EP2085493A1 - Procédé de fabrication d'acier cémenté à haute concentration - Google Patents

Procédé de fabrication d'acier cémenté à haute concentration Download PDF

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Publication number
EP2085493A1
EP2085493A1 EP07830687A EP07830687A EP2085493A1 EP 2085493 A1 EP2085493 A1 EP 2085493A1 EP 07830687 A EP07830687 A EP 07830687A EP 07830687 A EP07830687 A EP 07830687A EP 2085493 A1 EP2085493 A1 EP 2085493A1
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Prior art keywords
carburization
temperature
steel material
primary
quenching
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EP07830687A
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German (de)
English (en)
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EP2085493A4 (fr
Inventor
Toshiyuki Morita
Masaomi Saruyama
Hiroyuki Tsuyuzaki
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Honda Motor Co Ltd
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Honda Motor Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising
    • C23C8/22—Carburising of ferrous surfaces
    • 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
    • C21D1/06—Surface hardening
    • 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
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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

Definitions

  • the present invention relates to a manufacturing method for high-concentration carburized steel and, more particularly, to a manufacturing method for high-concentration carburized steel in which fine and spherical carbides can be precipitated in a large amount in the surface thereof by carburization treatment.
  • Carburization means a treatment of heating steel in a carburizing atmosphere to thereby enhance carbon concentration in the surface.
  • Carburization is generally applied to low-carbon steel, which is quenched after carburization to use.
  • Materials having been subjected to such carburizing-quenching treatment are called case-hardened steel or carburized steel and are commercially used as mechanical members such as shafts, bearings, gear wheels, piston pins, and cams since they have a hard surface and a soft interior.
  • a treatment of enhancing the carbon concentration in the vicinity of the surface of the material to precipitate carbides is specifically called "high-concentration carburization".
  • Materials obtained by the high-concentration carburization contains hard carbides dispersed in their structure, and hence they are characterized in that they have higher abrasion resistance and higher surface fatigue strength than those materials have which are obtained by conventionally performed eutectoid carburization.
  • characteristic properties of the materials having been subjected to the high-concentration carburization treatment are strongly influenced by the dispersion state of carbides, it is necessary to disperse carbides finely in a spherical form in a large amount so as to obtain high strength (see, non-patent document 1). In particular, coarse carbides precipitated at the grain boundaries cause reduction in strength.
  • patent document 1 discloses a method of carburization treatment of steel, which subjecting following steps on a machine structure member made of steel having C:0.05-0.45% :
  • patent document 2 discloses a carburization heat treatment method of a steel member. The method includes:
  • the primary carburization treatment is performed mainly for the purpose of solid-dissolving carbon in a high concentration in the surface so as to precipitate fine carbides in a large amount upon re-heating for performing the secondary carburization treatment.
  • the secondary carburization treatment is performed mainly for the purpose of allowing fine carbides generated upon re-heating to grow. For such purposes, it is desirable that the difference in temperature between the primary carburization treatment and the secondary carburization treatment is large enough.
  • the manufacturing method for high-concentration carburized steel of the invention includes:
  • the difference between the primary carburization temperature T1 and the secondary carburization temperature T2 can be made large enough even when the primary carburization temperature T1 is a comparatively low temperature, by separating the secondary carburization treatment into a secondary carburization initial step of performing carburization at a secondary carburization temperature T2 which is lower than the quenching temperature Tq and a secondary carburization late step of performing carburization at a quenching temperature Tq.
  • fine and spherical carbides can be dispersed in a large amount without shortening the furnace life and generating serious deformation after carburization treatment.
  • a steel material to which the manufacturing method for high-concentration carburized steel of the invention is applied contains alloy elements as described below, and the balance thereof is Fe and unavoidable impurities.
  • Kinds of the alloy elements, ranges of the components, and reasons for restricting the ranges are as follows.
  • the amount of C is preferably 0.15 mass% or more.
  • the amount of C is preferably 0.30 mass% or less.
  • the amount of Si is preferably 0.40 mass% or more.
  • the amount of Si is preferably 0. 80 mass% or less.
  • the amount of Mn is preferably 0.3 mass% or more.
  • the amount of Mn is preferably 0.8 mass% or less.
  • the amount of Cr is small, the amount of generated carbides is reduced, which reduces strength. Also, ferrite is generated in the core portion, which reduces strength. Therefore, the amount of Cr is preferably 1.25 mass% or more. On the other hand, if the amount of Cr is excessive, hardness of the material is enhanced, which reduces productivity (particularly machinability). Therefore, the amount of Cr is 2.00 mass% or less.
  • the manufacturing method for high-concentration carburized steel of the invention includes a primary carburization step, a cooling step, a secondary carburization initial step, a secondary carburization late step, and a quenching step.
  • the primary carburization step is a step of carburizing a steel material having the above-described composition at a primary carburization temperature T1 (°C) so that the surface carbon concentration C becomes Ceu ⁇ C ⁇ C(Acm). It suffices for the primary carburization temperature T1 to be temperature higher than the secondary carburization start temperature T2s to be described hereinafter by 100°C or more. In general, as the primary carburization temperature T1 becomes higher, carburization to a predetermined carbon concentration can be achieved in a shorter time. To be specific, the primary carburization temperature T1 is preferably 900°C or higher.
  • the primary carburization temperature T1 is preferably 1,100°C or lower, more preferably 1,000°C or lower.
  • C of a steel material becomes Ceu ⁇ C ⁇ C (Acm).
  • surface carbon concentration means an average carbon concentration within the region of 10 ⁇ m from the surface.
  • Ceu means an eutectoid carbon concentration of a steel material containing Si, Mn, and Cr in the above-described ranges, respectively. With every above-described steel material, the eutectoid carbon concentration is 0.5 mass% or more.
  • C(Acm) means a carbon concentration corresponding to the Acm line of a steel material containing Si, Mn, and Cr in the above-described ranges, respectively, at the primary carburization temperature T1. To perform carburization till C ⁇ C(Acm) means to perform the primary carburization at temperature at which the surface temperature of the steel material becomes the Acm line or higher (i.e., temperature at which the surface becomes a single phase of ⁇ -phase).
  • the surface carbon concentration C is small, carbides would not be precipitated within the matrix during the temperature-raising procedure in the secondary carburization to be described hereinafter. If carbides are not precipitated within the matrix, coarse carbides would be generated at the grain boundaries during the secondary carburization. Therefore, the primary carburization must be performed so that the surface carbon concentration C can become larger than Ceu. On the other hand, if the carbon concentration C of the surface becomes excessive, carbides would be generated at the grain boundaries during the primary carburization. Since carbides generated in the primary carburization remain as such, generation of coarse carbides must be prevented. Specifically, absence of coarse carbides of 5 ⁇ m or more in long diameter is preferred.
  • the primary carburization must be performed so that the surface carbon concentration C can become C(Acm) or less.
  • C(Acm) becomes from about 1.25 to about 1.4 mass% when the primary carburization temperature T1 is from 950 to 1,000°C.
  • the carburization method upon performing the primary carburization is not particularly limited, and various methods may be employed.
  • gas carburization and vacuum carburization are preferred as the carburization methods since handling is easy and treating period is short.
  • the surface carbon concentration C can be controlled within the above-described range by optimizing the carburizing conditions.
  • gas carburization carburization is performed by heating a steel material in an atmosphere of a carburizing gas.
  • the amount of carburization can be controlled through carbon potential of the carburizing atmosphere. Carbon potential is the surface equilibrium carbon concentration of pure iron equilibrated with the atmosphere and is dependent upon the CO/CO 2 ratio and the amount of H 2 O in the atmosphere.
  • the surface carbon concentration can be increased in a shorter time when the carbon potential becomes higher and/or when the primary carburization temperature T1 becomes higher.
  • carburization can be performed by, for example, reducing the pressure inside the furnace into which a steel material has been introduced to about 1.3 Pa, and then heating to the carburization temperature with introducing thereinto a hydrocarbon gas such as methane or propane.
  • a hydrocarbon gas such as methane or propane.
  • the amount of carburization can be controlled through the time of introducing the hydrocarbon gas.
  • the carbon concentration in the vicinity of the surface may become too high. In such case, it is general to perform diffusion treatment of stopping supply of the hydrocarbon gas after carburization and retaining in the same state.
  • the cooling step is a step of cooling, after completion of the primary carburization step, the steel material at a cooling rate of 1°C/min or more to 700°C or lower. After completion of the primary carburization, the steel material is once cooled to temperature of 700°C or lower.
  • the reason for cooling to temperature of 700°C or lower is that, upon re-heating in the secondary carburization, fine carbides be precipitated within grains. In this case, when the cooling rate is too slow, flake-like, coarse carbides are formed at the grain boundaries during cooling, thus too slow cooling rate is not preferred. The coarse carbides generated during cooling will not disappear in the step to be described hereinafter, and can cause reduction of strength of the steel material. Therefore, the cooling rate of 1°C/min or more is preferred. A faster cooling rate is more preferred.
  • the secondary carburization initial step is a step wherein the temperature of the cooled steel material is raised to the secondary carburization start temperature T2s and the steel material is carburized at the secondary carburization temperature T2.
  • the term "secondary carburization start temperature T2s" means the temperature which satisfies the condition of the following formula (1). Ac ⁇ 1 point °C ⁇ T ⁇ 2 ⁇ s °C ⁇ primary carburization temperature T ⁇ 1 - 100 ⁇ °C ⁇ Acm line temperature °C ⁇ corresponding to the surface carbon concentration of the steel material immediately after initiation of secondary carburization
  • the temperature difference between the secondary carburization start temperature T2s and the primary carburization temperature T1 is preferably 100°C or more.
  • the secondary carburization start temperature T2s must be equal to, or higher than, Ac1 point and must be equal to, or lower than, the Acm line temperature corresponding to the surface carbon concentration of a steel material immediately after initiation of the secondary carburization. This means to initiate the secondary carburization when the surface temperature of the steel material is between Ac1 point and Acm line (i.e., the temperature at which the surface becomes ⁇ +Fe 3 C phase).
  • secondary carburization temperature T2 means the temperature which satisfies the conditions of the following formula (2). T ⁇ 2 ⁇ s ⁇ T ⁇ 2 ⁇ Acm line temperature C corresponding to the surface carbon concentration of the aforesaid steel material
  • the secondary carburization temperature T2 may be the same as the secondary carburization start temperature T2s or may be temperature higher than that. If the secondary carburization temperature T2 is the same as the secondary carburization start temperature T2s, the retaining time at the secondary carburization temperature T2 may be such that, when the temperature is raised to the quenching temperature Tq to be described hereinafter, the surface temperature of the steel material does not exceed the Acm line temperature.
  • the surface carbon concentration increases as the time of retaining at the secondary carburization temperature T2 is prolonged, and hence carburization can be performed with keeping the surface temperature of the steel material at Acm line or less.
  • the retaining time at the secondary carburization temperature T2 is preferably 15 minutes or longer.
  • the secondary carburization temperature T2 may be reached by raising the temperature stepwisely or continuously from the secondary carburization start temperature T2s.
  • stepwisely means to repeat the procedures of retaining the temperature at a definite level for a predetermined time, then raising the temperature with a predetermined temperature width, and retaining the temperature at the predetermined temperature for a predetermined time.
  • stepwisely raising the temperature carburization can be performed with retaining the surface temperature of the steel material at Acm line or less by optimizing the temperature-raising width and the temperature-retaining time.
  • the term “continuously” means to raise the temperature at a predetermined temperature-raising rate. When continuously raising the temperature, carburization can be performed with retaining the surface temperature of the steel material at Acm line or less by optimizing the temperature-raising rate.
  • the secondary carburization late step is a step of subsequently raising, after completion of the secondary carburization initial step, the temperature of the steel material up to the quenching temperature Tq (°C), and further performing carburization at the quenching temperature Tq, provided that Tq ⁇ Acm line temperature (°C) corresponding to the surface carbon concentration of the aforesaid steel material.
  • the secondary carburization late step is a step of not only raising the temperature of the steel material to the quenching temperature Tq but also adjusting the surface carbon concentration to an intended carbon concentration in a short time without precipitation of flake-like, coarse carbides at the grain boundaries. Therefore, the quenching temperature Tq must be equal to, or less than, the Acm line temperature corresponding to the surface carbon concentration of the steel material.
  • the temperature can be raised up to the quenching temperature Tq with retaining the surface temperature of the steel material at Acm line temperature or less.
  • the quenching temperature Tq is preferably equal to, or higher than, the temperature at which the core portion of the steel material becomes an austenite single phase.
  • the time of retaining the temperature at the quenching temperature Tq is not particularly limited, and an optimal time is to be selected depending upon composition of the steel material, quenching temperature Tq, characteristic properties required for the steel material, and the like. In general, as the temperature-retaining time is prolonged, the surface carbon concentration of the steel material can be more increased. In order to obtain high-concentration carburized steel excellent in abrasion resistance and surface fatigue strength, the temperature-retaining time at the quenching temperature Tq (i.e., carburization time) is preferably 15 minutes or longer.
  • quenching may immediately be performed substantially without performing carburization at the quenching temperature Tq after the temperature reaches the quenching temperature Tq as long as a sufficient carburization amount is obtained at the point when the temperature reaches the quenching temperature Tq and when soaking of the steel material is sufficient.
  • the quenching step is a step of quenching the steel material after completion of the secondary carburization late step. Quenching is to be performed for transforming the surface carburized layer and the core portion to martensite. For this, the steel material after completion of the secondary carburization late step is to be preferably quenched.
  • the quenching method there are specifically an oil quenching method and a gas quenching method.
  • Figs. 1A to Fig. 1D are schematic views showing structural changes when performing high-concentration carburization under various conditions. Additionally, phase diagrams are also shown in Figs. 1A to Fig. 1D .
  • the high-concentration carburization it is performed twice in many case, that is, the primary carburization and the secondary carburization.
  • the surface carbon concentration upon completion of the primary carburization is lower than the Acm line concentration corresponding to the carburization temperature as shown in the phase diagram of Fig. 1A .
  • the surface after the completion of the primary carburization is in a state of austenite single phase. Therefore, when the steel material is cooled to 700°C or lower from this state at a predetermined cooling rate, the structure of the steel material becomes the state wherein coarse carbides are not generated at the grain boundaries as shown in the left drawing of Fig. 1A .
  • the temperature of the steel material is raised to the secondary carburization temperature, spherical and fine carbides are generated in the course of raising the temperature in the secondary carburization as shown in the middle drawing of Fig. 1A .
  • the secondary carburization is performed at temperature lower than the Acm line temperature corresponding to the surface carbon concentration of the steel material (i.e., the temperature at which the surface becomes ⁇ +Fe 3 phase), and carbon diffusion rate becomes smaller than in the primary carburization, thus carbides being difficultly precipitated in the grain boundaries.
  • the fine carbides generated during temperature-raising procedure act as nuclei to allow growth of carbides as shown in the right drawing of Fig. 1A .
  • the temperature upon completion of the primary carburization must be higher than the Acm line, and the temperature upon initiation of the secondary carburization must be lower than the Acm line. Since produced steel materials are not uniform in composition between lots, the position of the Acm line varies to some extent between individual steel materials. Hence, in order to surely obtain the structure as shown in Fig. 1A , it is necessary to provide a sufficient temperature difference between the primary carburization temperature and the secondary carburization temperature. However, when the primary carburization temperature is raised for the purpose of providing the sufficient temperature difference, durability of the furnace is decreased. On the other hand, when the secondary carburization temperature is decreased in order to avoid this, the carbon diffusion rate in the secondary carburization is reduced, leading to serious decrease in productivity.
  • the two-step carburization treatment with the Acm line being put between the two steps.
  • the primary carburization temperature is above the Acm line while retaining the secondary carburization temperature at the same temperature as in the conventional art and lowering the primary carburization temperature
  • the structure of the steel material after completion of the primary carburization is in the state that coarse carbides are not generated at the grain boundaries as shown in the left drawing of Fig. 1B .
  • the structure of the steel material after completion of the primary carburization is in the state that coarse carbides are not generated at the grain boundaries as shown in the left drawing of Fig. 1D .
  • the secondary carburization start temperature is lower than the primary carburization temperature by 100°C or more while raising, after cooling the steel material, the temperature to the secondary carburization start temperature, the surface temperature of the steel material can surely be adjusted to temperature lower than the Acm line. Therefore, at the point where the temperature reaches the secondary carburization start temperature, fine carbides are generated within the grains as shown in the middle drawing of Fig. 1D .
  • the primary carburization In order to prevent precipitation of flake-like, coarse carbides at the grain boundaries, the primary carburization must be performed at temperature higher than the Acm line and the secondary carburization must be performed at temperature lower than the Acm line.
  • the manufacturing method for high-concentration carburized steel of the invention can provide a sufficient temperature difference between after completion of the primary carburization and upon initiation of the secondary carburization, and hence generation of flake-like, coarse carbides can surely be suppressed even when steel materials are not uniform in composition between lots. Also, since it is not necessary to raise the temperature of the primary carburization for providing a sufficient temperature difference, durability of the furnace is not reduced. Further, since carburization is continued, after a predetermined time after the temperature reaches the secondary carburization start temperature, by raising the temperature to the quenching temperature, the carbon concentration of the surface can reach the intended concentration in a short time.
  • Carburization is performed with steel materials having various compositions under various conditions. Additionally, every carburization is performed in two steps of the primary carburization and the second carburization. Also, except for Example 15 and Comparative Example 1, the secondary carburization is performed in two steps of the secondary initial step of retaining the temperature for a predetermined time at a definite level (low temperature) and the secondary carburization late step of raising the temperature to the quenching temperature (high temperature) and retaining at the temperature for a predetermined time.
  • a typical carburization treatment pattern is shown in Fig. 2 .
  • the surface carbon concentration after completion of the primary carburization is determined by measuring distribution of cross-sectional carbon concentration through EPMA and calculating an average carbon concentration in the region of 10 ⁇ m from the surface. Also, diameter of carbide after completion of the primary carburization and diameter after quenching are measured by photographing using SEM after corroding the cross-section of the sample with picral, with the maximum value of the particle size of carbides existing in 1 mm 2 being taken as "particle size of carbides”. Further, fatigue strength after quenching is measured by the rotating bending fatigue test (according to JIS Z 2274).
  • Compositions of individual steel materials, carburization conditions, and test results are shown in Table 1.
  • Comparative Example 1 coarse carbides of larger than 10 ⁇ m are generated after quenching. This may be attributed to that, since the secondary carburization initial step is omitted and the secondary carburization late step at 885°C is immediately performed, fine carbides generated in the course of the secondary carburization again undergoes solid dissolution.
  • Comparative Example 2 coarse carbides of larger than 10 ⁇ m are generated after quenching. The reason for this is that the primary carburization is excessive and, at the point of completion of the primary carburization, coarse carbides are already generated.
  • Comparative Example 3 coarse carbides of larger than 6 ⁇ m are generated.
  • the fatigue strength is 700 MPa or more. This may be attributed to that, since the primary carburization, secondary carburization initial procedure, and secondary carburization late procedure are performed under proper conditions, fine and spherical carbides are formed in a large amount within the grains without generating flake-like, coarse carbides at the grain boundaries.
  • the manufacturing method for high-concentration carburized steel of the invention can be used as a manufacturing method for mechanical members such as shafts, bearings, gear wheels, piston pins, and cams.

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EP07830687A 2006-11-06 2007-10-26 Procédé de fabrication d'acier cémenté à haute concentration Withdrawn EP2085493A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006299836A JP4971751B2 (ja) 2006-11-06 2006-11-06 高濃度浸炭鋼の製造方法
PCT/JP2007/070953 WO2008056552A1 (fr) 2006-11-06 2007-10-26 Procédé de fabrication d'acier cémenté à haute concentration

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EP2085493A1 true EP2085493A1 (fr) 2009-08-05
EP2085493A4 EP2085493A4 (fr) 2009-11-25

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US (1) US20100126632A1 (fr)
EP (1) EP2085493A4 (fr)
JP (1) JP4971751B2 (fr)
CN (1) CN101535522B (fr)
WO (1) WO2008056552A1 (fr)

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CN104726819B (zh) * 2015-03-20 2017-09-19 上海人本集团有限公司 渗碳钢的热处理渗碳工艺
CN104949769B (zh) * 2015-06-23 2018-04-03 南车戚墅堰机车有限公司 一种不依靠测温系统快速发现渗碳温度场变化的方法
CN109201966A (zh) * 2018-10-30 2019-01-15 安徽芜湖海螺建筑安装工程有限责任公司 抗崩裂锚固件折弯切刀组件
CN109321871A (zh) * 2018-10-30 2019-02-12 安徽芜湖海螺建筑安装工程有限责任公司 抗崩裂锚固件折弯切刀材料及其制备方法
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CN101535522B (zh) 2011-05-18

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