JP6610062B2 - Titanium plate - Google Patents
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本発明は、成形加工性と耐疵付き性の両方に優れ、安価に製造することのできるチタン板に関するものである。 The present invention relates to a titanium plate that is excellent in both moldability and scratch resistance and can be manufactured at low cost.
チタン板は耐食性に優れていることから、化学・電力及び食品製造プラントなどの熱交換器に使用されている。その中でもプレート式熱交換器は、プレス成形によりチタン板に凹凸を付けて表面積をかせぎ熱交換効率を高めており、深い凹凸をつけるため成形性が必要である。 Titanium plates have excellent corrosion resistance and are used in heat exchangers such as chemical / electric power and food production plants. Among them, the plate heat exchanger increases the surface area by increasing the surface area of the titanium plate by press forming to increase the heat exchange efficiency, and requires moldability to add deep unevenness.
ＪＩＳに規定された工業用純チタンは、加工性に優れる成分系であるため、加工性を必要とする用途に用いられる。一方、工業用純チタンを用いた薄板であっても、薄板表面に酸素、炭素、窒素など軽元素が富化した脆く深い硬化層が存在すると、成形時に割れなどが発生することがあり、加工性を低下させることとなる。 Industrially pure titanium specified in JIS is a component system that excels in workability, and is therefore used for applications that require workability. On the other hand, even if it is a thin plate made of industrial pure titanium, cracks may occur during molding if there is a brittle and deep hardened layer enriched with light elements such as oxygen, carbon, and nitrogen on the thin plate surface. It will reduce the nature.
成形性に悪影響を及ぼす硬化層を除去するため、連続焼鈍或いは真空雰囲気焼鈍後に酸洗溶削する方法が一般的である。また硬化層の形成を抑えるため特許文献１では、硬化層形成の原因となる冷間圧延で焼き付き付着した油分を、焼鈍前に硝フッ酸水溶液にて酸洗し除去した後、更に７×１０-5Ｔｏｒｒ以下と相当真空度の良い高真空相当雰囲気で焼鈍することにより、焼鈍時に形成される硬化層も抑制する方法が提案されている。ただしこの方法では、硬化層は軽減され素材の加工性は良くなる方向であるが、酸化膜などの表面皮膜が薄いため容易に工具と金属チタンが接触し、摩擦係数が高まり潤滑に不具合が生じやすいといった問題があった。また、成形加工時、あるいは成形加工後のチタン板表面が軟質であるため、中間製品や最終製品の表面が疵付きやすいという問題を有していた。 In order to remove the hardened layer that adversely affects the formability, a method of pickling and cutting after continuous annealing or vacuum atmosphere annealing is common. In order to suppress the formation of the hardened layer, in Patent Document 1, the oil component seized by cold rolling that causes the hardened layer formation is pickled and removed with an aqueous solution of nitric hydrofluoric acid before annealing, and further 7 × 10. There has been proposed a method for suppressing a hardened layer formed during annealing by annealing in an atmosphere equivalent to a high vacuum with a degree of vacuum equivalent to -5 Torr or less. However, in this method, the hardened layer is reduced and the workability of the material is improved, but the surface film such as an oxide film is thin, so the tool and metal titanium easily come into contact with each other, increasing the friction coefficient and causing problems in lubrication. There was a problem that it was easy. In addition, since the surface of the titanium plate during or after the molding process is soft, there is a problem that the surface of the intermediate product or the final product is easily wrinkled.
特許文献２には、冷間圧延後にチタン板の表面を０．２μｍ以上除去した後、窒化・酸化雰囲気中にて焼鈍するチタン薄板の製造方法が開示されている。冷間圧延後にチタン薄板の表面を０．２μｍ以上除去することにより、冷間圧延で焼き付き付着した油分を除去し、表面付着炭素起因の硬化層が形成されないので加工性が良好である。また窒化・酸化雰囲気中にて焼鈍するので表面に窒化膜・酸化膜が形成され、工具との潤滑性と耐疵付き性を高める表面特性を有している。 Patent Document 2 discloses a method for manufacturing a titanium thin plate that is annealed in a nitriding / oxidizing atmosphere after removing 0.2 μm or more of the surface of the titanium plate after cold rolling. By removing 0.2 μm or more of the surface of the titanium thin plate after the cold rolling, the oil component seized and adhered by the cold rolling is removed, and the hardened layer due to the surface-attached carbon is not formed, so that the workability is good. Further, since annealing is performed in a nitriding / oxidizing atmosphere, a nitride film / oxide film is formed on the surface, and it has surface characteristics that enhance the lubricity and scratch resistance with the tool.
特許文献３は、成形性及び潤滑性に優れたチタン材に関するものであり、チタン材の表層において、窒素と酸素と炭素の濃度総和が表面から０．５μｍ深さで１〜８質量％、５μｍ深さで０．２質量％以下である表層を有することを特徴とする成形性及び潤滑性に優れたチタン材が記載されている。実態としては、表面の窒素量を所定の量以上に制御することにより、成形性、潤滑性を向上させるという発明の効果を得ており、表層付近における炭素濃度を増大させた例は記載されていない。 Patent Document 3 relates to a titanium material excellent in formability and lubricity. In the surface layer of the titanium material, the total concentration of nitrogen, oxygen, and carbon is 1 to 8% by mass and 5 μm at a depth of 0.5 μm from the surface. A titanium material excellent in formability and lubricity characterized by having a surface layer having a depth of 0.2% by mass or less is described. As a matter of fact, the effect of the invention of improving moldability and lubricity is obtained by controlling the amount of nitrogen on the surface to a predetermined level or more, and examples of increasing the carbon concentration in the vicinity of the surface layer are described. Absent.
チタン板を冷間圧延と焼鈍の工程で製造するに際し、冷間圧延で表面に付着した油分を除去せずに焼鈍を行うと、表面に濃化した炭素による硬化層に起因して加工性が低下する現象が見られた。そのため、チタン板を良好な加工性を必要とする用途に用いる場合、酸洗によって表面を除去した上で焼鈍を行い、加工性を確保していた（特許文献１、特許文献２参照）。ただし、表面に硬化層を有していないチタン板は、表面が軟質であるため、耐疵付き性や潤滑性が不十分である。そこで、特許文献２、特許文献３に記載のものは、焼鈍によって表面に窒素濃化層を形成することによって表面を硬質化し、成形性と潤滑性・耐疵付き性の両立を図っている。 When manufacturing titanium plates in the cold rolling and annealing processes, if annealing is performed without removing the oil adhering to the surface by cold rolling, the workability is reduced due to the hardened layer of carbon concentrated on the surface. A decreasing phenomenon was observed. Therefore, when using a titanium plate for the use which requires favorable workability, it annealed, after removing the surface by pickling (refer patent document 1 and patent document 2). However, a titanium plate that does not have a hardened layer on the surface has a soft surface, and thus has insufficient scratch resistance and lubricity. Therefore, the ones described in Patent Document 2 and Patent Document 3 harden the surface by forming a nitrogen-concentrated layer on the surface by annealing, thereby achieving both formability, lubricity, and anti-flaw resistance.
ところが、窒素雰囲気での焼鈍によってチタン板表面に形成される窒素濃化層は非常に薄いため、例えばプレート式熱交換器をプレス成形で製造した場合、プレス成形時の潤滑性と耐疵付き性は確保できるものの、プレス成形後には窒素濃化層が十分に残存しないため、プレス成形後の熱交換器プレートの耐疵付き性を十分に確保できないことがあった。また、冷間圧延後焼鈍前に酸洗によってチタン板表面を除去する工程が入るため、工程追加及び歩留まり低下によるコストアップが避けられなかった。 However, since the nitrogen-concentrated layer formed on the titanium plate surface by annealing in a nitrogen atmosphere is very thin, for example, when a plate heat exchanger is manufactured by press molding, lubricity and scratch resistance during press molding However, after the press molding, the nitrogen-concentrated layer does not remain sufficiently, so that the heat resistance of the heat exchanger plate after press molding may not be sufficiently secured. In addition, since a step of removing the surface of the titanium plate by pickling before annealing after cold rolling is performed, an increase in cost due to an additional step and a decrease in yield is inevitable.
本発明は、成形加工性と耐疵付き性の両方に優れ、プレス成形後も耐疵付き性を確保し、安価に製造することのできるチタン板を提供することを目的とする。 An object of the present invention is to provide a titanium plate that is excellent in both molding processability and scratch resistance, ensures scratch resistance even after press molding, and can be manufactured at low cost.
即ち、本発明の要旨とするところは以下のとおりである。
（１）工業用純チタンＪＩＳ１種〜２種、ＪＩＳ１１種、１４種、１７種のいずれかに規定する成分を含有し、平均荷重１ｋｇｆ表面ビッカース硬度ＨＶ1≦１５０であって、ＧＤＳによって測定された表面から１μｍまでの平均炭素濃度Ｃｓが０．６質量％以上であり、ＧＤＳによって測定された表面から１〜１０μｍの領域における平均炭素濃度Ｃｄが０．１質量％以下であるチタン板。
（２）さらに質量％で、Ｐｄ，Ｒｕ，Ｐｔ，Ａｇ，Ｍｏ，Ｎｂ，Ｎｉ，Ｃｒの１種以上をそれぞれ０．５％以下、及び／又は、Ｃｕ：１％以下、Ａｌ：０．５％以下、Ｓｎ：０．５％以下、Ｖ：０．５％以下、Ｃｏ：０．３％以下、Ｚｒ：０．５％以下、Ｓｉ：０．１％以下、Ｍｎ：０．５％以下、Ｔａ：０．３％以下、Ｗ：０．３％以下、Ｈｆ：０．３％以下の１種以上、を含有することを特徴とする上記（１）に記載のチタン板。
（３）前記Ｃｓが１．０質量％以上であることを特徴とする上記（１）又は（２）に記載のチタン板。
（４）荷重１０ｇｆ表面ビッカース硬度ＨＶ0.01＜２００の発生率が２５％以下であることを特徴とする上記（１）〜（３）のいずれか１つに記載のチタン板。
That is, the gist of the present invention is as follows.
(1) Pure titanium for industrial use JIS 1 to 2 types, JIS 11 types, 14 types, and 17 types of components are included, average load 1 kgf surface Vickers hardness HV 1 ≦ 150, measured by GDS A titanium plate having an average carbon concentration Cs from the surface to 1 μm of 0.6% by mass or more and an average carbon concentration Cd in the region of 1 to 10 μm from the surface measured by GDS of 0.1% by mass or less.
(2) Further, by mass%, at least one of Pd, Ru, Pt, Ag, Mo, Nb, Ni, and Cr is 0.5% or less and / or Cu: 1% or less, Al: 0.5 % Or less, Sn: 0.5% or less, V: 0.5% or less, Co: 0.3% or less, Zr: 0.5% or less, Si: 0.1% or less, Mn: 0.5% or less Ta: 0.3% or less, W: 0.3% or less, Hf: one or more of 0.3% or less, and the titanium plate according to (1) above.
( 3 ) The titanium plate according to (1) or (2) , wherein the Cs is 1.0% by mass or more.
( 4 ) The titanium plate according to any one of the above (1) to ( 3 ) , wherein the rate of occurrence of load 10 gf surface Vickers hardness HV 0.01 <200 is 25% or less.
本発明のチタン板は、平均荷重１ｋｇｆ表面ビッカース硬度ＨＶ1≦１５０であって、ＧＤＳによって測定された表面から１μｍまでの平均炭素濃度Ｃｓが０．６質量％以上であり、ＧＤＳによって測定された表面から１〜１０μｍの領域における平均炭素濃度Ｃｄが０．１質量％以下であることにより、成形加工性と耐疵付き性の両方に優れ、プレス成形後も耐疵付き性を確保し、焼鈍前に酸洗を行わないことから安価に製造することができる。 The titanium plate of the present invention has an average load of 1 kgf surface Vickers hardness HV 1 ≦ 150, an average carbon concentration Cs from the surface measured by GDS to 1 μm is 0.6% by mass or more, and was measured by GDS. When the average carbon concentration Cd in the region of 1 to 10 μm from the surface is 0.1% by mass or less, it is excellent in both molding processability and scratch resistance, ensuring scratch resistance after press molding, and annealing. Since it is not pickled before, it can be manufactured at low cost.
チタン板を冷間圧延と焼鈍の工程で製造するに際し、冷間圧延で表面に付着した油分を酸洗除去した上で焼鈍を行う従来材を、ここでは「従来軟質材」と呼ぶ。加工性は良好であるが、表面が軟質であるため、耐疵付き性や加工時の潤滑性が不十分である。また冷間圧延で表面に付着した油分を除去せずに焼鈍をおこなう従来材を、ここでは「従来硬質材」と呼ぶ。表面に濃化した炭素による硬化層を有するので耐疵付き性は良好であるが、加工性が低下するため、優れた加工性を必要とする用途に用いるには問題がある。なお、焼鈍で窒化膜や酸化膜が形成されないよう、焼鈍雰囲気は真空焼鈍あるいは不活性ガス雰囲気焼鈍する。 A conventional material that is annealed after pickling and removing oil adhering to the surface by cold rolling when the titanium plate is manufactured in the cold rolling and annealing processes is referred to as “conventional soft material”. Workability is good, but since the surface is soft, scratch resistance and lubricity during processing are insufficient. A conventional material that is annealed without removing oil adhering to the surface by cold rolling is referred to herein as a “conventional hard material”. Since it has a hardened layer made of carbon concentrated on the surface, the scratch resistance is good, but since the workability is lowered, there is a problem in using it for applications that require excellent workability. The annealing atmosphere is vacuum annealing or inert gas atmosphere annealing so that a nitride film or an oxide film is not formed by annealing.
上記従来軟質材と従来硬質材について、グロー放電発光分光分析（以下「ＧＤＳ」という。）によって、表面から深さ方向のＯ、Ｎ、Ｃ濃度（質量％）分布を評価した。図１に従来軟質材、図２に従来硬質材の評価結果を示す。従来軟質材と従来硬質材の元素分布を比較すると、両者で大きく相違するのは炭素の分布である。従来軟質材（図１）は表面まで炭素がほとんど含まれていないのに対し、従来硬質材（図２（Ａ））については、表面付近の炭素含有量が極めて高く、表面からの深さが１μｍ付近位置から表面に向かって炭素濃度が上昇している。また、表面からの深さ１μｍ位置よりも深い側についても、従来硬質材の炭素濃度は従来軟質材よりも高い値を示しており、深さ１０μｍ位置においてもまだ炭素濃度に有意な差が見られる。図２（Ｂ）には、図２（Ａ）と同じ試料について、横軸を２０μｍまで拡大した図における炭素と窒素の分布を示す。表面から１５〜２０μｍ付近まで、炭素を含有する領域が存在することがわかる。なお、表面から深さ方向の窒素濃度分布については、従来軟質材、従来硬質材のいずれも、ほとんど差がなく、表面近傍から内部に至るまでほぼ一定となっている。バルクでの窒素の分析結果は０．００５％（質量％）であり、ＧＤＳでの結果は、後述するように窒素の基準材がチタンではなかったために高い値を示したものと考えられ、実際には窒素は従来軟質材と従来硬質材の両方で存在していない。これは窒素雰囲気での焼鈍を行っていないためである。酸素濃度分布については、熱間圧延やその後の歪み取り焼鈍を大気中で行っているためにそれらの工程で酸素が侵入したものであるが、このような侵入酸素による品質への影響はわずかであることがわかっており、また、従来軟質材と従来硬質材、あるいは後述の本発明品に同じような分布で含まれており、相互の品質に差を及ぼすものではない。 About the said conventional soft material and the conventional hard material, the O, N, and C density | concentration (mass%) distribution of the depth direction from the surface was evaluated by the glow discharge emission spectroscopic analysis (henceforth "GDS"). FIG. 1 shows the evaluation results of the conventional soft material, and FIG. 2 shows the evaluation results of the conventional hard material. Comparing the element distributions of the conventional soft material and the conventional hard material, the carbon distribution is greatly different between the two. The conventional soft material (FIG. 1) contains almost no carbon up to the surface, whereas the conventional hard material (FIG. 2A) has a very high carbon content near the surface and a depth from the surface. The carbon concentration increases from the position near 1 μm toward the surface. Also, the carbon concentration of the conventional hard material is higher than that of the conventional soft material on the side deeper than the 1 μm depth from the surface, and there is still a significant difference in the carbon concentration even at the depth of 10 μm. It is done. FIG. 2B shows the distribution of carbon and nitrogen in the diagram in which the horizontal axis is enlarged to 20 μm for the same sample as FIG. It can be seen that there is a carbon-containing region from the surface to around 15 to 20 μm. Note that the nitrogen concentration distribution in the depth direction from the surface is almost constant for both the conventional soft material and the conventional hard material, and is almost constant from the vicinity of the surface to the inside. The analysis result of nitrogen in the bulk is 0.005% (mass%), and the result of GDS is considered to show a high value because the nitrogen reference material was not titanium as described later. Nitrogen is not present in both soft and conventional hard materials. This is because annealing is not performed in a nitrogen atmosphere. As for the oxygen concentration distribution, since hot rolling and subsequent strain relief annealing are performed in the atmosphere, oxygen has penetrated in those processes, but the influence of such invading oxygen on quality is slight. It has been found that there is a similar distribution in the conventional soft material and the conventional hard material, or the product of the present invention to be described later, and does not affect the quality of each other.
以上説明したように、図２の従来硬質材における表面からの炭素濃度分布について観察すると、表面付近で炭素濃度が急激に増大するのは表面からの深さが１μｍよりも表面側であり、この領域における炭素濃度は表面を硬化させ、耐疵付き性や加工時の潤滑性に影響を及ぼす可能性が高いと推測される。そこで、ＧＤＳによって測定された表面から１μｍまでの平均炭素濃度を「表層炭素Ｃｓ」と呼び、耐摩耗性や表面硬度との関係を評価することとした。 As described above, when observing the carbon concentration distribution from the surface in the conventional hard material of FIG. 2, the carbon concentration rapidly increases near the surface when the depth from the surface is more than 1 μm, and this It is presumed that the carbon concentration in the region hardens the surface and is likely to affect the scratch resistance and lubricity during processing. Therefore, the average carbon concentration from the surface measured by GDS to 1 μm is called “surface carbon Cs”, and the relationship with the wear resistance and surface hardness is evaluated.
一方、従来硬質材を従来軟質材と対比すると、表面から１〜１０μｍにおける炭素濃度が上昇している。従来硬質材は従来軟質材と比較して加工性が悪くなることがわかっており、表面から１〜１０μｍにおける炭素濃度の差が加工性に影響を及ぼしているのではないかと着想した。そこで、ＧＤＳによって測定された表面から１〜１０μｍの領域における平均炭素濃度を「中層炭素Ｃｄ」と呼び、成形性や板硬度との関係を評価することとした。 On the other hand, when the conventional hard material is compared with the conventional soft material, the carbon concentration at 1 to 10 μm is increased from the surface. Conventionally hard materials are known to have poor workability compared to conventional soft materials, and the inventors conceived that the difference in carbon concentration at 1 to 10 μm from the surface may affect the workability. Therefore, the average carbon concentration in the region of 1 to 10 μm from the surface measured by GDS is referred to as “intermediate carbon Cd”, and the relationship between formability and plate hardness is evaluated.
耐摩耗性の評価として、ボールオンディスク試験後の質量変化で評価した。ボールはφ３／１６インチのＳＵＪ２を用い、チタン板と接触して回転させた。試験は無潤滑で荷重３ｋｇ、半径１５ｍｍの円軌道を５００回転させた後の質量変化（ｍｇ）を求めた。回転速度は５０ｒｐｍで行った。 As an evaluation of wear resistance, the mass change after the ball-on-disk test was evaluated. The ball was rotated in contact with a titanium plate using SUJ2 of φ3 / 16 inch. In the test, a change in mass (mg) after 500 revolutions of a circular orbit with a load of 3 kg and a radius of 15 mm without lubrication was obtained. The rotation speed was 50 rpm.
成形性評価として、エリクセン試験を行った。エリクセン試験はＪＩＳ Ｚ ２２４７に基づいて行ったが、潤滑には摩擦係数が約０．０４の厚さ５０μｍのＰＴＦＥシートを用いた。成形性の評価として、結晶粒径の影響を除くため、酸洗した板を同じ条件で焼鈍し、それとの差をとり、「エリクセン値の変化量（ｍｍ）」として評価した。 An Erichsen test was performed as a moldability evaluation. The Eriksen test was performed based on JIS Z 2247, and a PTFE sheet having a friction coefficient of about 0.04 and a thickness of 50 μm was used for lubrication. As an evaluation of formability, in order to remove the influence of the crystal grain size, the pickled plate was annealed under the same conditions, and the difference was taken and evaluated as “the amount of change in Eriksen value (mm)”.
チタン板の硬さ評価を２種類の方法で行った。第１は、チタン板を１０ｇｆの荷重で測定したビッカース表面硬度ＨＶ０．０１である。表面硬化層の硬さを評価するＨＶ０．０１は圧子が約１〜２μｍ押し込まれており、この程度の押し込み深さであれば、表面から１μｍまでの平均炭素濃度（表層炭素Ｃｓ）による表面の硬化状況を評価することができる。また、板厚が０．１ｍｍであっても板厚に占める硬化層の割合は２〜４％であり、成形性には問題ないと考えられる。 The hardness of the titanium plate was evaluated by two types of methods. The first is a Vickers surface hardness HV 0.01 measured on a titanium plate with a load of 10 gf. HV 0.01, which evaluates the hardness of the surface hardened layer, has an indenter of about 1 to 2 μm. If the indentation is of this level, the surface is an average carbon concentration (surface carbon Cs) from the surface to 1 μm. The curing status of can be evaluated. Moreover, even if the plate thickness is 0.1 mm, the ratio of the hardened layer to the plate thickness is 2 to 4%, and it is considered that there is no problem in moldability.
チタン板の表層のみならず、板内部まで含めた全体の硬度を評価する目的で、荷重１ｋｇｆでのビッカース硬度ＨＶ１の測定を行った。ＨＶ1は圧子が約２０〜２８μｍ押し込まれており、この程度の押し込み深さであれば、板内部すなわち母材の硬度を評価できており、母材の加工性を評価する指標とできる。 In order to evaluate not only the surface layer of the titanium plate but also the entire hardness including the inside of the plate, the Vickers hardness HV 1 was measured at a load of 1 kgf. HV 1 indenter has pushed about 20～28Myuemu, if the indentation depth of the extent, which can evaluate the hardness of the plate inside That matrix can as an index for evaluating the processability of the base material.
冷間圧延によって、冷間圧延後のチタン板表面に圧延油起因の炭素含有成分が付着する。そして、冷間圧延後の焼鈍において、チタン板表面に付着した炭素が板の内部に拡散する。表面から１μｍまでの平均炭素濃度（表層炭素Ｃｓ）については、冷間圧延後に表面に付着する炭素分が多いほど高い値となり、焼鈍での拡散が進行しすぎると表面から１μｍよりも深い部分にまで拡散する炭素分が増大するため、表層Ｃｓは減少することとなる。表面から１〜１０μｍの領域における平均炭素濃度（中層炭素Ｃｄ）については、焼鈍での拡散によって表面から炭素分が拡散することによって増大する。拡散の程度が大きくなるほど、中層炭素Ｃｄが増大し、また焼鈍前の表面炭素分が多い場合には中層炭素Ｃｄも増大する。 By cold rolling, carbon-containing components due to rolling oil adhere to the surface of the titanium plate after cold rolling. And in the annealing after cold rolling, the carbon adhering to the titanium plate surface diffuses inside the plate. About the average carbon concentration (surface layer carbon Cs) from the surface to 1 μm, the higher the carbon content adhering to the surface after cold rolling, the higher the value. If the diffusion by annealing proceeds too much, the surface becomes deeper than 1 μm from the surface. Therefore, the surface layer Cs decreases. The average carbon concentration (intermediate carbon Cd) in the region of 1 to 10 μm from the surface increases due to the diffusion of carbon from the surface by diffusion during annealing. As the degree of diffusion increases, the middle layer carbon Cd increases, and the middle layer carbon Cd also increases when the surface carbon content before annealing increases.
冷間圧延条件と冷間圧延後の板表面に付着する炭素量との関係については、１回当たりの圧減率が大きいほど、冷間圧延パス回数が少ないほど、冷間圧延総圧延率が大きいほど、冷間圧延後の板表面に付着する炭素量が増大する。また、使用する圧延油の炭素含有量が多いほど、付着する炭素量は増大する。焼鈍条件と炭素の拡散については、焼鈍温度が高いほど、焼鈍時間が長いほど、拡散の程度が大きくなる。 Regarding the relationship between the cold rolling conditions and the amount of carbon adhering to the sheet surface after cold rolling, the larger the reduction rate per time, the smaller the number of cold rolling passes, The larger the amount, the greater the amount of carbon adhering to the plate surface after cold rolling. Moreover, the amount of adhering carbon increases as the carbon content of the rolling oil used increases. Regarding annealing conditions and carbon diffusion, the higher the annealing temperature and the longer the annealing time, the greater the degree of diffusion.
工業用純チタンＪＩＳ１種の成分を有するチタンを用い、冷間圧延と真空焼鈍を行って板厚０．５ｍｍのチタン板を製造するに際し、冷間圧延条件と焼鈍条件（温度、時間）を種々変更することにより、種々の表層炭素Ｃｓ、中層炭素Ｃｄを有するチタン板を製造した。 When manufacturing titanium plate with 0.5mm thickness by cold rolling and vacuum annealing using titanium with industrial pure titanium JIS 1 type, various cold rolling conditions and annealing conditions (temperature, time) By changing, titanium plates having various surface carbon Cs and middle carbon Cd were produced.
図３には、横軸を表面から１μｍまでの平均炭素濃度（表層炭素Ｃｓ）、縦軸を摩耗量としたグラフを示す。図３から明らかなように、表層炭素Ｃｓが増大するほど摩耗量は減少し、表層炭素Ｃｓが０．６質量％以上であれば、摩耗量が０．８ｍｇ以下となり、従来軟質材と比較して耐摩耗性が改善する。表層炭素Ｃｓが０．７質量％以上であれば、摩耗量が０．７ｍｇ以下なり、より好ましい。 FIG. 3 shows a graph in which the horizontal axis is the average carbon concentration (surface carbon Cs) from the surface to 1 μm, and the vertical axis is the amount of wear. As is apparent from FIG. 3, the amount of wear decreases as the surface carbon Cs increases, and if the surface carbon Cs is 0.6% by mass or more, the amount of wear is 0.8 mg or less, compared with the conventional soft material. This improves wear resistance. If the surface carbon Cs is 0.7% by mass or more, the wear amount is 0.7 mg or less, which is more preferable.
図４には、横軸を表面から１〜１０μｍの領域における平均炭素濃度（中層炭素Ｃｄ）、縦軸をエリクセン値の変化量としたグラフを示す。図４から明らかなように、中層炭素Ｃｄが低下するほどエリクセン値の変化量は改善し、中層炭素Ｃｄが０．１質量％以下であれば、従来硬質材と比較して成形性が改善する。中層炭素Ｃｄが０．０９質量％以下であればより好ましい。０．０８質量％以下であればさらに好ましい。 FIG. 4 shows a graph in which the horizontal axis is the average carbon concentration (intermediate carbon Cd) in the region of 1 to 10 μm from the surface, and the vertical axis is the amount of change in the Erichsen value. As is clear from FIG. 4, the amount of change in the Erichsen value is improved as the middle-layer carbon Cd is decreased. If the middle-layer carbon Cd is 0.1% by mass or less, the moldability is improved as compared with the conventional hard material. . More preferably, the middle layer carbon Cd is 0.09% by mass or less. If it is 0.08 mass% or less, it is more preferable.
以上のように、中層炭素Ｃｄに着目すると、中層炭素Ｃｄを低くするほど、加工性が向上する。一方、チタン板における加工性は、中層炭素濃度以外の影響を受ける。結晶粒径が小さい場合や未再結晶組織、加工組織の場合にはバルクの硬度が高く、加工性が低下する。また、１０μｍを下回るような細粒組織の場合にも加工性は低下し、合金組成（酸素、炭素、窒素、鉄などの不純物含む）によっても加工性は変化する。そのため、本発明においてチタン板の加工性を十分に確保する上では、中層炭素Ｃｄ以外の指標が必要となる。本発明では、内部の硬度を評価している荷重１ｋｇｆでのビッカース硬度ＨＶ1を規定することによってチタン板の加工性を担保することとした。ＨＶ1が１５０以下であれば十分に加工性を確保できるのでよい。望ましくは１４０以下であり、さらに望ましくは１３５以下、さらに望ましくは１３０以下である。また、工業的に不純物元素を低減できる限度があり、ＨＶ1は８０以上である。 As described above, focusing on the middle-layer carbon Cd, the lower the middle-layer carbon Cd, the more the workability is improved. On the other hand, the workability of the titanium plate is affected by other than the middle-layer carbon concentration. In the case where the crystal grain size is small, or in the case of an unrecrystallized structure or a processed structure, the bulk hardness is high and the workability is lowered. Also, in the case of a fine grain structure of less than 10 μm, the workability is lowered, and the workability changes depending on the alloy composition (including impurities such as oxygen, carbon, nitrogen, iron, etc.). Therefore, in order to sufficiently secure the workability of the titanium plate in the present invention, an index other than the middle-layer carbon Cd is required. In the present invention, the workability of the titanium plate is secured by defining the Vickers hardness HV 1 at a load of 1 kgf for evaluating the internal hardness. If HV 1 is 150 or less, sufficient workability can be ensured. It is desirably 140 or less, more desirably 135 or less, and further desirably 130 or less. Further, there is a limit that can be industrially reduce impurity elements, HV 1 is 80 or more.
ＨＶ1≦１５０を確保するためには、上記のように中層炭素Ｃｄを０．１質量％以下とするとともに、使用するチタン素材として、工業用純チタンＪＩＳ１種〜２種やＪＩＳ１１種、１４種、１７種などで規定する成分のものを用いると好ましい。すなわち、材質として高強度でなければ本発明を適用することが可能である。また、チタン素材には種々の不純物元素が含まれてもよい。耐食チタン合金に含有されるＰｄ，Ｒｕ，Ｐｔ，Ａｇ，Ｍｏ，Ｎｂ，Ｎｉ，Ｃｒなどが含有されてもよい。このような不純物元素含有が許容されることで、用途の多いＴｉ−６Ａｌ−４Ｖや純チタンほどの活用が容易ではない合金スクラップ利用の幅を広げるために有効である。また、腐食環境下での利用の場合で必要とされる場合には、Ｐｄなどの元素によって耐食性を向上させたチタン材を用いることが望ましく、Ｐｄ，Ｐｔ，Ｒｕなどを意図的に添加してもよい。すなわち、ＨＶ1≦１５０を確保できる場合は不純物元素もしくは添加元素として各種合金元素が含有されてもよい。上記各元素の含有量は目安として０．５質量％以下であるが、Ｃｕは１質量％でも成形性が劣化しない。また、焼鈍温度については、再結晶させるために６００℃以上が望ましく、β相の析出を抑制するために８５０℃以下とするとよい。これにより、α相の形状が針状組織とならず、母材の強度と延性のバランスを確保することができる。 In order to ensure HV 1 ≦ 150, the middle layer carbon Cd is set to 0.1% by mass or less as described above, and as a titanium material to be used, industrial pure titanium JIS types 1 to 2 and JIS 11 types, 14 types It is preferable to use those defined by 17 types. That is, the present invention can be applied if the material is not strong. Further, the titanium material may contain various impurity elements. Pd, Ru, Pt, Ag, Mo, Nb, Ni, Cr, etc. contained in the corrosion resistant titanium alloy may be contained. By allowing such an impurity element to be contained, it is effective to widen the range of use of alloy scrap, which is not as easily utilized as Ti-6Al-4V and pure titanium, which have many uses. Further, when it is required in the case of use in a corrosive environment, it is desirable to use a titanium material whose corrosion resistance is improved by an element such as Pd, and Pd, Pt, Ru, etc. are added intentionally. Also good. That is, when HV 1 ≦ 150 can be ensured, various alloy elements may be contained as impurity elements or additive elements. The content of each of the above elements is 0.5% by mass or less as a guide, but the moldability does not deteriorate even when Cu is 1% by mass. The annealing temperature is preferably 600 ° C. or higher for recrystallization, and 850 ° C. or lower for suppressing the precipitation of β phase. Thereby, the shape of the α phase does not become a needle-like structure, and a balance between strength and ductility of the base material can be ensured.
以上のとおり、本発明のチタン板において、平均荷重１ｋｇｆ表面ビッカース硬度ＨＶ1≦１５０であって、ＧＤＳによって測定された表面から１μｍまでの平均炭素濃度（表層炭素Ｃｓ）が０．６質量％以上であり、ＧＤＳによって測定された表面から１〜１０μｍの領域における平均炭素濃度（中層炭素Ｃｄ）が０．１質量％以下であることにより、耐摩耗性と加工性がともに良好なチタン板とすることができる。前記Ｃｓが１．０質量％以上であるとより好ましい。 As described above, in the titanium plate of the present invention, the average load 1 kgf surface Vickers hardness HV 1 ≦ 150, and the average carbon concentration (surface carbon Cs) from the surface measured by GDS to 1 μm is 0.6% by mass or more. Since the average carbon concentration (intermediate carbon Cd) in the region of 1 to 10 μm from the surface measured by GDS is 0.1% by mass or less, a titanium plate having good wear resistance and workability is obtained. be able to. The Cs is more preferably 1.0% by mass or more.
本発明のチタン板は、焼鈍前のチタン板表面に炭素を付着し、焼鈍において表層下に炭素が拡散し、表面から１μｍまでの領域に高濃度の炭素を含有することによって表面硬度の増大を実現している。表面硬化層が、表面から１μｍという十分な深さを有しているため、成形加工によっても表面硬化層が失われることはなく、成形加工後の表面は十分な硬度を有し、耐疵付き性が優れるという格別な効果を奏することができる。 In the titanium plate of the present invention, carbon adheres to the surface of the titanium plate before annealing, carbon diffuses under the surface layer during annealing, and increases the surface hardness by containing a high concentration of carbon in the region from the surface to 1 μm. Realized. Since the surface hardened layer has a sufficient depth of 1 μm from the surface, the surface hardened layer is not lost even by molding, and the surface after molding has sufficient hardness and is resistant to wrinkles. It is possible to achieve a special effect that the property is excellent.
本発明のチタン板は、表層炭素Ｃｓを０．６質量％以上とすることによって耐摩耗性を確保している。本発明ではこれに加え、表面に窒化膜あるいは酸化膜を形成し、窒化膜や酸化膜による表面硬化を上乗せすることとしても良い。 The titanium plate of the present invention ensures wear resistance by setting the surface carbon Cs to 0.6% by mass or more. In the present invention, in addition to this, a nitride film or an oxide film may be formed on the surface, and surface hardening by the nitride film or the oxide film may be added.
次に、チタン板を１０ｇｆの荷重で測定したビッカース表面硬度ＨＶ0.01と、耐摩耗性との関係について評価した。前述のように、ＨＶ0.01は圧子が約１〜２μｍ押し込まれており、表面の硬化状況を評価することができる。１枚の試料についてランダムに１０点で表面硬度ＨＶ0.01を計測し、その平均値を平均表面硬度ＨＶ0.01とした。図５には、平均表面硬度ＨＶ0.01と摩耗量との関係を示す。図５によると、平均表面硬度ＨＶ0.01が２５０の付近には、摩耗量が少なく良好なものと、摩耗量が多いものとが混在している。そこで、図６において、表面硬度ＨＶ0.01＜２００の発生率と摩耗量との関係を評価してみた。図６から明らかなように、表面硬度ＨＶ0.01＜２００の発生率が２５％以下であれば、摩耗量を確実に低減でき、耐摩耗性の良好なチタン板とすることができることがわかった。なお、ＨＶ0.01＜２００の発生率はランダムに１００点測定して求めた。 Next, the relationship between the Vickers surface hardness HV 0.01 measured with a load of 10 gf on the titanium plate and the wear resistance was evaluated. As described above, in HV 0.01, the indenter is pushed in by about 1 to 2 μm, and the surface curing state can be evaluated. The surface hardness HV 0.01 was measured at 10 points at random for one sample, and the average value was defined as the average surface hardness HV 0.01 . FIG. 5 shows the relationship between the average surface hardness HV 0.01 and the amount of wear. According to FIG. 5, in the vicinity of the average surface hardness HV 0.01 of 250, a good one with a small wear amount and a high wear amount are mixed. Therefore, in FIG. 6, the relationship between the occurrence rate of the surface hardness HV 0.01 <200 and the wear amount was evaluated. As is apparent from FIG. 6, it was found that if the occurrence rate of the surface hardness HV 0.01 <200 is 25% or less, the wear amount can be reliably reduced and a titanium plate having good wear resistance can be obtained. The occurrence rate of HV 0.01 <200 was determined by randomly measuring 100 points.
次に、本発明のチタン板の製造方法について説明する。製造方法の重要なポイントについてはすでに説明を行っているが、ここにあらためてまとめて説明する。 Next, the manufacturing method of the titanium plate of this invention is demonstrated. The important points of the manufacturing method have already been explained, but here they will be explained together.
チタン表面中の炭素は、焼鈍後もしくは焼鈍前に酸洗する場合には、ほとんど存在しなくなり、窒素も窒素雰囲気での焼鈍を行わない限り、ほとんど存在しない。しかし、一般に、冷延焼鈍板の表層に形成される炭素を含む表面硬化層は、圧延する際の圧延油等によって炭素を主成分とした表面付着物が形成される。冷間圧延後に酸洗せずに焼鈍することにより、表面付着物が付着したままで焼鈍されるので、炭素が表面より内部方向に拡散浸透し、表層炭素Ｃｓが上がることにより、表面硬化層となる。ところが、通常の方法で、圧延油を用いて圧延し、そのまま圧延油が通常の状態で残ったまま焼鈍すると、表層炭素Ｃｓが増大するのみならず、中層炭素Ｃｄまでも増大し、チタン板の加工性を低下させる。 Carbon in the titanium surface hardly exists when pickling after annealing or before annealing, and nitrogen is hardly present unless annealing is performed in a nitrogen atmosphere. However, generally, in the surface hardened layer containing carbon formed on the surface layer of the cold-rolled annealed plate, a surface deposit containing carbon as a main component is formed by rolling oil or the like at the time of rolling. By annealing without pickling after cold rolling, annealing is performed with the surface deposits attached, so that carbon diffuses and penetrates inward from the surface, and the surface carbon Cs rises. Become. However, when the rolling oil is rolled by a normal method and annealed with the rolling oil remaining in a normal state as it is, not only the surface layer carbon Cs increases but also the middle layer carbon Cd increases. Reduces workability.
本発明に規定するような、表層炭素Ｃｓを高めて所定の量とし、一方で中層炭素Ｃｄを十分に低い値とするためには、焼鈍前の表面の炭素量と焼鈍後の板面平面内の炭素分布が重要である。ここで、焼鈍前の表面の炭素量が少ないと、焼鈍後の面内硬度分布に引き継がれる。そのため、表面に適切な量の炭素を存在させておく必要がある。 In order to increase the surface layer carbon Cs to a predetermined amount as specified in the present invention, while making the middle layer carbon Cd have a sufficiently low value, the amount of carbon on the surface before annealing and in the plane of the plate after annealing The carbon distribution of is important. Here, if the amount of carbon on the surface before annealing is small, the in-plane hardness distribution after annealing is succeeded. Therefore, an appropriate amount of carbon needs to be present on the surface.
ただし、これは最終焼鈍の前においてのみ重要である。すなわち、仕上げ焼鈍前に冷延板表面に炭素を分布させておく必要がある。そのため、仕上げ冷延と仕上げ焼鈍、または炭素の付着工程が重要であり、中間冷延や中間焼鈍は特に問わない。 However, this is only important before the final annealing. That is, it is necessary to distribute carbon on the surface of the cold rolled sheet before finish annealing. Therefore, finishing cold rolling and finishing annealing, or carbon adhesion processes are important, and intermediate cold rolling and intermediate annealing are not particularly limited.
本発明において、焼鈍前のチタン表面に付着する炭素源として、冷間圧延の圧延油を用いることができる。それ以外の方法として、均一性を重視した蒸着や、汎用設備で実施可能な冷間圧延、グラファイト粉の散布など方法は問わない。冷間圧延やグラファイト粉散布では均一に付着させるために、凹凸を低減した圧延や圧延油の種類、サンプルするグラファイト粉の粒度などを製造方法にあった条件に設定すると好ましい。 In the present invention, a cold rolling oil can be used as a carbon source attached to the titanium surface before annealing. As other methods, there are no limitations such as vapor deposition that emphasizes uniformity, cold rolling that can be performed by general-purpose equipment, and dispersion of graphite powder. In order to uniformly adhere in cold rolling or graphite powder dispersion, it is preferable to set the rolling with reduced unevenness, the type of rolling oil, the particle size of the graphite powder to be sampled, etc. to conditions suitable for the production method.
焼鈍前の炭素量を制御するにあたって、冷間圧延条件は表面炭素を増加させるには、１パスあたりの圧下率の増加、総圧下率増加、パス数低減、圧延油中の炭素量増加等を行うことで可能である。 In controlling the amount of carbon before annealing, the cold rolling conditions are to increase the surface carbon by increasing the rolling reduction per pass, increasing the total rolling reduction, reducing the number of passes, increasing the amount of carbon in the rolling oil, etc. It is possible by doing.
所定の炭素を表面に付着させたのちには、仕上げ焼鈍を行う。この目的は、表面硬化層以外の内部を焼鈍により十分に軟化させて成形性を確保するためである。あわせて、焼鈍前に表面に付着していた炭素が内部に拡散する。焼鈍条件を選択する上では、付着させた炭素の拡散の結果、表層炭素Ｃｓを０．６質量％以上に保持するとともに、中層炭素Ｃｄを０．１質量％以下に保持することのできる焼鈍条件を選択することが重要である。 After the predetermined carbon is adhered to the surface, finish annealing is performed. The purpose of this is to sufficiently soften the inside other than the surface hardened layer by annealing to ensure formability. At the same time, carbon adhering to the surface before annealing diffuses inside. In selecting the annealing conditions, as a result of the diffusion of the adhered carbon, the annealing conditions can maintain the surface carbon Cs at 0.6% by mass or more and the intermediate carbon Cd at 0.1% by mass or less. It is important to choose.
焼鈍方法はバッチ式でも、連続式でもよく、昇温や冷却条件は特に制限するものではない。しかし、焼鈍温度は重要であり、６００℃以上８５０℃以下が望ましい。これは再結晶させるために６００℃以上が望ましく、β相の析出を抑制するために８５０℃以下とする。これは、β相が存在して冷却すると、α相の形状が針状組織となり、母材の強度と延性のバランスを損ねるためである。 The annealing method may be a batch type or a continuous type, and the temperature rise and cooling conditions are not particularly limited. However, the annealing temperature is important, and is preferably 600 ° C. or higher and 850 ° C. or lower. This is preferably 600 ° C. or higher for recrystallization, and 850 ° C. or lower for suppressing the precipitation of β phase. This is because when the β phase is present and cooled, the shape of the α phase becomes a needle-like structure, and the balance between strength and ductility of the base material is lost.
また、焼鈍条件では、高温、長時間で１〜１０μｍまでの炭素量（中層炭素Ｃｄ）は増加し、表面〜１μｍの炭素量（表層炭素Ｃｓ）は低下する。当然ながら、同じ焼鈍条件でも焼鈍前に炭素が表面に多量に存在する方が焼鈍後の各領域の炭素量は増加する。すなわち、焼鈍温度は、６００℃以上８５０℃以下の範囲内においても、焼鈍前の表面炭素付着量により、調整する必要がある。焼鈍温度が高いと表面からの炭素が深く浸透するため、付着炭素量が高いほど焼鈍温度を低くしなければ１μｍ〜１０μｍの深さのＣｄを低くすることはできない。 Under annealing conditions, the carbon content (intermediate carbon Cd) up to 1 to 10 μm increases at a high temperature for a long time, and the carbon content (surface carbon Cs) from the surface to 1 μm decreases. Of course, the amount of carbon in each region after annealing increases when a large amount of carbon is present on the surface before annealing even under the same annealing conditions. That is, the annealing temperature needs to be adjusted by the surface carbon adhesion amount before annealing even in the range of 600 ° C. or more and 850 ° C. or less. Since carbon from the surface penetrates deeply when the annealing temperature is high, the Cd having a depth of 1 μm to 10 μm cannot be lowered unless the annealing temperature is lowered as the amount of attached carbon increases.
仕上げ焼鈍後は形状矯正、調質圧延などを実施してもかまわない。しかし、過度な形状矯正などの塑性加工は母材の成形性を低下させる原因となるため、適切な条件は矯正方法に応じて設定する。 After finish annealing, shape correction and temper rolling may be performed. However, since plastic processing such as excessive shape correction causes a decrease in the formability of the base material, appropriate conditions are set according to the correction method.
なお、焼鈍方法は外観を損ねないようにＡｒガスなどの非酸化雰囲気で行うことが好ましい。ただし、窒素雰囲気は外観の観点からは好ましくない。これは、窒化物膜形成によって変色するためである。そのため、美観を重視するならば、Ａｒもしくは真空雰囲気が望ましい。一方、窒素雰囲気で焼鈍を行うことにより、表層に濃化した炭素に基づく表面硬化と、表面に窒化膜を形成することによる表面硬化との相乗効果を得ることもできる。また、酸化性雰囲気で焼鈍を行うことにより、表層に濃化した炭素に基づく表面硬化と、表面に酸化膜を形成することによる表面硬化との相乗効果を得ることもできる。 The annealing method is preferably performed in a non-oxidizing atmosphere such as Ar gas so as not to impair the appearance. However, a nitrogen atmosphere is not preferable from the viewpoint of appearance. This is because the color changes due to the formation of the nitride film. For this reason, Ar or a vacuum atmosphere is desirable if aesthetics are important. On the other hand, by performing annealing in a nitrogen atmosphere, it is possible to obtain a synergistic effect between surface hardening based on carbon concentrated on the surface layer and surface hardening by forming a nitride film on the surface. Further, by performing annealing in an oxidizing atmosphere, a synergistic effect between surface hardening based on carbon concentrated on the surface layer and surface hardening by forming an oxide film on the surface can be obtained.
工業用純チタンＪＩＳ１種の熱間圧延板に歪取り焼鈍を行い、表面の酸化スケールを表面切削して除去した。その後、総冷延率２０〜９５％で板厚０．５ｍｍまで５パスで圧延した。圧延油は炭素の含有量が８０％以上の鉱物油を用いた。加えて、表面硬化層を形成しないように冷延板を酸洗した板も作製した（比較例１）。これに、５７０〜８２０℃での真空焼鈍を行った。比較例１が従来軟質材、比較例３が従来硬質材に該当する（以上表１参照）。また、表２、３に示すように、ＪＩＳ２種（本発明例１１）および各種不純物元素を含む場合（本発明例１２〜３０）のチタン材についても行った。 An industrial pure titanium JIS type 1 hot-rolled sheet was subjected to strain relief annealing, and the surface oxide scale was removed by surface cutting. Thereafter, rolling was performed in 5 passes to a plate thickness of 0.5 mm at a total cold rolling rate of 20 to 95%. As the rolling oil, a mineral oil having a carbon content of 80% or more was used. In addition, a cold-rolled plate was pickled so as not to form a hardened surface layer (Comparative Example 1). This was subjected to vacuum annealing at 570 to 820 ° C. Comparative Example 1 corresponds to a conventional soft material, and Comparative Example 3 corresponds to a conventional hard material (see Table 1 above). Moreover, as shown in Tables 2 and 3, it was also performed on titanium materials in the case of containing JIS 2 types (Invention Example 11) and various impurity elements (Invention Examples 12 to 30).
焼鈍後のチタン板表面付近の深さ方向炭素分布は、ＧＤＳ（ＨＯＲＩＢＡ製 ＧＤ−Ｐｒｏｆｉｌｅｒ２）により評価した。φ４ｍｍの領域を表面から深さ２０μｍ以上の領域まで測定した。測定した元素は、酸素、窒素、炭素、チタンであり、酸素、窒素および炭素定量化に際しては、各測定値を、酸素については酸化亜鉛（酸素を１９．８質量％）を、窒素についてはオーステナイト系ステンレス鋼（窒素を０．３質量％含有）を、炭素についてはチタン合金（炭素を０．１２質量％含有）をそれぞれ用いて較正し、純チタン（ＪＩＳ１種）における測定部位（深さ）に対応させることにより、各元素の深さ方向分析を行った。また、深さ方向に表面〜１μｍまでを１０００点以上、１〜１０μｍまでを２０００点以上となる測定点数で測定した。深さ方向の測定間隔は一定とし行った。この結果から、最表面から深さ１μｍを超えない１μｍに最も近い位置の点までの平均炭素濃度（表層炭素Ｃｓ）、および深さ１μｍを超える最も１μｍに近い点から深さ１０μｍを超えない最も１０μｍに近い点までの平均炭素濃度（中層炭素Ｃｄ）を求めた。純チタン（ＪＩＳ１種）における測定部位（深さ）に対応させることにより、各元素の深さ方向分析を行った。 The carbon distribution in the depth direction near the surface of the titanium plate after annealing was evaluated by GDS (GD-Profiler 2 manufactured by HORIBA). A region of φ4 mm was measured from the surface to a region having a depth of 20 μm or more. The measured elements are oxygen, nitrogen, carbon, and titanium. In quantification of oxygen, nitrogen, and carbon, each measured value is measured; for oxygen, zinc oxide (19.8% by mass of oxygen); for nitrogen, austenite Stainless steel (containing 0.3% by mass of nitrogen) and calibrating carbon using a titanium alloy (containing 0.12% by mass of carbon), respectively, and the measurement site (depth) in pure titanium (JIS class 1) The depth direction analysis of each element was performed. Moreover, it measured by the number of measurement points which becomes 1000 points or more to 1-10 micrometers in the depth direction from surface to 1 micrometer, and becomes 2000 points or more. The measurement interval in the depth direction was made constant. From this result, the average carbon concentration (surface layer carbon Cs) from the outermost surface to a point closest to 1 μm not exceeding 1 μm in depth, and the most not exceeding 10 μm in depth from the point closest to 1 μm exceeding 1 μm in depth. The average carbon concentration (intermediate carbon Cd) up to a point close to 10 μm was determined. The depth direction analysis of each element was performed by making it correspond to the measurement site | part (depth) in pure titanium (JIS1 type).
耐摩耗性の評価として、ボールオンディスク試験後の質量変化で評価した。ボールはφ３／１６インチのＳＵＪ２を用い、チタン板と接触して回転させた。試験は無潤滑で荷重３ｋｇ、半径１５ｍｍの円軌道を５００回転させた後の質量変化を求めた。回転速度は５０ｒｐｍで行った。摩耗量０．８ｍｇ以下を合格とした As an evaluation of wear resistance, the mass change after the ball-on-disk test was evaluated. The ball was rotated in contact with a titanium plate using SUJ2 of φ3 / 16 inch. In the test, the change in mass after unrotated, 500 revolutions of a circular track with a load of 3 kg and a radius of 15 mm was determined. The rotation speed was 50 rpm. Wear amount of 0.8mg or less was accepted
成形性評価として、エリクセン試験を行った。エリクセン試験はＪＩＳ Ｚ ２２４７に基づいて行ったが、潤滑には摩擦係数が約０．０４の厚さ５０μｍのＰＴＦＥシートを用いた。成形性の評価として、結晶粒径の影響を除くため、酸洗した板を同じ条件で焼鈍し、それとの差をとることで評価した。エリクセン値の変化量が−０．３ｍｍ以上を合格とした。 An Erichsen test was performed as a moldability evaluation. The Eriksen test was performed based on JIS Z 2247, and a PTFE sheet having a friction coefficient of about 0.04 and a thickness of 50 μm was used for lubrication. As an evaluation of the formability, in order to remove the influence of the crystal grain size, the pickled plate was annealed under the same conditions, and the difference was evaluated. The amount of change in the Erichsen value was accepted as -0.3 mm or more.
荷重１０ｇｆおよび１ｋｇｆでの表面ビッカース硬度試験を行った。１０ｇｆでは５×５ｍｍの領域をランダムに１００点測定し、面内分布を測定した。１ｋｇでは５回測定し、これらの平均値で評価した。 A surface Vickers hardness test was conducted at a load of 10 gf and 1 kgf. At 10 gf, 100 points were randomly measured in a 5 × 5 mm area, and the in-plane distribution was measured. The measurement was performed 5 times at 1 kg, and the average value was evaluated.
製造条件と試験結果を表１〜３に示した。 Production conditions and test results are shown in Tables 1 to 3.
本発明例１〜１０は、いずれも、表層炭素Ｃｓが本発明範囲内であって摩耗量が少なく、中層炭素Ｃｄも本発明範囲内であって成形性は表面硬化層を除去した従来軟質材である比較例１と同等の成形性を有している。 Examples 1 to 10 of the present invention are all conventional soft materials in which the surface carbon Cs is within the range of the present invention and the wear amount is small, the middle layer carbon Cd is also within the range of the present invention, and the moldability is removed from the surface hardened layer It has the same moldability as Comparative Example 1 which is.
一方、比較材２、３は、製造時の冷延率が高く、焼鈍温度も比較的高いことから、中層炭素Ｃｄが規定より高くなりすぎているためにエリクセン値が−０．５〜−０．８ｍｍと基準値より悪化しており成形性に劣る。また、比較材１は表面炭素濃化層を酸洗除去し表面に炭素を含まず、比較例４は圧延率が低すぎて表面炭素量が不足していることから、いずれも表層炭素Ｃｓが規定に達しておらず、耐摩耗性が不十分であった。 On the other hand, since the comparative materials 2 and 3 have a high cold rolling ratio during production and a relatively high annealing temperature, the middle-layer carbon Cd is too higher than specified, so that the Erichsen value is −0.5 to −0. .8 mm, which is worse than the standard value and inferior in moldability. Moreover, since the comparative material 1 pickles and removes a surface carbon concentration layer and does not contain carbon on the surface, since the comparative example 4 is too low and the amount of surface carbon is insufficient, surface carbon Cs is all. The regulation was not reached and the wear resistance was insufficient.
表２、３に示す本発明例１１〜３０では高酸素もしくは合金元素を含有するが、工業用純チタンＪＩＳ１種を用いた表１に示す本発明例と同様の効果を得ることができた。 Invention Examples 11 to 30 shown in Tables 2 and 3 contain high oxygen or alloy elements, but the same effects as those of the invention examples shown in Table 1 using industrial pure titanium JIS type 1 could be obtained.
Claims (4)
平均荷重１ｋｇｆ表面ビッカース硬度ＨＶ1≦１５０であって、ＧＤＳによって測定された表面から１μｍまでの平均炭素濃度Ｃｓが０．６質量％以上であり、ＧＤＳによって測定された表面から１〜１０μｍの領域における平均炭素濃度Ｃｄが０．１質量％以下であるチタン板。 Contains the components specified in any one of industrial pure titanium JIS 1 to 2 types, JIS 11 types, 14 types, 17 types,
Average load 1 kgf Surface Vickers hardness HV 1 ≦ 150, average carbon concentration Cs from the surface measured by GDS to 1 μm is 0.6% by mass or more, and 1 to 10 μm from the surface measured by GDS The titanium plate whose average carbon density | concentration Cd in is 0.1 mass% or less.
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