EP1431412A1 - Automatenlegierung - Google Patents

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EP1431412A1
EP1431412A1 EP04004046A EP04004046A EP1431412A1 EP 1431412 A1 EP1431412 A1 EP 1431412A1 EP 04004046 A EP04004046 A EP 04004046A EP 04004046 A EP04004046 A EP 04004046A EP 1431412 A1 EP1431412 A1 EP 1431412A1
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Prior art keywords
mass
alloy
content
range
free cutting
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EP04004046A
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English (en)
French (fr)
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EP1431412B1 (de
Inventor
Kiyohito Ishida
Katsunari Oikawa
Takashi c/o Tohoku Tokushuko K.K. Ebata
Takayuki Inoguchi
Tetsuya Shimizu
Michio Okabe
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Daido Steel Co Ltd
Tohoku Tokushuko KK
Tohoku Steel Co Ltd
Tohoku Techno Arch Co Ltd
Japan Research Industries and Industrial Technology Association (JRIA)
Original Assignee
Daido Steel Co Ltd
Tohoku Tokushuko KK
Tohoku Steel Co Ltd
Tohoku Techno Arch Co Ltd
Japan Research Industries and Industrial Technology Association (JRIA)
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Priority claimed from JP2000070257A external-priority patent/JP3425114B2/ja
Priority claimed from JP2000221433A external-priority patent/JP3425124B2/ja
Priority claimed from JP2000251626A external-priority patent/JP3425129B2/ja
Priority claimed from JP2000251602A external-priority patent/JP3425128B2/ja
Application filed by Daido Steel Co Ltd, Tohoku Tokushuko KK, Tohoku Steel Co Ltd, Tohoku Techno Arch Co Ltd, Japan Research Industries and Industrial Technology Association (JRIA) filed Critical Daido Steel Co Ltd
Publication of EP1431412A1 publication Critical patent/EP1431412A1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • 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
    • C22C38/50—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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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

Definitions

  • the present invention relates to free cutting alloy excellent in machinability.
  • a free cutting alloy excellent in machinability is, in a case, selected for improvement of productivity.
  • free cutting alloy containing an element improving machinability such as S, Pb, Se or Bi (hereinafter referred to as machinability-improving element) is widely used.
  • machinability-improving element an element improving machinability such as S, Pb, Se or Bi
  • an object of the present' invention is to provide free cutting alloy excellent in machinability, showing outstanding characteristics as an alloy such as corrosion resistivity, hot workability and cold workability or specific magnetic characteristics, which are comparable to those of conventional alloys.
  • a free cutting alloy of the present invention is characterized by that the free cutting alloy wherein a (Ti,Zr) based compound is formed in a matrix metal phase, and said (Ti,Zr) based compound contains: one or more of Ti and Zr as a metal element component, C being an indispensable element as a bonding component with the metal element component, and one or more of S, Se and Te, wherein " (Ti,Zr)" means one or two of Ti and Zr.
  • Machinability of an alloy can be improved by forming the above described (Ti, Zr) based compound in a matrix metal phase of the alloy. Furthermore, by forming this compound in the alloy, formation of compounds such as MnS and (Mn,Cr)S, easy to reduce corrosion resistivity and hot workability of the alloy, can be prevented or suppressed, thereby enabling corrosion resistivity, hot workability and cold workability to be retained at good levels. That is, according to the present invention, a free cutting alloy excellent in machinability can be realized without any degradation in useful characteristics as an alloy such as hardness, corrosion resistivity, hot workability, cold workability and specific magnetic characteristics.
  • a (Ti,Zr) based compound formed in a free cutting alloy of the present invention can be dispersed in the alloy structure. Machinability of an alloy can be further increased especially by dispersing the compound in an alloy structure.
  • a particle size of the (Ti,Zr) based compound as observed in the structure of a polished section of the alloy is preferably, for example, approximately in the range of 0.1 to 30 ⁇ m on the average and further, an area ratio of the compound in the structure is preferably in the range of 1 to 20 %, wherein the particle size is defined by the maximum distance between two parallel lines circumscribing a particle in observation when parallel lines are drawn intersecting on a region including the particle in observation while changing a direction of the parallel lines.
  • the above described (Ti,Zr) based alloy can include at least a compound expressed in a composition formula (Ti,Zr) 4 (S,Se,Te) 2 C 2 (hereinafter also referred to as carbo-sulfide/selenide), wherein one or more of Ti and Zr may be included in the compound and one or more of S, Se and Te may be included in the compound.
  • a compound in the form of the above described composition formula not only can machinability of an alloy be improved, but corrosion resistivity is also improved.
  • identification of a (Ti,Zr) based compound in an alloy can be performed by X-ray diffraction (for example, a diffractometer method), an electron probe microanalysis method (EPMA) and the like technique.
  • X-ray diffraction for example, a diffractometer method
  • EPMA electron probe microanalysis method
  • the presence or absence of the compound of (Ti,Zr) 4 (S,Se,Te) 2 C 2 can be confirmed according to whether or not a peak corresponding to the compound appear in a diffraction chart measured by an X-ray diffractometer.
  • a region in the alloy structure in which the compound is formed can also be specified by comparison between two-dimensional mapping results on characteristic X-ray intensities of Ti, Zr, S, Se or C obtained from a surface analysis by EPMA conducted on a section structure of the alloy.
  • the present invention to be concrete, can be preferably applied on an alloy constituted as stainless steel.
  • an alloy constituted as stainless steel.
  • a free cutting alloy constituted as stainless steel of the present invention can be, to be more detailed, ferrite containing stainless steel (hereinafter referred to as a first selection invention).
  • a composition of the free cutting alloy of the present invention is as follows:
  • a free cutting alloy of the present invention constituted as stainless steel can be martensite containing stainless steel (hereinafter referred to a second selection invention).
  • a composition of the free cutting alloy of the present invention is as follows:
  • Martensitic stainless steel is in more of cases used in equipment and parts requiring hardness and corrosion resistivity as performances. Since martensitic stainless steel increases hardness thereof by a quenching heat treatment, there was a case where machining was performed in an annealed state and thereafter, quenching and tempering were performed, such that workability was improved. However, in the case, strain was produced in stainless steel by a quenching heat treatment and thereby, machining had to be, in a case, performed after a quenching heat treatment when precision processing was intended.
  • martensite containing stainless steel is a generic name for stainless steel forming a martensitic phase in the matrix by a quenching heat treatment.
  • compositions of the martensite containing stainless steel there can be named: corresponding kinds of stainless steel, such as SUS 403, SUS 410, SUS 410S, SUS 420J1, SUS 420J2, SUS 429J1, SUS 440C and the like, all shown within JIS G 4304.
  • martensitic heat resisting steel is handled as conceptually included in martensite containing stainless steel.
  • composition of martensitic heat resisting steel there can be named corresponding kinds of steel whose compositions are defined in JIS G 4311 and G 4312, such as SUH 1, SUH 3, SUH 4, SUH 11, SUH 600 and SUH 616.
  • free cutting alloys of the first and second selection inventions of the present invention constituted as ferrite containing stainless steel and martensite containing stainless steel, respectively can contain: 2 mass % or lower, including zero Si; 2 mass % or lower, including zero Mn; 2 mass % or lower, including zero Cu; and 2 mass % or lower, including zero Co.
  • the free cutting alloys can further contain one or more of Mo and W in the respective ranges of 0.1 to 4 mass % for Mo and 0.1 to 3 mass % for W.
  • Free cutting alloy of the present invention constituted as stainless steel can be austenite containing stainless steel (hereinafter referred to a third selection invention).
  • the free cutting alloy contains: 2 to 50 mass % Ni; 12 to 50 mass % Cr; 5 to 85.95 mass % Fe; and 0.01 to 0.4 mass % C.
  • austenite containing stainless steel means stainless steel containing not only Fe as a main component, but an austenitic phase in the structure. While there are below exemplified corresponding kinds of steel exhibited in JIS G 4304, neither of elements Ti, Zr, S and Se as essential features of the present invention is naturally expressed in compositions described in the standard. In this case, part of Fe content of each of the above described kinds of stainless steel is replaced with the above described elements in the respective above described compositional ranges and thereby martensite containing stainless steel of the present invention is obtained. Therefore, while in description of the present specification, the same JIS Nos. are used, those actually means alloys specific to the present invention, which alloys have compositions defined in JIS standards as a base only.
  • a composition may have the following components and contents thereof in order to achieve better characteristics. That is, the composition can be 4 mass % or lower, including zero Si; 4 mass % or lower, including zero Mn; 4 mass % or lower, including zero Cu; and 4 mass % or lower, including zero Co. Description will be given of the reason why the composition has the elements and contents thereof as follows:
  • the stainless steel can contain one or more of Mo and W in the respective ranges of 0.1 to 10 mass % for Mo and 0.1 to 10 mass % for W. Addition of Mo and W can improve corrosion resistivity due to strengthened passivation and furthermore attain improved hardness due to second hardening. It is preferable to add Mo and W in each content of 0.1 mass % or higher in order to make the effect exerted clearly. On the other hand, when in excess, hot workability is reduced and therefore, the content of Mo and W combined is preferably set to 10 mass % as the upper limit.
  • the stainless steels can contain: 0.05 mass % or lower P; and 0.03 mass % O; and 0.05 mass % or lower N.
  • the stainless steels can further contain one or more of Te, Bi and Pb in the respective ranges of 0.005 to 0.1 mass % for Te; 0.01 to 0.2 mass % for Bi; and 0.01 to 0.3 mass % for Pb. Description will be given of the reason why the elements and contents thereof are defined as follows:
  • the alloy when a free cutting alloy of the present invention is constituted as stainless steel, the alloy can contain one or more selected from the group consisting of Ca, Mg, B and REM (one or more of metal elements classified as Group 3A in the periodic table of elements) in the range of 0.0005 to 0.01 mass % for one element or as a total content in a case of two or more elements.
  • the elements are useful for improving hot workability of steel.
  • the effect of improving hot workability obtainable by addition of the elements is more conspicuously exerted in the range of 0.0005 mass % or higher for one element or as a total content of more than one elements combined.
  • the elements are added in excess, the effect is saturated and hot workability is then reduced on the contrary.
  • the content of a single element or total content of the elements combined is set to 0.01 mass % as the upper limit.
  • REM since low radioactivity elements are easy to be handled when being mainly used, from this viewpoint, it is useful to use one or more selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. It is desirable to use light rare earth elements, especially La or Ce from the viewpoint of conspicuous exertion of the effect and price. However, there arises no trouble with mixing-in of a trace of radioactive rare earth elements such as Th and U inevitably remaining, without being excluded, in a process to separate rare earth elements. Further, from the viewpoint of reduction in raw material cost, there can be used not-separated rare earth elements such as mish metal and didymium.
  • a free cutting alloy of the present invention constituted as stainless steel can contain one or more selected from the group consisting of Nb, V, Ta and Hf in each range of 0.01 to 0.5 mass %. Since Nb, V, Ta and Hf has an effect of forming carbo-nitrides to miniaturize crystalline particles of steel and increase toughness. Hence, the elements can add in each content up to 0.5 mass % and desirably contain 0.01 mass % or higher in the range.
  • a free cutting alloy of the present invention constituted as the above described stainless steel can contain the Wso value of which is less than 0.035 mass % when the following test is performed: an alloy test piece of said free cutting alloy is prepared so as to have the shape of rectangular prism in size of 15 mm in length, 25 mm in width and 3 mm in thickness with the entire surface being polished with No.
  • a (Ti, Zr) based compound being a feature of the present invention is formed and in the course of the formation, added S is included in the stainless steel as a constituting element of the (Ti, Zr) based compound which is more stable chemically than MnS or the like. And therefore, a S amount released into the air from the stainless steel decreases. Consequently, an out-gas resistivity of the stainless steel can also be improved by formation of the(Ti, Zr) based compound.
  • a S component released from the test piece as a sulfur containing gas is forced to be absorbed in the silver foil as a getter and a sulfur content Wso in the silver foil is measured to quantitatively determine the out-gas resistivity of a material.
  • a S content absorbed in the silver foil is defined using the W SO value and set to 0.035 mass % or lower in W SO .
  • Stainless steel of the present invention controlled so as to be 0.035 mass % or lower in Wso is hard to cause sulfur contamination in the peripheral parts when exposed to the air since a S component released from the stainless steel into the air is very small and thereby the stainless steel can be preferably used as parts of industrial equipment requiring the out-gas resistivity.
  • a factor determining out-gas resistivity of a material mainly is a composition of the material, it is desirable to fix S as carbo-sulfides of Ti and Zr for improvement on out-gas resistivity of the material.
  • a S content is desirably determined such that a value of W S /(W Ti + 0.52W Zr ) is 0.45 or less, or alternatively a value of W S /W C is 0.4 or less and W S /(W Ti + 0.52W Zr ) is 0.45 or less, wherein W S and W C denote a S content and a C content, respectively.
  • machinability as an alloy is required not only in the above described stainless steel, but also in an electromagnetic alloy used as a functional material.
  • electromagnetic alloys are in many cases poor machinability, not only corrosion resistivity and cold workability but also electromagnetic characteristics were in cases deteriorated when machinability-improving elements such as S and Pb were added for improvement on machinability.
  • characteristics of the alloy are largely changed by subtle shifts in balances between constituting elements, it has been difficult that machinability is improved while retaining excellent electromagnetic characteristics. According to the present invention, an effect of improving machinability can be achieved while the characteristics in the electromagnetic alloy is maintained.
  • the present invention can be preferably used as an electromagnetic alloy (hereinafter referred to as a fourth selection invention).
  • the present inventors have acquired the following findings and completed the fourth selection invention based thereon:
  • a content of one or more of Ti and Zr is in the range of 0.05 to 0.5 mass % in terms of Ti % + 0.52 Zr % (which is indicated by X);
  • a content of C is in the ranges of 0.02X to 0.06 X mass %, 0.19 X to 0.26 X mass % or 0.02 X to 0.26 X;
  • a content of one or more of S, Se and Te is in the ranges of (Z - 0.07)X to (Z + 0.07)X mass %, (Z + 0.07)X to (Z + 0.45)X mass %, or (Z + 0.45) X to
  • a free cutting alloy relating to the fourth selection invention contains: 0.01 to 3 mass % Si; 2 mass % or lower Mn; 5 to 25 mass % Cr; 0.01 to 5 mass % Al; one or more of Ti and Zr in the range of 0.05 to 0.5 mass % in terms of X of the following formula 1; C in the range of 0.02 X to 0.26 X mass % when X is expressed by the following formula 1; one or more of S, Se and Te in the range of (Z + 0.45)X to (Z + 0.70)X mass % when X, Z and Y are indicated by the respective following formulae 1, 3 and 2, and further according to a necessity contains one or more selected from the group consisting of Ni, Cu, Mo, Nb and V in contents of 2 mass % or lower Ni; 2 mass % or lower Cu; 2 mass % or lower Mo; 1 mass % or lower Nb; 1 mass % or lower V; and the balance being Fe and inevitable impurities.
  • the composition is specified by a combination of a content of one or more of Ti and Zr, a content of C and a content of one or more of S, Se and Te, which are mainly included in the ferritic stainless steel; in addition to one or more of Ti and Zr, C and one or more of S, Se and Te, contains: 0.01 to 3 mass % Si; 2 mass % or lower Mn; 5 to 25 mass % Cr; 0.01 to 5 mass % Al, further according to a necessity contains one or more selected from the group consisting of Ni, Cu, Mo, Nb and V in the ranges of 2 mass % or lower for Ni; 2 mass % or lower for Cu; 2 mass % or lower for Mo; 1 mass % or lower for Nb and 1 mass % or lower for V and still further according to a necessity contains one or more of Pb, B and REM in the respective contents of 0.15 mass % or lower for Pb; 0.01 mass %
  • a mark ⁇ with a number in Fig. 1 indicates a specimen No. of fourth selection inventive steel of the present invention of Example 4 and a mark ⁇ indicates a specimen No. of an inventive steel of Example 4.
  • the reason why the C content is set to the compositional range of 0.02 X to 0.26 X mass % (0.02 ⁇ C/X ⁇ 0.26), wherein 0.07 ⁇ ⁇ ⁇ 0.45, is that electromagnetic stainless steel with good machinability, good soft magnetic characteristics and good cold workability can be attained by formation of (Ti,Zr) 4 C 2 (S,Se,Te) 2 and (Ti,Zr)(S,Se,Te) excellent in corrosion resistivity, in a slightly increased amount.
  • the reason why the ranges of a C content are set to compositional range of 0.02 X to 0.26 X mass % (0.02 ⁇ C/X ⁇ 0.26), wherein 0.45 ⁇ ⁇ ⁇ 0.70, is that because of increase in (Ti,Zr)S, Cr(S,Se,Te) and Mn(S,Se,Te), electromagnetic stainless steel can be obtained with machinability especially excellent, corrosion resistivity and soft magnetic characteristics are at practical levels, though cold workability with a high working ratio is hard to be attained.
  • Y is set higher than(Z + 0.70)X mass %, that is when Y/X is set higher than 32(C/X - 0.125) 2 + 0.70, machinability is further excellent due to increase in (Ti,Zr)S, Cr(S,Se,Te) and Mn(S,Se,Te); while since cold workability, corrosion resistivity and soft magnetic characteristics decrease lower than a level of practicability, Y is set in the range of (Z + 0.45)X to (Z + 0.70)X mass %.
  • 0.15 mass % or lower Pb; 0.01 mass % or lower B; and 0.1 mass % or lower REM Pb is an element included for more of improvement on machinability and since the effect of improving machinability more than in a conventional case can be exerted with a Pb content a half that in the conventional case, the Pb content is set to 0.15 mass % or lower.
  • B and REM are elements useful for improving cold workability more in a steel of a free cutting alloy relating to the fourth selection invention, the elements are added in the steel. However, when the contents exceed the respective above described upper limits, hot and cold workabilities decrease and accordingly, the contents are set as described above.
  • REM since low radioactivity elements are easy to be handled when being mainly used and from this viewpoint, it is useful to use one or more selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. It is desirable to use light rare earth elements, especially La or Ce from the viewpoint of conspicuous exertion of the effect and price.
  • the present invention can be preferably applied for (Fe, Ni) based electromagnetic alloy, (Fe, Ni) based heat resisting alloy and (Fe,Ni) based alloy such as Invar alloy, Elinvar alloy and the like with a small thermal expansion coefficient, a small thermal coefficient of an elastic modulus in room temperature, for use in precision machine parts (hereinafter referred to as a fifth selection invention).
  • Ni based electromagnetic alloy the alloy including 20 to 80 mass % Ni is generally used, and there can be exemplified as the alloy; for example, alloys called Permalloy or Perminver.
  • Ni heat resisting alloy including 40 to 80 mass % Ni is widely used.
  • the fifth selection invention of the present invention constituted as (Fe, Ni) based electromagnetic alloy, (Fe, Ni) based heat resisting alloy or the like can contain 20 to 82 mass % Ni; and the balance mainly consists of one or more of Fe and Cr; further containing: one or more of Ti and Zr in the range satisfying a relation of 0.05 ⁇ X ⁇ 3 (hereinafter referred to as a condition formula (1)), one or more of S, Se and Te in the range satisfying a relation of 0.01 ⁇ Y ⁇ 0.5 X (hereinafter referred to as a condition formula (2)), C in the range satisfying a relation of 0.2 Y ⁇ W C ⁇ 0.3 (hereinafter referred to as a condition formula (3)), wherein when a Ti content is indicated by W Ti in mass %, a Zr content by W Zr in mass %, a C content by W C in mass %, a S content by W S mass %, a Se content by W Se and a Te content by W Te
  • the present inventors had findings that in (Fe, Ni) based alloy for use in electromagnetic material and/or heat resistant material (for example Ni or Fe based heat resistant alloy of a solid solution strengthening type), (Ti,Zr) based compound (for example, a compound in the form of (Ti,Zr) 4 (S,Se,Te) 2 C 2 )) is formed and thereby, machinability of the alloy is improved.
  • (Fe, Ni) based alloy for use in electromagnetic material and/or heat resistant material for example Ni or Fe based heat resistant alloy of a solid solution strengthening type
  • (Ti,Zr) based compound for example, a compound in the form of (Ti,Zr) 4 (S,Se,Te) 2 C 2
  • a free cutting alloy of the present invention with the following composition is excellent in machinability and hot workability without deterioration in excellent performances as electromagnetic material and/or heat resistant material, the composition being: one or more of Ti and Zr in the range satisfying a relation of 0.05 ⁇ X ⁇ 3 (hereinafter referred to as a condition formula (1)), one or more of S, Se and Te in the range satisfying a relation of 0.01 ⁇ Y ⁇ 0.5 X (hereinafter referred to as a condition formula (2)), C in the range satisfying a relation of 0.2 Y ⁇ W C ⁇ 0.3 (hereinafter referred to as a condition formula (3)), wherein when a Ti content is indicated by W Ti in mass %, a Zr content by W Zr in mass %, a C content by W C in mass %, a S content by W S mass %, a Se content by W Se and a Te content by W Te , the following formulae (1) and (2) are given in order to define X and Y:
  • the fifth selection invention of the present invention constituted as (Fe,Ni) based alloy can contain one or more of Si, Mn and Al in the respective ranges of 1 mass % or lower for Si; 1 mass % or lower for Mn; and 1 mass % or lower for Al. Description will be given of the reason why the elements and contents thereof are selected as follows:
  • the above described free cutting alloy using (Fe,Ni) based alloy as base can contain Mo or Cu in the ranges of 7 mass % or lower for Mo; and 7 mass % or lower for Cu. Description will be given of the reason why the elements and contents thereof are selected as follows:
  • a free cutting alloy of the present invention can contain 12 mass % or lower Cr and moreover, 18 mass % or lower Co.
  • magneto-striction acts so as reduce a volume in company with reduction in spontaneous magnetization, which cancels thermal expansion in the ordinary sense.
  • 36 at % Ni-Fe alloy is generally called Invar alloy and a thermal expansion coefficient in the vicinity of environment temperature is very small, which makes the alloy find a practically important application.
  • the alloy is in many cases used in precision machine material such as of a spring for a measuring instrument. By adding Cr or Co to such an alloy, it is possible to effectively control a thermal expansion coefficient and an elastic constant and thereby, desired performances to match with an intended application can be attained.
  • the elements are not limited to the use in the controls.
  • Cr or Co are added in excess of the respective above described ranges, an unfavorably large change occurs in compositional conditions on the elements of Ti, Zr, S, Se, Te and C associated with formation of (Ti,Zr) 4 (S,Se,Te) 2 C 2 .
  • the Cr and Co contents are set to 12 mass % or lower and 18 mass % or lower, respectively.
  • an alloy composition means a composition in which part of Fe and Ni as main components is replaced with the elements of Ti, Zr, S, Se, C and the like effective for improvement on machinability in the compositional ranges defined in the present invention.
  • alloys under the trade names mean alloys specific to the present invention composed with the alloys of compositions under product specifications as a base only (it should be appreciated that the alloy compositions inherent in products under respective trade names are described in a literature (Revised 3 rd Version Kinzoku (Metal) Data Book published by Maruzen, p 223), therefore detailed description thereof is omitted):
  • test alloy relating to the present invention is referred to as inventive steel or inventive alloy
  • test alloy relating to each of the selection inventions is referred to as a selection inventive steel or a selection inventive alloy.
  • a free cutting alloy constituted as ferrite containing stainless steel (a first selection inventive steel) were confirmed by the following experiment.
  • 50 kg steel blocks with respective compositions in mass % shown in Table 1 were molten in a high frequency induction furnace and ingots prepared from the molten blocks were heated at a temperature in the range of from 1050 to 1100°C and the ingots were forged in a hot state into rods with a circular section of 20 mm diameter and the rods were further heated at 800°C for 1 hr, followed by air cooling (annealing) as a source for test pieces.
  • an inventive steel of the present invention was (Ti,Zr) 4 (S,Se) 2 C 2
  • other inclusions such as (Ti,Zr)S and (Ti,Zr)S 3 are locally recognized in the matrix.
  • (Mn, Cr)S is recognized, though in a trace amount.
  • An identification method for inclusions was performed in the following way: A test piece in a proper amount was sampled from each of the rods. A metal matrix portion of the test piece was dissolved by electrolysis using a methanol solution including tetramethylammonium chloride and acetylaceton at 10 % as a electrolytic solution.
  • first selection inventive steel of the present invention is comparable with conventional ferrite containing stainless steel in hot workability, cold workability and corrosion resistivity and moreover, is better in machinability than the conventional ferrite containing stainless steel. Further, it is found from Table 2 when comparing with comparative steel specimens Nos. 16 and 18 that the first selection inventive steel of the present invention is smaller in Wso and better in out-gas resistivity. The reason why kinds of steel of comparative alloy specimens Nos. 16 and 18 each have a high Wso is considered that since the steel of the kinds has neither Ti nor Zr, carbo-sulfide is hard to be formed, whereby a S amount in the matrix is excessively high. In comparative alloy specimen No. 18, hot workability is poor and therefore, evaluation of machinability was not performed.
  • the following experiment was performed on martensite containing stainless steel and second selection inventive steel of the present invention.
  • 50 kg steel blocks of compositions in mass % shown in Table 3 were molten in a high frequency induction furnace to form respective ingots.
  • the ingots were heated at temperature in the range of from 1050 to 1100°C to be forged in a hot state and be formed into rods each with a circular section, of a diameter of 20 mm.
  • the rods were further heated at 750°C for 1 hr, followed by air cooling to be applied to the test.
  • specimens Nos. 1 to 19 are second selection inventive steels of the present invention constituted as martensite containing stainless steel. Further, in comparative examples, specimens correspond to stainless steel: a specimen No. 20 corresponds to SUS 410, a specimen No. 21 to SUS 416, a specimen No. 22 to SUS 420F and a specimen No. 23 to SUS 440F. Further, specimens Nos. 24 to 26 are of stainless steel, wherein a C content of each does not satisfy the formulae A and B, and although alloy of the specimens is outside the scope of the second selection invention, the alloy still falls within the scope of the present invention.
  • inclusions of the inventive steel of the present invention was of (Ti,Zr) 4 (S,Se) 2 C 2
  • other inclusions such as (Ti,Zr)S and (Ti,Zr)S 3 are locally recognized in the matrix.
  • (Mn,Cr)S was recognized, though in a small amount.
  • An identification of inclusions was performed in the following way: A test piece in a proper amount was sampled from each of the rods. A metal matrix portion of the test piece was dissolved by electrolysis using a methanol solution including tetramethylammonium chloride and acetylaceton at 10 % as a electrolytic solution.
  • EDX Electronic Dispersive X-ray spectrometer
  • a compound was identified based on peaks of a diffraction chart.
  • a composition of a compound particle in the steel structure was separately analyzed by EDX and a compound with a composition corresponding to a compound observed by EDX was confirmed based on formation from two dimensional mapping results.
  • Fig. 4 shows EDX analytical results of arbitrary inclusions in a second selection inventive steel specimen No.2 and from the results, formation of (Ti,Zr) based compound can be recognized.
  • Fig. 5 shows optical microphotograph of second selection inventive steel specimens Nos. 2 and 13.
  • the reason why the second selection inventive steel was improved in hardness as compared with the inventive steel is considered that a C content satisfies the formulae A and B and thereby, a C content constituting a (Ti,Zr) based compound and a C content as additive establishes an adjusted balance and thereby, a C component is sufficiently dispersed in a Fe based matrix phase. Further, the reason why out gas resistivity was improved is considered that S is added excessively relative to an amount of a (Ti,Zr) based compound that can be formed.
  • the specimen No. 19 corresponds to SUS 304, the specimen No. 20 to SUS 303, the specimen No. 27 to SUS 329J4L.
  • the specimens Nos. 1 to 21 are kinds of steel for use in application of a non-magnetism
  • the specimens Nos. 22 to 29 are kinds of steel for use in application other than non-magnetism.
  • the specimens Nos. 1 to 24 and 27 were heated at 1050°C for 1 hr and thereafter water-cooled, while the other kinds of steel were heated at 750°C for 1 hr and thereafter water-cooled. Thereafter, both group of kinds of steel were further heated at 650°C for 2 hr and thereafter water-cooled, followed by tests.
  • All the test pieces of inventive steels obtained each had a main phase in which at least an austenitic phase was formed.
  • Main phases of third selection inventive steels are shown in Table 5, wherein A denotes an austenitic phase, B a ferritic phase and C a martensitic phase.
  • a free cutting alloy constituted as austenite containing stainless steel of the present invention is comparable with conventional stainless steel in hot workability, cold workability and corrosion resistivity and moreover, is improved in machinability compared with conventional stainless steel. Further, it is found that when comparing with comparative steel of the specimen No. 19, third selection inventive steels of the specimens Nos. 1 to 18 are improved in machinability. Further it is found that when comparing with comparative steel specimen No. 20, the specimens Nos. 1 to 18 are smaller in Wso and excellent in out-gas resistivity. Further, when comparing with comparative steel specimens Nos. 27 to 29, it is found that third selection inventive steel Nos. 22 to 26 are improved on machinability. That is, the third selection inventive steel is comparable with the comparative steel in corrosion resistivity and hot workability and in addition, improved on machinability and out-gas resistivity.
  • specimens Nos. 1 to 38 are test rods of fourth selection inventive steels and specimens Nos. 39 to 47 are test rods of inventive steels.
  • the test rods were measured on magnetic characteristics, electric resistivity, machinability, cold workability and corrosion resistivity by measuring methods described below, which will be described below:
  • specimens Nos. 8, 10, 19, 21, 30 and 32 including Pb as a component each have a short boring time compared with specimens of inventive steel of the present invention with respective ⁇ values close to those of the specimens including Pb.
  • specimens Nos. 8, 9 to 11, 19 to 22 and 30 to 33 including B and/or REM as a component each have a large cracking threshold working ratio compared with specimens of inventive steel of the present invention with respective ⁇ values close to those of the specimens including B and/or REM.
  • Vc is in the range of - 80 ⁇ Vc ⁇ 0 in mV and good corrosion resistivity is shown.
  • Vc is in the range of 0.07 ⁇ ⁇ ⁇ 0.45, Vc is in the range of - 50 ⁇ Vc ⁇ 70 in mV and better corrosion resistivity is shown. While Vc decreases further in the range of 0.45 ⁇ ⁇ ⁇ 0.70, Vc is considered to be practically useful as far as Vc > - 150 mV.
  • specimens Nos. 6, 7, 10, 11, 17, 18, 21, 22, 28, 29, 32 and 33 including Ni, Cu, Mo, Nb and V, which improve corrosion resistivity, have high Vc compared with specimens of inventive steel of the present invention with respective ⁇ values close to the specimens including Ni, Cu, Mo, Nb and V.
  • specimens Nos. 27 and 38 including an element which improves corrosion resistivity keep Vc of the same order as those of specimens of inventive steel of the present invention with respective ⁇ values smaller than the specimens including the corrosion resistivity improving element.
  • Specimens Nos. 39 to 47 of inventive steel of the present invention are outside the scope of the fourth selection inventive steel, as shown in Fig. 1.
  • the fourth selection inventive steel is superior in cold workability.
  • the fourth selection inventive steel is more excellent than the inventive steel in magnetic characteristics and corrosion resistivity.
  • the fourth selection inventive steel is better than the inventive steel in machinability.
  • inventive steels of specimens Nos. 43 and 44 and fourth selection inventive steels it is found that while both kinds of steel show almost the same level of machinability, the fourth selection inventive steels are better than the inventive steels in the other characteristics and when comparing inventive steels of specimens Nos. 45 to 47 with fourth selection inventive steels, it is found that the fourth selection inventive steels have better magnetic characteristics and better corrosion resistivity.
  • Fig. 13 shows dependencies of solubility products on temperature of compounds of TiO, TiN, Ti 4 C 2 S 2 , TiC, TiS and CrS in ⁇ -Fe (an austenitic phase). Since Zr has a chemical property analogous to Ti, and Se and Te have a chemical property analogous to S, it is considered that compounds are formed in the descending order of priority of (Ti,Zr)O > (Ti, Zr)N > (Ti,Zr) 4 C 2 (S,Se,Te) > (Ti,Zr)C > (Ti,Zr)(S,Se,Te) > Cr(S,Se,Te). Further, it was confirmed that the above described compounds were present in steel by X-ray analysis.
  • a free cutting alloy of the present invention constituted with Ni based alloy used as (Fe,Ni) based electromagnetic material and (Fe,Ni) based heat resisting material (the fifth selection invention) was prepared in the following way to be applied to tests: First, Test alloy of various compositions in mass % shown in Tables 11, 12 and 13, which is 7 kg blocks, were molten in a high frequency furnace in an Ar stream to be formed into ingots of 80 mm in diameter. Then, the ingots were processed in hot forging at a temperature in the range of 950 to 1100°C into rods having a circle section, 24 mm in diameter. Thereafter, the rods were machined to a diameter of 23 mm, followed by cold rolling into a diameter of 22 mm, to obtain test alloys.
  • inclusions in the structure was performed by a method similar to Example 1. While main inclusion in inventive steel of the present invention was (Ti,Zr) 4 (S,Se)C 2 , inclusions such as (Ti,Zr)S and (Ti,Zr)S 3 were locally recognized. A trace of (Mn,Cr)S was recognized in each of specimens Nos. 2, 14, 19, 29, 36, 39, 49 and 55, all having a high Mn content. An optical microphotograph of a specimen No. 30 of a third selection inventive alloy is shown in Fig. 14.
  • Ni based alloys of the compositions were evaluated on not only hot workability and machinability, but also characteristics required of Ni alloy among magnetic characteristics, a thermal expansion coefficient and an elastic constant. Evaluation methods for respective characteristics are as follows:
  • the fifth selection inventive alloy has hot workability better than the comparative alloys and the inventive alloys of the present invention have, regardless of a magnitude of each of contents of additive elements Si, Mn, Al and Mo, each in the range of 1 % or lower. This is considered because, in such conditions, since a percent of inclusions of carbo-sulfide based (Ti,Zr) 4 C 2 (S,Se,Te) 2 especially stable among sulfide based inclusions is large, formation of (Mn,Cr,Ni)S being a cause for hot-work cracking is controlled. This mechanism was confirmed by actual analysis on components of the inclusions. That is, it is found that machinability is improved in the inventive alloy of the present invention and moreover, not only machinability but also hot workability are improved in the fifth selection inventive alloy.
  • the fifth selection inventive alloy of the present invention to which Ti and Zr, and S, Se and Te are added so as to satisfy the condition formulae (1) to (3) has no reduction in hot workability and furthermore, almost no deterioration in functional performances inherited from the base alloy.
  • specimens Nos. 17 to 26 of fifth selection inventive alloys an effect of improving machinability can be attained even if Cr is added with 12 mass % as the upper limit.
  • specimens Nos. 20 to 23 of fifth selection inventive alloys with specimen No. 61 of a comparative alloy, as a base composition which is a constant-modulus alloy whose elastic characteristics are constant in the vicinity of room temperature, has not only good hot workability, but also greatly increased machinability, and in addition, a temperature coefficient of a Young's modulus is almost not affected either, thereby enabling use as constant modulus alloy in a proper manner.
  • Fig. 16 is a graph obtained by plotting a drill boring time on alloy in Example 5 against Y in mass %. As can be seen in the graph, when Y is less than 0.01 mass %, it is seen that a boring time tends to accelerate its increase.
  • the present invention can be applied to not only Fe based alloy shown in Examples, but other alloy requiring machinability.
  • the present invention can be applied to Ni based alloy, Co based alloy, Ti based alloy, Cu based aloy, or the like as well and when applied to these kinds of alloy, a (Ti, Zr) based compound are preferably formed in the alloy structure by substituting (Ti,Zr)C and (S,Se,Te) for part of the alloy composition.

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JP4895434B2 (ja) 2001-06-04 2012-03-14 清仁 石田 快削性Ｎｉ基耐熱合金
EP1378578B1 (de) * 2002-06-05 2007-11-07 Kiyohito Ishida Hochtemperaturfeste Nickelbasislegierung mit guter Zerspannbarkeit
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DE102013214464A1 (de) * 2013-07-24 2015-01-29 Johannes Eyl Verfahren zum Herstellen einer chromhaltigen Legierung und chromhaltige Legierung
RU2551328C1 (ru) * 2014-03-12 2015-05-20 Павел Сергеевич Кучин Литейный сплав на основе железа
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