EP1966407A1 - Spring steel, method for producing a spring using said steel and a spring made from such steel - Google Patents
Spring steel, method for producing a spring using said steel and a spring made from such steelInfo
- Publication number
- EP1966407A1 EP1966407A1 EP06841905A EP06841905A EP1966407A1 EP 1966407 A1 EP1966407 A1 EP 1966407A1 EP 06841905 A EP06841905 A EP 06841905A EP 06841905 A EP06841905 A EP 06841905A EP 1966407 A1 EP1966407 A1 EP 1966407A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel
- traces
- spring
- fatigue
- hardness
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 131
- 239000010959 steel Substances 0.000 title claims abstract description 131
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229910000639 Spring steel Inorganic materials 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims description 40
- 238000005260 corrosion Methods 0.000 claims description 40
- 238000010791 quenching Methods 0.000 claims description 31
- 230000000171 quenching effect Effects 0.000 claims description 31
- 238000005496 tempering Methods 0.000 claims description 20
- 150000004767 nitrides Chemical class 0.000 claims description 15
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000009749 continuous casting Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000003303 reheating Methods 0.000 claims description 2
- IOUVKUPGCMBWBT-QNDFHXLGSA-N phlorizin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 IOUVKUPGCMBWBT-QNDFHXLGSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052719 titanium Inorganic materials 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011651 chromium Substances 0.000 abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052804 chromium Inorganic materials 0.000 abstract description 14
- 239000011572 manganese Substances 0.000 abstract description 14
- 239000010955 niobium Substances 0.000 abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011733 molybdenum Substances 0.000 abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052748 manganese Inorganic materials 0.000 abstract description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 206010016256 fatigue Diseases 0.000 description 68
- 235000019589 hardness Nutrition 0.000 description 48
- 229910052720 vanadium Inorganic materials 0.000 description 19
- 230000007547 defect Effects 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 150000001247 metal acetylides Chemical class 0.000 description 9
- -1 chromium carbides Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000009661 fatigue test Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 241000237858 Gastropoda Species 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 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 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RIDBVMYKOLOOOM-UHFFFAOYSA-I [V+5].N(=O)[O-].N(=O)[O-].N(=O)[O-].N(=O)[O-].N(=O)[O-] Chemical class [V+5].N(=O)[O-].N(=O)[O-].N(=O)[O-].N(=O)[O-].N(=O)[O-] RIDBVMYKOLOOOM-UHFFFAOYSA-I 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 208000016254 weariness Diseases 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- 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
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
-
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
-
- 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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- 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
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
Definitions
- the invention relates to iron and steel, and more specifically to the field of spring steels.
- FR-A-2,740,476 and JP-A-3,474,373 disclose a spring steel grade having good resistance to embrittlement by hydrogen and good strength. in the case of fatigue, in which the inclusions of carbonitrosulfides comprising at least one of titanium, niobium, zirconium, tantalum or hafnium, are controlled so as to have a reduced average size, less than 5 ⁇ m in diameter, and be very numerous (10,000 or more on a section of cut).
- this type of steel leads, after quenching and tempering according to the industrial process of manufacturing springs, to a hardness level of only 50HRC or a little more, corresponding to a tensile strength of 1700 MPa or a little more , but hardly greater than 1900MPa, corresponding to a hardness of 53.5HRC. Because of this moderate hardness level, this steel has only moderate scuff resistance, and steel with higher tensile strength is required to improve the scuff resistance. Thus, such a steel does not provide an excellent compromise between a high strength, which would be greater than 2100MPa, a hardness that would be greater than 55HRC, a high resistance to fatigue in the air and a resistance to fatigue under corrosion. less equivalent, and even superior, to what is necessary for springs.
- the object of the invention is to propose means for producing, simultaneously with known spring steels, an increase in the hardness and the tensile strength of the springs, the higher fatigue properties in the air, the properties in corrosion fatigue at least equivalent and even higher, a resistance to slackening of the upper spring and less sensitivity to surface defects that can be generated during the twisting of the spring.
- the subject of the invention is a spring steel with high fatigue strength in air and under corrosion and with high resistance to cyclic wear, of composition, in weight percentages:
- Ceq% [C%] + 0.12 [Si%] + 0.17 [Mn%] - 0.1 [Ni%] + 0.13 [Cr%] - 0.24 [V%] is between 0.80 and 1.00%, and whose hardness, after quenching and tempering, is greater than or equal to 55HRC.
- 0.5mm of the surface of a bar, or a wire rod, a piece or a spring on 100mm 2 of the cutting surface is preferably less than or equal to 20 ⁇ m, said size being the square root of the surface inclusions considered as squares.
- the composition of the steel is:
- N 0.0020 - 0.0110% the rest being iron and impurities resulting from the elaboration.
- the invention also relates to a method of manufacturing a spring steel with high fatigue resistance in air and under corrosion and with high resistance to cyclic scumming, according to which a liquid steel is produced in a converter or an electric furnace, its composition is adjusted, it is cast in the form of blooms or continuous casting billets or ingots which are allowed to cool to room temperature, it is rolled in the form of bars, wire rods or slugs and it is transformed into springs, characterized in that:
- the steel is of the previous type; blooms, billets or ingots are imposed during or after their solidification, a minimum average cooling rate of 0.3 ° C / s between 1450 and 1300 0 C;
- the invention also relates to springs made of such steel, and springs made of a steel obtained by the above method.
- FIG. 1 shows the results of hardness and cyclic wear tests for steels according to the invention and reference steels;
- FIG. 2 which shows the results of fatigue tests in the air as a function of the hardness of the steel, for steels according to the invention and reference steels;
- FIG. 3 which shows the results of Charpy resilience tests as a function of the hardness of the steel, for steels according to the invention and reference steels;
- - Figure 4 which shows the results of corrosion fatigue tests as a function of the hardness of the steel for steels according to the invention and reference steels.
- the composition of the steel according to the invention must meet the following requirements.
- the carbon content must be between 0.45 and 0.7%. Carbon, after quenching and tempering, increases the tensile strength and hardness of steel. If the carbon content is less than 0.45%, in the temperature range usually used for the manufacture of the springs, no quenching and tempering treatment leads to a high strength and high hardness of the steel described in the invention. On the other hand, if the carbon content exceeds 0.7% or even 0.65%, coarse and very hard carbides combined with chromium, molybdenum and vanadium may remain undissolved during austenitization performed prior to quenching, and can significantly affect fatigue life in air, fatigue resistance under corrosion and also toughness. As a result carbon contents above 0.7% are to be excluded. Preferably, they should not exceed 0.65%.
- the silicon content is between 1.65 and 2.5%. Silicon is an important element for ensuring, thanks to its presence in solid solution, high levels of strength and hardness, as well as high Ceq equivalent carbon and resistance values. To obtain the values of tensile strength and hardness of the steel according to the invention, the Silicon content should not be less than 1.65%. In addition, silicon contributes at least partially to the deoxidation of the steel. If its content exceeds 2.5% or even 2.2%, the oxygen content of the steel may be, by thermodynamic reaction, greater than 0.0020 or even 0.0025%. This reflects the formation of oxides of various compositions that are detrimental to the fatigue resistance in the air.
- silicon contents greater than 2.5% segregations of various combined elements such as manganese, chromium or the like may occur during solidification after casting. These segregations are very damaging to fatigue behavior in the air and resistance to fatigue under corrosion.
- silicon content greater than 2.5% the decarburization on the surface of the bars or wires intended to form the springs becomes too important for the properties in service of the spring. This is why the silicon content should not exceed 2.5%, and preferably 2.2%.
- the manganese content is between 0.20 and 0.75%.
- Manganese in combination with residual sulfur between trace amounts and 0.015%, must be added at a level at least greater than ten times the sulfur content so as to avoid the formation of iron sulphides which are extremely damaging to the laminability of the iron. 'steel. As a result, a minimum manganese content of 0.20% is required.
- manganese contributes to solid solution hardening during the quenching of steel, in the same way as nickel, chromium, molybdenum and vanadium, which makes it possible to obtain the values of tensile strength and high hardness and equivalent carbon Ceq values of the steel according to the invention.
- the chromium content must be between 0.60 and 2%, and preferably between 0.80 and 1.70%. Chromium is added to obtain, in solid solution after austenitization, quenching and tempering, high values of resistance tensile strength and hardness, and to help achieve the equivalent value of carbon Ceq, but also to increase resistance to fatigue under corrosion.
- the chromium content should be at least 0.60%, and preferably at least 0.80%. Above 2%, or even 1.7%, particular, coarse and very hard chromium carbides, in combination with vanadium and molybdenum, may remain after the austenitization treatment performed prior to quenching. Such carbides greatly affect the fatigue resistance in the air. This is why the chromium content must not exceed 2%.
- the nickel content is between 0.15 and 1%. Nickel is added to increase the hardenability of the steel, as well as the tensile strength and hardness after quenching and tempering.
- nickel contributes to the hardening of steel, just like chromium, molybdenum and vanadium, without the formation of particular coarse and hard carbides that would not be dissolved during the austenitization performed before quenching. and could be harmful to the fatigue resistance in the air. It also makes it possible to adjust the equivalent carbon between 0.8 and 1% in the steel according to the invention as necessary.
- nickel improves fatigue resistance under corrosion. To ensure that these effects are significant, the nickel content should not be less than 0.15%. On the contrary, above 1% or even 0.80%, nickel can lead to a too high residual austenite content, the presence of which is very damaging to the resistance to fatigue under corrosion. In addition, high levels of nickel significantly increase the cost of steel. For all these reasons, the nickel content should not exceed 1%, better 0.80%
- the molybdenum content must be between traces and 1%. Like chromium, molybdenum increases the hardenability of steel, as does its strength. In addition it has a low oxidation potential. For these two reasons, molybdenum is conducive to fatigue resistance in the air and under corrosion. But for contents higher than 1%, even 0.80%, coarse and very hard molybdenum carbides may remain, possibly combined with vanadium and chromium, after austenitization prior to quenching. These Particular carbides are very damaging to fatigue resistance in the air. Finally, addition of molybdenum exceeding 1% unnecessarily increases the cost of steel. This is why the molybdenum content should not exceed 1%, better 0.80%.
- the vanadium content should be between 0.003 and 0.8%.
- Vanadium is an element that increases quenchability, tensile strength and hardness after quenching and tempering.
- vanadium makes it possible to form a large number of fine vanadium or vanadium nitrites and submicroscopic titanium to refine the grain and increase the levels of tensile strength and hardness. , thanks to a structural hardening.
- vanadium must be present with a minimum content of 0.003%. But this element is expensive and must be kept close to this lower limit if a compromise between the cost of elaboration and the refining of the grain is sought.
- the vanadium should not exceed 0.8% and preferably 0.5%, because above this value a precipitation of carbides containing coarse and very hard vanadium combined with chromium and molybdenum can remain in the undissolved state during the austenitization which takes place before quenching. This can be very unfavorable to the resistance to air fatigue, for the high values of strength and hardness of the steel according to the invention. And an addition of vanadium above 0.8% unnecessarily increases the cost of steel.
- the copper content must be between 0.10 and 1%. Copper is an element that hardens steel when in solid solution after tempering and tempering treatment. Thus, it can be added with other elements contributing to increase the strength and hardness of the steel. Since it does not combine with carbon, it provides hardening of the steel without formation of hard and coarse carbides damaging the fatigue resistance in the air. From the electrochemical point of view, its passivation potential is higher than that of iron and, consequently, it is favorable to the resistance to corrosion fatigue of steel. To ensure that its effects are significant, the copper content should not be less than 0.10%. On the contrary, for contents above 1% even 0.90%, copper has a very damaging influence on the hot rolling behavior. This is why the copper content should not exceed 1%, better 0.90%.
- the titanium content should be between 0.020 and 0.2%. Titanium is added to form, in combination with nitrogen, or even carbon and / or vanadium, fine submicroscopic nitrides or carbonitrides to refine the austenitic grain during the austenitization treatment that takes place before quenching. Thus, it increases the surface of the grain boundaries in the steel, thus leading to a reduction in the amount of unavoidable impurities segregated at grain boundaries, such as phosphorus. Such intergranular segregation would be very detrimental to toughness and fatigue resistance in the air if present at high concentrations per unit area at the grain boundaries.
- titanium leads to the formation of other nitrides or fine carbonitrides producing an irreversible trapping effect of certain elements, such as the hydrogen formed during corrosion reactions, which can be extremely damaging to fatigue resistance under corrosion.
- the titanium content should not be less than 0.020%.
- above 0.2% or even 0.15% titanium can lead to the formation of coarse and hard nitrides or carbonitrides, very damaging to the resistance to fatigue in the air. This last effect is even more damaging to the high levels of tensile strength and hardness of the steel according to the invention.
- the titanium content should not exceed 0.2%, better 0.15%.
- niobium content must be between traces and 0.2%.
- Niobium is added to form, in combination with carbon and nitrogen, extremely fine submicroscopic precipitates of nitrides and / or carbides and / or carbonitrides which allow, especially when the aluminum content is low (0.002% by example), to complete refinement of the austenitic grain during the austenitization treatment performed before quenching.
- niobium increases the surface of grain boundaries in steel, and contributes to the same favorable effect as titanium with respect to embrittlement. grain boundaries by unavoidable impurities such as phosphorus, the effect of which is very damaging to the tenacity and resistance to fatigue under corrosion.
- niobium nitrides or carbonitrides contribute to the hardening of the steel by structural hardening.
- the niobium content must not exceed 0.2% or even 0.15%, so that the nitrides or carbonitrides remain very fine, to ensure refinement of the austenitic grain and avoid the formation of cracks or crevices during rolling. hot.
- the niobium content should not exceed 0.2%, better still 0.15%.
- the aluminum content must be between 0.002 and 0.050%.
- Aluminum can be added to complete the deoxidation of the steel and obtain oxygen levels as low as possible, and in any case less than 0.0020% in the steel according to the invention.
- aluminum contributes to refinement of the grain by the formation of submicroscopic nitrides.
- an aluminum content of not less than 0.002% is required.
- an aluminum content exceeding 0.05% can lead to the presence of large isolated inclusions or to finer but hard and angular aluminates, in the form of long strings, damaging to the fatigue life in the air and cleanliness of the steel. Therefore, the aluminum content must not exceed 0.05%.
- the phosphorus content must be between traces and 0.015%.
- Phosphorus is an inevitable impurity in steel.
- elements such as chromium or manganese with the former austenitic grain boundaries. This results in a reduction of the cohesion of the grain boundaries and an intergranular embrittlement which is very damaging to the tenacity and to the resistance to fatigue in the air. These effects are even more damaging to the high tensile strengths and hardness required for the steels according to the invention.
- the phosphorus content In order to simultaneously obtain a high tensile strength and a high hardness of the spring steel and a good resistance to fatigue in the air and fatigue under corrosion, the phosphorus content must be as low as possible and should not exceed 0.015%, preferably 0.010%.
- the sulfur content is between traces and 0.015%. Sulfur is an inevitable impurity in steels. Its content should be as low as possible, between traces and 0.015%, and preferably not more than 0.010%. It is thus desired to avoid the presence of sulfides that are unfavorable to the resistance to fatigue under corrosion and to the resistance to fatigue in the air, for the high values of strength and hardness of the steel according to the invention.
- the oxygen content must be between traces and 0.0020%.
- Oxygen is also an inevitable impurity in steels. Combined with deoxidizing elements, oxygen can lead to the appearance of coarse inclusions, isolated, very hard and angular, or to thinner inclusions but in the form of long chains which are very damaging to the fatigue resistance in the air. These effects are even more damaging to the high values of tensile strength and hardness of the steels according to the invention. For these reasons, in order to ensure a good compromise between high tensile strength and hardness and high resistance to fatigue in the air and fatigue under corrosion for the steel according to the invention, the oxygen content must not exceed 0.0020%.
- the nitrogen content must be between 0.0020 and 0.0110%.
- the nitrogen must be controlled in this range so as to form, in combination with titanium, niobium, aluminum or vanadium very fine nitrides, carbides or carbonitrides submicroscopic sufficient, allowing a grain refinement.
- the minimum nitrogen content should be 0.0020%. Its content must not exceed 0,0110% so as to avoid the formation of coarse and hard titanium nitrides or carbonitrides larger than 20 ⁇ m, observed at 1.5 mm + 0.5 mm from the surface of the bars or wire rods used to the manufacture of springs. This location is the most critical location for fatigue loading of springs.
- such nitrides or carbonitrides of large size are very unfavorable to the resistance to fatigue in the air for the high values of strength and hardness of the steels according to the invention, given that during fatigue tests in the air, spring break occurs at the location of such large inclusions precisely located in the vicinity of the surface of the springs as mentioned, when these inclusions are present.
- inclusions are considered squares and their size is equal to the square root of their surface.
- a non-limiting example of a process for producing a steel according to the invention is as follows.
- the liquid steel is produced either in a converter or in an electric furnace and then undergoes a pocket metallurgy treatment during which alloying element additions and deoxidation are performed, and in general all secondary metallurgy operations.
- a steel having the composition according to the invention and avoiding the formation of complex sulfides or "carbonitrosulfides" of elements such as titanium and / or niobium and / or vanadium.
- complex sulfides or "carbonitrosulfides" of elements such as titanium and / or niobium and / or vanadium.
- the inventors unexpectedly discovered that the contents of the various elements, in particular those of titanium, nitrogen, vanadium and sulfur, must be carefully controlled. within the aforementioned limits.
- the steel is then cast, either by continuous casting in the form of blooms or billets, or in the form of ingots.
- the average cooling rate of these products must be regulated in such a way that to be equal to 0.3 ° C / s or more between 1450 and 1300 0 C.
- the products having the precise composition according to the invention are then heated and rolled between 1200 and 800 0 C in the form of son son, or bars in a single or double sequence of heating and rolling.
- the bars, the wires, the plots, or even the springs produced from these bars or machine wires are then subjected to a quenching treatment at the same time.
- This quenching treatment is then followed by a treatment of income executed specifically between 300 and 55O 0 C, to obtain the high levels of the required tensile strength and hardness of the steel, and to avoid on the one hand a microstructure that would lead to income fragility, and on the other hand an excessively high presence of residual austenite. It has been found that an embrittlement to the income and an excessive presence of residual austenite are extremely damaging to the resistance to corrosion fatigue of the steel according to the invention.
- the springs are made from untreated heat bars or from machine wires or slugs from such bars, the above mentioned treatments (quenching and tempering) shall be carried out on the springs themselves under the conditions which have been said. In the case where the springs are manufactured by cold forming, these heat treatments can be conducted on the bars, or on the machine wires or slugs from these bars before the spring is made.
- the invention makes it possible to obtain spring steels capable of reconciling a high and improved hardness and tensile strength with respect to the prior art, together with fatigue properties in the air and resistance to fatigue. improved wear properties, corrosion-resistant properties at least equivalent to those of the steels known for this use, or even better, and less sensitivity to the stress concentrations produced by the surface defects that may occur during the manufacture of the spring, thanks to addition of microalloy elements, a reduction of residual elements and a control of the analysis and production chain of the steel.
- Table 1 shows the steel compositions according to the invention and reference steels.
- the equivalent carbon Ceq is given by the following formula:
- Ceq [C] + 0.12 [Si] + 0.17 [Mn] - 0.1 [Ni] + 0.13 [Cr] - 0.24 [V] where [C], [Si], [ Mn], [Ni], [Cr] and [V] represent the content of each element in percentages by weight.
- Table 1 Chemical compositions of the steels tested (in%)
- Table 2 shows the hardness values obtained for steels according to the invention and reference steels, as a function of the tempering temperature applied to them.
- Table 2 Hardness and tensile strength as a function of the tempering temperature.
- Table 3 shows the maximum size of titanium nitride or carbonitride inclusions observed at 1.5mm of the surface of steels according to the invention and of reference steels, as defined above. The titanium contents of the various steels have also been reported.
- the maximum size of inclusions of nitrides or carbonitrides of titanium is determined as follows. On a section of rod or wire rod from a given steel casting, a 100mm 2 surface is examined at a location 1.5mm + 0.5mm below the surface of the bar or wire rod. After these observations, the size of the inclusion of titanium nitride or carbonitride with the largest area is determined by considering that the inclusions are squares and that the size of each of these inclusions, including inclusion having the largest surface, is equal to the square root of this area. All inclusions are observed on a bar or wire rod cut for springs, observations being made on 100mm 2 of this section.
- the steel casting is in accordance with the invention when the maximum size of the abovementioned inclusions observed over 100mm 2 at 1.5mm + 0.5mm below the surface is less than 20 ⁇ m.
- the corresponding results obtained on steels according to the invention and reference steels are given in Table 3. With regard to the reference tests 1 and 3, their titanium content is practically zero and the size of the nitrides and carbonitrides observed is not applicable.
- Table 3 Maximum sizes of the largest inclusions of titanium nitrides or carbonitrides found at 1.5mm from the surface of the samples.
- Fatigue test sample preparation includes coarse machining, austenitization, oil quenching, tempering, grinding, and shot blasting. These samples were tested for fatigue-torsion in the air. The shear stress applied was 856 + 494MPA and the number of cycles to failure was counted. The tests were stopped after 2.10 6 cycles if the samples were not broken.
- Sample preparation for fatigue testing includes coarse machining, austenitization, oil quenching, tempering, grinding, and shot blasting. These samples were tested for corrosion fatigue, that is, corrosion was applied at the same time as a fatigue load. Load in fatigue is a shear stress equal to 856 + 300MPa. The applied corrosion was cyclic corrosion in two stages alternating:
- Moisture resistance was determined using a cyclic compression test on cylindrical samples. The diameter of the samples was 7mm and their height 12mm. They were taken from the steel bars.
- the manufacture of the specimens of chill tests included rough machining, austenitization, oil quenching, tempering and final fine grinding.
- the height of the sample was measured precisely before the start of the test using a comparator with a precision of 1 ⁇ m.
- a preload was applied to simulate the pretensioning of the springs, this pretensioning being a compressive stress of 2200MPa.
- Table 4 Results of fatigue tests, fatigue under corrosion and slump.
- the reference steel 1 has, in particular, a sulfur content too high to achieve a good compromise between the fatigue resistance in the air and the fatigue content under corrosion.
- its manganese content is too high, resulting segregations damaging to the homogeneity of the steel and fatigue resistance in the air.
- Reference steel 2 has a carbon content and a carbon equivalent that is too low to ensure high hardness. Its tensile strength is too low for good resistance to fatigue in the air.
- the reference steel 3 has, in particular, a silicon content that is too low to ensure good resistance to scumming, and also good resistance to fatigue in the air.
- the wear resistance is higher for the steels of the invention than for the reference steels, as shown in FIG. 1, where it is clear that, according to the abovementioned abatement measurements, the wear-out values are at least 32% lower for the worst case of the steels of the invention (steel of the invention 1) compared to the best case of the reference steels (reference steel 1).
- the fatigue life in the air is significantly higher for the steels of the invention compared to the reference steels. This is due to the increase in hardness, as shown in Figure 2. But an increase in hardness is not enough.
- steels of high hardness are all the more sensitive to defects, such as inclusions and surface defects, the hardness is higher.
- the steels according to the invention are less sensitive to defects, in particular to large inclusions such as titanium nitrides or carbonitrides, in view of the fact that the invention avoids the appearance of such oversized inclusions.
- Table 3 the largest inclusions found in the steels according to the invention do not exceed the size of 14.1 ⁇ m, whereas inclusions larger than 20 ⁇ m are in the reference steel 2.
- the slightest sensitivity to surface defects such as those that may occur during the manufacture of the spring or other operations when using steels of the invention can be illustrated by resilience tests performed on the steels of the invention and reference steels heat-treated and having hardnesses of 55HRC or more, see Figure 3.
- the values measured in Charpy resiliency tests on the steels of the invention (where the notch of the specimen simulates a concentration of stresses as other stress concentrations that may be encountered on surface defects produced during the spring manufacturing or other operations) are higher than those measured on the reference steels. This shows that the steels according to the invention are less sensitive to the concentrations of stress on the defects than the reference steels according to the prior art. It is known that an increase in hardness reduces the resistance to fatigue under corrosion.
- the steels according to the invention have the advantage that their resistance to fatigue under corrosion is higher than that of the reference steels according to the prior art, and in particular for hardnesses greater than 55HRC as shown
- the invention makes it possible to obtain a higher hardness with a good compromise between the fatigue life in the air and a resistance to weariness which are greatly increased, and a service life of fatigue under corrosion which is better than that of the reference steel according to the prior art.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MEP-2009-344A ME01062B (en) | 2005-12-15 | 2006-12-11 | Spring steel, method for producing a spring using said steel and a spring made from such steel |
SI200630437T SI1966407T1 (en) | 2005-12-15 | 2006-12-11 | Spring steel, method for producing a spring using said steel and a spring made from such steel |
PL06841905T PL1966407T3 (en) | 2005-12-15 | 2006-12-11 | Spring steel, method for producing a spring using said steel and a spring made from such steel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0512775A FR2894987B1 (en) | 2005-12-15 | 2005-12-15 | SPRING STEEL, AND METHOD OF MANUFACTURING A SPRING USING THE SAME, AND SPRING REALIZED IN SUCH A STEEL |
PCT/FR2006/002700 WO2007080256A1 (en) | 2005-12-15 | 2006-12-11 | Spring steel, method for producing a spring using said steel and a spring made from such steel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1966407A1 true EP1966407A1 (en) | 2008-09-10 |
EP1966407B1 EP1966407B1 (en) | 2009-10-07 |
Family
ID=36933407
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06841905A Active EP1966407B1 (en) | 2005-12-15 | 2006-12-11 | Spring steel, method for producing a spring using said steel and a spring made from such steel |
Country Status (18)
Country | Link |
---|---|
US (1) | US20080308195A1 (en) |
EP (1) | EP1966407B1 (en) |
JP (1) | JP4869051B2 (en) |
KR (1) | KR101048946B1 (en) |
CN (1) | CN101400818B (en) |
AT (1) | ATE445026T1 (en) |
BR (1) | BRPI0619892B1 (en) |
CA (1) | CA2633153C (en) |
DE (1) | DE602006009705D1 (en) |
ES (1) | ES2331539T3 (en) |
FR (1) | FR2894987B1 (en) |
ME (1) | ME01062B (en) |
NO (1) | NO341748B1 (en) |
PL (1) | PL1966407T3 (en) |
RS (1) | RS51070B (en) |
RU (1) | RU2397270C2 (en) |
SI (1) | SI1966407T1 (en) |
WO (1) | WO2007080256A1 (en) |
Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2084179B1 (en) | 2006-11-22 | 2013-05-22 | Novo Nordisk A/S | Method for making activated carboxypeptidases |
CN102268604A (en) | 2007-07-20 | 2011-12-07 | 株式会社神户制钢所 | Steel wire material for spring and its producing method |
JP4694537B2 (en) * | 2007-07-23 | 2011-06-08 | 株式会社神戸製鋼所 | Spring wire with excellent fatigue characteristics |
JP5653022B2 (en) * | 2009-09-29 | 2015-01-14 | 中央発條株式会社 | Spring steel and spring with excellent corrosion fatigue strength |
US8789817B2 (en) * | 2009-09-29 | 2014-07-29 | Chuo Hatsujo Kabushiki Kaisha | Spring steel and spring having superior corrosion fatigue strength |
CN102151693B (en) * | 2010-12-02 | 2012-01-11 | 大冶特殊钢股份有限公司 | Method for rolling low-hardness small-sized spring steel |
JP5711539B2 (en) | 2011-01-06 | 2015-05-07 | 中央発條株式会社 | Spring with excellent corrosion fatigue strength |
CN103014533B (en) * | 2011-10-19 | 2015-02-04 | 宝钢集团新疆八一钢铁有限公司 | Technique for prolonging fatigue life of 50CrVA plate spring |
KR101353649B1 (en) | 2011-12-23 | 2014-01-20 | 주식회사 포스코 | Wire rod and steel wire having high corrosion resistance, method of manufacturing spring and steel wire for spring |
CN104040004A (en) | 2012-01-11 | 2014-09-10 | 株式会社神户制钢所 | Steel for bolts, bolt, and method for producing bolt |
CN102735749A (en) * | 2012-06-28 | 2012-10-17 | 吴江市宏达探伤器材有限公司 | Magnetic particle inspection test block and preparation method thereof |
JP2015034324A (en) | 2013-08-08 | 2015-02-19 | 山陽特殊製鋼株式会社 | Steel excellent in rolling fatigue life |
CN103499595B (en) * | 2013-10-17 | 2016-01-13 | 武汉钢铁(集团)公司 | Spring steel clip foreign material chemical composition microcell method for quantitative measuring |
KR101446135B1 (en) | 2013-12-26 | 2014-10-02 | 주식회사 세아베스틸 | Steel for suspension spring with high strength and excellent fatigue and method producing the same |
JP6282571B2 (en) * | 2014-10-31 | 2018-02-21 | 株式会社神戸製鋼所 | Manufacturing method of high strength hollow spring steel |
CN105112799A (en) * | 2015-09-01 | 2015-12-02 | 广西南宁智翠科技咨询有限公司 | Special spring wire for vehicle engine |
CN105178224B (en) * | 2015-10-09 | 2017-05-03 | 耿志斌 | Road and bridge collision avoidance protective device |
KR101776462B1 (en) * | 2015-12-04 | 2017-09-20 | 현대자동차주식회사 | Coil spring steel |
KR101745192B1 (en) | 2015-12-04 | 2017-06-09 | 현대자동차주식회사 | Ultra high strength spring steel |
KR101745196B1 (en) * | 2015-12-07 | 2017-06-09 | 현대자동차주식회사 | Ultra high strength spring steel |
KR101776491B1 (en) * | 2016-04-15 | 2017-09-20 | 현대자동차주식회사 | High strength spring steel having excellent corrosion resistance |
KR101776490B1 (en) * | 2016-04-15 | 2017-09-08 | 현대자동차주식회사 | High strength spring steel having excellent corrosion resistance |
JP6356309B1 (en) * | 2016-10-19 | 2018-07-11 | 三菱製鋼株式会社 | High-strength spring, method for manufacturing the same, steel for high-strength spring, and method for manufacturing the same |
DE102017107487A1 (en) | 2017-04-07 | 2018-10-11 | Schaeffler Technologies AG & Co. KG | Method for producing a torsion bar spring and stabilizer for a chassis of a motor vehicle |
JP7078042B2 (en) * | 2017-05-25 | 2022-05-31 | 住友電気工業株式会社 | Diagonal springs and connectors |
KR20200004407A (en) * | 2017-06-15 | 2020-01-13 | 닛폰세이테츠 가부시키가이샤 | Rolled Wire for Spring Steel |
CN107550124A (en) * | 2017-09-07 | 2018-01-09 | 南通通联海绵塑料有限公司 | A kind of sponges spring mattress manufacture method |
EP3796101A1 (en) * | 2019-09-20 | 2021-03-24 | Nivarox-FAR S.A. | Hairspring for clock movement |
CN114134431B (en) * | 2021-05-10 | 2022-12-30 | 江阴兴澄特种钢铁有限公司 | 2000 Mpa-grade high-strength high-toughness high-hardenability spring steel by square billet continuous casting and rolling and manufacturing method thereof |
CN113930680B (en) * | 2021-09-29 | 2023-03-17 | 武汉钢铁有限公司 | Low-temperature-resistant high-strength spring flat steel and production method thereof |
JP2023120677A (en) | 2022-02-18 | 2023-08-30 | 日本発條株式会社 | Inclusion evaluation method |
CN115125450B (en) * | 2022-06-29 | 2023-03-21 | 浙江伊思灵双第弹簧有限公司 | Microalloyed spring and manufacturing process thereof |
CN114990451A (en) * | 2022-08-05 | 2022-09-02 | 山东联美弹簧科技股份有限公司 | Microalloyed steel for automobile spring stabilizer bar and preparation method thereof |
CN115961215A (en) * | 2022-12-09 | 2023-04-14 | 铜陵有色金神耐磨材料有限责任公司 | High-wear-resistance Cr-Mo steel lining plate for light semi-autogenous mill and preparation method thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3474373B2 (en) * | 1995-10-27 | 2003-12-08 | 株式会社神戸製鋼所 | Spring steel with excellent hydrogen embrittlement resistance and fatigue properties |
US5776267A (en) * | 1995-10-27 | 1998-07-07 | Kabushiki Kaisha Kobe Seiko Sho | Spring steel with excellent resistance to hydrogen embrittlement and fatigue |
JPH09324219A (en) * | 1996-06-05 | 1997-12-16 | Kobe Steel Ltd | Production of high strength spring excellent in hydrogen embrittlement resistance |
JPH10121201A (en) * | 1996-10-14 | 1998-05-12 | Kobe Steel Ltd | High strength spring excellent in delayed fracture resistance |
JPH10299803A (en) * | 1997-04-22 | 1998-11-13 | Kobe Steel Ltd | High strength spring favourable in environmental brittleness resistance |
JP3577411B2 (en) * | 1997-05-12 | 2004-10-13 | 新日本製鐵株式会社 | High toughness spring steel |
JP3246733B2 (en) * | 1999-10-29 | 2002-01-15 | 三菱製鋼室蘭特殊鋼株式会社 | High strength spring steel |
JP4476846B2 (en) * | 2005-03-03 | 2010-06-09 | 株式会社神戸製鋼所 | High strength spring steel with excellent cold workability and quality stability |
JP4476863B2 (en) * | 2005-04-11 | 2010-06-09 | 株式会社神戸製鋼所 | Steel wire for cold forming springs with excellent corrosion resistance |
-
2005
- 2005-12-15 FR FR0512775A patent/FR2894987B1/en not_active Expired - Fee Related
-
2006
- 2006-12-11 CN CN2006800474270A patent/CN101400818B/en active Active
- 2006-12-11 EP EP06841905A patent/EP1966407B1/en active Active
- 2006-12-11 WO PCT/FR2006/002700 patent/WO2007080256A1/en active Application Filing
- 2006-12-11 BR BRPI0619892A patent/BRPI0619892B1/en active IP Right Grant
- 2006-12-11 PL PL06841905T patent/PL1966407T3/en unknown
- 2006-12-11 US US12/097,313 patent/US20080308195A1/en not_active Abandoned
- 2006-12-11 DE DE602006009705T patent/DE602006009705D1/en active Active
- 2006-12-11 RS RSP-2009/0515A patent/RS51070B/en unknown
- 2006-12-11 ES ES06841905T patent/ES2331539T3/en active Active
- 2006-12-11 CA CA2633153A patent/CA2633153C/en active Active
- 2006-12-11 ME MEP-2009-344A patent/ME01062B/en unknown
- 2006-12-11 KR KR1020087017219A patent/KR101048946B1/en active IP Right Grant
- 2006-12-11 RU RU2008128865/02A patent/RU2397270C2/en not_active IP Right Cessation
- 2006-12-11 SI SI200630437T patent/SI1966407T1/en unknown
- 2006-12-11 AT AT06841905T patent/ATE445026T1/en active
- 2006-12-12 JP JP2006334660A patent/JP4869051B2/en active Active
-
2008
- 2008-06-16 NO NO20082766A patent/NO341748B1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO2007080256A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN101400818B (en) | 2012-08-29 |
KR101048946B1 (en) | 2011-07-12 |
BRPI0619892B1 (en) | 2016-06-07 |
FR2894987B1 (en) | 2008-03-14 |
NO20082766L (en) | 2008-07-14 |
JP2007224413A (en) | 2007-09-06 |
EP1966407B1 (en) | 2009-10-07 |
DE602006009705D1 (en) | 2009-11-19 |
FR2894987A1 (en) | 2007-06-22 |
RU2397270C2 (en) | 2010-08-20 |
RU2008128865A (en) | 2010-01-20 |
BRPI0619892A2 (en) | 2011-10-25 |
ME01062B (en) | 2012-10-20 |
NO341748B1 (en) | 2018-01-15 |
PL1966407T3 (en) | 2010-04-30 |
CN101400818A (en) | 2009-04-01 |
JP4869051B2 (en) | 2012-02-01 |
ATE445026T1 (en) | 2009-10-15 |
KR20080090424A (en) | 2008-10-08 |
US20080308195A1 (en) | 2008-12-18 |
RS51070B (en) | 2010-10-31 |
CA2633153C (en) | 2013-05-07 |
ES2331539T3 (en) | 2010-01-07 |
SI1966407T1 (en) | 2009-12-31 |
CA2633153A1 (en) | 2007-07-19 |
WO2007080256A1 (en) | 2007-07-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1966407B1 (en) | Spring steel, method for producing a spring using said steel and a spring made from such steel | |
CA2442299C (en) | Steel and steel tube for high-temperature use | |
JP5114689B2 (en) | Case-hardened steel and method for producing the same | |
CA2607446C (en) | Tempered martensitic steel, method of producing a part from said steel and part thus obtained | |
KR101745224B1 (en) | Steel for carburizing | |
FR2942808A1 (en) | LOW-ALLOY STEEL WITH HIGH ELASTICITY LIMIT AND HIGH RESISTANCE TO CRUSHING UNDER SULFIDE STRESS. | |
FR2933990A1 (en) | LOW-COBALT HARDENED CURED MARTENSITIC STEEL, METHOD FOR MANUFACTURING A WORKPIECE THEREFROM, AND PIECE OBTAINED THEREBY | |
JP5607956B2 (en) | Steel for machine structure and friction welding parts suitable for friction welding | |
FR2757877A1 (en) | STEEL AND PROCESS FOR THE MANUFACTURE OF A STEEL PART SHAPED BY COLD PLASTIC DEFORMATION | |
EA027733B1 (en) | Duplex stainless steel casting and method of its manufacture | |
JP2015096657A (en) | Case hardened steel and carburized material | |
FR2990218A1 (en) | Hardened microalloyed bainitic steel useful for the production of e.g. automobile parts, comprises carbon, silicon, manganese, sulfur, copper, nickel, chromium, molybdenum, vanadium, iron and incidental impurities | |
FR2931166A1 (en) | HOT FORGED STEEL WITH HIGH MECHANICAL CHARACTERISTICS OF THE PARTS PRODUCED | |
FR2765890A1 (en) | PROCESS FOR MANUFACTURING A MECHANICAL PIECE OF CEMENTED OR CARBONITURATED STEEL AND STEEL FOR MANUFACTURING THE SAME | |
EP1051531B1 (en) | Steel and method for making cleavable mechanical parts | |
EP2134882B1 (en) | Microalloyed steel with good resistance to hydrogen for the cold-forming of machine parts having high properties | |
CA2980878C (en) | Parts with a bainitic structure having high strength properties and manufacturing process | |
JP7205112B2 (en) | carbonitriding steel | |
JP5323369B2 (en) | Case-hardened steel with excellent machinability and grain coarsening prevention properties | |
FR2784692A1 (en) | Case hardenable low alloy constructional steel, especially for automobile gear wheels, comprises chromium, manganese, nickel, molybdenum, silicon, copper, sulfur, carbon, and aluminum | |
WO2022253912A1 (en) | Hot-formed steel part and manufacturing method | |
JP2007031747A (en) | Steel wire rod for spring, and method for judging its fatigue resistance | |
KR20240013186A (en) | Steel and a crankshaft made of the steel | |
MX2008007563A (en) | Spring steel, method for producing a spring using said steel and a spring made from such steel |
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 |
|
17P | Request for examination filed |
Effective date: 20080610 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
17Q | First examination report despatched |
Effective date: 20081013 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602006009705 Country of ref document: DE Date of ref document: 20091119 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: EP Ref document number: 20090402804 Country of ref document: GR |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2331539 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: SK Ref legal event code: T3 Ref document number: E 6328 Country of ref document: SK |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20091007 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100207 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091007 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100208 |
|
REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E007172 Country of ref document: HU |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091007 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091007 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091007 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091007 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20100708 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091007 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP Owner name: ASCO INDUSTRIES, FR Effective date: 20141222 Ref country code: FR Ref legal event code: GC Effective date: 20141222 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20150910 AND 20150916 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602006009705 Country of ref document: DE Representative=s name: LAVOIX MUNICH, DE Ref country code: DE Ref legal event code: R081 Ref document number: 602006009705 Country of ref document: DE Owner name: ASCO INDUSTRIES, FR Free format text: FORMER OWNER: ASCOMETAL, COURBEVOIE, FR Ref country code: DE Ref legal event code: R082 Ref document number: 602006009705 Country of ref document: DE Representative=s name: VIERING, JENTSCHURA & PARTNER MBB PATENT- UND , DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602006009705 Country of ref document: DE Representative=s name: VIERING, JENTSCHURA & PARTNER MBB PATENT- UND , DE |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: FH1C Free format text: FORMER REPRESENTATIVE(S): BARANYI EVA, DANUBIA SZABADALMI ES JOGI IRODA KFT, HU Representative=s name: DANUBIA SZABADALMI ES JOGI IRODA KFT., HU Ref country code: HU Ref legal event code: GB9C Owner name: ASCO INDUSTRIES, FR Free format text: FORMER OWNER(S): ASCOMETAL, FR |
|
REG | Reference to a national code |
Ref country code: SK Ref legal event code: PC4A Ref document number: E 6328 Country of ref document: SK Owner name: ASCO INDUSTRIES, HAGONDANGE, FR Free format text: FORMER OWNER: ASCOMETAL, COURBEVOIE, FR Effective date: 20160315 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CZ Payment date: 20161124 Year of fee payment: 11 Ref country code: CH Payment date: 20161222 Year of fee payment: 11 Ref country code: GB Payment date: 20161221 Year of fee payment: 11 Ref country code: LU Payment date: 20161121 Year of fee payment: 11 Ref country code: SK Payment date: 20161123 Year of fee payment: 11 Ref country code: MC Payment date: 20161123 Year of fee payment: 11 Ref country code: NL Payment date: 20161117 Year of fee payment: 11 Ref country code: FI Payment date: 20161124 Year of fee payment: 11 Ref country code: HU Payment date: 20161122 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20161219 Year of fee payment: 11 Ref country code: RO Payment date: 20161129 Year of fee payment: 11 Ref country code: PL Payment date: 20161124 Year of fee payment: 11 Ref country code: AT Payment date: 20161124 Year of fee payment: 11 Ref country code: GR Payment date: 20161122 Year of fee payment: 11 Ref country code: BG Payment date: 20161129 Year of fee payment: 11 Ref country code: SI Payment date: 20161123 Year of fee payment: 11 Ref country code: BE Payment date: 20161216 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20161205 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: RG Effective date: 20180606 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20180101 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 445026 Country of ref document: AT Kind code of ref document: T Effective date: 20171211 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20171211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171212 Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 |
|
REG | Reference to a national code |
Ref country code: SK Ref legal event code: MM4A Ref document number: E 6328 Country of ref document: SK Effective date: 20171211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180101 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 |
|
REG | Reference to a national code |
Ref country code: SI Ref legal event code: KO00 Effective date: 20180807 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20171231 Ref country code: BE Ref legal event code: PD Owner name: ASCO INDUSTRIES; FR Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), AFFECTATION / CESSION; FORMER OWNER NAME: ASCOMETAL Effective date: 20160202 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171212 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171212 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171231 Ref country code: SK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171231 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171231 Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180705 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180706 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171211 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20230109 Year of fee payment: 17 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230522 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602006009705 Country of ref document: DE Owner name: KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, L, JP Free format text: FORMER OWNER: ASCO INDUSTRIES, HAGONDANGE, FR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602006009705 Country of ref document: DE Owner name: KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, L, JP Free format text: FORMER OWNER: ASCOMETAL FRANCE HOLDING SAS, HAGONDANGE, FR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602006009705 Country of ref document: DE Owner name: KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, L, JP Free format text: FORMER OWNER: KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.), KOBE-SHI, HYOGO, JP |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20231110 Year of fee payment: 18 Ref country code: FR Payment date: 20231108 Year of fee payment: 18 Ref country code: DE Payment date: 20231031 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240110 Year of fee payment: 18 |