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(11) | EP 1 431 411 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Free cutting alloy Automatenlegierung Alliage de décolletage |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
Background Art
[0002] Alloy has widespread applications because of a variety of characteristics thereof. A free cutting alloy excellent in machinability is, in a case, selected for improvement of productivity. In order to improve machinability, for example, 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. Especially in a case where machinability is particularly required because of precise finishing in machining or for other reasons, not only is a content of such a machinability-improving element increased in an alloy, but the elements are also added to an alloy in combination.
[0003] While S, which has widely been used for improvement of machinability, is in many cases added in the form of MnS, addition thereof in an alloy in a large content causes for degrading corrosion resistivity, hot workability and cold workability of the alloy. Moreover, when the alloy is exposed to the air, a sulfur component included in the alloy is released into the air in the form of a sulfur containing gas, which causes sulfur contamination in peripheral areas of parts with ease. Therefore, there arises a necessity of suppressing release of sulfur containing gas (hereinafter referred to as improvement on out-gas resistivity). Elements such as S, Se and Te, however, deteriorate magnetic properties to a great extent in an electromagnetic stainless steel and the like.
[0004] Therefore, various proposals have been made: a Mn content is limited, a Cr content in sulfide is increased or in a case where S is contained, Ti is added in combination with S in order to disperse sulfide in the shape of a sphere (for example, see JP-A-98-46292 or JP-A-81-16653). To increase a Cr content in sulfide, however, tends to greatly decrease in machinability and hot workability and therefore, such a alloy has been restricted on its application in many cases.
[0005] R. Kiessling et al. "Non metallic inclusions in steel", 1978 relates to sulphide inclusions in steel.
[0006] GB 1 519 313 relates to a stainless steel alloy and to a ferritic free-machining steel having an excellent machinability and a high corrosion resistance.
[0007] It is accordingly 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.
Summary of the Invention
[0008] In order to achieve the above described object, a free cutting alloy of the present invention is characterized by the free cutting alloy of claim 1. (Ti,Zr)" means one or two of Ti and Zr.
[0009] 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.
[0010] Further, a (Ti,Zr) based compound formed in a free cutting alloy of the present invention is dispersed in the alloy structure. Machinability of an alloy can be further increased especially by dispersing the compound in an alloy structure. In order to increase the effect, 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 µm 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.
[0011] The above described (Ti,Zr) based alloy can include at least a compound expressed in a composition formula (Ti,Zr)4(S,Se,Te)2C2 (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. By forming 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.
[0012] It should be appreciated that 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. For example, the presence or absence of the compound of (Ti,Zr)4(S,Se,Te)2C2 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. Further, 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.
Brief Description of the Drawings
[0013]
Fig. 1 is a graph showing an X-ray diffraction chart of an inventive steel specimen No. 5 in experiment of Example 1 (Reference);
Fig. 2 is an optical microphotograph of the third selection inventive steel specimen No. 2 in Example 3;
Fig. 3 is a graph showing EDX analytical results of a reference specimen No.2 in Example 2 (Reference);
Fig. 4 is optical microphotograph of reference steels specimen Nos. 2 and 13 in Example 2 (Reference);
Fig. 5 is a representation describing measuring points for a hardness test in Example 2 (Reference);
Fig. 6 is a graph showing an example of Schaeffler diagram;
Fig. 7 is graphs showing EDX analytical results of a third selection inventive steel specimen No.2 in experiment of Example 3;
Fig. 8 is an optical microphotograph of the reference steel specimen No.5 in Example 1 (Reference);
Fig. 9 is a graph showing dependencies of solubility products on temperature of components of TiO, TiN, Ti4C2S2, TiC, TiS and CrS in γ-Fe;
Preferred Embodiments of the Invention
[0014] The present invention, to be concrete, is applied on an alloy constituted as stainless steel. In this case, in order to form a (Ti,Zr) based compound without any degradation in characteristics as stainless steel, such an alloy preferably contains one or more of Ti and Zr such that WTi + 0.52 WZr = 0.03 to 3.5 mass %, wherein WTi and WZr denote respective contents in mass % of Ti and Zr; and one or more of S and Se in the respective ranges of 0.01 to 1.0 mass % for S and 0.01 to 0.8 mass % for Se.
(1) The Ti and Zr content being defined such that WTi + 0.52 WZr = 0.03 to 3.5 mass %, wherein WTi and Wzr denote respective contents in mass % of Ti and Zr
[0016] 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. When a value of WTi + 0.52 WZr 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- On the other hand, when in excess of the value, machinability is reduced on the contrary. For this reason, the value of WTi + 0.52 WZr is required to be suppressed to 3.5 mass % or lower. The above effect exerted when Ti and Zr are added into an alloy is determined by the sum of the numbers of atoms (or the sum of the numbers of values in mol), regardless of kinds of metals, Ti or Zr. Since a ratio between atomic weights is almost 1 : 0.52, Ti of a smaller atomic weight exerts a larger effect with a smaller mass. Thus, a value of WTi + 0.52 WZr is said to be compositional parameter reflects the sum of the numbers of atoms of Zr and Ti included in an alloy.
(2) 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
[0017] S and Se are elements for useful in improving machinability. By adding S and Se into an alloy, in an alloy structure, formed is 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)2C2). Therefore, contents of S and Se are specified 0.01 mass % as the lower limit. When the contents are excessively large, there arises a chance to cause a problem of deteriorating hot workability and therefore, there have to be the upper limits: The S content is set to 1 mass % and the Se content is set to 0.8 mass % as the respective upper limits. Further, 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.
[0018] Free cutting alloy of the present invention constituted as stainless steel is austenite containing stainless steel (hereinafter referred to a third selection invention), wherein 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.
[0019] Herein, 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.
(1) Austenitic stainless steel is stainless steel showing an austenitic structure even in room temperature and can be exemplified as follows: SUS 201, SUS 202, SUS 301,SUS 301J, SUS 302, SUS 302B, SUS 304, SUS 304N1, SUS 304N2, SUS 305, SUS 309S, SUS 310S, SUS 316, SUS 316N, SUD 316J1, SUS 317, SUS 317J1, SUS 321, SUS 347, SUS XM15J1, SUS 836L, SUS 890L and so on.
(2) Austenitic-ferritic stainless steel is stainless steel showing a dual phase structure of austenite and ferrite and can be exemplified SUS 329J4L and so on.
(3) Precipitation hardening stainless steel is a stainless steel obtained by adding elements such as aluminum and copper, and precipitating a compound with the elements as main components by a heat treatment to harden and can be exemplified SUS 630, SUS 631 and so on. It should be appreciated that a concept of "stainless steel" includes heat resisting steel exemplified below as well:
(4) Austenitic heat resisting steel
Compositions are stipulated in JIS G 4311 and G 4312, for example, and can be exemplified
as follows: SUS 31, SUH 35, SUH 36, SUH 37, SUH 38, SUB 309, SUH 310, SUH 330, SUH
660, SUH 661 and so on.
[0020] Description will be given of the reason why the constituting elements and preferable ranges in content thereof are defined in the third selection invention of the present invention constituted as austenite containing stainless:
(3) 2 to 50 mass % Ni
[0021] 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. 6 can be utilized for determination of the Ni content. An austenite forming element and a ferrite forming element are converted to equivalents of Ni and Cr amounts and a relationship between the equivalents and the structure is shown in Fig. 6 (see Revised 5th version Kinzoku Binran (Metal Hand Book) published by Maruzen in 1990, p. 578). However, it is required to obtain a necessary amount of Ni in consideration of exclusion of an amount in Ti and/or Zr compound from constituting elements of the matrix. Since not only does excessive addition of Ni result in cost-up, but specific characteristics as stainless steel are also degraded, a Ni content is limited to 50 mass % or lower.
(4) 12 to 50 mass % Cr
[0022] 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.
[0023] Furthermore, a problem occurs since high temperature embrittlement becomes conspicuous, therefore a Cr content is limited to 50 mass % or lower. For this reason, 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. Desirably, a Cr content is set in the range of 15 to 30 mass % and more desirably in the range of 17 to 25 mass %.
(5) 5 to 85.95 mass % Fe
[0024] 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 %.
(6) 0.01 to 0.4 mass % C
[0025] C is an indispensable component for improvement on machinability and added in a content of 0.01 mass % or higher. With C being included in the matrix, a (Ti,Zr) based compound is formed, and formation of the compound is considered to improves machinability of stainless steel. When 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. On the other hand, when 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. It is considered that residual C not included, as a constituting element, in the(Ti,Zr) based compound contributing to improvement on machinability is dissolved in the matrix phase of stainless steel in a solid state and the residual C in solid solution gives birth to an effect of increasing a hardness of the stainless steel as well. Therefore, 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. In consideration of the above described circumferences, 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 %.
[0026] In a free cutting alloy of the present invention constituted as austenite containing stainless steel, 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:
(7) 4 mass % or lower, including zero Si
[0027] Si can be added as a deoxidizing agent for steel. However, when 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 δ-ferrite phase is formed, thereby deteriorating hot workability of the steel. Hence, the upper limit of Si in content is set to 4 mass %. Especially, when cold workability and hot workability are both regarded as important characteristics, a Si content is desirably set to 1 mass % or lower and more desirably to 0.5 mass % or lower, including zero.
(8) 4 mass % or lower, including zero Mn
[0028] Mn not only acts as a deoxidizing agent of the steel, but also exerts an effect to suppress formation of a δ-ferrite phase. Furthermore, Mn has an effect to stabilize an austenitic phase. Since Mn forms a compound useful for increase in machinability in co-esistence 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. Therefore, the Mn content is set to 4 mass % or lower, including zero. Especially, when corrosion resistivity and cold workability are both regarded as important characteristics, the Mn content is desirably set to 1 mass % or lower, including zero and more desirably to 0.5 mass % or lower, including zero.
(9) 4 mass % or lower, including zero Cu
[0029] 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.
(10) 4 mass % or lower, including zero Co
[0030] 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.
[0031] In the third selection invention constituted as austenite containing stainless steel, 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.
[0032] In the austenite containing stainless steel described above, contents of other elements are as follows: the stainless steels can contain: 0.05 mass % or lower P; and 0.03 mass % O; and 0.05 mass % or lower N. Moreover, 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:
(11) 0.05 mass % or lower, including zero P
[0033] P is segregated at grain boundaries and not only increases intergranular corrosion sensibility but also sometimes reduces toughness. Therefore, 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.
(12) 0.03 mass % or lower, including zero O
[0034] 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.
(13) 0.05 mass % or lower, including zero N
[0035] 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.
(14) 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
[0036] Since 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. On the other hand, since excessive addition reduces hot workability, the upper limits are set as follows: 0.1 mass % Te; 0.2 mass % Bi; and 0.3 mass % Pb.
[0037] Furthermore, the free cutting alloy of the present invention constituted as stainless steel, 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. On the other hand, when the elements are added in excess, the effect is saturated and hot workability is then reduced on the contrary. Therefore, the content of a single element or total content of the elements combined is set to 0.01 mass % as the upper limit. As for 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.
[0038] 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.
[0039] 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. 400 emery paper; a silver foil in size of 10 mm in length, 5 mm in width and 0.1 mm in thickness with a purity of 99.9 % or higher as a S getter; 0.5 cm3 of pure water are sealed in a vessel of an inner volume of 250 cm3 together with said test piece; the temperature in said vessel is raised to 85°C and said temperature is then kept there for 20 hr; and thereafter, the S content in mass % in said silver foil piece is analyzed, then S content obtained is defined as said Wso.
[0040] 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.
[0041] In this case, when the out-gas resistivity test is performed, 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 WSO value and set to 0.035 mass % or lower in WSO. 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.
[0042] While 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. For the purpose, a S content is desirably determined such that a value of WS/(WTi + 0.52WZr) is 0.45 or less, or alternatively a value of WS/WC is 0.4 or less and WS/(WTi+ 0.52WZr) is 0.45 or less, wherein WS and WC denote a S content and a C content, respectively. With such a range of components adopted, a S content which is chemically in unstable condition can be limited and thereby, the out-gas resistivity of the matrix metal phase of stainless steel can be improved.
Examples
[0043] The following experiments were performed in order to confirm the effects of the present invention. It should be appreciated that in the following description, test alloy relating to the present invention is referred to as inventive steel or inventive alloy, or as a selection inventive steel or a selection inventive alloy.
Example 1 Ferrite containing stainless steel (Reference only)
[0044] The effects of a free cutting alloy constituted as ferrite containing stainless steel (a reference steel) were confirmed by the following experiment. First, 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.
Table 1
[0045] While main inclusions of reference steel was (Ti,Zr)4(S,Se)2C2, other inclusions such as (Ti,Zr)S and (Ti,Zr)S3 are locally recognized in the matrix. Further, in a specimen No. 7 high in Mn content, (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. The electrolytic solution after the electrolysis was subjected to filtration and compounds not dissolved in steel were extracted from the filtrate. The extract was dried and subjected to chemical analysis by an X-ray diffraction method with a diffractometer. 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 EPMA and a compound with a composition corresponding to a compound observed by X-ray diffraction was confirmed based on formation from two dimensional mapping results. Fig. 1 shows an X-ray diffraction chart of a steel No. 5 by a diffractometer and Fig. 8 is an optical microphotograph of a steel specimen No. 5. Further, specimens Nos. 1 to 14 in Table 1 are kinds of steel corresponding to reference steel and specimens Nos. 15 to 28 are kinds of steel as comparative examples.
1) Hot workability test
[0047] Evaluation of hot workability was effected based on visual observation of whether or not defects such as cracks occur in hot forging. [○] indicates that substantially no defect occurred in hot forging, [×] indicates that large scale cracks were recognized in hot forging and Δ indicates that small cracks occurred in hot forging.
2) Evaluation of machinability
[0048] 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 µm Ra) on a test piece surface after the machining. Moreover, chip shapes were visually observed and when friability was good, the result is indicated by [G] and when friability is bad and all chips are not separated but partly connected, the result is indicated by [B] and when evaluation of chip shapes is intermidiate of [G] and [B], the result is indicated by [I].
3)
4)Evaluation of out-gas resistivity
[0049] Evaluation of out-gas resistivity was performed by determining an amount of released S. To be concrete, 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 cm3 together with a silver foil having a size of 10 mm in length, 5 mm in width and 0.1 mm in thickness and 0.5 cm3 of pure water, and a temperature in the vessel was maintained at 85°C for 20 hr. A S content WSO in the silver foil after the process for the test was measured by a combustion type infrared absorbing analysis method.
4) Cold workability test
[0050] 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 ln (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. Reference 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.
5) Evaluation of corrosion resistivity
[0051] 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.
Table 2
[0052] It is found from Table 2 that a reference steel 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 reference steel 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.
Example 2 Martensite containing stainless steel (Reference only)
[0053] The following experiment was performed on martensite containing stainless steel. First, 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.
Table 3
[0054] In Table 3, specimens Nos. 1 to 19 are reference steels 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, i.e. reference specimens.
[0055] While main inclusions of the inventive steel of the present invention was of (Ti,Zr)4(S,Se)2C2, other inclusions such as (Ti,Zr)S and (Ti,Zr)S3 are locally recognized in the matrix. Further, in a specimen No. 9 high in a Mn content and the like, (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. The electrolytic solution after the electrolysis was subjected to filtration and compounds not dissolved in steel were extracted from the filtrate. The extract was dried and subjected to chemical analysis by EDX (Energy 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. 3 shows EDX analytical results of arbitrary inclusions in a reference steel specimen No.2 and from the results, formation of (Ti,Zr) based compound can be recognized. Further, Fig. 4 shows optical microphotograph of reference steel specimens Nos. 2 and 13.
1) Hot workability test
[0057] Evaluation of hot workability was effected based on visual observation of whether or not defects such as cracks occur in hot forging. While workability in hot forging was at levels at which processing can be performed with no problem, as not only inclusions but an amount of alloy elements increase, deterioration in the workability was a tendency observed in the test. It was found that kinds of steel of the present invention in which one or more of Ca, B, Mg and REM was included had good hot workability when comparing with a kind of steel in which none of the elements was included.
2) Evaluation of machinability
[0058] Evaluation of 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 µm 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 (Reference).
[0059] The following evaluations were performed using material subjected to treatments in which the material is kept at 980 to 1050°C for 30 min, thereafter subjected to a quenching heat treatment and still further subjected to a tempering treatment of holding at 180°C for 1 hr, followed by air cooling.
3) Hardness test
[0060] Measurement of hardness on a test piece was performed on a C scale Rockwell hardness by the Rockwell hardness test stipulated in JIS Z 2245. The Rockwell hardness was obtained as the average of measurements at arbitrary 5 measuring points S on a circle drawn on a cross section of a rod test piece having a circular section, the circle drawn on the cross section being a circle satisfying a relation of PS = 0.25 PG, wherein G denotes a point almost coinciding with a center of the circular section, P denotes an arbitrary point on the outer periphery of the test piece and a point S is on a line segment PG
4) Evaluation of out-gas resistivity
5) Evaluation of corrosion resistivity
[0062] Evaluation of corrosion resistivity was performed by a method similar to in Example 1 (Reference). 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. An evaluation method was such that when no rust was confirmed, the test piece was evaluated [A], 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]. The results are shown in Table 4.
Table 4
[0063] It is found from Table 4 that while in stainless steel of comparative specimens Nos. 20 to 23, hardness is sufficiently ensured, machinability is poor. It is further found that specimens Nos. 21 to 23 are inferior in corrosion resistivity and out-gas resistivity. When a reference steel is compared with a steel in accordance with Reference Example 2, it is found that the reference steel has improved machinability, while the steel in accordance with Reference Example 2 has improved hardness, improved corrosion resistivity and improved out-gas resistivity. The reason why the steel in accordance with Reference Example 2 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.
Example 3 Austenite containing stainless steel
[0064] An experiment was performed on a free cutting alloy of the present invention constituted as austenite containing stainless steel (a third selection inventive steel). 50 kg blocks of compositions in mass % shown in Table 5 were molten in a high frequency induction furnace to form ingots. The ingots were heated at a temperature in the range from 1050 to 1100°C and hot forging was applied on the ingot at the same temperature to be formed into rods each having a circular section, of a diameter of 20 mm. Specimens Nos. 1 to 18 and 22 to 26 are steel corresponding to third selection inventive steels and specimens Nos. 19 to 21 and 27 to 29 are of comparative steels.
[0065] The specimen No. 19 corresponds to SUS 304, the specimen No. 20 to SUS 303, the specimen No. 27 to SUS 329J4L. Among them, the specimens Nos. 1 to 21 are kinds of steel for use in application of a non-magnetism and the specimens Nos. 22 to 29 are kinds of steel for use in application other than non-magnetism. Among them, 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.
Table 5
[0066] While main inclusions of the inventive steel of the present invention was of (Ti,Zr)4(S,Se)2C2, other inclusions such as (Ti,Zr)S and (Ti,Zr)S3 are locally recognized. Further, in specimens Nos. 9, 10 and 13 high in a Mn content and the like, (Mn,Cr)S was recognized, though in a small amount. Identification of inclusions was performed similar to in Reference Example 2. Fig. 7 shows EDX analytical results of arbitrary inclusions in the third selection inventive steel specimen No.2 and from the results, formation of (Ti,Zr) based compound can be recognized. Further, Fig. 2 shows an optical microphotograph of the third selection inventive steels specimen No. 2.
[0067] The following experiments were performed on the above described test pieces for 1) hot workability test, 2) evaluation of machinability, 3) evaluation of out-gas resistivity, 4) cold workability test and 5) evaluation of corrosion resistivity by methods similar to those in Reference Example 1. The experiment on the evaluation of machinability adopted a circumferential speed of a cutting tool of cermet at 120 m/min. The results obtained are shown in Table 6.
Table 6
[0068] It is found from Table 6 that 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.
2 to 50 mass % Ni; 12 to 50 mass % Cr; 5 to 85.95 mass % Fe; and 0.01 to 0.4 mass % C;
one or more of Ti and Zr such that WTi + 0.52 WZr = 0.03 to 3.5 mass %, wherein WTi and WZr denote respective contents in mass % of Ti and Zr; and 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;
and wherein a (Ti, Zr) based compound containing 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 is dispersed in a matrix metal phase; optionally further containing:
4 mass % or lower, including zero Si; 4 mass % or lower, including zero Mn; 4 mass % or lower, including zero Cu; 4 mass % or lower, including zero Co;
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;
0.05 mass % or lower, including zero P; 0.03 mass % or lower, including zero O; 0.05 mass % or lower, including zero N;
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; 0.01 to 0.3 mass % for Pb;
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 of more than one elements combined;
one or more selected from the group consisting of Nb, V, Ta and Hf in each range of 0.01 to 0.5 mass %, the balance being Fe and inevitable impurities.
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. 400 emery paper;
a silver foil in size of 10 mm in length, 5 mm in width and 0.1 mm in thickness with a purity of 99.9 % or higher as a S getter;
0.5 cm3 of pure water are sealed in a vessel of an inner volume of 250 cm3 together with said test piece;
the temperature in said vessel is raised to 85°C and said temperature is then kept there for 20 hr;
and thereafter, the S content in mass % in said silver foil piece is analyzed, then S content obtained is defined as said Wso.
2 bis 50 Massen-% Ni; 12 bis 50 Massen-% Cr; 5 bis 85,95 Massen-% Fe; und 0,01 bis 0,4 Massen-% C;
ein oder mehrere aus Ti und Zr, sodass WTi + 0,52 WZr = 0,03 bis 3,5 Massen-% erfüllt ist, worin WTi und WZr die jeweiligen Mengen in Massen-% von Ti und Zr angeben;
und ein oder mehrere aus S und Se in den jeweiligen Bereichen von 0,01 bis 1 Massen-% für S und 0,01 bis 0,8 Massen-% für Se;
und worin eine (Ti, Zr)-basierte Verbindung, enthaltend ein oder mehrere aus Ti und Zr als eine Metall-Element-Komponente, wobei C ein unabdingbares Element als eine Bindungskomponente mit der Metall-Element-Komponente darstellt, und ein oder mehrere aus S, Se und Te in einer Matrix-Metallphase dispergiert sind; wahlweise weiterhin enthaltend:
4 Massen-% oder weniger, einschließlich null, Si; 4 Massen-% oder weniger, einschließlich null, Mn; 4 Massen-% oder weniger, einschließlich null, Cu; 4 Massen-% oder weniger, einschließlich null, Co;
ein oder mehrere aus Mo und W in den jeweiligen Bereichen von 0,1 bis 10 Massen-% für Mo und 0,1 bis 10 Massen-% für W;
0,05 Massen-% oder weniger, einschließlich null, P; 0,03 Massen-% oder weniger, einschließlich null, O; 0,05 Massen-% oder weniger, einschließlich null, N;
ein oder mehrere aus Te, Bi und Pb in den jeweiligen Bereichen von 0,005 bis 0,1 Massen-% für Te; 0,01 bis 0,2 Massen-% für Bi; 0,01 bis 0,3 Massen-% für Pb;
ein oder mehrere, ausgewählt aus der Gruppe, bestehend aus Ca, Mg, B und REM (ein oder mehrere der in dem Periodensystem der Elemente als Gruppe 3A klassifizierten Metallelemente) in dem Bereich von 0,0005 bis 0,01 Massen-% für ein Element oder als Gesamtgehalt von mehr als einem Element in Kombination;
ein oder mehrere, ausgewählt aus der Gruppe, bestehend aus Nb, V, Ta und Hf in dem jeweiligen Bereich von 0,01 bis 0,5 Massen-%, wobei der Rest Fe und unvermeidbare Verunreinigungen darstellt.
ein Legierungsteststück der Automatenlegierung wird derartig hergestellt, dass es die Form eines rechteckigen Prismas der Größe von 15 mm in der Länge, 25 mm in der Breite und 3 mm in der Dicke aufweist, wobei die Gesamtoberfläche mit einem Schmirgelpapier der Nr. 400 poliert wurde;
eine Silberfolie der Größe von 10 mm in der Länge, 5 mm in der Breite und 0,1 mm in der Dicke mit einer Reinheit von 99,9% oder mehr als S-Getter;
0,5 cm3 reines Wasser werden in ein Gefäß mit einem Innenvolumen von 250 cm3 zusammen mit dem Teststück versiegelt;
die Temperatur in dem Gefäß wird auf 85°C erhöht, und die Temperatur wird anschließend 20 Stunden lang dort gehalten;
und anschließend wird der S-Gehalt in Massen-% in der Silberfolie analysiert, wobei der erhaltene S-Gehalt als der Wso definiert ist.
de 2 à 50 % en masse de Ni ; de 12 à 50 % en masse de Cr ; de 0,01 à 0,4 % en masse de C ; un ou plusieurs éléments choisis parmi Ti et Zr de telle façon que WTi + 0,52 WZr = 0,03 à 3,5 % en masse, WTi et WZr représentant les teneurs respectives en % en masse de Ti et Zr ;
et un ou plusieurs éléments choisis parmi S et Se dans les plages respectives de 0,01 à 1 % en masse pour S et de 0,01 à 0,8 % en masse pour Se ;
un composé de (Ti, Zr) contenant un ou plusieurs éléments choisis parmi Ti et Zr en tant que composant de type élément de métal, C étant un élément indispensable en tant que composant de liaison avec le composant de type élément de métal, et un ou plusieurs éléments choisis parmi S, Se et Te, ledit composé étant dispersé dans une phase métallique formant matrice ; contenant en outre éventuellement :
4 % en masse ou moins, 0 inclus, de Si ; 4 % en masse ou moins, 0 inclus, de Mn ; 4 % en masse ou moins, 0 inclus, de Cu ; 4 % en masse ou moins, 0 inclus, de Co ;
un ou plusieurs éléments choisis parmi Mo et W dans les plages respectives de 0,1 à 10 % en masse pour Mo et de 0,1 à 10 % en masse pour W ;
0,05 % en masse ou moins, 0 inclus, de P ; 0,03 % en masse ou moins, 0 inclus, de O ; 0,05 % en masse ou moins, 0 inclus, de N ;
un ou plusieurs éléments choisis parmi Te, Bi et Pb dans les plages respectives de 0,005 à 0,1 % en masse pour Te ; de 0,01 à 0,2 % en masse pour Bi ; de 0,01 à 0,3 % en masse pour Pb;
un ou plusieurs éléments choisis parmi le groupe consistant en Ca, Mg, B et les éléments de métal de terre rare (REM) (un ou plusieurs éléments de métal classés en tant que groupe 3A dans le tableau périodique des éléments) dans la plage de 0,0005 à 0,01 % en masse pour un élément participant, ou en tant que teneur totale en plus d'un élément associé ;
un ou plusieurs éléments choisis parmi le groupe consistant en Nb, V, Ta et Hf chacun dans une plage de 0,01 à 0,5 % en masse, le reste consistant en masse de Fe, et en impuretés inévitables.
une éprouvette d'alliage du dit alliage de décolletage est préparée de façon à avoir la forme d'un prisme rectangulaire d'une taille de 15 mm de longueur, de 25 mm de largeur et de 3 mm d'épaisseur dont la totalité de la surface est polie avec du papier d'émeri N° 400 ;
on prévoit une feuille d'argent d'une taille de 10 mm de longueur, de 5 mm de largeur et de 0,1 mm d'épaisseur, ayant une pureté de 99,9 % ou plus, en tant que piège pour S;
on enferme hermétiquement 0,5 cm3 d'eau pure dans un récipient d'un volume intérieur de 250 cm3 ensemble avec ladite éprouvette ;
la température du dit récipient est accrue jusqu'à 85 °C, et ladite température est ensuite maintenue pendant 20 h ; et
la teneur en S exprimée en % en masse dans ladite pièce de feuille d'argent, est ensuite analysée, la teneur en S obtenue étant alors définie comme étant ladite valeur WSO.