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CN103069027A - Titanium material - Google Patents

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Publication number
CN103069027A
CN103069027A CN2010800687875A CN201080068787A CN103069027A CN 103069027 A CN103069027 A CN 103069027A CN 2010800687875 A CN2010800687875 A CN 2010800687875A CN 201080068787 A CN201080068787 A CN 201080068787A CN 103069027 A CN103069027 A CN 103069027A
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titanium
recrystallized
less
titanium plate
strength
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白井善久
濑户英人
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Nippon Steel Corp
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/183High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18High-melting or refractory metals or alloys based thereon

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  • Metallurgy (AREA)
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Abstract

The present invention addresses the problem of providing a titanium material having high strength and superior workability. To solve this problem, the present invention provides a titanium material having an iron content of 0.60% by mass or less and an oxygen content of 0.15% by mass or less with the remainder being formed from titanium and inevitable impurities. In this titanium material, there are a deformation texture formed by processing that is accompanied by plastic deformation and a recrystallization texture formed by annealing after that processing. The titanium material is formed such that the average grain size of the crystal grains for this recrystallization texture is 1 [mu]m - 5 [mu]m, and the area of the portion of the cross-sectional area that is not recrystallized is greater than 0% and less than or equal to 30%.

Description

钛材Titanium

技术领域technical field

本发明涉及钛材,具体而言,涉及强度和加工性优异的钛材。The present invention relates to a titanium material, and specifically relates to a titanium material excellent in strength and workability.

背景技术Background technique

以往,由钛合金、纯钛等材料形成的板状或棒状的部件被广泛使用。Conventionally, plate-shaped or rod-shaped members made of materials such as titanium alloys and pure titanium have been widely used.

例如工业制品广泛使用板状的钛材(以下也称为“钛板”),对前述钛板实施弯曲加工、鼓凸成形、拉深加工等伴随有塑性变形的各种加工而形成各种制品。For example, plate-shaped titanium materials (hereinafter also referred to as "titanium plates") are widely used in industrial products, and the titanium plates are subjected to various processes involving plastic deformation such as bending, bulging, and drawing to form various products.

对于实施这种加工的钛板要求优异的加工性。Excellent workability is required for the titanium plate subjected to such processing.

另外,最近从材料成本的降低、制品的轻量化等观点考虑,要求钛板的薄板化。In addition, recently, from the viewpoint of material cost reduction, product weight reduction, etc., thinning of the titanium plate is required.

其结果要求提高钛板的强度。As a result, it is required to increase the strength of the titanium plate.

但是,以往钛板的加工性与强度处于权衡关系,形成难以同时满足它们的状况。However, conventionally, the workability and strength of a titanium plate are in a trade-off relationship, and it has been difficult to satisfy both of them.

即,以往的钛板存在若屈服强度增大时则难以进行成形加工(加工性差)的问题。That is, the conventional titanium plate has a problem that forming is difficult (poor in formability) when the yield strength is increased.

对此,下述非专利文献1中示出了通过圆筒深拉深试验对成分、结晶粒径不同的钛薄板评价加工性得到的结果,记载了晶粒越微细则加工性越良好(第103页、第5行~)。On the other hand, the following Non-Patent Document 1 shows the results obtained by evaluating the processability of titanium thin plates with different components and crystal grain sizes by a cylindrical deep drawing test, and it is described that the finer the crystal grains, the better the processability (No. Page 103, line 5~).

而且,下述专利文献1中公开了纯钛薄板的制造方法,记载了最终的退火在大气气氛下以(600~800)℃×(2~5)分钟的连续退火方式进行,进一步实施酸洗处理,将制品的平均结晶粒径(以下称为粒径)调整到3~60μm,从而制造表面的光泽得到抑制的纯钛薄板。Furthermore, the following Patent Document 1 discloses a method for producing a pure titanium thin plate, and describes that the final annealing is carried out in an air atmosphere by a continuous annealing method at (600-800)°C×(2-5) minutes, and further pickling is performed. The treatment adjusts the average crystal grain size (hereinafter referred to as the grain size) of the product to 3 to 60 μm, thereby producing a pure titanium thin plate with suppressed surface gloss.

另外,下述专利文献2中公开了建筑材料用纯钛、纯钛板及其制造方法,记载了所含有的氧为900ppm以下、Fe为100ppm以上且600ppm以下,进一步Ni和Cr的含量得到限制的建筑材料用钛材。In addition, the following Patent Document 2 discloses pure titanium for building materials, a pure titanium plate, and a method for producing the same. It describes that the contained oxygen is 900 ppm or less, and Fe is 100 ppm or more and 600 ppm or less. Furthermore, the content of Ni and Cr is limited. Titanium is used as a building material.

另外,专利文献2中对在冷轧退火后用硝酸氢氟酸水溶液实施了酸洗处理的平均结晶粒径为70μm以下的建筑材料用钛材进行了记载。In addition, Patent Document 2 describes a titanium material for building materials having an average crystal grain size of 70 μm or less, which was pickled with an aqueous solution of nitric acid and hydrofluoric acid after cold rolling and annealing.

但是,该专利文献1、2中几乎未示出评价5μm以下微小结晶粒径的数据,专利文献2中虽然示出了结晶粒径为3μm的实施例,但是同时在段落[0026]中记载了“实际生产上,下限为5μm左右”,对于结晶粒径为5μm以下为否定性的记载。However, in these patent documents 1 and 2, there is almost no data for evaluating the fine crystal grain size of 5 μm or less, and in patent document 2, although an example with a crystal grain size of 3 μm is shown, it is also described in paragraph [0026] "In actual production, the lower limit is about 5 μm" is a negative statement that the crystal grain size is 5 μm or less.

认为这是由于,这些文献的目的在于得到光泽得到抑制的作为建筑材料用优异的钛材,对于鼓凸成形、深拉深等的加工性未进行充分研究。This is considered to be because the purpose of these documents is to obtain a titanium material excellent as a construction material with suppressed luster, and the processability of bulge forming, deep drawing, etc. has not been sufficiently studied.

另外,下述专利文献4中公开了加工性优异的钛板,然而虽然其加工性优异,但是强度(屈服强度)低,不能兼具加工性和强度两者。In addition, the following Patent Document 4 discloses a titanium plate excellent in workability. However, although the workability is excellent, the strength (yield strength) is low, and both workability and strength cannot be achieved at the same time.

现有技术文献prior art literature

专利文献patent documents

专利文献1:日本特开昭63-103056号公报Patent Document 1: Japanese Patent Application Laid-Open No. 63-103056

专利文献2:日本特开平9-3573号公报Patent Document 2: Japanese Patent Application Laid-Open No. 9-3573

专利文献3:日本特开2006-316323号公报Patent Document 3: Japanese Patent Laid-Open No. 2006-316323

专利文献4:日本特开昭63-60247号公报Patent Document 4: Japanese Patent Laid-Open No. 63-60247

非专利文献non-patent literature

非专利文献1:“チタン”(《钛》),Vol.57、No.2(社团法人日本钛协会、平成21年4月发行)Non-Patent Document 1: "チタン" ("Titanium"), Vol.57, No.2 (issued by Japan Titanium Association, April 2011)

发明内容Contents of the invention

发明要解决的问题The problem to be solved by the invention

本发明的目的在于,提供高强度且加工性优异的钛板。An object of the present invention is to provide a titanium plate having high strength and excellent workability.

用于解决问题的方案solutions to problems

钛材主要可以添加氧(O)、铁(Fe)来增大强度(屈服强度),但是若添加它们则延展性降低、加工性也降低。Titanium materials can mainly be added with oxygen (O) and iron (Fe) to increase the strength (yield strength), but if they are added, the ductility will decrease and the workability will also decrease.

例如,JIS1类中规定的钛材料中,由于氧、铁的含量少,因此使用这种JIS1类的材料的钛板,通常强度(屈服强度)低,但是延展性优异、加工性优异。For example, titanium materials specified in JIS 1 have low oxygen and iron content, so titanium plates using such JIS 1 materials generally have low strength (yield strength), but are excellent in ductility and workability.

若使用氧、铁的含量多于该JIS1类的JIS2类的钛材料,则与使用JIS1类的钛材料的钛材相比,存在强度(屈服强度)增大,另一方面延展性降低、加工性降低的趋势。If the content of oxygen and iron is more than the JIS2 titanium material of the JIS1 category, the strength (yield strength) will increase compared with the titanium material using the JIS1 category titanium material, and the ductility will decrease on the other hand. declining trend.

进而,氧、铁的含量多的JIS3类及JIS4类,强度(屈服强度)进一步增大,但是延展性进一步降低、加工性大幅降低。Furthermore, the JIS 3 type and JIS 4 type with high content of oxygen and iron have a further increase in strength (yield strength), but a further decrease in ductility and a significant decrease in workability.

即,强度(屈服强度)与加工性存在一定的关系(以下将这种关系也称为“强度(屈服强度)-加工性平衡”)。That is, there is a certain relationship between strength (yield strength) and workability (hereinafter, this relationship is also referred to as "strength (yield strength)-workability balance").

另外,使用钛材料而成的板材、线材,实施轧制、拉丝这些伴随有塑性变形的加工来形成。In addition, a plate material and a wire material made of a titanium material are subjected to processing involving plastic deformation such as rolling and wire drawing.

这种实施了伴随有塑性变形的加工的板材、线材,由于通常以如此的状态在内部形成加工组织,为了进行组织的再结晶化,实施被称为最终退火的工序而提供给市场。Such sheets and wires subjected to processing involving plastic deformation usually form a processed structure inside in such a state, and are supplied to the market by performing a process called final annealing in order to recrystallize the structure.

例如,若为钛板则如下进行:进行冷轧等加工而调整为规定厚度后,实施间歇退火、连续退火等,使内部的加工组织再结晶化,形成等轴状的晶粒(以下称为“再结晶晶粒”)。For example, in the case of a titanium plate, after processing such as cold rolling to adjust to a predetermined thickness, batch annealing, continuous annealing, etc. are performed to recrystallize the internal processed structure and form equiaxed crystal grains (hereinafter referred to as "recrystallized grains").

并且,该再结晶晶粒随着退火时间的推移等而生长变大,特别是在再结晶晶粒的粒径小的再结晶刚开始之后,再结晶晶粒的生长速度快,结果在比较短的时间内形成超过5μm的大的粒径。In addition, the recrystallized grains grow larger as the annealing time elapses, and especially immediately after the recrystallization starts when the recrystallized grains have a small grain size, the growth rate of the recrystallized grains is fast, resulting in a relatively short A large particle size exceeding 5 μm is formed within a short period of time.

而且,若再结晶晶粒生长至这种尺寸,则通常不残留未再结晶部(加工组织),在钛材内部仅形成通过再结晶晶粒形成的等轴状组织。Furthermore, when the recrystallized grains grow to such a size, usually no non-recrystallized portion (worked structure) remains, and only an equiaxed structure formed by the recrystallized grains is formed inside the titanium material.

本发明人等对上述问题进行深入地研究,结果发现,通过以往作为提高强度(屈服强度)的手段未受到关注的组织的调整(通过残留未再结晶部进行的晶粒的微细化),可以实现钛材的强度(屈服强度)的提高。The inventors of the present invention conducted intensive studies on the above-mentioned problems, and found that by adjustment of the structure (refinement of crystal grains by remaining unrecrystallized parts), which has not been paid attention to as a means of increasing the strength (yield strength) in the past, it is possible to Improvement of the strength (yield strength) of the titanium material is achieved.

具体而言,本发明人等使用电炉在真空中对冷轧至规定厚度的工业用纯钛板进行最终退火,改变其温度和时间来试制组织不同的各种钛板,通过拉伸试验和埃里克森试验对它们的强度(屈服强度)和加工性(延展性)进行评价,从而完成本发明。Specifically, the present inventors used an electric furnace to perform final annealing of industrial pure titanium plates cold-rolled to a specified thickness in vacuum, and changed the temperature and time to trial-produce various titanium plates with different structures. The strength (yield strength) and workability (ductility) of these were evaluated by the Rickson test, and the present invention was completed.

该评价的结果中,晶粒越细则存在强度(屈服强度)越大、加工性(埃里克森值)越降低的倾向,但是若再结晶晶粒的平均粒径为规定的尺寸以下则埃里克森值不怎么降低,发现与以往的钛材相比,可以提高“强度(屈服强度)-加工性平衡”。According to the results of this evaluation, the finer the crystal grains, the greater the strength (yield strength) and the lower the workability (Erickson value). The Rickson value did not decrease so much, and it was found that the "strength (yield strength)-workability balance" could be improved compared with conventional titanium materials.

另外,即使再结晶晶粒的平均结晶粒径为规定以下,也存在加工性(埃里克森值)降低、与以往的钛材相比不能提高“强度(屈服强度)-加工性平衡”的情况。In addition, even if the average grain size of the recrystallized grains is below the specified value, the workability (Erickson value) is lowered, and the "strength (yield strength)-workability balance" cannot be improved compared with conventional titanium materials. Condition.

而对该钛板的显微组织进行详细调查,结果发现,除了通过最终退火而再结晶而成的晶粒之外,未再结晶部也多。On the other hand, when the microstructure of this titanium plate was investigated in detail, it was found that in addition to crystal grains recrystallized by final annealing, there were also many non-recrystallized parts.

基于该未再结晶部的量,对“强度(屈服强度)-加工性平衡”进行研究后发现,特别是未再结晶部在钛板的截面积中所占的面积率超过30%时加工性极端降低。Based on the amount of this non-recrystallized portion, after studying the "strength (yield strength)-workability balance", it was found that, in particular, when the area ratio of the non-recrystallized portion in the cross-sectional area of the titanium plate exceeds 30%, the workability Extremely reduced.

需要说明的是,在此未再结晶部指的是残留的经过塑性加工形成的加工组织的部分。It should be noted that the non-recrystallized portion here refers to the portion where the processed structure formed by plastic working remains.

即,涉及用于解决前述问题的钛材的本发明,其特征在于,所述钛材中的铁的含量为0.60质量%以下、氧的含量为0.15质量%以下,剩余部分由钛和不可避免的杂质组成,所述钛材具有实施伴随有塑性变形的加工而形成的加工组织、和前述加工后实施退火而形成的再结晶组织,形成为该再结晶组织的晶粒的平均粒径为1μm以上且5μm以下,未再结晶部在截面积中所占的面积超过0%且为30%以下。That is, the present invention related to a titanium material for solving the aforementioned problems is characterized in that the content of iron in the titanium material is 0.60% by mass or less, the content of oxygen is 0.15% by mass or less, and the balance is composed of titanium and unavoidable The impurity composition of the titanium material has a processed structure formed by processing accompanied by plastic deformation, and a recrystallized structure formed by annealing after the aforementioned processing, and the average grain size of the crystal grains formed in the recrystallized structure is 1 μm More than 5 μm and less than 5 μm, and the area occupied by the non-recrystallized portion in the cross-sectional area is more than 0% and 30% or less.

发明的效果The effect of the invention

根据本发明,可以提供高强度且加工性优异的钛材。According to the present invention, a titanium material having high strength and excellent workability can be provided.

附图说明Description of drawings

图1是用透射式电子显微镜观察到的实施例的钛板的显微组织照片(再结晶晶粒之间的一部分发现未再结晶部)Fig. 1 is a photo of the microstructure of the titanium plate of the example observed with a transmission electron microscope (unrecrystallized part is found in a part between the recrystallized grains)

图2是表示屈服强度与埃里克森值的关系的图。Fig. 2 is a graph showing the relationship between yield strength and Ericsson value.

具体实施方式Detailed ways

以下以钛板为例对本发明的钛材的优选实施方式进行说明。A preferred embodiment of the titanium material of the present invention will be described below by taking a titanium plate as an example.

本实施方式中的钛板通过下述钛材料形成,所述钛材料中的铁(Fe)的含量为0.60质量%以下、氧(O)的含量为0.15质量%以下,剩余部分由钛(Ti)和不可避免的杂质组成。The titanium plate in this embodiment is formed of a titanium material in which the content of iron (Fe) is 0.60% by mass or less, the content of oxygen (O) is 0.15% by mass or less, and the remainder is made of titanium (Ti ) and unavoidable impurities.

该钛板在实施伴随有塑性变形的加工后实施退火来形成,内部具有伴随前述加工的加工组织、和伴随前述退火的再结晶组织,而且形成为该再结晶组织的晶粒的平均粒径为1μm以上且5μm以下并且未再结晶部在钛板的截面积中所占的面积超过0%且为30%以下。This titanium plate is formed by performing annealing after performing processing accompanied by plastic deformation, and has a processed structure accompanied by the aforementioned processing and a recrystallized structure accompanied by the aforementioned annealing inside, and the average grain size of the crystal grains formed as the recrystallized structure is 1 μm or more and 5 μm or less and the area occupied by the non-recrystallized portion in the cross-sectional area of the titanium plate is more than 0% and 30% or less.

如上所述,前述铁(Fe)以0.60质量%以下的比率含有。As mentioned above, the said iron (Fe) is contained in the ratio of 0.60 mass % or less.

需要说明的是,Fe的含量的上限值为0.60质量%是由于:在钛材料中,Fe为β相稳定化元素,若Fe的含量超过0.60质量%则在构成钛板的组织中,除了α相之外还有可能生成大量β相。It should be noted that the upper limit of the content of Fe is 0.60% by mass because: in titanium materials, Fe is a β-phase stabilizing element, and if the content of Fe exceeds 0.60% by mass, in the structure of the titanium plate, except In addition to the α phase, it is also possible to generate a large amount of β phase.

即,由于根据所形成的β相的尺寸而延展性大幅降低或耐腐蚀性降低,因此形成本实施方式的钛板的钛材料中含有的Fe的含量为0.60质量%以下,这在形成高强度且加工性优异的钛板方面是重要的。That is, since the ductility is greatly reduced or the corrosion resistance is reduced depending on the size of the formed β phase, the content of Fe contained in the titanium material forming the titanium plate of the present embodiment is 0.60% by mass or less, which contributes to the formation of high strength. Furthermore, the aspect of a titanium plate having excellent workability is important.

需要说明的是,在形成高强度且加工性优异的钛板方面,对Fe的含量的下限值没有特别要求,如果想要制造Fe小于0.01质量%的钛板则必须以价格昂贵的高纯度海绵钛作为原料,结果钛板的材料成本有可能增大。It should be noted that, in terms of forming a high-strength and excellent processability titanium plate, there is no special requirement for the lower limit of the content of Fe. If you want to manufacture a titanium plate with Fe less than 0.01% by mass, you must use an expensive high-purity Sponge titanium is used as a raw material, and as a result, the material cost of the titanium plate may increase.

因此,从钛板的成本等观点考虑,优选Fe的含量为0.01质量%以上且0.60质量%以下。Therefore, from the viewpoint of the cost of the titanium plate, etc., the content of Fe is preferably not less than 0.01% by mass and not more than 0.60% by mass.

例如镁热还原法(Kroll法)中,通常表现出0.60质量%以上的Fe含量的钛材料仅形成在容器附近的少许区域。For example, in the magnesium thermal reduction method (Kroll method), a titanium material generally showing an Fe content of 0.60% by mass or more is formed only in a small area near the container.

因此,本实施方式中的钛板,通过使得作为其成分的铁的含量为0.01~0.60质量%,可以利用通过Kroll法得到的海绵钛的大部分材料。Therefore, the titanium plate in the present embodiment can utilize most of the titanium sponge obtained by the Kroll method by setting the content of iron as its component to 0.01 to 0.60% by mass.

即,本实施方式中的钛板在几乎不对海绵钛的使用部位施加限制方面考虑,适合作为消耗材。That is, the titanium plate in the present embodiment is suitable as a consumable material since it hardly imposes restrictions on the use site of the titanium sponge.

前述氧(O)在钛材料中以0.15质量%以下的含量含有。The aforementioned oxygen (O) is contained in the titanium material at a content of 0.15% by mass or less.

形成本实施方式的钛板的钛材料中的O含量为0.15质量%以下是由于:若O含量超过0.15质量%则即使想要使晶粒变细来实现“强度-加工性平衡”的提高,强度也会过强而有可能不能充分赋予加工性,难以形成适于鼓凸成形、深拉深等加工的钛板。The reason why the O content in the titanium material forming the titanium plate of this embodiment is 0.15% by mass or less is that if the O content exceeds 0.15% by mass, even if the crystal grains are intended to be finer to achieve an improvement in the "strength-workability balance", There is also a possibility that the strength is too high to provide sufficient workability, and it is difficult to form a titanium plate suitable for processing such as bulge forming and deep drawing.

需要说明的是,对O含量的下限量没有特别规定,但是如果想要使构成钛板的钛材料中的O含量小于0.015质量%则有可能必须以价格昂贵的高纯度海绵钛作为原料来制造。It should be noted that there is no special regulation on the lower limit of the O content, but if the O content in the titanium material constituting the titanium plate is to be less than 0.015% by mass, it may be necessary to use expensive high-purity sponge titanium as a raw material to manufacture .

因此,O含量优选为0.015质量%以上且0.15质量%以下。Therefore, the O content is preferably not less than 0.015% by mass and not more than 0.15% by mass.

另外,对于碳(C)、氮(N)、氢(H)等不可避免的杂质,从确保成形加工中的良好的加工性目的考虑,为相当于JIS2类的含量以下是重要的。In addition, it is important that the content of unavoidable impurities such as carbon (C), nitrogen (N), and hydrogen (H) be equal to or less than JIS 2 for the purpose of ensuring good processability during molding.

具体而言,C、N、H的含量分别小于0.02质量%是重要的。Specifically, it is important that the contents of C, N, and H are each less than 0.02% by mass.

进一步优选C的含量为0.01质量%以下,N的含量为0.01质量%以下,H的含量为0.01质量%以下。More preferably, the C content is 0.01 mass % or less, the N content is 0.01 mass % or less, and the H content is 0.01 mass % or less.

从钛板的加工性观点考虑,对上述C、N、H的含量不规定下限,但是如果想要极端降低它们的含量则钛板的制造成本有可能大幅增大。From the standpoint of workability of the titanium plate, there is no lower limit for the content of C, N, and H. However, if the content of these C, N, and H is extremely reduced, the production cost of the titanium plate may increase significantly.

从抑制这种成本升高的观点考虑,优选C的含量为0.0005质量%以上,N的含量为0.0005质量%以上,H的含量为0.0005质量%以上。From the viewpoint of suppressing such an increase in cost, the content of C is preferably 0.0005% by mass or more, the content of N is 0.0005% by mass or more, and the content of H is 0.0005% by mass or more.

如以上所述,本发明的钛板在内部具有加工组织和再结晶组织,而且形成为该再结晶组织的晶粒的平均粒径为1μm以上且5μm以下并且未再结晶部在钛板的截面积中所占的面积超过0%且为30%以下。As described above, the titanium plate of the present invention has a processed structure and a recrystallized structure inside, and the average grain size of the crystal grains formed in the recrystallized structure is 1 μm or more and 5 μm or less, and the non-recrystallized portion is at the cross section of the titanium plate. The area occupied in the area exceeds 0% and is 30% or less.

前述再结晶组织的平均粒径的上限值为5μm是由于:若进行再结晶而生成的等轴状的α粒的平均结晶粒径超过5μm则晶粒的微细化的效果减小,难以实现优异的“强度-加工性平衡”。The upper limit of the average grain size of the above-mentioned recrystallized structure is 5 μm because: if the average grain size of the equiaxed α grains generated by recrystallization exceeds 5 μm, the effect of refining the crystal grains will be reduced, and it will be difficult to achieve Excellent "strength-workability balance".

另外,下限值为1μm是由于:若实际生产上(工业上可以实施的方法)进行加工(轧制、锻造等)、然后进行退火时平均晶粒小于1μm,则后段中所述的未再结晶部(加工组织)的面积率增多,强度变得非常大,但是延展性大幅降低,难以实现优异的“强度-加工性平衡”。In addition, the lower limit value of 1 μm is because if the average grain size is less than 1 μm when processing (rolling, forging, etc.) in actual production (industrially applicable methods) and then annealing is performed, the non-existent conditions described in the latter paragraph The area ratio of the recrystallized zone (worked structure) increases, and the strength becomes very large, but the ductility is greatly reduced, and it is difficult to achieve an excellent "strength-workability balance".

前述未再结晶部由通过加工(冷轧、锻造等)进行塑性变形、晶粒被压碎而成的加工组织形成,通过使该加工组织残留在钛板中,可以提高其强度。The non-recrystallized portion is formed of a processed structure formed by plastic deformation and crushed crystal grains by working (cold rolling, forging, etc.), and the strength can be improved by leaving this processed structure in the titanium plate.

由通过冷轧等形成的加工组织构成的钛板表现出高的强度,另一方面延展性非常小。A titanium plate composed of a worked structure formed by cold rolling or the like exhibits high strength, but has very little ductility.

因此,以往通过退火使加工组织再结晶化而形成等轴状的组织,以钛板中不残留加工组织的程度设置充分的退火时间。Therefore, conventionally, the worked structure is recrystallized by annealing to form an equiaxed structure, and a sufficient annealing time is set so that the worked structure does not remain in the titanium plate.

另一方面,本实施方式的钛板中,通过采用后段中所述的退火条件使前述加工组织残留在钛板中,而且如上所述调整再结晶晶粒的粒径。On the other hand, in the titanium plate of the present embodiment, the above-mentioned processed structure remains in the titanium plate by adopting the annealing conditions described later, and the grain size of the recrystallized grains is adjusted as described above.

前述未再结晶部(加工组织)以在钛板的截面中所占的面积比率为30%以下的方式设置,这在得到优异的“强度-加工性平衡”方面是重要的。It is important to provide the non-recrystallized portion (worked structure) so that the area ratio in the cross section of the titanium plate is 30% or less in order to obtain an excellent "strength-workability balance".

若该未再结晶部的面积率大于30%则虽然钛板的强度进一步增大,但是延展性降低、难以使钛板发挥优异的加工性。If the area ratio of the non-recrystallized portion exceeds 30%, the strength of the titanium plate will further increase, but the ductility will decrease, making it difficult for the titanium plate to exhibit excellent workability.

其结果,有可能不能得到优异的“强度-加工性平衡”。As a result, there is a possibility that an excellent "strength-workability balance" cannot be obtained.

在可以更切实地对钛板赋予这种优异的“强度-加工性平衡”方面考虑,优选未再结晶部的面积率为10%以下。The area ratio of the non-recrystallized portion is preferably 10% or less in view of being able to more reliably impart such an excellent "strength-workability balance" to the titanium plate.

需要说明的是,对下限值没有特别限定,但是若未再结晶部消失(面积率为0%)则再结晶晶粒的粒径急速增大。The lower limit is not particularly limited, but when the non-recrystallized portion disappears (the area ratio is 0%), the grain size of the recrystallized grains increases rapidly.

因此,在可以更切实地将再结晶晶粒的粒径调整到上述范围内方面考虑,优选未结晶部的面积率为0.1%以上。Therefore, the area ratio of the uncrystallized portion is preferably 0.1% or more since the grain size of the recrystallized grains can be adjusted more reliably within the above-mentioned range.

为了进行上述再结晶晶粒的粒径的调整、未再结晶部的形成,可列举出通过通常的轧制工序等将钛板调整为所希望的厚度后,实施规定条件下的最终退火的方法。In order to adjust the grain size of the above-mentioned recrystallized grains and form the non-recrystallized part, the method of performing final annealing under predetermined conditions after adjusting the titanium plate to a desired thickness by a usual rolling process etc. .

在前述最终退火中可以采用的退火方法可以大致分为连续式和间歇式。The annealing methods that can be employed in the aforementioned final annealing can be roughly classified into continuous type and batch type.

其中,连续式最终退火为展开冷轧卷材并使钛板以固定速度通过退火炉内、由此进行退火的方法,可以通过通板速度来控制加热温度的保持时间。Among them, the continuous final annealing is a method in which the cold-rolled coil is unwound and the titanium plate is passed through the annealing furnace at a fixed speed to perform annealing, and the holding time of the heating temperature can be controlled by the plate passing speed.

以往的钛板的最终退火中,在连续式的情况下,加热温度为700~800℃,加热时间为数十秒~2分钟左右。In conventional final annealing of a titanium plate, in the case of a continuous method, the heating temperature is 700 to 800° C., and the heating time is about several tens of seconds to 2 minutes.

另一方面,间歇式最终退火为对钛板的卷材直接以卷材的状态在退火炉内进行加热的方法,为了减小卷材的表层部与内部的热的施加方式的差异而缓慢地加热,冷却速度也非常慢。On the other hand, batch final annealing is a method of directly heating the coil of titanium plate in the annealing furnace in the state of the coil. In order to reduce the difference in the heat application method between the surface layer and the inside of the coil, it is slowly annealed. Heating, cooling rate is also very slow.

以往的钛板的最终退火中,在间歇式的情况下,加热温度为550~650℃,加热时间为3小时~30小时左右。In conventional final annealing of a titanium plate, in the case of a batch type, the heating temperature is 550 to 650° C., and the heating time is about 3 hours to 30 hours.

与此相对,作为制作本实施方式的钛板时实施的最终退火,例如若为连续式则优选在580℃以上且低于600℃的温度、1分钟以上且10分钟以下的加热条件下,或者在600℃以上且650℃以下的温度、10秒以上且小于2分钟的加热条件下实施。On the other hand, as the final annealing performed when producing the titanium plate of this embodiment, for example, if it is a continuous method, it is preferably at a temperature of 580° C. or higher and lower than 600° C., under heating conditions of 1 minute or more and 10 minutes or less, or It implements at the temperature of 600 degreeC or more and 650 degreeC or less, and the heating conditions of 10 seconds or more and less than 2 minutes.

作为这种优选的加热条件选择10秒以上的时间是由于:若保持温度的时间短于10秒,则为了对钛板实施规定的退火,通板速度、加热温度等操作条件的适当范围变得非常狭窄,对装置、其操作要求精度高的管理。The reason why the time of 10 seconds or more is selected as this preferred heating condition is because: if the time for maintaining the temperature is shorter than 10 seconds, in order to implement prescribed annealing to the titanium plate, the appropriate range of operating conditions such as plate passing speed and heating temperature becomes Very narrow and requires precise management of the device and its operation.

另一方面,作为加热时间优选为10分钟以下的条件是由于:若花费超过10分钟的时间则必须减慢通板速度,生产率降低。On the other hand, the condition that the heating time is preferably 10 minutes or less is because if it takes more than 10 minutes, the plate passing speed must be slowed down, and the productivity is lowered.

另外,作为优选的加热温度的条件选择580℃以上的温度是由于:在低于580℃的加热温度下,难以以10分钟以下的保持时间使钛板产生规定的再结晶,未再结晶部的面积率超过30%的情况增多。In addition, the reason for selecting a temperature of 580° C. or higher as a preferred heating temperature condition is that at a heating temperature lower than 580° C., it is difficult to cause a predetermined recrystallization of the titanium plate with a holding time of 10 minutes or less, and the non-recrystallized portion The cases where the area ratio exceeds 30% are increasing.

进而,选择650℃以下的加热温度是由于:在高于650℃的温度下,即使为10秒的加热时间,也会完成钛板的再结晶,再结晶晶粒有可能生长至5μm以上的平均粒径。Furthermore, the heating temperature below 650°C is selected because: at a temperature higher than 650°C, even if the heating time is 10 seconds, the recrystallization of the titanium plate will be completed, and the recrystallized grains may grow to an average thickness of 5 μm or more. particle size.

另外,作为制作本实施方式的钛板时实施的最终退火,若为间歇式则优选为420℃以上且低于550℃的温度,3小时以上且50小时以下的加热条件。In addition, as the final annealing performed when producing the titanium plate of this embodiment, if it is a batch type, it is preferably a temperature of 420° C. or higher and lower than 550° C., and a heating condition of 3 hours or more and 50 hours or less.

作为该加热时间优选为3小时以上的条件是由于,若加热时间短于3小时,则虽然取决于卷材的尺寸,但是卷材的内部的温度有可能未达到规定的温度。The reason why the heating time is preferably 3 hours or more is because if the heating time is shorter than 3 hours, the temperature inside the coil may not reach a predetermined temperature depending on the size of the coil.

另一方面,作为加热时间优选为50小时以下的条件是由于,若花费超过50小时的时间,则退火所需要的时间过长而钛板的生产率降低。On the other hand, the condition that the heating time is preferably 50 hours or less is because if it takes more than 50 hours, the time required for annealing becomes too long and the productivity of the titanium plate decreases.

另外,优选加热温度为420℃以上是由于:在低于420℃的加热温度下,难以以50小时以下的保持时间使钛板产生规定的再结晶,未再结晶部的面积率超过30%的情况增多。In addition, it is preferable that the heating temperature is 420° C. or higher because: at a heating temperature lower than 420° C., it is difficult to cause a predetermined recrystallization of the titanium plate with a holding time of 50 hours or less, and the area ratio of the non-recrystallized portion exceeds 30%. The situation increased.

或者为了确保规定的生产量,而必须保有几台退火炉(加热设备),设备费价格昂贵并且必需用于设置退火炉的宽阔空间。Or, in order to secure a predetermined throughput, it is necessary to keep several annealing furnaces (heating equipment), and the equipment costs are expensive, and a large space for installing the annealing furnace is required.

需要说明的是,由于间歇式中直接以卷材的状态进行加热,卷材的表层部与内部温度的升高速度不同,达到目标温度所需的时间也不同。It should be noted that since the coil is directly heated in the batch mode, the temperature rise rate of the surface layer and the internal temperature of the coil are different, and the time required to reach the target temperature is also different.

虽然取决于卷材的尺寸、加热温度、退火炉的加热能力,但是通常达到目标温度的时间有数十分钟~数小时的差异。Although it depends on the size of the coil, the heating temperature, and the heating capacity of the annealing furnace, the time to reach the target temperature usually varies from tens of minutes to several hours.

因此,即使加热时间稍微不同,再结晶的粒径也不怎么产生差异,即,在再结晶晶粒的生长速度慢的温度范围内加热是重要的。Therefore, even if the heating time is slightly different, there is not much difference in the recrystallized grain size, that is, it is important to heat in a temperature range in which the growth rate of recrystallized grains is slow.

而且,优选加热温度低于550℃是由于,在550℃以上的温度下再结晶的晶粒生长速度快,因此若适应卷材表层部而缩短加热时间则卷材内部仍然未达到目标温度,有可能形成未再结晶的未再结晶部多于30%的状态,相反地若适应卷材内部而延长加热时间,则卷材表层部中再结晶晶粒过度生长而平均结晶粒径有可能为5μm以上。Moreover, it is preferable that the heating temperature is lower than 550° C. because the recrystallized grain growth rate is fast at a temperature above 550° C., so if the heating time is shortened according to the surface layer of the coil, the inside of the coil still does not reach the target temperature, and there are A state where more than 30% of the non-recrystallized portion is not recrystallized may be formed. Conversely, if the heating time is extended to accommodate the interior of the coil, the recrystallized grains in the surface layer of the coil may grow excessively and the average grain size may be 5 μm. above.

需要说明的是,以连续式或间歇式进行的最终退火优选在真空中或非活性气体气氛下实施。It should be noted that the continuous or batch final annealing is preferably performed in vacuum or under an inert gas atmosphere.

如以上所述,通过退火条件来调整再结晶的平均粒径和未再结晶部(加工组织)的残留比率,由此可以得到具有优异的“强度-加工性平衡”的钛板。As described above, by adjusting the average grain size of recrystallization and the remaining ratio of unrecrystallized parts (processed structure) according to the annealing conditions, a titanium plate having an excellent "strength-workability balance" can be obtained.

需要说明的是,虽然在此未进行详细说明,但是在不显著损害本发明效果的范围内,本发明中也可以采用以往的钛板以及钛板制造方法中公知的事项。It should be noted that, although not described in detail here, known items in conventional titanium plates and titanium plate manufacturing methods may be employed in the present invention as long as the effects of the present invention are not significantly impaired.

另外,本实施方式中举出钛板作为钛材的例子,但是在发挥优异的“强度-加工性平衡”方面考虑,并不限于钛板,例如对于线材、棒材、管材等各种形态的钛材也是相同的,这些钛材也在本发明谋求的范围内。In addition, in this embodiment, a titanium plate is given as an example of a titanium material, but it is not limited to a titanium plate in consideration of exerting an excellent "strength-workability balance". The same applies to titanium materials, and these titanium materials are also within the scope of the present invention.

实施例Example

下面举出实施例进一步详细说明本发明,但是本发明并不限定于这些实施例。The following examples are given to further describe the present invention in detail, but the present invention is not limited to these examples.

<评价1><Evaluation 1>

(样品No.1~45)(Sample No.1~45)

(试验片的制作)(production of test piece)

通过小型真空电弧熔解制作铸锭(φ140mm),将该铸锭加热到1050℃后,进行锻造而制作50mm厚度的板坯。An ingot (φ140 mm) was produced by small-scale vacuum arc melting, and after heating the ingot to 1050° C., forging was performed to produce a slab with a thickness of 50 mm.

将该板坯在850℃下热轧至5mm厚度后,在750℃下进行退火,并进行喷丸、酸洗,除去表面的氧化皮而制作板材。This slab was hot-rolled at 850° C. to a thickness of 5 mm, annealed at 750° C., shot blasted and pickled to remove surface scale to produce a plate.

进一步将板材冷轧而制作0.5mm厚度的板状试样(钛板)。Furthermore, the plate material was cold-rolled, and the plate-shaped sample (titanium plate) of 0.5 mm thickness was produced.

在400~800℃的温度下,在氩气气氛中对该0.5mm厚度的钛板实施48小时以下的最终退火,制作晶粒得到调整的试验片。At a temperature of 400 to 800° C., final annealing was performed on the titanium plate with a thickness of 0.5 mm in an argon atmosphere for 48 hours or less to prepare a test piece in which crystal grains were adjusted.

(成分测定)(composition determination)

使用表面的氧化皮被切削了的热轧后的板材,对钛板中含有的铁量和氧量进行测定。The amount of iron and oxygen contained in the titanium plate was measured using the hot-rolled plate material from which the scale on the surface was removed.

铁含量根据JIS H1614测定,氧含量根据JIS H1620测定。The iron content was measured in accordance with JIS H1614, and the oxygen content was measured in accordance with JIS H1620.

(拉伸强度测定)(Measurement of tensile strength)

另外,根据JIS Z 2241对如上所述结晶粒度得到调整的试验片(钛板)的拉伸强度进行测定。In addition, the tensile strength of the test piece (titanium plate) whose crystal grain size was adjusted as described above was measured according to JIS Z 2241.

(加工性评价)(processability evaluation)

另外,对如上所述结晶粒度得到调整的试验片(钛板)的加工性进行评价。In addition, the processability of the test piece (titanium plate) whose crystal grain size was adjusted as described above was evaluated.

评价基于JIS Z2247通过使用石墨润滑脂作为润滑剂的埃里克森值的测定来实施。The evaluation was carried out by measuring the Ericsson value using graphite grease as a lubricant based on JIS Z2247.

(组织调查)(organization survey)

观察钛板的显微组织,得到晶粒(再结晶的α粒)、未再结晶部(加工组织)的组织照片。The microstructure of the titanium plate was observed to obtain microstructure photographs of crystal grains (recrystallized α grains) and non-recrystallized parts (processed structure).

需要说明的是,观察使用光学显微镜或透射式电子显微镜。In addition, an optical microscope or a transmission electron microscope were used for observation.

通过透射式电子显微镜观察得到的组织照片的例子如图1(样品No.28的显微组织)所示。An example of a photograph of the structure obtained by observation with a transmission electron microscope is shown in Fig. 1 (microstructure of sample No. 28).

该组织照片中,映现了再结晶的α粒和未再结晶部。In this micrograph, recrystallized α-grains and non-recrystallized portions appear.

(该图1所示的照片中,“A”所示的部位为未再结晶部。)(In the photograph shown in FIG. 1 , the portion indicated by "A" is the non-recrystallized portion.)

对于该照片,使用图像分析软件求出未再结晶部以外的面积,求出再结晶的α粒的平均面积,通过计算求出具有与该平均面积相同的面积的圆的直径,作为再结晶晶粒的平均粒径。For this photograph, use image analysis software to obtain the area other than the non-recrystallized part, obtain the average area of the recrystallized α grains, and obtain the diameter of a circle having the same area as the average area by calculation, and use it as a recrystallized crystal The average particle size of the particles.

另外,由未再结晶部的面积求出未再结晶部的面积率。In addition, the area ratio of the non-recrystallized portion was calculated from the area of the non-recrystallized portion.

以上的结果如表1所示。The above results are shown in Table 1.

[表1][Table 1]

上述样品No.1~30中,再结晶晶粒的平均粒径为5μm以下,钛板的截面以小于30%的面积率观察到未再结晶部,No.31~42是如以往的钛板那样未残留未再结晶部的状态的例子。In the above-mentioned samples No. 1 to 30, the average grain size of the recrystallized grains was 5 μm or less, and the non-recrystallized part was observed at an area ratio of less than 30% in the cross section of the titanium plate. Nos. 31 to 42 were conventional titanium plates This is an example of a state where no unrecrystallized portion remains.

另外,样品No.43~45中,调整退火条件以特意残留未再结晶部,但是未再结晶部以其面积率超过30%的状态残留。In addition, in Sample Nos. 43 to 45, the annealing conditions were adjusted so that non-recrystallized parts remained intentionally, but the non-recrystallized parts remained in a state where the area ratio exceeded 30%.

上述样品No.1~30和No.31~42,虽然使用氧含量、铁含量大致相同的钛材料,但是通过退火条件的不同来调整晶粒的尺寸(α相的圆当量平均粒径)和未再结晶部的量。The above-mentioned samples Nos. 1 to 30 and Nos. 31 to 42 use titanium materials with approximately the same oxygen content and iron content, but the grain size (circle-equivalent average grain size of the α phase) and Amount of unrecrystallized fraction.

由该表1可知,通过含有未再结晶部,可以将平均粒径抑制得小,从而发挥大的屈服强度。As can be seen from Table 1, by containing the non-recrystallized portion, the average particle size can be suppressed to be small, and a large yield strength can be exhibited.

上述评价中,总的来说有屈服强度越大则加工性(埃里克森值)越低的倾向,但是若以同等程度的加工性(埃里克森值)进行比较,则可知通过存在未再结晶部,屈服强度增大、强度高(例如参照样品No.1与31、9与34、15与39的比较)。In the above evaluation, generally speaking, the greater the yield strength, the lower the workability (Erickson value) tends to be. In the non-recrystallized part, the yield strength is increased and the strength is high (for example, refer to the comparison of samples No. 1 and 31, 9 and 34, and 15 and 39).

即可知,若晶粒为5μm以下的尺寸且未再结晶部为30%以下,则“屈服强度-加工性平衡”良好。That is, it can be seen that the "yield strength-workability balance" is good when the crystal grain size is 5 μm or less and the non-recrystallized portion is 30% or less.

另一方面,如样品No.43~45所示,若在最终退火后未再结晶部的面积多于30%则加工性(埃里克森值)大幅降低。On the other hand, as shown in Sample Nos. 43 to 45, when the area of the non-recrystallized portion exceeds 30% after the final annealing, the workability (Erickson value) decreases significantly.

由此可知,根据本发明可以提供高强度且加工性优异的钛板。From this, it can be seen that according to the present invention, a titanium plate having high strength and excellent workability can be provided.

<评价2><Evaluation 2>

(样品No.A~H)(Sample No.A~H)

(实机试验)(real machine test)

(试验卷材的制作)(production of test coil)

通过真空电弧熔解制作铸锭(φ750mm),将该铸锭加热到850~1000℃后,进行锻造而制作厚度170mm的板坯。An ingot (φ750 mm) was produced by vacuum arc melting, and the ingot was heated to 850 to 1000° C., followed by forging to produce a slab with a thickness of 170 mm.

加热该板坯直至达到850℃的温度后,热轧至3.5mm厚度,对该经过热轧后的轧制品在750℃的温度下进行退火后,进行喷丸、酸洗,除去表面的氧化皮而制作热轧卷材。After heating the slab until it reaches a temperature of 850°C, it is hot-rolled to a thickness of 3.5mm, and the hot-rolled rolled product is annealed at a temperature of 750°C, followed by shot blasting and pickling to remove surface oxidation. To make hot-rolled coils.

将该热轧卷材冷轧而形成厚度0.4~0.8mm的冷轧卷材。This hot-rolled coil is cold-rolled to form a cold-rolled coil with a thickness of 0.4 to 0.8 mm.

该冷轧卷材在洗涤除去冷轧油等油脂类后插入到真空退火炉中。The cold-rolled coil is inserted into a vacuum annealing furnace after washing to remove grease such as cold-rolling oil.

使容纳冷轧卷材的真空退火炉的炉内形成真空后,用氩气进行置换,实施加热到450~650℃并保持4~36小时的间歇式退火,从而调整再结晶晶粒的尺寸。Vacuum the interior of the vacuum annealing furnace containing the cold-rolled coil, replace it with argon, and perform batch annealing by heating to 450-650°C and maintaining it for 4-36 hours to adjust the size of the recrystallized grains.

为了与上述评价1同样地评价“成分测定”、“拉伸强度测定”、“加工性评价”、“组织调查”,从所得到的钛板选取必要尺寸的试样,实施前述评价。结果如表2所示。In order to evaluate "component measurement", "tensile strength measurement", "processability evaluation", and "structure investigation" similarly to the above-mentioned evaluation 1, a sample of required size was selected from the obtained titanium plate, and the above-mentioned evaluation was carried out. The results are shown in Table 2.

[表2][Table 2]

Figure BDA00002859679000151
Figure BDA00002859679000151

上述样品No.A~E中,再结晶晶粒的平均粒径为5μm以下、钛板的截面以小于30%的面积率观察到未再结晶部,No.F~H是如以往的钛板那样未残留未再结晶部的状态的例子。In the above samples No.A to E, the average grain size of the recrystallized grains is 5 μm or less, and the non-recrystallized part is observed in the cross section of the titanium plate with an area ratio of less than 30%, and Nos. F to H are conventional titanium plates This is an example of a state where no unrecrystallized portion remains.

上述样品No.A、B、C中,得到屈服强度为200MPa以上且埃里克森值为13mm左右的加工性优异的钛板。In the above-mentioned sample Nos. A, B, and C, a titanium plate having a yield strength of 200 MPa or more and an Ericsson value of about 13 mm was obtained, which was excellent in workability.

另外,样品No.D、E中,得到虽然为屈服强度为400MPa左右的高强度、但是埃里克森值为10mm左右的加工性良好的钛板。In addition, in sample No.D, E, although the yield strength is about 400 MPa high strength, but the Ericsson value is about 10 mm, the titanium plate with good workability was obtained.

另一方面,样品No.F~H中,虽然加工性优异,但是屈服强度小于200MPa,强度不充分。On the other hand, in sample Nos. F to H, although the workability was excellent, the yield strength was less than 200 MPa, and the strength was insufficient.

由此可知,根据本发明可以提供高强度且加工性优异的钛板。From this, it can be seen that according to the present invention, a titanium plate having high strength and excellent workability can be provided.

Claims (1)

1. a titanium material is characterized in that, the content of the iron in the described titanium material is that 0.60 quality % is following, the content of oxygen is below the 0.15 quality %, and remainder is comprised of titanium and inevitable impurity,
Described titanium material has that the worked structure implementing to be attended by the processing of viscous deformation and form and described processing are implemented to anneal afterwards and the recrystallized structure that forms, the median size that forms the crystal grain of this recrystallized structure is that 1 μ m is above and below the 5 μ m, and non-recrystallization section shared area in sectional area surpasses 0% and be below 30%.
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