EP1085105A2 - Automatenlegierung - Google Patents

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Publication number
EP1085105A2
EP1085105A2 EP00118990A EP00118990A EP1085105A2 EP 1085105 A2 EP1085105 A2 EP 1085105A2 EP 00118990 A EP00118990 A EP 00118990A EP 00118990 A EP00118990 A EP 00118990A EP 1085105 A2 EP1085105 A2 EP 1085105A2
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Prior art keywords
mass
range
free cutting
alloy according
stainless steel
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EP00118990A
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English (en)
French (fr)
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EP1085105A3 (de
EP1085105B1 (de
Inventor
Kiyohito Ishida
Katsunari Oikawa
Takashi c/o Tohoku Tokushuko K.K. Ebata
Takayuki Inoguchi
Tetsuya Shimizu
Michio Okabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ISHIDA, KIYOHITO
OIKAWA, KATSUNARI
Daido Steel Co Ltd
Tohoku Tokushuko KK
Tohoku Techno Arch Co Ltd
Japan Research Industries and Industrial Technology Association (JRIA)
Original Assignee
Kogyo Gijutsuincho
Daido Steel Co Ltd
Tohoku Tokushuko KK
Tohoku Steel Co Ltd
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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
Priority to EP04004046A priority Critical patent/EP1431412B1/de
Priority to EP04004044A priority patent/EP1431410B1/de
Priority to EP04004043A priority patent/EP1431409B1/de
Application filed by Kogyo Gijutsuincho, Daido Steel Co Ltd, Tohoku Tokushuko KK, Tohoku Steel Co Ltd filed Critical Kogyo Gijutsuincho
Priority to EP04004045A priority patent/EP1431411B1/de
Publication of EP1085105A2 publication Critical patent/EP1085105A2/de
Publication of EP1085105A3 publication Critical patent/EP1085105A3/de
Publication of EP1085105B1 publication Critical patent/EP1085105B1/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.
  • Ti and Zr are indispensable elements for forming a (Ti,Zr) based compound playing a central role in exerting the effect of improving machinability of a free cutting alloy of the present invention.
  • a value of W Ti + 0.52 W Zr is lower than 0.03 mass %, the (Ti,Zr) based compound is insufficiently formed in amount, thereby disabling the effect of improving machinability to be satisfactorily exerted.
  • machinability is reduced on the contrary. For this reason, the value of W Ti + 0.52 W Zr is required to be suppressed to 3.5 mass % or lower.
  • One or more of S and Se in the respective ranges of 0.01 to 1 mass % for S and. 0.01 to 0.8 mass % for Se S and Se are elements for useful in improving machinability.
  • a compound useful for improving machinability for example, a (Ti,Zr) based compound expressed in the form of a composition formula (Ti,Zr) 4 (S,Se) 2 C 2 ). Therefore, contents of S and Se are specified 0.01 mass % as the lower limit.
  • a S content is set to 1 mass % and a Se content is set to 0.8 mass % as the respective upper limits.
  • S and Se are both desirably added into an alloy in a necessary and sufficient amount in order to form a compound improving machinability of the alloy, such as the above described (Ti,Zr) based compound. An excessive addition of S results in deterioration of the out-gas resistivity.
  • 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:
  • C is an important element forming a compound improving machinability. When a content thereof is lower than 0.005 mass %, however, an effect exerting sufficient machinability can not be imparted to the alloy, while when in excess of 0.4 mass %, much of a single carbide not effective for improving machinability is formed.
  • Addition of C is preferably set in the range of 0.01 to 0.1 mass %, wherein it is preferable that addition of C is adjusted so properly that the effect of imparting machinability on the alloy is optimized depending on an amount of a constituting element of a compound improving machinability such as a (Ti,Zr) based compound.
  • Ni can be added according to a necessity since the element is effective for improving corrosion resistivity, particularly in an environment of a reducing acid. Excessive addition, however, not only reduce stability of a ferrite phase, but also causes cost-up and therefore, a content thereof has the upper limit of 2 mass %, wherein a case of no addition of Ni may be included.
  • Cr is an indispensable element for ensure corrosion resistivity and is added in the range of 12 mass % or higher. On the other hand, excessive addition is not only harmful to hot workability but also causes reduction in toughness and therefore the upper limit is set to 35 mass %.
  • 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 bad to be, in a case, performed alter 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.
  • Ni can be added according to a necessity since the element is effective for improving corrosion resistivity, particularly in an environment of a reducing acid. Excessive addition, however, not only reduces a martensitic transformation temperature (Ms point), but also increases stability of an austenitic phase of the matrix phase excessively, whereby a case arises in which an amount of martensite necessary to ensure hardness is hard to be obtained. Moreover, hardness after annealing becomes high producing a solid solution hardening effect caused by Ni in excess, which sometimes makes performances such as machinability decrease. For the above described reason, a Ni content has the upper limit of 2 mass %.
  • Cr is an indispensable element for ensuring corrosion resistivity and added 9 mass % or higher in content.
  • a Cr content is desirably set in the range of 11 to 15 mass % and more desirably in the range of 12 to 14 mass %.
  • 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.
  • Si is added as a deoxidizing agent for steel. That Si is added in excess, however, is unfavorable because not only cold workability is deteriorated, but formation of ⁇ ferrite increases in amount, thereby degrading hot workability of steel. Moreover, a Ms point decreases in excess in a case of martensite containing stainless steel. Consequently, a Si content has the upper limit of 2 mass %. In a case where cold workability is particularly regarded as important, the Si content is preferably set 0.5 mass % or lower, including zero.
  • Mn acts an deoxidizing agent for steel.
  • a compound useful for increase in machinability in co-existence with S or Se there arises a necessity of addition when machinability is highly thought of.
  • MnS especially deteriorates corrosion resistivity, affects cold workability adversely and moreover, reduces a Ms point excessively in martensite containing stainless steel, therefore a Mn content has the upper limit of 2 mass %.
  • a Mn content is desirably limited to 0.4 mass % or lower, including zero.
  • Cu can be added according to a necessity since the element is effective for improving corrosion resistivity, particularly in an environment of a reducing acid. It is preferable to contain 0.3 mass % or higher in order to obtain a more conspicuous effect of the kind.
  • a Cu content When in excess, however, not only does hot workability decrease, but in martensite containing stainless steel, a Ms point decreases and quenchability is also deteriorated, whereby it is preferable for a Cu content to be set 2 mass % or lower, including zero.
  • hot workability is regarded as important, it is more desirably to suppress the Cu content to 0.5 mass % or lower, including zero.
  • Co is an element effective for improving corrosion resistivity, particularly in an environment of a reducing acid and in addition, can also be added to martensite containing stainless steel depending on a necessity since Co increases a Ms point and improves quenchability.
  • To contain Co in content equal to 0.3 mass % or higher is preferable in order to obtain more of conspicuousness in the effects.
  • a content of Co is more desirably suppressed to 0.5 mass % or lower, including zero.
  • Mo and W can further increase corrosion resistivity and a strength, the elements may be added according to a necessity.
  • the lower limits are both 0.1 %, where the effects thereof become clearly recognized.
  • the upper limits of Mo and W are set 4 mass % and 3 mass %, respectively.
  • 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.
  • Ni is necessary to be added to stainless steel in a content of at least 2 mass % in order to stabilize an austenitic phase in the stainless steel. Moreover, while Ni has many chances to be added into the matrix since Ni is useful for improving corrosion resistivity in an environment of a reducing acid, it is preferable to add at 2 mass % or higher in content from the viewpoint of improvement on corrosion resistivity. Moreover, when non-magnetism is desired, a necessary amount of Ni is required to be added so as to stabilize an austenitic phase more and thereby obtain an alloy as austenite containing stainless steel, considering connection with contents of other elements such as Cr and Mo. In this case, a Schoeffler diagram shown in Fig. 7 can be utilized for determination of the Ni content.
  • Cr is an indispensable element for ensuring corrosion resistivity of stainless steel. Hence, Cr is added in a content equal to 12 mass % or higher. When a Cr content is lower than 12 mass %, corrosion resistivity as stainless steel cannot be ensured due to intergranular corrosion caused by increased sensitivity at grain boundaries. On the other hand, when added in excess, there arises a risk that not only is hot workability degraded, but toughness is also reduced due to formation of a compound such as CrS.
  • a Cr content is limited to 50 mass % or lower.
  • a Cr content is preferably set in the range of 12 to 50 mass % and performances specific to stainless steel are, in a case, degraded outside the range in content of Cr.
  • a Cr content is set in the range of 15 to 30 mass % and more desirably in the range of 17 to 25 mass %.
  • Fe is an indispensable component for constituting stainless steel. Therefore, a Fe content is at 5 mass % or higher. When an Fe content is lower than 5 mass %, the Fe content is not preferable since no strength specific to stainless steel can be obtained. That an Fe content exceeds 85.95 mass % is impossible in connection with required contents of other components. Consequently, an Fe content is in the range of 5 to 85.95 mass %.
  • An Fe content is desirably set in the range of 15 to 75 mass % and more desirably in the range of 40 to 65 mass %.
  • C is an indispensable component for improvement on machinability and added in a content of 0.01 mass % or higher.
  • a (Ti,Zr) based compound is formed, and formation of the compound is considered to improves machinability of stainless steel.
  • a C content is lower than 0.01 mass %, formation of the (Ti,Zr) based compound is insufficient and the effect of improving machinability is not sufficiently attainable.
  • the content exceeds 0.4 mass %, a carbide not useful for improvement on machinability is excessively formed and therefore, machinability is deteriorated on the contrary.
  • a C content is preferably set in a proper manner taking into consideration not only that C is added such that a machinability improvement effect is exerted in best conditions according to an amount of constituting elements of a compound improving machinability, such as the (Ti,Zr) based compound, but also the effect of improving hardness exerted by the residual C dissolved in a solid solution state in the matrix phase.
  • a C content is desirably in the range of 0.03 to 0.3 mass % and more desirably in the range of 0.05 to 0.25 mass %.
  • 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:
  • Si can be added as a deoxidizing agent for steel.
  • a content of Si is excessive high, not only is a hardness after solid solution heat treatment disadvantageously high, which in turn leads to poor cold workability, but an increased amount of a ⁇ -ferrite phase is formed, thereby deteriorating hot workability of the steel.
  • the upper limit of Si in content is set to 4 mass %.
  • a Si content is desirably set to 1 mass % or lower and more desirably to 0.5 mass % or lower, including zero.
  • Mn not only acts as a deoxidizing agent of the steel, but also exerts an effect to suppress formation of a ⁇ -ferrite phase. Furthermore, Mn has an effect to stabilize an austenitic phase. Since Mn forms a compound useful for increase in machinability in co-existence with S and Se, Mn may added to the matrix when machinability is regarded as an important characteristic. When an effect of improving machinability is expected to be conspicuous, a Mn content is preferably set to 0.6 mass % or higher. When Mn is added, MnS is formed with ease. However, since MnS not only degrades corrosion resistivity to a great extent, but also reduces cold workability, formation of MnS is unwelcome.
  • the Mn content is set to 4 mass % or lower, including zero.
  • the Mn content is desirably set to 1 mass % or lower, including zero and more desirably to 0.5 mass % or lower, including zero.
  • Cu is not only useful for increase in corrosion resistivity, particularly for improving corrosion resistivity in an environment of a reducing acid, but also reduces work hardenability and improves moldability. Moreover, since an antibacterial property can be improved by a heat treatment or the like processing, Cu may added if necessary. However, when Cu is excessively added, hot workability is degraded and therefore, a Cu content is preferably set to 4 mass % or lower, including zero. Especially, when hot workability is regarded as an important characteristic, the Cu content is more desirably set to 1 mass % or lower, including zero.
  • Co is an element not only useful for improving corrosion resistivity, particularly in an environment of a reducing acid, but to exert an effect of ensuring non-magnetism and therefore, may added to the matrix if necessary. It is preferable to add in content of 1 mass % or higher in order to obtain more of conspicuousness of the effect. However, when Co is added in excess, not only is hot workability reduced but cost-up occurs on raw material. Hence, a Co content is preferably set to 4 mass % or lower, including zero. Especially, when hot workability or cost is taken seriously, the Co content is more desirably suppressed to 0.3 mass % or lower, including zero.
  • 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:
  • a P content is preferably set as low as possible and to 0.05 mass % or lower, including zero. Although the P content is more desirably set to 0.03 mass % or lower, including zero, reduction in content more than necessary has a chance to be reflected on increased production cost.
  • O combines with Ti or Zr both of which are constituting elements of a compound useful for improving machinability and forms oxides not useful for improving machinability. Therefore, an O content should be suppressed as low as possible and is set to 0.03 mass % as the upper limit.
  • the O content is desirably set to 0.01 mass % or lower if allowable in consideration of increase in production cost.
  • N combines with Ti or Zr both of which are constituting elements of a compound useful for improving machinability and forms nitrides not useful for improving machinability. Therefore, a N content should be suppressed as low as possible and is set to 0.05 mass % as the upper limit.
  • the N content is desirably set to 0.03 mass % or lower, including zero and more desirably to 0.01 mass %, if allowable in consideration of increase in production cost.
  • 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
  • Te, Bi and Pb can further improve machinability, the elements may add if necessary.
  • the lower limits thereof at which the respective effects are exerted to clearness are as follows: 0.005 mass % Te; 0.01 mass % Bi and 0.01 mass % Pb, respectively.
  • the upper limits are set as follows: 0.1 mass % Te; 0.2 mass % Bi; and 0.3 mass % Pb.
  • 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 W SO 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 Wso value and set to 0.035 mass % or lower in Wso.
  • Stainless steel of the present invention controlled so as to be 0.0 35 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.
  • Si is useful not only as a deoxidizing agent, but also for contributing to increase in the maximum magnetic permeability and reduction in coercive force among soft magnetic characteristics as an electromagnetic stainless steel and furthermore, useful for increase in electric resistivity and improvement on responsibility in a high-frequency band, and therefore, Si is added for the purposes. While a Si content is necessary to be 0.01 % or higher in order to attain the effect, since when the content is excessive high, hardness increases and cold workability is degraded, the content is reduced when cold workability is regarded as a more important characteristic and intended increases in the soft magnetic characteristics and a high-frequency responsibility are compensated mainly by addition of Al, described later, corresponding to decrease in Si content. However, when machinability is regarded as an important characteristics, the upper limit of the Si content is set to 3 mass %.
  • Mn is an element useful as a deoxidizing agent, but since when a Mn content exceeds 2 mass %, soft magnetic characteristics are degraded, the Mn content is set to 2 mass % or lower.
  • Cr is useful for improvement on corrosion resistivity and electric resistivity of steel, but for improvement on machinability by forming Cr(S,Se,Te) with S, Se and Te, which will be described later. Therefore, Cr is added for the improvements. Although it is necessary for Cr to be included in the range of 5 mass % or higher, the Cr content in excess of 25 mass % reduces cold workability and accordingly, the Cr content is set to 5 to 25 mass %.
  • Al is useful not only as a deoxidizing agent, but for contributing increase in the maximum magnetic permeability and reduction in coercive force and furthermore, useful for increase in electric resistivity and improvement on responsibility in a high-frequency band, similar to Si. Therefore, Al is included for the improvements. Although it is necessary for Al to be included exceeding 0.01 mass % in order to exert the effects, not only a specific refining method is required but cold workability is also degraded when an Al content exceeds 5 mass % and accordingly, the Al content is set to from 0.01 to 5 mass %.
  • Ti and Zr forms (Ti,Zr) 4 C 2 (S,Se,Te) 2 and/or (Ti,Zr)(S,Se,Te) in co-existence with C, S. Se and Te to contribute to increase in machinability and since among the two, (Ti,Zr) 4 C 2 (S,Se,Te) 2 especially deteriorates neither soft magnetic characteristics nor corrosion resistivity and contributes to improvement on machinability without any loss of cold workability, due to fine dispersion thereof, the elements are therefore added for the improvements.
  • the content of the elements singly or in combination is required to be 0.05 mass % of higher in terms of X in order to exert the effects, the soft magnetic characteristics are degraded when the content in terms of X exceeds 0.5 mass % and accordingly, the content is set to the range of 0.05 to 0.5 mass % in terms of X.
  • 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 in the range of (Z + 0.07)X to (Z + 0.45)X mass % (0.07 ⁇ ⁇ 0.45) and C is set in the range of 0.02X to 0.26X mass % (0.02 ⁇ C/X ⁇ 0.26) is that in electromagnetic stainless steel with the composition, there are realized excellent corrosion resistivity and machinability better than when Y is in the range of (Z- 0.07)X to (Z + 0.07)X mass % and in addition, good soft magnetic characteristics and good cold workability due to formation of (Ti,Zr) 4 C 2 (S,Se,Te) 2 and (Ti,Zr)(S,Se,Te), slightly increased in amount.
  • Y is set in the compositional range of (Z + 0.45)X to (Z + 0.70)X mass % (0.45 ⁇ ⁇ 0.70) and C is set in the range of 0.02X to 0.26X mass % (0.02 ⁇ C/X ⁇ 0.26) is that in electromagnetic stainless steel with the composition, electromagnetic stainless steel can be obtained with especially excellent machinability, corrosion resistivity and soft magnetic characteristics thereof are at practical levels due to increase in (Ti,Zr)S, Cr(S,Se,Te) and Mn(S,Se,Te), 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 %.
  • Ni. Cu, Mo, Nb and V are all useful for more of improvement on corrosion resistivity in a free cutting alloy relating to the fourth selection invention and therefore, the elements are included in the electromagnetic stainless steel. However, when the elements are added in excess of the respective upper limits, soft magnetic characteristics and cold workability are deteriorated. Accordingly, the contents are set as described above.
  • 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.
  • Free cutting alloy relating to the fourth selection invention has a composition with 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, the elements being included in conventional electromagnetic stainless steel, wherein the contents are individually specified and the elements in combinations of the contents are included in the alloy and therefore, electromagnetic stainless steel of the fourth selection invention can be produced by a production method similar to a conventional production method for electromagnetic stainless steel.
  • 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:
  • a free cutting alloy of the fifth selection invention of the present invention includes (Fe,Ni) based electromagnetic alloy and (Fe,Ni) based heat resisting alloy. Accordingly, Ni is an indispensable element for the free cutting alloy of the fifth selection invention of the present invention. Further, (Fe,Ni) based electromagnetic alloy and (Fe,Ni) based heat resisting alloy are widely employed with content of the range of 20 to 82 mass % for Ni and since the alloys including Ni in content of this range are particularly required improvement on machinability, the Ni content is limited to the range.
  • (Ti,Zr) based compounds for example, mainly (Ti,Zr) 4 (S,Se,Te) 2 C 2 and/or a small amount of (Ti,Zr)(S,Se,Te), are formed and therefore, Ti and Zr are useful for improvement on machinability.
  • Ti and Zr are also useful for prevention of cracking in hot working and the free cutting alloy of the fifth selection invention can maintain excellent characteristics as (Fe,Ni) based electromagnetic alloy or (Fe,Ni) based heat resisting alloy such as a thermal expansion coefficient, an elastic constant, magnetic characteristics or a high temperature strength. While Ti and Zr is required to be included in the range of 0.05 mass % or higher in X of a compositional parameter in order to attain an effect of improving machinability, X in excess of 3 mass % is not preferable since when X is in excess of 3 mass %, a specific refining method is required, being accompanied with poor productivity.
  • the range of the parameter X is preferably set in the range of 0.05 to 3 mass % and more preferably in the range of 0.1 to 0.5 mass %. Further, when Ti and Zr are included in the range satisfying the condition formula(1), either one of Ti and Zr or both Ti and Zr may be included.
  • S, Se and Te are indispensable elements for formation of the above described (Ti, Zr) based compound. Therefore, the elements are indispensable components for improvement on machinability and are required to be included in the range of 0.01 mass % or higher in terms of the parameter Y. When the elements are added in excess, a compound not useful for improving machinability is formed and in a case, performances of the alloy are deteriorated.
  • C forms (Ti,Zr) based compound in co-existence with Ti and Zr, and S, Se and Te and, it is an indispensable element for improvement on machinability. Moreover, C acts usefully for prevention of cracking occurrence in hot workability. Especially, since C accelerates formation of (Ti,Zr) 4 (S,Se,Te) 2 C 2 more stable than (Ti,Zr)(S,Se,Te), improvement by C on machinability is more effective. It is necessary to include C so as to satisfy the condition formula (3) for achievement of the effects. That is, C is required to be included in the range of at least more than 0.2 times the parameter Y(a parameter on which a total number of S, Se and Te atoms is reflected).
  • the C content W C is preferably limited to 0.3 mass % or lower.
  • the C content exceeds 0.3 mass %, loss of performances of Ni based alloy becomes large.
  • the C content is desirably set in the range of Y/4 to 0.2 mass % and more desirably in the range of Y/4 to Y/2 mass %.
  • 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:
  • Si is an element useful as a deoxidizing agent and in addition, for adjustment of hardness and electric resistivity and accordingly, added depending on a necessity.
  • an additive amount of Si is in excess, hardness after heat treatment for solid solution is excessively high, which disadvantageously brings poor workability. Characteristics such as thermal expansion, an elastic constant, magnetic characteristics, heat resistance (high temperature strength) and the like are degraded in some cases. Accordingly, the Si content is limited to 1 mass % as the upper limit and when cold workability is regarded as an important requirement, the Si content is preferably set to 0.5 mass % or lower.
  • Mn is an element useful as an deoxidizing agent and further, since Mn forms a compound excellent in machinability in co-existence with S and Se, Mn is added to alloy according to a requirement especially when machinability is regarded as important.
  • the Mn content is desirably set to 0.1 mass % or higher in order to attain more conspicuousness of the effect.
  • corrosion resistivity and cold workability are degraded and deterioration sometimes occurs in characteristics such as thermal expansion, an elastic constant, magnetic characteristics, heat resistivity (high temperature strength) and the like as well. Accordingly, the Mn content is preferably limited to 1 mass % or lower and more desirably to 0.5 mass % or lower.
  • Al is an element useful as a deoxidizing agent and added to alloy in necessary since Al is effective for adjustment for hardness and electric resistivity. However, when added in excess, deterioration sometimes occurs in characteristics such as thermal expansion, an elastic constant, magnetic characteristics, heat resistivity (high temperature strength) and the like. Accordingly, the Al content is limited to 1 mass % or lower.
  • 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:
  • Mo is an element useful for improvement on corrosion resistivity and strength.
  • Mo is preferably included in the range of 0.2 mass % or higher.
  • the Mo content is preferably limited to 1 mass % or lower and more desirably to 0.7 mass % or lower.
  • C is not only useful for improvement on corrosion resistivity, especially in an environment of a reducing acid, but effective for improvement on moldability, decreasing work hardenability.
  • Cu since an antibacterial property can also be improved by heat treatment or the like processing, Cu may be added to the alloy according to a necessity. However, since when added in excess, hot workability decreases, the Cu content is preferably set to 7 mass % or lower and especially when hot workability is regarded as important, the Cu content is desirably suppressed to 4 mass % or lower.
  • 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.
  • 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 . Accordingly, 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.
  • Evaluation of machinability was collectively effected based on cutting resistance in machining, finished surface roughness and chip shapes.
  • a cutting tool made of cermet was used to perform machining under a dry condition at a circumferential speed of 150 m/min, a depth of cutting per revolution of 0.1 mm and a feed rate per revolution of 0.05 mm.
  • a cutting resistance in N as a unit was determined by measuring a cutting force generating in the machining.
  • the finished surface roughness was measured by a method stipulated in JIS B 0601 and a value thereof was an arithmetic average roughness (in ⁇ m Ra) on a test piece surface after the machining.
  • test pieces in use each had the shape of a rectangular prism of 15 mm in length, 25 mm in width and 3 mm in thickness and the entire surface of each were polished with No. 400 emery paper.
  • a test piece was placed in a sealed vessel having an inner volume of 250 cc together with a silver foil having a size of 10 mm in length, 5 mm in width and 0.1 mm in thickness and 0.5cc of pure water, and a temperature in the vessel was maintained at 85°C for 20 hr.
  • a S content W S0 in the silver foil after the process for the test was measured by a combustion type infrared absorbing analysis method.
  • Evaluation of cold workability was performed by measuring a threshold compressive stain in a compression test on specimens Nos. 1 to 5 and 13.
  • Test pieces for compression each had the shape of a cylinder of 15 mm in diameter and 22.5 mm in height and each piece was compressed by a 600 t oil hydraulic press to obtain a threshold compressive strain, wherein the threshold compressive strain is defined as In (H0/H) or a natural logarithm of H0/H, H0 being an initial height of the test piece and H being a threshold height which is a maximum height at which no cracking has occurred.
  • First selection inventive alloys of the specimens Nos. 1 to 5 were confirmed to have high threshold compressive ratios almost equal to comparative steel specimen No. 15 and higher than comparative steel specimen No. 16 by about 20 %, and have a good cold workability as well.
  • Evaluation of corrosion resistivity was performed by a salt spray test. Test pieces each were prepared so to have the shape of a cylinder of 10 mm in diameter and 50 mm in height. The entire surface of each test piece was polished with No. 400 emery paper and cleaned. A test piece was exposed to a fog atmosphere of 5 mass % NaCl aqueous solution at 35°C for 96 hr. Final evaluation was visually performed with the naked eye. As a result, the inventive steel of the present invention was confirmed to maintain good corrosion resistivity. The results are shown in Table 2.
  • 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 W S0 and better in out-gas resistivity. The reason why kinds of steel of comparative alloy specimens Nos. 16 and 18 each have a high W S0 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.
  • machinability was collectively effected based on tool ware loss in machining, finished surface roughness and ship shapes.
  • a cutting tool made of cermet was used to perform machining under a wet condition by water-soluble cutting oil at a circumferential speed of 120 m/min, a depth of cutting per revolution of 0.1 mm and a feed rate per revolution of 0.05 mm.
  • the tool ware loss was measured at a flank of the cutting tool after 60 min machining with ⁇ m as a unit of the tool wear loss.
  • the finished surface roughness and chip shapes were evaluated by a method similar to that in Example 1.
  • Test pieces each were prepared so to have the shape of a cylinder of 15 mm in diameter and 50 mm in height. The entire surface of each test piece was polished. Each test piece was polished and thereafter, a test piece was held in a thermohygrostat at a temperature of 60°C and a relative humidity of 90 % RH for 168 hr.
  • test piece was evaluated [A]
  • test piece when dot-like stains were recognized at several points on a test piece, the test piece was evaluated [B], when red rust was recognized in an area of an area ratio of 5 % or less, the test piece was evaluated [C] and when red rust was recognized in an area wider than an area ratio of 5 %, the test piece was evaluated [D].
  • Table 4 The results are shown in Table 4.
  • 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 W S0 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:
  • a test piece in the shape of a ring, of 10mm in outer diameter, 5 mm in inner diameter and 5 mm in thickness was prepared for measurement of magnetic characteristics.
  • the test piece received magnetic annealing at 950°C and thereafter, direct current magnetic characteristics including a magnetic flux density and a direct current coercive force were measured by a B-H loop tracer: a magnetic flux density B1 (KG) under a magnetic field of 1 Oe and a magnetic flux density B10 (KG) under a magnetic field of 10 Oe and a direct current coercive force Hc (A/cm). Relations between a magnetic flux density B1 or a coercive force Nc and ⁇ are shown in Fig. 10.
  • Electric resistivity was measured on test pieces, which were each prepared by subjecting a test rod to cold wire-drawing to obtain a wire of 1 mm in diameter, and then performing vacuum annealing at 950°C thereon.
  • Machinability was evaluated as follows: a SKH 51 drill of 5 mm in diameter was used on a test piece of steel for machining at a number of revolution of 915 rpm under a load of 415 N on a cutting edge thereof and a time in sec consumed for boring a hole of 10 mm in depth was measured. Machinability was evaluated by a length of the time in sec.
  • a cracking threshold working ratio was evaluated by a cracking threshold working ratio and a procedure was as follows: a test piece was prepared in the shape of a cylinder, 20 mm in diameter and 30 mm in height. The test piece was annealed at 720°C and thereafter a compression test was performed on the test piece under a hydraulic pressure of 400 t to evaluate a cracking threshold working ratio. Relations of a boring time or a cracking threshold working ratio and ⁇ are shown in Fig. 11.
  • a test piece was prepared in the shape of a disc whose size is 18 mm in diameter and 2 mm in thickness.
  • the test piece was polished with sand papers up to No. 800 and subjected to magnetic annealing at 950° for 2 hr in a vacuum. Thereafter, a pitting potential Ve in mV was measured on the test piece in a 3.5 % NaCl aqueous solution at 30°C.
  • Fig. 12 shows a relation between a pitting potential and ⁇ . The measuring results are shown in Tables 9 and 10.
  • 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 a 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:
  • Machinability was evaluated as follows: a SKH 51 drill of 5 mm in diameter was used on a test piece of steel for machining at a number of revolution of 915 rpm under a load of 415 N on a cutting edge thereof and a time in sec consumed for boring a hole of 10 mm in depth on steel was measured. Machinability was evaluated by a length of the time. A relation between a parameter Y in mass % and a boring time is shown Fig. 16.
  • Test pieces each in the shape of a ring, of 10 mm in outer diameter, 4.5 mm in inner diameter and 5 mm in thickness were prepared for measurement of magnetic characteristics.
  • a test piece received magnetic annealing at 1000°C and thereafter, direct current magnetic characteristics including a magnetic flux density, a maximum magnetic permeability and a direct current coercive force were measured by a B-H loop tracer: a magnetic flux density B1 (T) under a magnetic field of 1 Oe, a magnetic flux density B5 (T) under a magnetic field of 5 Oe, and a magnetic flux density B10 (T) under a magnetic field of 10 Oe, a maximum magnetic permeability( ⁇ m) and a direct current coercive force He (A/cm).
  • test alloy pieces which were each shaped into a cylinder of 5 mm in diameter and 50 mm in height. The thermal expansion coefficient was measured at temperatures ranging from 0 to 80°C, after the pieces were annealed at 830°C.
  • temperature coefficient of Young's modulus test alloy pieces were each shaped into a cylinder of 5 mm in diameter and 80 mm in height and thereafter, processed in a solution treatment at 1000°C, followed by rapid cooling. After the rapid cooling, an alloy cylinder as an intermediate was subjected to an aging heat treatment at temperatures from 580 to 590°C into a final test alloy piece. Young's modulus was measured on the test alloy pieces at temperatures ranging from 20 to 100°C using a free resonance elastic modulus tester. The results are shown in Tables 14 and 15.
  • 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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EP1262572A1 (de) * 2001-06-01 2002-12-04 Daido Steel Company Limited Automatenstahl
EP1262573A1 (de) * 2001-06-01 2002-12-04 Daido Steel Company Limited Automatenstahl
EP1378578A1 (de) * 2002-06-05 2004-01-07 Kiyohito Ishida Hochtemperaturfeste Nickelbasislegierung mit guter Zerspannbarkeit
US6752883B2 (en) 2001-06-04 2004-06-22 Kiyohito Ishida Free-cutting Ni-base heat-resistant alloy
CN102723158A (zh) * 2012-07-06 2012-10-10 白皞 含稀土的高磁导率Ni-Fe软磁合金及其制备方法和用途
RU2551328C1 (ru) * 2014-03-12 2015-05-20 Павел Сергеевич Кучин Литейный сплав на основе железа
CN105033501A (zh) * 2015-08-03 2015-11-11 合肥通用机械研究院 一种乙烯裂解炉管用微合金化35Cr45NiNb焊丝
RU2600467C1 (ru) * 2015-06-25 2016-10-20 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Высокопрочная бериллийсодержащая сталь
CN109321806A (zh) * 2018-10-16 2019-02-12 李访 一种秸秆颗粒机秆体粉碎头及其制备方法
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DE102013214464A1 (de) * 2013-07-24 2015-01-29 Johannes Eyl Verfahren zum Herstellen einer chromhaltigen Legierung und chromhaltige Legierung
RU2586949C1 (ru) * 2015-06-08 2016-06-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Уральский государственный университет" (национальный исследовательский университет) (ФГБОУ ВПО "ЮУрГУ" (НИУ)) Мартенситно-ферритная коррозионно-стойкая хромоникелевая сталь с улучшенной обрабатываемостью резанием
CN110819918A (zh) * 2019-11-12 2020-02-21 段劲松 一种具有高耐磨耐蚀性的球磨机用耐磨钢球

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1262572A1 (de) * 2001-06-01 2002-12-04 Daido Steel Company Limited Automatenstahl
EP1262573A1 (de) * 2001-06-01 2002-12-04 Daido Steel Company Limited Automatenstahl
US6752883B2 (en) 2001-06-04 2004-06-22 Kiyohito Ishida Free-cutting Ni-base heat-resistant alloy
EP1378578A1 (de) * 2002-06-05 2004-01-07 Kiyohito Ishida Hochtemperaturfeste Nickelbasislegierung mit guter Zerspannbarkeit
CN102723158A (zh) * 2012-07-06 2012-10-10 白皞 含稀土的高磁导率Ni-Fe软磁合金及其制备方法和用途
CN102723158B (zh) * 2012-07-06 2015-12-02 白皞 含稀土的高磁导率Ni-Fe软磁合金及其制备方法和用途
RU2551328C1 (ru) * 2014-03-12 2015-05-20 Павел Сергеевич Кучин Литейный сплав на основе железа
RU2600467C1 (ru) * 2015-06-25 2016-10-20 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Высокопрочная бериллийсодержащая сталь
CN105033501A (zh) * 2015-08-03 2015-11-11 合肥通用机械研究院 一种乙烯裂解炉管用微合金化35Cr45NiNb焊丝
CN110438510A (zh) * 2018-05-02 2019-11-12 温州酷乐餐桌用品有限公司 一种减少不锈钢餐刀中重金属含量处理方法
CN110438510B (zh) * 2018-05-02 2021-07-06 温州酷乐餐桌用品有限公司 一种减少不锈钢餐刀中重金属含量处理方法
CN109321806A (zh) * 2018-10-16 2019-02-12 李访 一种秸秆颗粒机秆体粉碎头及其制备方法

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DE60029063D1 (de) 2006-08-10
EP1085105A3 (de) 2001-05-16
DE60029261D1 (de) 2006-08-17
EP1431411A1 (de) 2004-06-23
DE60030175D1 (de) 2006-09-28
DE60029260T2 (de) 2007-08-30
EP1085105B1 (de) 2006-06-28
DE60029260D1 (de) 2006-08-17
DE60029364D1 (de) 2006-08-24
EP1431411B1 (de) 2006-07-05
DE60029261T2 (de) 2007-02-01
DE60030175T2 (de) 2007-08-30
EP1431409A1 (de) 2004-06-23
EP1431409B1 (de) 2006-07-05
EP1431412B1 (de) 2006-08-16
EP1431410B1 (de) 2006-07-12
DE60029063T2 (de) 2007-06-28
DE60029364T2 (de) 2007-08-09
EP1431410A1 (de) 2004-06-23

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