a total content ranging from more than 0.02% by weight to 1 % in weight.
Cet acier comprend en poids : 10 à 28% de nickel, 1 à 3% de molybdène, 8 à 18% de chrome, jusqu'à 0,12% de carbone, jusqu'à 2% de manganèse, jusqu'à 1% de silicium, de 0 à 0,03% de soufre, de 0 à 0,2% de phosphore, de 0 à 0,65% de titane, de 0 à 0,008% de bore, plus de 0,02 jusqu'à 1% au total d'au moins un élément choisi parmi l'étain, le germanium et l'antimoine, le reste étant constitué par du fer et des impuretés accidentelles.This steel comprises by weight: 10 to 28% nickel, 1 to 3% molybdenum, 8 to 18% chromium, up to 0.12% carbon, up to 2% manganese, up to 1% silicon, 0 to 0.03% sulfur, 0 to 0.2% phosphorus, 0 to 0.65% titanium, 0 to 0.008% boron, more than 0.02 to 1 % in total of at least one element chosen from tin, germanium and antimony, the remainder consisting of iron and accidental impurities.
La présente invention a pour but de remédier à ces inconvénients en luttant contre les effets néfastes du voile biologique, par l'introduction dans l'acier d'éléments "poisons" pour les organismes vivants constituant ce voile.The object of the present invention is to remedy these drawbacks by combating the harmful effects of the biological veil, by introducing into the steel elements "poisons" for the living organisms constituting this veil.
L'acier inoxydable seLon l'invention est caractérisé en ce que sa composition pondérale est la suivante :
- 0,5 à 4% d'étain,
- 0,010 à 0,040% de carbone,
- 0,050 à 5% de manganèse,
- 0,050 à 1% de silicium,
- 16 à 27% de chrome,
- 0 à 25% de nickel,
- 0 à 0,40% d'azote,
- 0 à 6% de molybdéne,
- 0 à 3% de cuivre
- étain inférieur ou égal à 1%,
- manganèse inférieur ou égal à 2%,
- chrome inférieur ou égal à 18%,
- nickel supérieur ou égal à 10%,
- molybdène compris entre 1 et 3%.
- 0.5 to 4% tin,
- 0.010 to 0.040% carbon,
- 0.050 to 5% manganese,
- 0.050 to 1% silicon,
- 16 to 27% chromium,
- 0 to 25% nickel,
- 0 to 0.40% nitrogen,
- 0 to 6% molybdenum,
- 0 to 3% copper
- tin less than or equal to 1%,
- manganese less than or equal to 2%,
- chromium less than or equal to 18%,
- nickel greater than or equal to 10%,
- molybdenum between 1 and 3%.
Les mesures électrochimiques et les analyses du biofilm effectuées dans le cadre de la présente invention montrent que, en milieu marin, l'effet de la colonisation de la surface sur les phénomènes électrochimiques n'est pas dû au voile qui se forme pendant les premiers stades de la colonisation, mais est essentiellement lié au changement dans la composition du voile biologique qui se produit après une dizaine de jours d'immersion de l'acier inoxydable.The electrochemical measurements and the biofilm analyzes carried out within the framework of the present invention show that, in marine environment, the effect of the colonization of the surface on the electrochemical phenomena is not due to the haze which forms during the first stages of colonization, but is essentially linked to the change in the composition of the biological veil which occurs after ten days of immersion of stainless steel.
Les comportements des aciers en eau de mer "vivante" et en eau de mer "synthétique" sont en effet peut différents dans les premiers stades de l'immersion.The behavior of steels in "living" seawater and in "synthetic" seawater is indeed quite different in the early stages of immersion.
Par contre, au bout d'un certain temps d'immersion, les évènements suivants se produisent:
- une modification de la composition du voile biologique,
- une augmentation du potentiel de corrosion,
- une dépolarisation des réactions cathodiques,
- une augmentation importante des courants anodiques dans le domaine de passivité,
- et une chute de la valeur de la résistance de transfert à des valeurs très faibles qui semblent peu dépendantes de la nuance et de sa cinétique de corrosion.
- a change in the composition of the biological veil,
- increased corrosion potential,
- depolarization of reactions cathodic,
- a significant increase in anode currents in the passivity domain,
- and a drop in the value of the transfer resistance to very low values which seem to be little dependent on the grade and its corrosion kinetics.
L'addition d'étain selon une teneur comprise entre 0,5 et 4% en masse dans un acier inoxydable contenant notamment du chrome et du nickel diminue d'une façon significative l'effet néfaste du voile biologique.The addition of tin at a content of between 0.5 and 4% by mass in a stainless steel containing in particular chromium and nickel significantly reduces the harmful effect of the biological veil.
En effet, les essais ont montré que l'addition d'étain limite le processus de montée du potentiel de corrosion et modifie la colonisation des surfaces par le voile biolgique.Indeed, tests have shown that the addition of tin limits the process of rising corrosion potential and modifies the colonization of surfaces by the biological veil.
En particulier, le développement des espèces responsables de l'agressivité du voile biologique, qui apparaissent après une dizaine de jours d'immersion, est fortement inhibé en présence d'étain dans l'acier inoxydable.In particular, the development of the species responsible for the aggressiveness of the biological veil, which appear after ten days of immersion, is strongly inhibited in the presence of tin in stainless steel.
L'effet favorable de l'étain est dû à une action fongicide qui retarde et limite la formation du voile biologique qui est le principal responsable de l'agressivité de l'eau de mer.The favorable effect of tin is due to a fungicidal action which delays and limits the formation of the biological veil which is the main responsible for the aggressiveness of sea water.
Claims (1)
- Stainless steel for use in natural aquatic media, characterised in that its composition by weight is as follows:0.5 to 4% tin,0.010 to 0.040 % carbon,0,050 to 5 % manganese,0.050 to 1 % silicon,16 to 27 % chromium,0 to 25 % nickel,0 to 0.40 % nitrogen,0 to 6 % molybdenum,0 to 3 % copper,but excluding the following composition:tin less than or equal to 1 %,manganese less than or equal to 2 %,chromium less than or equal to 18 %,nickel greater than or equal to 10 %,molybdenum between 1 and 3 %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9006170 | 1990-05-17 | ||
| FR9006170A FR2662181B1 (en) | 1990-05-17 | 1990-05-17 | STAINLESS STEEL FOR USE IN NATURAL AQUATIC MEDIA. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0457658A1 EP0457658A1 (en) | 1991-11-21 |
| EP0457658B1 true EP0457658B1 (en) | 1996-03-20 |
Family
ID=9396699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91401215A Expired - Lifetime EP0457658B1 (en) | 1990-05-17 | 1991-05-07 | Stainless steel for use in native water environments |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0457658B1 (en) |
| DE (1) | DE69118015T2 (en) |
| FR (1) | FR2662181B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI460293B (en) * | 2011-10-21 | 2014-11-11 | Nippon Steel & Sumikin Sst | Duplex stainless steel, duplex stainless steel slab, and duplex stainless steel material |
| JP5873406B2 (en) * | 2012-08-10 | 2016-03-01 | Ｋｙｂ株式会社 | Shock absorber |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE731409C (en) * | 1939-02-01 | 1943-02-09 | Krupp Ag | Use of iron-chromium alloys for objects subject to magnetic stress |
| DE764286C (en) * | 1940-04-25 | 1952-11-24 | Fried Krupp A G | Use of iron-chromium alloys as a material for magnetically stressed objects |
| US4101347A (en) * | 1977-05-06 | 1978-07-18 | Daido Tokushuko Kabushiki Kaisha | Ferrite-austenite stainless steel castings having an improved erosion-corrosion resistance |
| JPS5910494A (en) * | 1982-07-12 | 1984-01-19 | Kawasaki Steel Corp | Weld metal of austenitic stainless steel having excellent resistance to crevice corrosion |
| FR2591612A1 (en) * | 1985-12-17 | 1987-06-19 | Commissariat Energie Atomique | AUSTENITIC STAINLESS STEEL, PARTICULARLY USEFUL AS SHEATHING MATERIAL IN FAST NEUTRON REACTORS. |
| KR910003482B1 (en) * | 1987-04-30 | 1991-06-01 | 산요덴끼 가부시끼가이샤 | Ni-cr stainless steel having improved corrosion resistance and machinability |
-
1990
- 1990-05-17 FR FR9006170A patent/FR2662181B1/en not_active Expired - Fee Related
-
1991
- 1991-05-07 DE DE1991618015 patent/DE69118015T2/en not_active Expired - Fee Related
- 1991-05-07 EP EP91401215A patent/EP0457658B1/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| J. P. Audouard, G. Hernandez, J. Guezennec, 8th Intern. Congress on Marine Corrosion and Fouling, September 21-25, 1992 Taranto, Italy, * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69118015T2 (en) | 1996-09-05 |
| EP0457658A1 (en) | 1991-11-21 |
| FR2662181A1 (en) | 1991-11-22 |
| DE69118015D1 (en) | 1996-04-25 |
| FR2662181B1 (en) | 1993-07-16 |
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