US20160237518A1 - High tensile strength steel wire - Google Patents

High tensile strength steel wire Download PDF

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US20160237518A1
US20160237518A1 US15/027,856 US201415027856A US2016237518A1 US 20160237518 A1 US20160237518 A1 US 20160237518A1 US 201415027856 A US201415027856 A US 201415027856A US 2016237518 A1 US2016237518 A1 US 2016237518A1
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weight percent
steel wire
tensile strength
high tensile
strength steel
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US15/027,856
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Christophe Mesplont
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Bekaert NV SA
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Bekaert NV SA
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • 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
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • 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
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C21D2211/008—Martensite

Definitions

  • the present invention relates to a high tensile strength steel wire, to a process for manufacturing a high tensile strength steel wire and to the uses or applications of such a high tensile strength steel wire as spring wire or an element for producing a rope.
  • Springs are usually made from alloys of steel. The most common spring steels are music wire, oil tempered wire, chrome silicon, chrome vanadium, and 302 and 17-7 stainless. Spring wires made of chrome silicon or chrome vanadium are higher quality, higher strength versions of oil tempered wire.
  • Tensile strength is a material's ability to resist forces that attempt to pull apart or stretch it. Tensile strength is an important property for wires for spring applications. For instance, extension springs operating above their tensile strength will break.
  • drawn steel wire for high strength spring use is quenched and tempered to impart higher material strength in the drawn steel wire, and then is cold coiled to obtain a coil spring shape. For this reason, first drawn then heat treated steel wire for high strength spring use is required to have not only high strength, but also to have a high enough workability that it will not break at the cold coiling.
  • the springs in particular which are used for automobile engines, clutches, etc. are being required to offer more advanced performance in order to deal with the trend toward lighter weights and higher performances of automobiles. For this reason, steel wires with higher strength and higher durability are desired for springs.
  • a major trend for improving properties is to adjust the composition of steels for spring wires.
  • An example is disclosed in US 2012/0291927 A1, wherein the contents of C, Si, Mn and Cr in the steel wire are proposed to be strictly controlled and in the meantime both Cr and Si in the steel wire are set at a suitable amount. It has been found, nevertheless, that increasing mechanical strength beyond certain limits causes such steels to have inadequate ductility, taking into account the pre-shaping and bending operations that have to be carried out with the spring wire. A lot of effort has been done on the improvement of steel wires to have higher tensile strength and simultaneously have acceptable ductility.
  • the present invention describes a steel wire having very high strength and ductility thanks to the oriented martensitic microstructure, and a method to produce such a steel wire in a continuous process.
  • a high tensile strength steel wire with following steel composition:
  • At least 20 volume percent of martensite are oriented. More preferably, at least 30 volume percent of martensite are oriented. Most preferably, at least 40 volume percent of martensite are oriented.
  • martensitic steel is a polycrystalline material.
  • the grains of polycrystalline material are randomly oriented, the polycrystalline material is not oriented or non-textured.
  • the grains of polycrystalline material can be preferably oriented, and in this case the polycrystalline material is called to be “oriented” or “textured”.
  • Two types of orientations are often confronted, i.e. “crystallographic orientation” and “microstructural orientation”.
  • Crystallographic orientation means grains are crystallographically oriented, such as with preferred alignment or orientation of certain crystallographic planes or crystallographic directions.
  • Preferred crystallographic orientation is usually determined from an analysis of the orientation dependence of the diffraction peak intensities (such as by X-Ray Diffraction (XRD) analysis or Electron Backscatter Diffraction (EBSD)) that have been measured in different spatial directions within the coordinate system of the sample.
  • XRD X-Ray Diffraction
  • EBSD Electron Backscatter Diffraction
  • the grains of polycrystalline material can also have “microstructural orientation” by such as uniaxial compression during formation of the polycrystalline.
  • Microstructural orientation implies that the anisotropic shaped grains are morphologically oriented in preferred directions or planes. This can be detected by image analysis such as scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • crystallographic orientation is often linked with microstructural orientation since the shape anisotropy of grains is often related to their crystallography.
  • Martensite occurs as lath- or plate-shaped crystal grains.
  • the lenticular (lens-shaped) crystal grains are sometimes described as Acicular (needle-shaped).
  • the term “oriented” means that the lenticular grains are either crystallographically oriented or microstructurally oriented, or oriented both crystallographically and microstructurally.
  • the volume percentage of the crystallographical alignment or orientation can be obtained by means of X-Ray Diffraction (XRD) analysis or Electron Backscatter Diffraction (EBSD).
  • XRD X-Ray Diffraction
  • EBSD Electron Backscatter Diffraction
  • the volume percentage of the microstructural alignment or orientation can be evaluated by image analysis.
  • the term “oriented” does not only mean that the crystallographic axis or the axis of lenticular grains are exactly oriented at the same direction as illustrated by a 1 and a 2 in FIG. 1 , but also refer to the orientation within a tolerance.
  • the directions of certain axes of grains are deviated, as presented by angle ⁇ in FIG. 1 , within 20°, preferably within 10°, more preferably within 5°, these grains are also considered as oriented.
  • the alignment or orientation at least refers to one dimensional preferred orientation, e.g. in the direction perpendicular to the plane of lenticular grains (direction as shown by a 1 , a 2 , e.g. [001], in FIG. 1 ).
  • the lenticular grains are randomly distributed in the directions on the lenticular plane (directions as shown by a 4 , a 5 , in FIG. 1 ).
  • the steel wire according to the present application has a yield strength Rp0.2 which is at least 80 percent of the tensile strength Rm.
  • Rp0.2 is the yield strength at 0.2% permanent elongation. More preferably, the yield to tensile ratio, i.e. Rp0.2/Rm, is between 80 percent to 95 percent. Therefore, the steel wire after elastic deformation can be still deformed to certain extent before breaking.
  • a steel wire according to the present application preferably has a corrosion resistance coating. More preferably, the steel wire has a corrosion resistance coating selected from any one of zinc, nickel, silver and copper, or their alloys. In such a case, the wires have a prolonged life time even in a harsh corrosive environment.
  • the steel wire according to the present application may be in a cold-drawn state and have a round cross-section.
  • the steel wire may have a tensile strength Rm of at least 2000 MPa for wire diameter above 5.0 mm, at least 2100 MPa for wire diameter above 3.0 mm and at least 2200 MPa for wire diameters above 0.5 mm.
  • the steel wire has a reduction in area after fracture of at least 45% and more preferably of at least 50%.
  • the ductility of steel wires is obtained by a tensile test.
  • the ductility of the steel wire is indicated by the reduction in area after fracture.
  • the “reduction in area” is the difference between original cross sectional area of a specimen and the area of its smallest cross section after testing. It is usually expressed as % decrease in original cross section. The smallest cross section is measured after fracture for steel wires.
  • Wire drawing is a metal working process used to reduce the cross-section of a wire by pulling the wire through a single, or series of, drawing die(s). It is known that wire drawing increases the tensile strength Rm of the steel wire and meanwhile decreases the ductility. However, in comparison with traditional cold-drawn steel wires, the invention steel wire with specific composition has a comparative ductility and an extremely high tensile strength.
  • the steel wire may be used as spring wire or an element for producing a rope.
  • a process of manufacturing a high tensile strength steel wire said steel wire having as steel composition:
  • the steel wire/wire rod was first deformed or work hardened to final dimension and thereafter quenched and tempered, as schematically shown in FIG. 2 .
  • the steel wire is first quenched to form martensitic microstructure. Tempering is followed thereafter.
  • the tempered martensitic steel wire is then deformed or work hardened, e.g. by drawing, into final dimension, as schematically shown in FIG. 3 .
  • the present invention receives unexpected technical results and advantages.
  • martensite has always been claimed as detrimental for drawing.
  • the tensile strength of the martensitic wire according to the present invention is very high and the combination of the level of tensile strength with the high level of ductility is uncommon.
  • the surprising result obtained by drawing the tempered martensite may be due to the special alloying of the steel (microalloyed with Cr and Si) versus conventional eutectoid steels.
  • the synergy effect of the composition and the process of the present application results in a martensitic steel wire having a preferred martensite orientation.
  • the orientation of martensite in the cold-drawn steel wire is the result of applied compression force via drawing on the quenched and tempered martensitic steel wires.
  • the process may further comprise a step of e) aging said work hardened steel wire at a temperature between 100° C. and 250° C.
  • said work hardening occurs at a temperature below 400° C. More preferably, said work hardening is cold drawing. Cold drawing has an added effect of work hardening and strengthening the material, and thus further improves the material's mechanical properties. It also improves the surface finish and holds tighter tolerances allowing desirable qualities that cannot be obtained by hot deformation.
  • said work hardening is a warm drawing occurring between 200° C. and 700° C., e.g. 200° C. to 400° C. For a similar reduction, the application of warm drawing significantly reduces the passes and simplifies the process.
  • FIG. 1 schematically shows grain alignment or orientation in poly-crystallographical materials.
  • FIG. 2 illustrates a thermo-mechanical process for steel wires according to the prior art.
  • FIG. 3 illustrates the thermo-mechanical process for steel wires according to the present invention.
  • FIG. 4 illustrates a temperature versus time curve for a thermal process according to the present invention.
  • FIG. 5 compares the strain hardening curves of prior art patented steel wire with the invention steel wire according to the first embodiment of the present invention.
  • FIG. 6 compares the tensile strength as a function of section reduction of three passes drawing process with six passes drawing process.
  • FIG. 7 ( a ) shows the scanning electron microstructure (SEM) of longitudinal cross-section of the steel wire according to the present invention while FIG. 7 ( b ) shows the scanning electron microstructure of longitudinal cross-section of a reference steel wire at a same magnification.
  • FIG. 8 ( a ) shows the scanning electron microstructure (SEM) of longitudinal cross-section of the steel wire according to the present invention at a lower magnification while FIG. 8 ( b ) shows the scanning electron microstructure (SEM) of longitudinal cross-section of a reference steel wire at a same magnification.
  • FIG. 4 illustrates a suitable temperature versus time curve applied to a steel wire or wire rod with a diameter of 5.29 mm and with following steel composition:
  • the starting temperature of martensite transformation M s of this steel is about 280° C. and the temperature M f , at which martensite formation ends is about 100° C.
  • Curve 18 is the temperature curve in the various equipment parts (furnace, bath . . . ) and curve 19 is the temperature of the steel wire.
  • the steel wire or wire rod after above thermal treatment mainly has martensitic microstructure. Since martensite is sensible to H-embrittlement, thermo-treated steel wire is cold drawn directly without pickling and oil can act as lubricant for the later drawing process.
  • the formed martensitic steel wire or wire rod is continued with a series of wire drawing process, e.g. of six passes.
  • the diameter, diameter reduction, section reduction, cumulative section reduction, tensile strength, tensile strength variation and reduction in area after each pass of the steel wire for this six passes process are summarized in table 1.
  • the “diameter reduction” and “section reduction” are referred to the reduction after each pass of drawing.
  • the “diameter reduction” implies the difference of the diameter of the steel wire before and after each pass and is expressed as % diameter decrease to its original diameter before passing the wire drawing dies.
  • the “section reduction” implies the difference of the cross-section areas of the steel wire before and after each pass and is expressed as % section decrease to its original section before passing the wire drawing dies.
  • the diameter reduction is about 5% for each pass.
  • the tensile strength of the steel wire further increases by passing more passes. After being drawn in six passes, the steel wire has a diameter of 3.86 mm and a tensile strength of 2151 N/mm 2 . Over six passes, the yield strength Rp0.2 of the steel wire is at least 80 percent of the tensile strength Rm.
  • the steel wire overall has sufficient ductility illustrated by the reduction in area being above 46.5% and the total elongation at fracture of the drawn wire being more than 2%.
  • a strain hardening curve of the cold drawn wire (Q&T CrSi) according to the invention in comparison with a reference wire (R-SW) is shown in FIG. 5 .
  • the reference wire contains 0.8 wt % Carbon and is patented in lead.
  • the reference wire has an initial diameter of 6.5 mm and a tensile strength of 1360 N/mm 2 .
  • fine tempered martensite can be obtained with tensile strength being at least 400 N/mm 2 higher than for a patented wire.
  • the strain hardening curve of the cold drawn tempered martensitic wire (Q&T CrSi) has a similar slope to that of a patented wire (R-SW). This means that both steel wires showed a comparable strength increase for a same or similar section reduction. For a same amount of section reduction, the invention wire will be at least 400 N/mm 2 stronger than a wire drawn after patenting.
  • This extremely high tensile strength of the invention wire may be attributed to the martensitic microstructure formation and in particular to the oriented certain percentage of martensitic grains, which are observed in image analysis, in the steel wires after deformation or work hardening.
  • the steel wire after thermal treatment mainly has martensitic microstructure.
  • the steel wire further undergoes six passes drawing steps with a diameter reduction to 2.8 mm.
  • the properties of the steel wire after each pass are shown in table 2.
  • an extreme high tensile strength is obtained after six passes, the steel wire still has sufficient ductility as indicated by a reduction in area of 52.8%.
  • the ductility of the steel wire is ensured during the whole drawing process, which can be verified by the reductions in area of the steel wires after one to six passes all being above 52.8% as shown in table 2.
  • the martensitic steel wire with 3.75 mm diameter is drawn by three passes.
  • the average diameter reduction of each pass is about 9.5% for three passes process which is almost a double of that of six passes process as shown in embodiment 1 and 2.
  • the tensile strength (Rm) of three passes drawn wire (SW3) as a function of section reduction ( ⁇ s) is plot in FIG. 6 in comparison with the tensile strength of six passes drawn wires of embodiment 1 (SW1) and embodiment 2 (SW2).
  • the increase of tensile strength is almost proportional to the increase of section reduction for both the three and the six passes drawn steel wires.
  • the slope of tensile strength trend curve of wire undergone three passes process (SW3) is slightly bigger, i.e.
  • the wire undergone three passes shows an average strength increase of 8 N/mm 2 for 1% section reduction while the wire undergone six passes shows an average strength increase of 6 N/mm 2 for 1% section reduction.
  • the steel wires drawn by three passes have even better ductility.
  • the reductions in area of the steel wires after one to three passes are all above 53.6%.
  • the drawn steel wire after three pass has excellent properties: tensile strength is 2300 N/mm 2 and reduction in area is 53.6%, which are exceeded the standard requirement for quenched and tempered spring wires.
  • the microstructure of the longitudinal cross-section of the steel wire undergone three passes according to the present invention is shown in FIG. 7 ( a ) while the microstructure of the longitudinal cross-section of the reference wire is shown in FIG. 7( b ) .
  • the longitudinal cross-section is a section in the longitudinal or lengthwise direction of the steel wire.
  • the reference wire appears a homogeneous martensitic microstructure.
  • the martensitic grains are randomly oriented over the whole area.
  • steel wire it presents a martensitic microstructure and the martensitic grains are preferably oriented as shown in FIG. 7( a ) .
  • the martensitic grains appear acicular (needle-shaped) and the long axis of acicular is aligned parallel to the drawing direction (a direction parallel to the scale bar in FIG. 7 ). This indicates that the normal of the lenticular (lens-shaped) crystal grains is preferably oriented perpendicular to the drawing direction.
  • FIGS. 8 ( a ) and ( b ) are respectively a microstructure of the longitudinal cross-section of an invention steel wire and a reference wire at lower magnification. It confirms an oriented martensitic microstructure ( FIG. 8 ( a ) ) of the steel wire according to the present invention vs. a randomly distributed martensitic microstructure of the reference wire ( FIG. 8( b ) ).
  • the steel wire according to the present invention undergone one passes shows at least 10 volume percent of oriented martensite and the steel wire undergone three passes shows at least 20 volume percent of oriented martensite.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
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EP13188231 2013-10-11
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EP (1) EP3055436B1 (ko)
KR (1) KR20160068765A (ko)
CN (1) CN105579595A (ko)
AU (1) AU2014334010A1 (ko)
BR (1) BR112016007217A2 (ko)
DK (1) DK3055436T3 (ko)
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HR (1) HRP20171447T1 (ko)
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US20170362679A1 (en) * 2015-01-30 2017-12-21 Nv Bekaert Sa High tensile steel wire
CN113474574A (zh) * 2019-02-26 2021-10-01 贝卡尔特公司 用于打开和关闭汽车的车门或尾门的执行器的螺旋压缩弹簧

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CN106399826A (zh) * 2016-08-30 2017-02-15 湖北立晋钢铁集团有限公司 一种汽车用弹簧扁钢及其制作方法
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KR102355675B1 (ko) * 2019-07-12 2022-01-27 주식회사 포스코 고강도 스프링용 선재, 강선 및 그 제조방법
CN110724795A (zh) * 2019-09-30 2020-01-24 江苏冠晟超导科技有限公司 导线用钢丝的等温淬火热处理工艺
KR102326263B1 (ko) * 2019-12-20 2021-11-15 주식회사 포스코 초고강도 스프링용 선재, 강선 및 그 제조방법
CN111304537A (zh) * 2020-03-25 2020-06-19 中国铁道科学研究院集团有限公司 一种强度2200MPa级预应力钢绞线及生产工艺
KR102401440B1 (ko) * 2020-08-28 2022-05-24 박철옥 마스크 노즈 와이어 제조방법 및 이 노즈 와이어용 철심 제조장치
CN113862435B (zh) * 2021-10-09 2023-05-05 中钢集团郑州金属制品研究院股份有限公司 一种适用于高强度异型弹簧钢丝的制备工艺

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AU2014334010A1 (en) 2016-03-03
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MY176216A (en) 2020-07-24
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PT3055436T (pt) 2017-09-13
RS56504B1 (sr) 2018-02-28

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