JP3916088B2 - Titanium alloy for corrosion resistant materials - Google Patents
Titanium alloy for corrosion resistant materials Download PDFInfo
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- JP3916088B2 JP3916088B2 JP2005377163A JP2005377163A JP3916088B2 JP 3916088 B2 JP3916088 B2 JP 3916088B2 JP 2005377163 A JP2005377163 A JP 2005377163A JP 2005377163 A JP2005377163 A JP 2005377163A JP 3916088 B2 JP3916088 B2 JP 3916088B2
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- 230000007797 corrosion Effects 0.000 title claims description 68
- 238000005260 corrosion Methods 0.000 title claims description 68
- 229910001069 Ti alloy Inorganic materials 0.000 title claims description 48
- 239000000463 material Substances 0.000 title claims description 29
- 229910052748 manganese Inorganic materials 0.000 claims description 29
- 229910052718 tin Inorganic materials 0.000 claims description 29
- 229910052804 chromium Inorganic materials 0.000 claims description 22
- 229910052758 niobium Inorganic materials 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910010977 Ti—Pd Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing 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
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Prevention Of Electric Corrosion (AREA)
- Catalysts (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、耐食材用チタン合金に関する。 The present invention relates to a titanium alloy for corrosion resistant materials.
チタンは表面に酸化膜が形成されることから、一般の金属に比べて腐食されにくく、耐食性が求められる場所において広く用いられている。しかし、このような用途においてはさらに耐食性に優れたものが要望されており、従来、チタンに別の元素を添加して耐食性を向上させることが行われている。
例えば、耐食性を向上させたチタンとしては、ＪＩＳ １１種、１２種、１３種にも規定されているようにＴｉ−Ｐｄ合金が知られている。これらは、純チタンにＰｄを０．１２〜０．２５質量％含有させた合金である。さらに、Ｐｄ以外にもＣｏやＮｉを含有させることなども行われている（特許文献１および２参照）。
Titanium has an oxide film formed on its surface, so it is less likely to be corroded than ordinary metals and is widely used in places where corrosion resistance is required. However, in such applications, a material having further excellent corrosion resistance is desired, and conventionally, another element has been added to titanium to improve the corrosion resistance.
For example, as titanium having improved corrosion resistance, Ti-Pd alloys are known as defined in JIS 11, 12, and 13 types. These are alloys in which 0.12 to 0.25% by mass of Pd is contained in pure titanium. In addition to Pd, Co and Ni are also included (see Patent Documents 1 and 2).
ところで、チタンは耐食性に優れるばかりでなく軽量で強度が高いなど一般的な金属に比べて優れた特性を有しており、種々の合金がゴルフクラブ、自転車などのスポーツ用品などをはじめとして各種の用途に用いられている。しかし、チタン合金は一般的な金属に比べて高価であることから、近年、チタン鉱石から製造されるスポンジチタンのみならず一旦製品化され、不要となったチタン合金などを再生させた安価な再生チタン合金の利用が検討されるようになってきている。
しかし、前述のような耐食性が求められるような場合においては、微量であっても他の元素が混入されていると、その元素を起点として腐食が発生するおそれがあることから、従来、耐食材用のチタン合金には、再生チタン合金が用いられていない。しかも、Ｐｄなどの白金族元素は、一般に、チタンよりも極めて高価であることから、耐食材用チタン合金は、従来、非常に高価なものとなっている。
すなわち、従来の耐食材用チタン合金は、耐食性の低下を抑制しつつ安価に製造することが困難であるという問題を有している。
By the way, titanium is not only excellent in corrosion resistance but also has excellent properties compared to general metals such as light weight and high strength, and various alloys are used in various sports equipment such as golf clubs and bicycles. Used for applications. However, since titanium alloys are more expensive than ordinary metals, in recent years, not only sponge titanium produced from titanium ore, but also products that have been commercialized once and have been regenerated such as titanium alloys that are no longer needed. The use of titanium alloys has been studied.
However, in the case where the above-mentioned corrosion resistance is required, since a small amount of other elements are mixed, there is a risk of corrosion starting from that element. As a titanium alloy for use, a recycled titanium alloy is not used. Moreover, since platinum group elements such as Pd are generally much more expensive than titanium, corrosion resistant titanium alloys have heretofore been very expensive.
That is, the conventional titanium alloy for corrosion resistant materials has a problem that it is difficult to manufacture at low cost while suppressing a decrease in corrosion resistance.
本発明の課題は、上記問題点に鑑み、耐食性の低下を抑制しつつ安価に製造し得る耐食材用チタン合金を提供することにある。 In view of the above problems, an object of the present invention is to provide a titanium alloy for corrosion resistant materials that can be manufactured at low cost while suppressing a decrease in corrosion resistance.
本発明者らは、前記課題を解決すべく、鋭意検討を行った結果、チタン合金にＡｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの一種以上が所定内の量で含有されている場合には、耐食性の低下を抑制させ得ることを見出し本発明の完成に到ったのである。
すなわち、本発明は、質量％で白金族元素の１種類以上が合計０．０１〜０．１２％含有され、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの内、少なくともＳｎとＭｎのいずれか一方を含む一種以上がさらに含有され、残部がＴｉおよび不純物からなり、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの合計含有量が質量％で５％以下であることを特徴とする耐食材用チタン合金を提供する。
As a result of intensive studies to solve the above problems, the present inventors have found that the titanium alloy contains one or more of Al, Cr, Zr, Nb, Si, Sn, and Mn in a predetermined amount. Thus, the inventors have found that the deterioration of corrosion resistance can be suppressed, and have completed the present invention.
That is, the present invention contains at least one platinum group element in a mass% of 0.01 to 0.12% in total , and at least Sn and Mn among Al, Cr, Zr, Nb, Si, Sn and Mn. One or more of any one of them is further contained, the balance is made of Ti and impurities, and the total content of Al, Cr, Zr, Nb, Si, Sn, and Mn is 5% or less by mass%. Provided is a titanium alloy for corrosion resistant materials.
なお、チタン合金に、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎが含有されているとは、チタン合金中に不可避的なレベル以上にＡｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎが存在する場合を意図している。これらの元素は、一般的に用いられる分析機器を用いることでその含有量を測定することができ、通常、チタン合金に不可避的なレベルとして存在するこれらの元素の含有量は、最大で、Ａｌ：０．００７質量％、Ｃｒ：０．００７質量％、Ｚｒ：０．００１質量％、Ｎｂ：０．００１質量％、Ｓｉ：０．００４質量％、Ｓｎ：０．００１質量％、Ｍｎ：０．００１質量％であることから、本明細書において「チタン合金に、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎが含有されている」とは、これらの元素がこれらの量を超えてチタン合金中に存在する場合を意図している。 Note that the titanium alloy contains Al, Cr, Zr, Nb, Si, Sn, and Mn that the Al, Cr, Zr, Nb, Si, Sn, and Mn are more than unavoidable in the titanium alloy. Is intended to exist. The content of these elements can be measured by using a commonly used analytical instrument, and the content of these elements, which are usually present as inevitable levels in titanium alloys, is Al, : 0.007 mass%, Cr: 0.007 mass%, Zr: 0.001 mass%, Nb: 0.001 mass%, Si: 0.004 mass%, Sn: 0.001 mass%, Mn: 0 Therefore, in this specification, “the titanium alloy contains Al, Cr, Zr, Nb, Si, Sn and Mn” means that these elements exceed these amounts. It is intended to be present in titanium alloys.
本発明によれば、耐食材用チタン合金にＡｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎなどを含有させることから、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎを一種以上含有するチタン合金が用いられている製品からの再生チタン合金を耐食材用チタン合金に再利用することが可能となる。しかも、本発明によれば、耐食材用チタン合金には白金族元素の１種類以上が合計０．０１〜０．１２％含有されており、含有されるＡｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの合計含有量が質量％で合計５％以下とされていることから、耐食性の低下を抑制させ得る。
すなわち、耐食性の低下を抑制しつつ安価に製造し得る耐食材用チタン合金を提供し得る。
According to the present invention, since the corrosion-resistant titanium alloy contains Al, Cr, Zr, Nb, Si, Sn and Mn, etc., it contains at least one of Al, Cr, Zr, Nb, Si, Sn and Mn. Recycled titanium alloys from products using titanium alloys can be reused as corrosion resistant titanium alloys. In addition, according to the present invention, the titanium alloy for corrosion resistant material contains a total of 0.01 to 0.12% of one or more platinum group elements, and the contained Al, Cr, Zr, Nb, Si, Since the total content of Sn and Mn is 5% or less in terms of mass%, it is possible to suppress a decrease in corrosion resistance.
That is, it is possible to provide a titanium alloy for corrosion resistant material that can be manufactured at a low cost while suppressing a decrease in corrosion resistance.
以下に本実施形態の耐食材用チタン合金について説明する。まず、耐食材用チタン合金に含有される各元素の量ならびにその量を決定する理由について説明する。
本実施形態の耐食材用チタン合金には、通常、白金族元素、ＣｏおよびＮｉのいずれか一方または両方、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの内、少なくともＳｎとＭｎのいずれか一方を含む一種以上が含有され、残部は、Ｔｉおよび不純物からなっている。
The titanium alloy for corrosion resistant materials according to this embodiment will be described below. First, the amount of each element contained in the titanium alloy for corrosion resistant materials and the reason for determining the amount will be described.
In the titanium alloy for corrosion-resistant material of the present embodiment, usually one or both of platinum group element, Co and Ni, Al, Cr, Zr, Nb, Si, Sn and Mn , at least any of Sn and Mn One or more types including either of them are contained, and the balance consists of Ti and impurities.
白金族元素は、耐食材用チタン合金に必須の成分で含有量は、質量％で０．０１〜０．１２％とされる。白金族元素の含有量が０．０１〜０．１２％とされるのは、白金族元素が質量％で０．０１％未満の場合には、耐食材用チタン合金の耐食性が十分なものとならずに、腐食を発生させるおそれのあるものとなるためである。一方、０．１２％を超えて含有されていてもそれ以上に耐食性の向上が期待できないばかりか、耐食材用チタン合金のコストが多大なものとなるおそれを有するためである。
この白金族元素としては、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、ＩｒおよびＰｔを用いることができるが、Ｐｄを用いることが好ましい。
The platinum group element is an essential component of the titanium alloy for corrosion resistant materials, and the content is 0.01 to 0.12% by mass. The content of the platinum group element is set to 0.01 to 0.12% when the platinum group element is less than 0.01% by mass and the corrosion resistance of the titanium alloy for corrosion resistant material is sufficient. In other words, corrosion may occur. On the other hand, even if the content exceeds 0.12%, not only the corrosion resistance cannot be expected to be further improved, but the cost of the titanium alloy for corrosion resistant material may increase.
As this platinum group element, Ru, Rh, Pd, Os, Ir and Pt can be used, but Pd is preferably used.
ＣｏとＮｉとは、任意成分であり、含有量は、質量％で０．０５〜２．００％とされる。これらを質量％で０．０５〜２．００％含有させることで、耐食性をさらに向上させつつ耐食材用チタン合金を高強度化させるという効果を奏する。このＣｏとＮｉとの合計量が０．０５％未満の場合には、耐食性をさらに向上させつつ耐食材用チタン合金を高強度化させるという効果を得ることが困難となる。 Co and Ni are optional components, and the content is 0.05 to 2.00% by mass. By containing these in an amount of 0.05 to 2.00% by mass, the effect of increasing the strength of the titanium alloy for corrosion resistant materials while further improving the corrosion resistance is achieved. When the total amount of Co and Ni is less than 0.05%, it is difficult to obtain the effect of increasing the strength of the titanium alloy for corrosion resistant material while further improving the corrosion resistance.
Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの内、少なくともＳｎとＭｎのいずれか一方が、耐食材用チタン合金に必須の成分でＡｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの合計含有量は、質量％で５％以下とされる。これらの元素の含有量がこのような範囲とされるのは、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの合計含有量が５％を超えて含有される場合には、耐食材用チタン合金の耐食性が低下して、腐食を発生させるためである。このような点において、これらの合計含有量は、３％以下とされることが好ましく、２％以下とされることがさらに好ましい。 Among Al, Cr, Zr, Nb, Si, Sn, and Mn , at least one of Sn and Mn is an essential component for a titanium alloy for corrosion resistant materials, and Al, Cr, Zr, Nb, Si, Sn, and Mn. The total content is 5% or less by mass. The content of these elements is within such a range when the total content of Al, Cr, Zr, Nb, Si, Sn, and Mn exceeds 5%. This is because the corrosion resistance of the titanium alloy is lowered and corrosion occurs. In such a point, the total content of these is preferably 3% or less, and more preferably 2% or less.
また、不純物としては、Ｃ、Ｏ、Ｈ、Ｆｅなどの不可避不純物を例示することができ、本実施形態の耐食材用チタン合金には、本発明の効果を損ねない範囲においてその他の元素を微量含有させることも可能である。特に、Ｖ、Ｍｏ、Ｗは、耐食性への影響が少ないことが既に知られており、これらを質量％で合計５％以下程度の量であれば耐食材用チタン合金に含有させることも可能である。 Further, as impurities, unavoidable impurities such as C, O, H, and Fe can be exemplified, and the titanium alloy for corrosion-resistant materials of the present embodiment contains trace amounts of other elements within a range not impairing the effects of the present invention. It can also be included. In particular, it is already known that V, Mo, and W have little influence on the corrosion resistance, and these can be included in the titanium alloy for corrosion resistant materials as long as the total amount is about 5% or less by mass%. is there.
このような耐食材用チタン合金は、例えば、２５０℃程度の濃硫酸や硫酸ニッケル、塩化ニッケルなどにさらされる環境で使用されるニッケル精錬プラントなどの配管、熱交換器、電界槽などに好適である。 Such a titanium alloy for corrosion resistant materials is suitable, for example, for piping, heat exchangers, electric tanks and the like of nickel refining plants used in an environment exposed to concentrated sulfuric acid, nickel sulfate, nickel chloride or the like at about 250 ° C. is there.
次に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.
（試料作成）
（実施例１〜８、比較例１〜１１、参考例１〜２１）
各実施例、比較例、参考例の耐食性評価用の試料を、純チタンと各成分とを用いてチタン合金に表１、２の成分が、表１、２の量で含有されるように調整して耐食材用チタン合金を作製した。なお、比較例１には、純チタンを用いた。このとき、まず、各組成のチタン合金を、ボタンアーク溶解にて２０ｍｍ厚さ×７０ｍｍ幅×９０ｍｍ長さの大きさに溶製した。次いで、この溶製したものを熱間圧延にて３ｍｍ厚さに圧延した後に、酸洗により表面のスケールを除去したものから５０ｍｍ幅×１００ｍｍ長さの試験片を切り出した。さらに、この試験片の片面を＃２００研磨紙で研磨し、この研磨面のみを表面に露出させるように、側面ならびに裏面側をシール剤を用いてシールし耐食性評価用の試料とした。
また、スポンジチタンなどから製造されていた従来の耐食材用チタン合金として、表３に示す成分が含有されてなる耐食材用チタン合金（従来例１〜４）を作製して、実施例、比較例の耐食材用チタン合金と同様に評価した。
(Sample preparation)
(Examples 1-8 , Comparative Examples 1-11 , Reference Examples 1-21 )
Samples for corrosion resistance evaluation of each example, comparative example , and reference example were adjusted using pure titanium and each component so that the components shown in Tables 1 and 2 were contained in the titanium alloy in the amounts shown in Tables 1 and 2. Thus, a titanium alloy for corrosion resistant material was produced. In Comparative Example 1, pure titanium was used. At this time, first, titanium alloys having respective compositions were melted to a size of 20 mm thickness × 70 mm width × 90 mm length by button arc melting. Next, the melted product was rolled to a thickness of 3 mm by hot rolling, and then a 50 mm wide × 100 mm long test piece was cut out from the surface scale removed by pickling. Furthermore, one side of this test piece was polished with # 200 abrasive paper, and the side and back sides were sealed with a sealant so that only this polished surface was exposed to the surface, and used as a sample for corrosion resistance evaluation.
Moreover, as a conventional titanium alloy for corrosion resistant materials manufactured from sponge titanium etc., the titanium alloy for corrosion resistant materials (conventional examples 1-4) in which the component shown in Table 3 was contained was produced, and an Example, comparison Evaluation was made in the same manner as the titanium alloy for the corrosion resistant material in the example.
（耐塩化ニッケル性試験）
各実施例、比較例、参考例、従来例の耐食性評価用試料を１００℃の２０％塩化ニッケル溶液に１００時間浸漬し、浸漬後の耐食性評価用試料の表面を肉眼ならびに光学顕微鏡で観察して表面性状の評価を行った。その結果、初期の耐食性評価用試料の表面状態と塩化ニッケル溶液浸漬後の耐食性評価用試料の表面に変化が確認されないものを「○」として判定し、僅かに凹凸などの増加が確認されたものを「△」、凹凸などの増加が明確に確認されたものを「×」として判定した。結果を表４に示す。
また、塩化ニッケル溶液浸漬前後において０．１ｍｇ単位まで測定可能な電子天秤を用いて耐食性評価用試料の重量を測定し、その差を重量減少（ΔＭ）として算出した。また、浸漬前の耐食性評価用試料の表面積（Ｓ）から以下の式により、減肉量を計算した。
減肉量（ｇ／ｍ2）＝ΔＭ（ｇ）／Ｓ（ｍ2）
結果を表４に示す。
(Nickel chloride resistance test)
Samples for corrosion resistance evaluation of each example, comparative example , reference example , and conventional example were immersed in a 20% nickel chloride solution at 100 ° C. for 100 hours, and the surface of the sample for corrosion resistance evaluation after immersion was observed with the naked eye and an optical microscope. The surface properties were evaluated. As a result, the surface state of the initial sample for corrosion resistance evaluation and the surface of the sample for corrosion resistance evaluation after immersion in a nickel chloride solution were judged as “◯”, and a slight increase in irregularities was confirmed. Was determined as “C”, and “×” was determined as a clear increase in irregularities. The results are shown in Table 4.
Moreover, the weight of the sample for corrosion resistance evaluation was measured using an electronic balance capable of measuring up to 0.1 mg before and after immersion in the nickel chloride solution, and the difference was calculated as weight loss (ΔM). Moreover, the amount of thinning was calculated by the following formula from the surface area (S) of the sample for corrosion resistance evaluation before immersion.
Thinning amount (g / m 2 ) = ΔM (g) / S (m 2 )
The results are shown in Table 4.
（耐熱硫酸性試験）
各実施例、比較例、参考例、従来例の耐食性評価用試料を２４０℃の５％硫酸水溶液に１時間浸漬し、耐塩化ニッケル性試験と同様にして減肉量を計算により求めた。結果を表４に示す。
(Heat-resistant sulfuric acid test)
Samples for corrosion resistance evaluation of Examples, Comparative Examples , Reference Examples , and Conventional Examples were immersed in a 5% sulfuric acid aqueous solution at 240 ° C. for 1 hour, and the amount of thinning was determined by calculation in the same manner as in the nickel chloride resistance test. The results are shown in Table 4.
（耐熱塩酸性試験）
各実施例、比較例、参考例、従来例の耐食性評価用試料を沸騰させた１０％塩酸水溶液に１時間浸漬し、耐塩化ニッケル性試験と同様にして減肉量を計算により求めた。結果を表４に示す。
(Heat resistant hydrochloric acid test)
The corrosion resistance evaluation samples of each Example, Comparative Example , Reference Example , and Conventional Example were immersed in a boiled 10% aqueous hydrochloric acid solution for 1 hour, and the amount of thinning was determined by calculation in the same manner as the nickel chloride resistance test. The results are shown in Table 4.
（耐すきま腐食性試験）
実施例、比較例、参考例、従来例の耐食性評価用試料を、表面を合わせるようにして各２枚ずつ重ね合わせて、塩酸にてｐＨ１に調整された９０℃の２０％ＮａＣｌ水溶液に１００時間浸漬して耐すきま腐食性試験を実施した。なお、試験後の試料を前述の耐塩化ニッケル性試験と同様に試料の表面に変化が確認されないものを「○」として判定し、僅かに凹凸などの増加が確認されたものを「△」、凹凸などの増加が明確に確認されたものを「×」として判定した。結果を表４に示す。
(Crevice corrosion resistance test)
Samples for corrosion resistance evaluation of Examples, Comparative Examples , Reference Examples , and Conventional Examples were overlapped with each other so that the surfaces were matched, and the sample was placed in a 20% NaCl aqueous solution at 90 ° C. adjusted to pH 1 with hydrochloric acid for 100 hours. The crevice corrosion resistance test was carried out by dipping. In addition, the sample after the test was judged as “◯” when no change was confirmed on the surface of the sample in the same manner as in the above-mentioned nickel chloride resistance test, and “△” when a slight increase in irregularities was confirmed. The case where the increase in unevenness was clearly confirmed was judged as “x”. The results are shown in Table 4.
この表４からも、質量％で白金族元素の１種類以上が合計０．０１〜０．１２％含有され、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの内、少なくともＳｎとＭｎのいずれか一方を含む一種以上がさらに含有され、残部がＴｉおよび不純物からなり、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの合計含有量が質量％で５％以下であることを特徴とする耐食材用チタン合金、あるいは、質量％で白金族元素の１種類以上が合計０．０１〜０．１２％含有され、ＣｏおよびＮｉの一方または両方が質量％で合計０．０５〜２．００％含有され、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの内、少なくともＳｎとＭｎのいずれか一方を含む一種以上がさらに含有され、残部がＴｉおよび不純物からなり、Ａｌ、Ｃｒ、Ｚｒ、Ｎｂ、Ｓｉ、ＳｎおよびＭｎの合計含有量が質量％で５％以下であることを特徴とする耐食材用チタン合金は、各比較例に比べて耐食性に優れ、従来のスポンジチタンが用いられた耐食材用チタン合金と同等の耐食性を有していることがわかる。 Also from Table 4, one or more platinum group elements are contained in a total of 0.01 to 0.12% by mass , and at least Sn and Mn among Al, Cr, Zr, Nb, Si, Sn and Mn. One or more of any one of them is further contained, the balance is made of Ti and impurities, and the total content of Al, Cr, Zr, Nb, Si, Sn, and Mn is 5% or less by mass%. One or more platinum group elements in a total of 0.01 to 0.12% by mass, or one or both of Co and Ni in a mass% in total of 0.05 to 2. 1% or more of Al, Cr, Zr, Nb, Si, Sn and Mn , and at least one of Sn and Mn is further contained, and the balance is Ti and impurities, Al, Cr, Zr, Nb The total content of Si, Sn, and Mn is 5% or less by mass, and the titanium alloy for corrosion resistant material is superior in corrosion resistance to each comparative example, and the conventional corrosion resistant material using sponge titanium It can be seen that it has the same corrosion resistance as the titanium alloy for use.
すなわち、本発明の耐食材用チタン合金は、再生チタン合金などを使用しつつも耐食性の低下を抑制させることができ、耐食性の低下を抑制しつつ安価に製造し得るものであることがわかる。 That is, it can be seen that the titanium alloy for corrosion-resistant materials of the present invention can suppress a decrease in corrosion resistance while using a recycled titanium alloy or the like, and can be manufactured at a low cost while suppressing a decrease in corrosion resistance.
Claims (2)
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| JP2005377163A JP3916088B2 (en) | 2005-12-28 | 2005-12-28 | Titanium alloy for corrosion resistant materials |
| RU2008130858/02A RU2405850C2 (en) | 2005-12-28 | 2006-07-31 | Titanium alloy for corrosion resistant materials |
| PCT/JP2006/315132 WO2007077645A1 (en) | 2005-12-28 | 2006-07-31 | Titanium alloy for corrosion-resistant material |
| US12/087,066 US20090004042A1 (en) | 2005-12-28 | 2006-07-31 | Titanium Alloy for Corrosion-Resistant Materials |
| CNA2006800444487A CN101316939A (en) | 2005-12-28 | 2006-07-31 | Titanium Alloys for Corrosion Resistant Materials |
| EP06782010.0A EP1978119B1 (en) | 2005-12-28 | 2006-07-31 | Titanium alloy for corrosion-resistant material |
| PL06782010T PL1978119T3 (en) | 2005-12-28 | 2006-07-31 | Titanium alloy for corrosion-resistant material |
| US12/815,527 US8741217B2 (en) | 2005-12-28 | 2010-06-15 | Titanium alloy for corrosion-resistant materials |
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| WO2014025059A1 (en) | 2012-08-10 | 2014-02-13 | 新日鐵住金株式会社 | Titanium alloy material |
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| KR101707284B1 (en) | 2011-07-26 | 2017-02-15 | 신닛테츠스미킨 카부시키카이샤 | Titanium alloy |
| JP5662928B2 (en) * | 2011-12-26 | 2015-02-04 | 株式会社神戸製鋼所 | Support device for solar cell module |
| RU2502819C1 (en) * | 2012-04-19 | 2013-12-27 | Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") | Titanium-base alloy |
| US9957836B2 (en) | 2012-07-19 | 2018-05-01 | Rti International Metals, Inc. | Titanium alloy having good oxidation resistance and high strength at elevated temperatures |
| JP5660253B2 (en) | 2013-01-25 | 2015-01-28 | 新日鐵住金株式会社 | Titanium alloy with excellent corrosion resistance in environments containing bromine ions |
| CN104878246A (en) * | 2015-06-02 | 2015-09-02 | 张亚南 | Alloy material for dental restoration and application of alloy material |
| US10441607B1 (en) | 2016-02-22 | 2019-10-15 | The Board Of Regents Of The University Of Texas System | Multifunctional linker technology containing an N4 group |
| CN107576216A (en) * | 2017-09-28 | 2018-01-12 | 江苏众众热能科技有限公司 | A kind of heat-exchangers of the plate type titanium plate |
| CN107746997A (en) * | 2017-10-23 | 2018-03-02 | 宝鸡市永盛泰钛业有限公司 | A kind of corrosion resistant titanium alloy and preparation method thereof |
| CN108467970B (en) * | 2018-03-23 | 2020-12-25 | 中国石油天然气集团公司管材研究所 | Iron-containing titanium alloy pipe for high-corrosivity oil gas development and preparation method thereof |
| RU2752094C1 (en) | 2018-04-10 | 2021-07-22 | Ниппон Стил Корпорейшн | Titanium alloy and method for production thereof |
| CN108893651A (en) * | 2018-07-25 | 2018-11-27 | 中南大学 | A kind of high-strength high-ductility corrosion titanium alloy and preparation method thereof |
| CN110373571A (en) * | 2019-08-28 | 2019-10-25 | 浙江海洋大学 | A kind of wave key preparation method of light alloy |
| CN114555842B (en) | 2019-10-30 | 2022-10-18 | 日本制铁株式会社 | Titanium alloy |
| CN113584345B (en) * | 2021-08-06 | 2022-03-08 | 东莞亿诚精密模具有限公司 | Golf club head material, preparation process thereof and club head striking face |
| CN116516214A (en) * | 2023-06-02 | 2023-08-01 | 中国科学院金属研究所 | Titanium alloy resistant to high Wen Xiaosuan corrosion and preparation method thereof |
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| JPS61194142A (en) * | 1985-02-21 | 1986-08-28 | Nippon Mining Co Ltd | Titanium alloy having superior corrosion resistance |
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| JPS6270543A (en) * | 1985-09-25 | 1987-04-01 | Nippon Mining Co Ltd | Titanium-base alloy excellent in corrosion resistance |
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| JPS62199744A (en) * | 1986-02-25 | 1987-09-03 | Sumitomo Metal Ind Ltd | Titanium alloy with excellent crevice corrosion resistance |
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| EP0479212B1 (en) * | 1990-10-01 | 1995-03-01 | Sumitomo Metal Industries, Ltd. | Method for improving machinability of titanium and titanium alloys and free-cutting titanium alloys |
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| WO2014025059A1 (en) | 2012-08-10 | 2014-02-13 | 新日鐵住金株式会社 | Titanium alloy material |
| KR20150030265A (en) | 2012-08-10 | 2015-03-19 | 신닛테츠스미킨 카부시키카이샤 | Titanium alloy material |
| EP3575422A1 (en) | 2012-08-10 | 2019-12-04 | Nippon Steel Corporation | Titanium alloy material |
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| PL1978119T3 (en) | 2017-06-30 |
| WO2007077645A1 (en) | 2007-07-12 |
| RU2008130858A (en) | 2010-02-10 |
| US20090004042A1 (en) | 2009-01-01 |
| RU2405850C2 (en) | 2010-12-10 |
| EP1978119B1 (en) | 2016-11-23 |
| JP2006193829A (en) | 2006-07-27 |
| CN101316939A (en) | 2008-12-03 |
| EP1978119A1 (en) | 2008-10-08 |
| EP1978119A4 (en) | 2014-07-02 |
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