EP3919633A1 - Procédé d'échange de chaleur, milieu d'échange de chaleur, dispositif d'échange de chaleur, procédé de patentage et fil d'acier au carbone - Google Patents

Procédé d'échange de chaleur, milieu d'échange de chaleur, dispositif d'échange de chaleur, procédé de patentage et fil d'acier au carbone Download PDF

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Publication number
EP3919633A1
EP3919633A1 EP20749310.7A EP20749310A EP3919633A1 EP 3919633 A1 EP3919633 A1 EP 3919633A1 EP 20749310 A EP20749310 A EP 20749310A EP 3919633 A1 EP3919633 A1 EP 3919633A1
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EP
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Prior art keywords
alloy
phase
liquid
carbon
heat exchange
Prior art date
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Pending
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EP20749310.7A
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German (de)
English (en)
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EP3919633A4 (fr
Inventor
Kazuhiro Ishimoto
Yoshihito Kawamura
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Kumamoto University NUC
Tokyo Rope Manufacturing Co Ltd
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Kumamoto University NUC
Tokyo Rope Manufacturing Co Ltd
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Publication of EP3919633A1 publication Critical patent/EP3919633A1/fr
Publication of EP3919633A4 publication Critical patent/EP3919633A4/fr
Pending legal-status Critical Current

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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
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/64—Patenting furnaces
    • 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
    • C21D1/26—Methods of annealing
    • C21D1/32—Soft annealing, e.g. spheroidising
    • 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
    • C21D1/34—Methods of heating
    • C21D1/44—Methods of heating in heat-treatment baths
    • C21D1/48—Metal baths
    • 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
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • 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
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/607—Molten salts
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • 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
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • C21D9/573—Continuous furnaces for strip or wire with cooling
    • C21D9/5732—Continuous furnaces for strip or wire with cooling of wires; of rods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C21D2211/009—Pearlite

Definitions

  • This invention relates to a heat exchange method, a heat exchange medium and a heat exchange apparatus.
  • the invention further relates to a patenting treatment and carbon-steel wire.
  • the drawn carbon-steel wire By drawing a carbon-steel wire on which a uniform and fine pearlite structure has been caused to precipitate, the drawn carbon-steel wire can be imparted with high strength and toughness.
  • the uniform and fine pearlite structure is caused precipitated by heating the carbon-steel wire in a heating furnace and cooling it in a cooling tank (cooling furnace) (this is so-called "patenting").
  • a carbon-steel wire is heated to about 900 to 1000°C in a heating furnace and then cooled to about 500 to 600°C in a cooling tank, although this will differ depending upon the constituents.
  • Lead molten lead
  • a fluidized bed has a low cooling capacity and water has the drawback of causing supercooling.
  • lead which has a boiling point of 1749°C and a melting point of 327.5°C, is still presently in wide use because it is in a stable liquid-phase state in the temperature range necessary for patenting (a temperature range for suitably cooling the heated carbon-steel wire and precipitating the pearlite structure).
  • lead (Pb) is suitable as the cooling medium in the patenting of carbon-steel wire, as mentioned above, there are instances where its use is restricted on account of its toxicity.
  • RoHS Restriction on Hazardous Substances
  • the marketing in EU member states of electronic and electrical equipment containing lead in excess of 1,000 ppm is restricted.
  • An object of the present invention is to provide a novel heat exchange medium to replace lead, as well as a heat exchange method which utilizes this medium.
  • a heat exchange method is characterized by: bringing an object into contact with or in close proximity to a liquid-phase Mg-Al-Ca alloy obtained by melting an Mg-Al-Ca alloy in which Mg, Al and Ca are main constituent elements; and exchanging (transferring) thermal energy between the object and the liquid-phase Mg-Al-Ca alloy.
  • a heat exchange medium according to the present invention is characterized by including a liquid-phase Mg-Al-Ca alloy obtained by melting an Mg-Al-Ca alloy in which Mg, Al and Ca are main constituent elements.
  • so-called unavoidable impurities namely those which exist in the raw materials or which inevitably become mixed in during the manufacturing process and are inherently unwanted but are allowed because they are in trace amounts and have no influence upon the characteristics of the product, are contained in the Mg-Al-Ca alloy or in the liquid-phase Mg-Al-Ca obtained by melting the alloy.
  • the present invention also provides a heat exchange apparatus.
  • the heat exchange apparatus according to the present invention includes a bath filled with a liquid-phase Mg-Al-Ca alloy obtained by melting an Mg-Al-Ca alloy in which Mg, Al and Ca are main constituent elements.
  • the present invention also provides a patenting treatment for cooling heated carbon steel, an example of which is carbon-steel wire.
  • the patenting treatment according to the present invention comprises: passing heated carbon steel through a bath filled with a liquid-phase Mg-Al-Ca alloy obtained by melting an Mg-Al-Ca alloy in which Mg, Al and Ca are main constituent elements; and cooling the heated carbon steel when it passes through the bath.
  • a liquid-phase Mg-Al-Ca alloy put in the liquid phase by heating and melting an Mg-Al-Ca alloy that is a solid at room temperature is used as a heat exchange medium (heating medium or cooling medium) for applying heat to (heating) an object or removing heat from (cooling) an object.
  • the object may be heated or cooled by bringing it into direct contact with the liquid-phase Mg-Al-Ca alloy, or the object can also be heated or cooled in contactless fashion by bringing the liquid-phase Mg-Al-Ca alloy into close proximity with the object without contacting it directly. For example, causing the liquid-phase Mg-Al-Ca alloy to flow through a pipe will heat or cool the pipe surroundings.
  • liquid-phase Mg-Al-Ca alloy used as a heating medium, it may be utilized in a bluing treatment, degreasing treatment or carbon spheroidizing treatment, for example.
  • liquid-phase Mg-Al-Ca alloy used as a cooling medium, it may be utilized in patenting (annealing of steel), cooling of a fuel rod and stepwise cooling of steel material.
  • the Mg-Al-Ca alloy is a ternary alloy the main constituent elements of which are Mg (magnesium), Al (aluminum) and Ca (calcium).
  • Mg manganesium
  • Al aluminum
  • Ca calcium
  • magnesium pure magnesium
  • rare earth elements such as, for example, Mn (manganese), Zr (zirconium), Ag (silver), Y (yttrium) or Nd (neodymium) may be added.
  • the Mg-Al-Ca alloy enables the liquidus temperature thereof to be lowered below the melting point (650°C) of magnesium, the melting point (660°C) of aluminum and the melting point (842°C) of calcium. Furthermore, it has been found that the liquid-phase Mg-Al-Ca alloy can transfer heat faster than molten lead.
  • the liquid-phase Mg-Al-Ca alloy can be used suitably as a heating medium or cooling medium in place of molten lead.
  • the main constituent elements Mg, Al and Ca of the liquid-phase Mg-Al-Ca alloy are all harmless metal elements and have no environmental impact.
  • the object may simply be immersed in the liquid-phase Mg-Al-Ca alloy or may be passed through the liquid-phase Mg-Al-Ca alloy while the object is being moved.
  • the bath When the bath is filled with the liquid-phase Mg-Al-Ca alloy, a thin film forms on the surface (liquid surface layer) of the liquid-phase Mg-Al-Ca alloy. Owing to the film that forms on the surface of the liquid-phase Mg-Al-Ca alloy collected in the bath, the liquid-phase Mg-Al-Ca alloy in the bath can be prevented from direct exposure to air (oxygen) or such exposure can be made unlikely to occur. This makes it difficult for the liquid-phase Mg-Al-Ca alloy filling the bath to combust. However, since the Mg-Al-Ca alloy used in the present invention is in the liquid-phase state, it is employed in a state in which it is less combustible in comparison with use in the solid phase (inclusive of use in powder form).
  • WO2015/060459 discloses a magnesium alloy obtained by adding other elements (such as Mn, Zn, Zr, Ag, Y, Nd) to an alloy (Mg, Al) 2 Ca, which is the result of adding calcium and aluminum to magnesium.
  • the magnesium alloy disclosed in WO2015/060459 can, in molten form, be used suitably as the liquid-phase Mg-Al-Ca alloy used in the heat exchange medium in the present invention.
  • the mechanical strength and toughness required in the solid phase are unnecessary and there is also no need to take corrosion resistance into consideration.
  • the temperature of the carbon-steel wire when it is immersed in the liquid-phase Mg-Al-Ca alloy will be about 900 to 1000°C.
  • the liquid-phase Mg-Al-Ca alloy used in the present invention therefore, preferably should have an ignition temperature of 900°C or higher, and 1000°C or higher for safety reasons.
  • a magnesium alloy having an ignition temperature of 1000°C or higher is disclosed in WO2015/060459 cited above.
  • the Mg-Al-Ca alloy in the present invention is used in the liquid phase, not the solid phase, and can be used without coming into direct contact with air. That is, it is used in a state in which it is positively less likely to combust in comparison with an Mg-Al-Ca alloy in the solid phase (powder form). Consequently, for example, even if the ignition temperature of a Mg-Al-Ca alloy in the solid phase (powder form) is less than 1000°C and a carbon-steel wire heated to 1000°C is immersed in liquid-phase Mg-Al-Ca alloy obtained by melting the solid-phase alloy, the liquid-phase Mg-Al-Ca alloy in unlikely to ignite immediately. Still, for safety reasons, it is preferred that the liquid-phase Mg-Al-Ca alloy used in the present invention have an ignition temperature of 1000°C or higher even when it is in the solid phase.
  • the amount of Ca be x ⁇ 0.015 (at%) or higher, where x (at%) is the amount of Mg.
  • the Mg-Al-Ca alloy if a liquidus temperature lower than the above-mentioned melting points of magnesium (650°C), aluminum (660°C) and calcium (842°C) is achieved, then it will suffice if the amount of Ca is made less than x ⁇ 0.1 + 10 (at%), where x (at%) is the amount of Mg.
  • the upper limit of the liquidus temperature of the Mg-Al-Ca alloy can be made 640°C.
  • the liquidus temperature of the Mg-Al-Ca alloy can be lowered down to below 550°C (460°C according to calculation) by adjusting the composition ratio of the Mg, Al and Ca occupying the Mg-Al-Ca alloy, thus enabling the alloy to be suitable for use in patenting in place of molten lead.
  • the liquid-phase Mg-Al-Ca alloy used as the heat exchange medium in the present invention can be put into a liquid-phase state which is stable in a temperature range of from about 1000°C to about 460°C.
  • a carbon-steel wire produced using the liquid-phase Mg-Al-Ca alloy as the cooling medium is processed into fine wire, it is less prone to delamination or experiences no delamination, i.e., its processing limit (marginal workability) is improved, in comparison with a carbon-steel wire produced using molten lead as the cooling medium.
  • a carbon-steel wire obtained by carrying out patenting using the liquid-phase Mg-Al-Ca alloy as the cooling medium followed by drawing exhibits a tensile strength higher than that of a carbon-steel wire produced using molten lead as the cooling medium.
  • Fig. 1 which illustrates an embodiment of the present invention, is a block diagram schematically showing patenting treatment of carbon-steel wire.
  • Fig. 2 is a cross-sectional view schematically showing a drawing process of carbon-steel wire.
  • a wire rope, steel cord or the like is produced by bundling and twisting together multiple carbon-steel wires obtained by a patenting treatment and drawing process.
  • a carbon-steel wire (starting-wire material) 1A with a circular cross-section manufactured by hot rolling is wound on each of a plurality of delivery reels 10.
  • the carbon-steel wire 1A delivered from each of the delivery reels 10 proceeds to a heating furnace 11 where it is heated to a predetermined temperature of, for example, 950°C.
  • the heated carbon-steel wire 1A proceeds to a cooling tank (cooling furnace) 12.
  • the cooling tank 12 contains a bath 12A filled with a liquid-phase Mg-Al-Ca alloy 20.
  • the bath 12A is heated.
  • the Mg-Al-Ca alloy which is a solid at room temperature, is melted and placed in the liquid phase by being heated in the bath 12A.
  • the bath 12A is heated to a temperature above the temperature (liquidus temperature) necessary to place the Mg-Al-Ca alloy in the liquid phase.
  • the liquidus temperature of the Mg-Al-Ca alloy used in the present invention is on the order of 460 to 640°C, as described below.
  • the liquidus temperature of the Mg-Al-Ca alloy varies depending on the weight ratios or element ratios (composition ratios) of respective ones of Mg, Al, Ca included in the Mg-Al-Ca alloy.
  • the liquid-phase Mg-Al-Ca alloy 20 in the bath 12A is maintained at a temperature of about 550°C.
  • the carbon-steel wire 1A that was heated in the heating furnace 11 is cooled from about 950°C to about 550°C.
  • a thin film (such as an oxide film) 21 forms on the surface of the liquid-phase Mg-Al-Ca alloy 20 in the bath 12A owing to exposure to air.
  • the liquid-phase Mg-Al-Ca alloy 20 collected in the bath 12A (the liquid-phase portion covered by the film 21 inside the bath 12A) is hardly exposed to air.
  • the carbon-steel wire 1A cooled by the liquid-phase Mg-Al-Ca alloy 20 is then cooled further in a bath 13 filled with water, after which it proceeds to a bath 14 filled with hydrochloric acid, where scale (an iron oxide film) is removed from the surface of the carbon-steel wire 1A.
  • the carbon-steel wire 1A from which the scale has been removed is washed in a bath 15 filled with water and finally proceeds to a bath 16 filled with zinc phosphate, where the surface is coated with zinc phosphate for purposes of rust prevention and lubrication.
  • the resultant carbon-steel wire 1B coated with the zinc phosphate is wound onto multiple take-up reels 17.
  • the carbon-steel wire 1B wound by the take-up reel 17 then proceeds to a wire drawing process.
  • the carbon-steel wire 1B is drawn to a predetermined diameter by a wire drawing machine equipped with a carbide alloy die 31 (the carbon-steel wire after being drawn is indicated by reference character 1C).
  • the carbon-steel wire 1C of small diameter is manufactured, carbon-steel wire having an intermediate diameter is manufactured and the above-described drawing process is repeated using this wire as a starting-wire material.
  • Fig. 3 is a liquid-phase diagram created using phase diagram calculation software for the Mg-Al-Ca alloy (ternary alloy) used as the cooling medium in the above-mentioned patenting treatment.
  • Fig. 3 shows the liquid-phase diagram of a ternary alloy, in which the main constituent components are Mg (magnesium), Al (aluminum) and Ca (calcium), in a rectangular coordinate system where the horizontal axis is a plot of the weight ratios of Mg and Al and the vertical axis is a plot of the weight ratio of Ca.
  • the horizontal axis shows the weight percent concentration (wt%) of Al that occupies the Mg-Al-Ca alloy, indicating that the weight ratio of Mg occupying the Mg-Al-Ca alloy is larger toward the left side and that the weight ratio of Al occupying the Mg-Al-Ca alloy is larger toward the right side.
  • the vertical axis shows the weight percent concentration of Ca that occupies the Mg-Al-Ca alloy.
  • the remainder of the weight percent concentration of Al (horizontal axis) and of the weight percent concentration of Ca (vertical axis) represents the weight percent concentration of Mg.
  • eutectic points E1, E2, E3, U4, U5 and U6 are illustrated in the liquid-phase diagram shown in Fig. 3 .
  • the liquidus temperatures of Mg-Al-Ca alloys having the composition ratios of these six eutectic points, as well as the weight ratios (element ratios) of Mg, Al and Ca, are as follows:
  • eutectic point E1 has the highest liquidus temperature (melting point), which is 515°C.
  • melting point liquidus temperature
  • an ideal Mg-Al-Ca alloy the Mg-Al-Ca alloy having the composition ratio indicated by the eutectic point
  • the Inventors actually prepared five samples of Mg-Al-Ca alloy having different composition ratios of Mg, Al and Ca and, for each alloy sample, the inventors analyzed the weight ratio (element ratio) of every constituent element using an ICP (Inductively Coupled Plasma) (high-frequency inductively coupled plasma) analyzer and checked whether the alloy sample was in the liquid phase at 550°C and whether it combusted at 1000°C.
  • ICP Inductively Coupled Plasma
  • ICP Inductively Coupled Plasma
  • one sample (Sample I described below) of the five alloy samples was melted for conversion to the liquid phase and was used in the above-described patenting treatment (namely the liquid-phase Mg-Al-Ca alloy 20 collected in the bath 12A in order to cool the heated carbon-steel wire 1A) and was subjected to drawing, thereby manufacturing a carbon-steel wire, and the manufactured carbon-steel wire was subjected to a tensile test and torsion test.
  • the results of analysis, confirmation and testing are described below.
  • Fig. 4 illustrates, for each of the five prepared Samples I to V of Mg-Al-Ca alloy, the composition ratios (both wt% and at%) of every constituent element analyzed using the ICP analyzer, as well as the results of confirming the phase state at heating to 550°C and the combustion state at heating to 1000°C.
  • Fig. 5 is a plot (indicated by mark ⁇ ) of the composition ratios of Mg, Al and Ca for each of Samples I to V in a form superimposed on the liquid-phase diagram shown in Fig. 3 .
  • Samples I to V are all Mg-Al-Ca alloys having composition ratios outside the eutectic points, it is confirmed by reference to Fig. 4 that all Samples I to V are completely in the liquid phase at 550°C and non-combustible at 1000°C, from which it will be understood that there is no problem in using them as cooling media in the patenting treatment.
  • Sample I has a liquidus temperature near 580°C and it might be thought that the solid phase (a state in which the liquid and solid phases are mixed) would be found at 550°C. However, the solid phase could not be confirmed.
  • Sample V is an Mg-Al-Ca alloy in which the element ratio of Mg is comparatively large and the element ratio of Ca comparatively small.
  • the ease with which the Mg-Al-Ca alloy combusts is related to the element ratio of Mg occupying the Mg-Al-Ca alloy; it is thought that the larger the element ratio of Mg, the higher the element ratio of Ca should be made in order to make the alloy less prone to combust.
  • the element ratio of Al occupying the Mg-Al-Ca alloy is increased, the element ratio of Ca can be reduced to make the alloy less prone to combust.
  • Fig. 6 is a plot of the composition ratios of Mg, Al and Ca for each of the prepared Samples I to V and for the eutectic alloys, which correspond to the eutectic points E1 to E3 and U4 to U6 shown in Fig. 3 , in a rectangular coordinate system in which the horizontal axis is a plot of the element ratios of Mg and Al and the vertical axis a plot of the element ratio of Ca (in units of at%).
  • the horizontal axis is a plot of the element ratios of Mg and Al and the vertical axis a plot of the element ratio of Ca (in units of at%).
  • Samples I to V are indicated by mark ⁇ and the eutectic points E1 to E3 and U4 to U6 by mark x, and sample identification symbols (I) to (V) and eutectic point identification symbols (points E1 to E3 and U4 to U6) are shown near the respective plots.
  • Sample V is near the limit value (lower-limit value) of Ca that should be added to make 1000°C the ignition temperature, and that the element ratio of Ca for making the Mg-Al-Ca alloy less prone to combust can be reduced if the element ratio of Al occupying the Mg-Al-Ca alloy is increased, then it can be inferred that the single-dot chain line shown in Fig.
  • FIG. 6 will be the approximate lower-limit value of Ca to make the ignition temperature of the liquid-phase Mg-Al-Ca alloy 20 greater than 1000°C.
  • the single-dot chain line shown in Fig. 6 is represented by "Mg ⁇ 0.015" with Mg (the element ratio thereof) (at%) that occupies the liquid-phase Mg-Al-Ca alloy 20 serving as the reference.
  • the solid line shown in Fig. 6 indicates a straight line represented by "Mg ⁇ 0.1 + 10", this indicating the upper-limit value of Ca for making the liquidus temperature of the Mg-Al-Ca alloy less than about 620 to 640°C.
  • the element ratio (at%) of Ca occupying the liquid-phase Mg-Al-Ca alloy 20 is made less than "Mg ⁇ 0.1 + 10"
  • the liquidus temperature of the liquid-phase Mg-Al-Ca alloy 20 will not exceed 620 to 640°C and it is thought that the liquidus temperature of the liquid-phase Mg-Al-Ca alloy 20 can be made lower than the melting point (650°C) of magnesium, the melting point (660°C) of aluminum and the melting point (842°C) of calcium.
  • Fig. 7 illustrates the results of a tensile strength test and torsion test and results of a fracture test of carbon-steel wire manufactured by using the Mg-Al-Ca alloy of Sample I in the above-described patenting treatment upon melting the alloy to convert it to the liquid phase.
  • carbon-steel wire manufactured using molten lead in the patenting treatment was subjected to similar tests.
  • Carbon-steel wire (SWRH72A) having a diameter of 5.500 mm was heated to about 950°C and then immersed for 1 min in the liquid-phase Mg-Al-Ca alloy 20 (550°C) obtained by melting the Mg-Al-Ca alloy of Sample I, after which the wire underwent water cooling. After scale was removed by hydrochloric acid and followed by washing with water, the wire was coated with zinc phosphate.
  • Wire diameter of the carbon-steel wire was gradually reduced by a drawing process multiple times to obtain wires with wire diameters of 1.748 mm, 1.553 mm, 1.408 mm and 1.248 mm, and each of these was subjected to the tensile test and torsion test.
  • the tensile strength (in units of Mpa) column in Fig. 7 shows the tensile strength of carbon-steel wires of diameters 1.748 mm, 1.553 mm, 1.408 mm and 1.248 mm using the liquid-phase Mg-Al-Ca alloy 20 and molten lead as the cooling media for each wire.
  • the carbon-steel wire was set in a torsion testing machine, both ends of the wire were gripped at a gripping spacing 100 times the diameter of the carbon-steel wire, and one end was rotated in one direction at a predetermined rotational speed.
  • FIG. 7 shows twist values (numbers of times twisted at time of breakage) and results of observing fracture (breakage surface) for the carbon-steel wires having diameters of 1.748 mm, 1.553 mm, 1.408 mm and 1.248 mm using the liquid-phase Mg-Al-Ca alloy 20 as the cooling medium, as well as twist values and results of observing fracture for the carbon-steel wires having diameters of 1.748 mm, 1.553 mm, 1.408 mm and 1.248 mm using molten lead as the cooling medium.
  • twist values were substantially the same regardless of whether the liquid-phase Mg-Al-Ca alloy or molten lead was used as the cooling medium.
  • Fig. 8 illustrates the results of other tests conducted under different test conditions.
  • Fig. 8 shows the results of a tensile strength test and torsion test applied to carbon-steel wire of smaller diameter manufactured using in the patenting treatment a liquid-phase Mg-Al-Ca alloy obtained by melting an Mg-Al-Ca alloy different from Sample I.
  • test results are also shown for carbon-steel wire manufactured using molten lead instead of liquid-phase Mg-Al-Ca alloy in the patenting treatment.
  • the wire diameter of the carbon-steel wire was gradually reduced by a drawing process multiple times, and carbon-steel wire of diameter reduced down to about 0.360 mm was subjected to the tensile test and torsion test and to observation of fracture.
  • the Mg-Al-Ca alloy having the above-described composition ratio took on a stable liquid phase by being heated at about 600°C and did not combust.
  • a carbon-steel wire fabricated using the liquid-phase Mg-Al-Ca alloy 20 as the cooling medium exhibits a higher tensile strength than a carbon-steel wire fabricated using molten lead as the cooling medium, even with regard to carbon-steel wire having a smaller diameter manufactured from starting wire material having a smaller diameter.
  • liquid-phase Mg-Al-Ca alloy 20 is used as the cooling medium for cooling the heated carbon-steel wire 1A.
  • the liquid-phase Mg-Al-Ca alloy 20 can also be used as a heating medium for heating an object.
  • the heated carbon-steel wire 1A is brought into direct contact with (immersed in) the liquid-phase Mg-Al-Ca alloy 20.
  • the liquid-phase Mg-Al-Ca alloy 20 can, for example, be brought into close proximity with the object without directly contacting it, and the object can be heated or cooled in contactless fashion.
  • the pipe surroundings can be heated or cooled.

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  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
EP20749310.7A 2019-01-31 2020-01-28 Procédé d'échange de chaleur, milieu d'échange de chaleur, dispositif d'échange de chaleur, procédé de patentage et fil d'acier au carbone Pending EP3919633A4 (fr)

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JP2019015517 2019-01-31
PCT/JP2020/002904 WO2020158704A1 (fr) 2019-01-31 2020-01-28 Procédé d'échange de chaleur, milieu d'échange de chaleur, dispositif d'échange de chaleur, procédé de patentage et fil d'acier au carbone

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EP3919633A1 true EP3919633A1 (fr) 2021-12-08
EP3919633A4 EP3919633A4 (fr) 2023-06-28

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US (1) US20210355561A1 (fr)
EP (1) EP3919633A4 (fr)
JP (1) JP7161735B2 (fr)
KR (2) KR20210118910A (fr)
CN (1) CN113227408A (fr)
WO (1) WO2020158704A1 (fr)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5062685A (en) * 1984-11-05 1986-06-03 Extramet Industrie S.A. Procede de traitement des metaux et alliages en vue de leur affinage
US6042369A (en) 1998-03-26 2000-03-28 Technomics, Inc. Fluidized-bed heat-treatment process and apparatus for use in a manufacturing line
JP3030338B1 (ja) * 1998-10-05 2000-04-10 工業技術院長 高強度難燃性マグネシウム合金の製造方法
BE1014868A3 (fr) 2002-06-06 2004-05-04 Four Industriel Belge Procede et dispositif de patentage de fils d'acier
JP4751206B2 (ja) * 2005-02-10 2011-08-17 新日本製鐵株式会社 高耐食性めっき鋼材及びその製造方法
JP5119465B2 (ja) * 2006-07-19 2013-01-16 新日鐵住金株式会社 アモルファス形成能が高い合金及びこれを用いた合金めっき金属材
US9169528B2 (en) 2008-04-30 2015-10-27 Nv Bekaert Sa Steel filament patented in bismuth
JP6569531B2 (ja) * 2013-10-23 2019-09-04 国立大学法人 熊本大学 マグネシウム合金及びその製造方法
JP6440062B2 (ja) * 2014-07-21 2018-12-19 株式会社戸畑製作所 マグネシウム系合金
AU2017392662A1 (en) * 2017-01-16 2019-08-15 Nippon Steel & Sumitomo Metal Corporation Plated steel material
CN108342548A (zh) * 2018-04-10 2018-07-31 广州宇智科技有限公司 一种新型含Re屈氏体热处理用无铅镁浴合金
CN108467927A (zh) * 2018-04-10 2018-08-31 广州宇智科技有限公司 具备高热容量的铅浴替代用含Os镁浴合金
CN108342549A (zh) * 2018-04-10 2018-07-31 广州宇智科技有限公司 屈氏体热处理中用于替代铅浴的含Cr镁浴合金

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KR20240019379A (ko) 2024-02-14
CN113227408A (zh) 2021-08-06
JPWO2020158704A1 (ja) 2021-12-02
US20210355561A1 (en) 2021-11-18
KR20210118910A (ko) 2021-10-01
EP3919633A4 (fr) 2023-06-28
WO2020158704A1 (fr) 2020-08-06
JP7161735B2 (ja) 2022-10-27

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