EP2889386B1 - Alliage de titane possédant une excellente résistance à la corrosion dans un environnement contenant des ions bromure - Google Patents

Alliage de titane possédant une excellente résistance à la corrosion dans un environnement contenant des ions bromure Download PDF

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EP2889386B1
EP2889386B1 EP14743073.0A EP14743073A EP2889386B1 EP 2889386 B1 EP2889386 B1 EP 2889386B1 EP 14743073 A EP14743073 A EP 14743073A EP 2889386 B1 EP2889386 B1 EP 2889386B1
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present
mass
titanium alloy
corrosion
corrosion resistance
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EP2889386A1 (fr
EP2889386A4 (fr
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Hideya Kaminaka
Hiroshi Kamio
Masaru Abe
Kouichi Takeuchi
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • 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

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  • the present invention relates to use of a titanium alloy, particularly to use of a titanium alloy having high corrosion resistance (crevice corrosion resistance, acid resistance, and the like in a bromine-ion-containing environment) and high economic efficiency.
  • Titanium is being actively used in the aircraft field and the like, utilizing its feature of lightness and strength. Further, having high corrosion resistance, titanium is beginning to be used in wide range of fields as a material for chemical industry equipment, a material for thermal and nuclear power generation equipment, and a material for seawater desalination equipment, and the like.
  • titanium can exhibit its high corrosion resistance
  • oxidizing acid nitric acid
  • neutral chloride environment such as seawater
  • Titanium does not have sufficient crevice corrosion resistance in a high-temperature chloride environment, nor sufficient corrosion resistance in a non-oxidizing acid solution such as hydrochloric acid (hereinafter, the crevice corrosion resistance and the corrosion resistance are simply referred to as "corrosion resistance” unless otherwise specified).
  • a titanium alloy in which titanium contains a platinum group element hereinafter referred to as "platinum-group-element-containing titanium alloy" is proposed and normalized to be used in various usages.
  • an anode electrode used for electrolysis is used in a high-concentration, 20% to 30% brine containing hydrochloric acid at a high temperature of 100°C or more.
  • a platinum-group-element-containing titanium alloy is used for a part where crevice corrosion may occur.
  • reaction vessel is subjected to a high-concentration sulfuric acid including slurry at a high temperature, which is higher than 100°C.
  • the reaction vessel is made of a platinum-group-element-containing titanium alloy
  • a heat exchanger tube used in the salt manufacture field is subjected to high-temperature and high-concentration salt water
  • a heat exchanger tube used for heat exchange of an exhaust gas of a furnace is subjected to an exhaust gas containing chorine, NO x , and SO x .
  • These heat exchanger tubes are made of a platinum-group-element-containing titanium alloy.
  • reaction vessel or the like of desulfurization equipment used at a time of oil refining is subjected to high-temperature hydrogen sulfide.
  • a reaction vessel is made of a platinum-group-element-containing titanium alloy.
  • a platinum-group-element-containing titanium alloy is considered to be applied to a separator material for a fuel cell, utilizing its high corrosion resistance.
  • Gr. 7 (Grade) complies with the ASTM standard. The same holds true in the following description.
  • Ti-0.15 Pd alloy is a titanium alloy that has been developed to have corrosion resistance in the above described usages. Pd contained in this titanium alloy reduces hydrogen overvoltage to maintain a natural potential within a passivation area. That is, Pd eluted from the alloy by corrosion is precipitated again on the surface of the alloy to be deposited, and thereby the hydrogen overvoltage of the alloy is reduced and the natural potential is maintained within the passivation area. Accordingly, this alloy has high corrosion resistance.
  • Patent Document 1 a titanium alloy (Gr. 17) having a lower content of Pd, which is 0.03 to 0.1 mass%, than Gr. 7, and also having high crevice corrosion resistance is proposed and put into practical use.
  • Patent Document 2 discloses, as a titanium alloy that can be manufactured at low cost while preventing a reduction in corrosion resistance, a titanium alloy containing one or more platinum group elements in 0.01 to 0.12 mass% in total, and one or more of Al, Cr, Zr, Nb, Si, Sn, and Mn in 5 mass% or less in total.
  • a titanium alloy containing one or more platinum group elements in 0.01 to 0.12 mass% in total, and one or more of Al, Cr, Zr, Nb, Si, Sn, and Mn in 5 mass% or less in total.
  • Non-Patent Document 1 by adding Co, Ni, or V, as a third element, to a Ti-Pd alloy, the crevice corrosion resistance is increased, but the content of Pd needs to be 0.05 mass% or more in order to obtain sufficient crevice corrosion resistance.
  • Patent Document 3 discloses a titanium alloy to which 0.005 to 0.2 mass% Ru is added. As shown in an example in this document, in order to obtain sufficient crevice corrosion resistance, the addition of Ru to this titanium alloy needs to be 0.05 mass% or more.
  • Patent Document 4 discloses a material of a system in which Ru and Ni are added in order to further increase corrosion resistance.
  • This material has not only crevice corrosion resistance, but also high corrosion resistance in an environment containing non-oxidizing acid such as sulfuric acid or hydrochloric acid.
  • Ti-0.06Ru-0.5Ni is an alloy having a structure within the range shown in Patent Document 4 below and is normalized as Gr. 13 to be used practically as a corrosion-resistant titanium alloy.
  • the addition of Ni results in a problem that a Ti 2 Ni compound is precipitated in the titanium alloy. Further, due to this compound precipitation, the processability of the titanium alloy, such as stretch, becomes inferior to that of Gr. 17.
  • Patent Document 5 and Patent Document 6 disclose materials to which a platinum group element, a rare earth element, and a transition element are added. Each of these materials is, however, a titanium alloy for an ultra-high vacuum vessel.
  • the platinum group element and the rare earth element are added in order to obtain an effect of preventing a phenomenon in which a gas component dissolved in a material is dispersed and released to a vacuum in the ultra-high vacuum. It is known that the platinum group element has a function of trapping hydrogen and that the rare earth element has a function of trapping oxygen in the titanium alloy.
  • Patent Document 5 and Patent Document 6 in addition to the platinum group element and the rare earth element, a transition element such as Co, Fe, Cr, Ni, Mn, or Cu is given as a necessary element. It is known that the transition element has a role of fixing atomic hydrogen that is adsorbed on the surface of the vacuum vessel by the platinum group element.
  • Patent Document 5 and Patent Document 6 is made considering corrosion resistance, and refers to corrosion resistance in a bromine-ion-containing environment.
  • the Japanese patent application JP2010 270360 discloses a low-cost titanium alloy that exhibits excellent corrosion resistance in non-oxidising environments such as sulfuric acid, high-temperature neutral chloride or fluoride-containing high-temperature neutral chloride environments.
  • the disclosed alloy contains 0.005-0.10% Ru, 0.005-0.10% Pd, 0.01-2.0% Ni, 0.01-2.0% Cr, 0.01-2.0% V and the balance being Ti.
  • the present invention has been made in view of the above problems, and aims to provide a titanium alloy having high corrosion resistance, particularly in a bromine-ion-containing environment.
  • the price of the titanium alloy can be lower than before.
  • FIG. 1 is a schematic diagram showing a mechanism by which corrosion resistances of a Ti-Pd alloy and a Ti-Pd-Co alloy are expressed.
  • the surface of the Ti-Pd alloy and the Ti-Pd-Co alloy is active in an initial state before being immersed in a solution.
  • an acid solution such as boiling hydrochloric acid
  • Ti and Pd on the surface, or Ti, Pd, and Co on the surface are melted, and the melted Pd, or Pd and Co is/are precipitated on the surface to be condensed. Accordingly, the hydrogen overvoltage of the entire titanium alloy is decreased.
  • the potential of the titanium alloy is maintained in a passivation area, and the titanium alloy has high corrosion resistance.
  • the present inventors have studied the Ti-Ru alloy and confirmed that the corrosion resistance of the Ti-Ru alloy is secured by the same mechanism as in Ti-Pd.
  • Pd and Ru in the same addition amount are compared with each other under the same conditions, Pd has a higher effect of increasing corrosion resistance. Therefore, it is revealed that a greater amount of Ru needs to be added in order to obtain the same level of corrosion resistance.
  • Patent Document 4 and Non-Patent Document 2 above disclose that high corrosion resistance can be obtained by precipitating a large amount of Ti 2 Ni 1-x Ru X (a compound including Ru instead of part of Ni in Ti 2 Ni) in a titanium base material by adding Ru and Ni without adding a large amount of Ru.
  • Ti 2 Ni 1-x Ru X a compound including Ru instead of part of Ni in Ti 2 Ni
  • the titanium alloy to which a large amount of Ni is added has poor processability such as stretch.
  • the present inventors have examined for a novel additive element that promotes an alloy base material to be melted at an initial stage after a Ti-Ru alloy is immersed in an acid solution in order to enable Ru to be precipitated immediately and uniformly on a surface to be condensed. It is considered that the addition of such a novel additive element to the Ti-Ru alloy causes the alloy base material to be melted in the initial stage in an active state area after being immersed in the acid solution. Accordingly, the Ru ion concentration is increased in the solution near the surface of the alloy, and a sufficient amount of Ru is immediately precipitated and condensed on the surface of the alloy so as to make the alloy have a potential in a passivation area.
  • Ru precipitation condensation Such precipitation of such an amount of Ru on the surface of the alloy is referred to as "Ru precipitation condensation". Even if the content of Ru is low in the alloy, when the Ru precipitation condensation occurs, it becomes possible to decrease the hydrogen overvoltage of the Ti-Ru alloy immediately so as to make the Ti-Ru alloy have a potential that is more noble and stable (a potential in the passivation area).
  • the Ru ion concentration and Ti ion concentration near the surface become higher than in a case in which the additive element is not added. Accordingly, the Ru precipitation condensation occurs. Thus, it can be considered that the hydrogen overvoltage of the alloy is immediately decreased and that the potential can be kept in the passivation area.
  • the Ru precipitation condensation propagates more immediately on a fresh surface generated by the damage than in a case of a conventional titanium alloy. Accordingly, it can be considered that the hydrogen overvoltage of the alloy reaches the passivation area, and the damage will be repaired. Therefore, corrosion starting from the damage is unlikely to propagate.
  • Non-Patent Document 3 in a bromine-containing environment, pitting or crevice corrosion is generated on pure titanium. It has been considered that crevice corrosion may not occur in a Ti-Pd-based titanium alloy, but crevice corrosion may sometimes be generated in an environment of a chloride containing bromine ions. The present inventors have intensively studied this problem, and have found out that the resistance to corrosion caused by bromine is increased by condensing Ru on the surface.
  • rare earth elements correspond to such an element, and that the resistance to corrosion caused by bromine is further increased by a synergetic effect of adding, in addition to Ru and a rare earth element, one or more selected from the group consisting of Ni, Co, Mo, Cr, V, and W.
  • Ru a platinum group element
  • Pd another platinum group element
  • the rare earth element itself does not have an effect of increasing corrosion resistance of an alloy. In this light, the rare earth element has a different function from the additive element disclosed in each of Patent Documents 2 to 4 and Non-Patent Document 1 above.
  • Patent Documents 5 and 6 The usage of the alloy and the function of the element in Patent Documents 5 and 6 are different from those in the present invention. That is, the function of the rare earth element in Patent Documents 5 and 6 are compared with that in the present invention as below (the content is weight%).
  • Patent Documents 5 and 6 The titanium alloy has high solid solubility of oxygen.
  • the rare earth element is added in order to fix oxygen as an oxide so as to prevent dissolved oxygen from being dispersed in the alloy and to prevent its release to a vacuum atmosphere in a gas state when being used in a high vacuum usage.
  • the lower limit of the rare earth element is set to 0.02%.
  • the added amount exceeds 0.5%, ductility is decreased by the precipitated oxide. Accordingly, the upper limit of the rare earth element is set to 0.5%.
  • the present invention When being immersed in an environment of a chloride aqueous solution, the titanium alloy containing a platinum group element is melted in an active state area, and the platinum group element is precipitated to be condensed on the surface, so that the potential of the alloy as a whole is shifted to be in a passivation area (the potential becomes noble).
  • the rare earth element has a function of shortening the time for the potential to become noble and a function of increasing the condensing degree of the platinum group element on the surface.
  • the rare earth element is desirably in a dissolving range of the titanium alloy.
  • the lower limit is 0.001% and the upper limit is 0.1 % in order to obtain this effect.
  • the amount exceeds 0.1 % a compound of titanium and the rare earth element is produced, which may degrade corrosion resistance.
  • the role of the rare earth element in Patent Documents 5 and 6 is to react with oxygen dissolved in the titanium alloy to produce an oxide.
  • the rare earth element has a largely different role of promoting the platinum group element to be condensed on the surface of the titanium alloy in a wet corrosion environment.
  • a desirable rare earth element component is within the dissolving range, which is a content lower than that in Patent Documents 5 and 6.
  • the present invention has been made on the basis of this knowledge and refers to a use of a titanium alloy as stated in the claims.
  • the present application discloses titanium alloys as described in (1) to (7) below.
  • the titanium alloy disclosed in the present application has high corrosion resistance, the corrosion resistance particularly in a bromine-ion-containing environment. Further, in a case of using Ru, which is an inexpensive platinum group element, the raw material cost of the titanium alloy becomes low. In a case in which the content of the platinum group element is high (for example, higher than 0.05 mass%), when a damage such as a removal of a passivation film is generated on the surface by a scratch or the like, corrosion starting from the damage is unlikely to propagate.
  • the titanium alloy contains, instead of part of Ti, one or more selected from the group consisting of Ni, Co, Mo, Cr, V, and W, the resistance to a high-concentration chloride environment containing bromine is also obtained.
  • Y is inexpensive among rare earth elements. In a case in which Y is contained as the rare earth element, the raw material cost becomes low.
  • the titanium alloy used in the present invention consists of, in mass%, a platinum group element: greater than or equal to 0.01 % and less than or equal to 0.10%, a rare earth element: greater than or equal to 0.001% and less than 0.02%, O: greater than or equal to 0% and less than 0.1%, and the balance: Ti and impurities.
  • a platinum group element greater than or equal to 0.01 % and less than or equal to 0.10%
  • a rare earth element greater than or equal to 0.001% and less than 0.02%
  • O greater than or equal to 0% and less than 0.1%
  • Ti and impurities Ti and impurities.
  • Platinum group elements have an effect of decreasing a hydrogen overvoltage of a titanium alloy and of maintaining a natural potential in a passivation area.
  • the titanium alloy according to the present invention contains Ru, for example. Ru is less expensive than other platinum group elements and is preferable to secure economic efficiency The market price of Ru was about 1/6 of that of Pd as of January in 2012.
  • the content of the platinum group element is 0.01 to 0.10 mass%.
  • corrosion resistance of the titanium alloy may be insufficient and corrosion may occur in a high-temperature and high-concentration chloride aqueous solution.
  • the content of the platinum group element is higher than 0.10 mass%, an increase in corrosion resistance is not expected, and in addition, the raw material cost becomes high and processability becomes poor.
  • the content of the platinum group element having a ⁇ -stabilizing function, such as Ru is preferably set to 0.01 to 0.05 mass%, for example.
  • the titanium alloy according to the present invention in which the content of the platinum group element is in this range, has corrosion resistance as high as a conventional titanium alloy in which the content of the platinum group element is higher than 0.05 mass%.
  • the Ru precipitation condensation propagates more immediately on a fresh surface generated by the scratch or the like as the content of Ru is higher in the titanium alloy, as described above by taking the Ti-Ru alloy as an example.
  • the titanium alloy according to the present invention is suitable for a usage in a harsh environment where a damage can be generated in the passivation film.
  • the present inventors have considered to add, to a Ti-0.04 mass% Ru alloy, a minute amount of various elements that are likely to be melted in an environment of a high-temperature and high-concentration chloride aqueous solution.
  • a titanium alloy containing such elements was immersed in a chloride aqueous solution to be melted in the active state area.
  • the present inventors have investigated whether an effect of shifting the potential of the entire alloy to the passivation area is obtained by promoting the Ru precipitation condensation on the surface of the titanium alloy. As a result, rare earth elements are confirmed as elements having this effect.
  • the titanium alloy containing Ru and the rare earth element can efficiently precipitate Ru on the surface. Even when a melted amount (corrosion amount) of the entire titanium alloy is small, and the titanium alloy containing Ru and the rare earth element can efficiently precipitate Ru and has high corrosion resistance. Note that although the description is made on Ru, another platinum group element such as Pd is similarly considered to have an effect of increasing the resistance to corrosion caused by bromine.
  • Rare earth elements include Sc, Y, light rare earth elements (La to Eu), and heavy rare earth elements (Gd to Lu). According to the present inventors' study, any of the rare earth elements has the above described effect. Further, it is not necessary to add only one element as the rare earth element. The above described effect has been confirmed also in a case of using a mixture or compound of rear earth elements, such as a mixture of rare earth elements (also referred to as mischmetal or "Mm” below) before separation purification or a didymium alloy (alloy including Nd and Pr).
  • a mixture or compound of rear earth elements such as a mixture of rare earth elements (also referred to as mischmetal or "Mm” below) before separation purification or a didymium alloy (alloy including Nd and Pr).
  • La, Ce, Nd, Pr, Sm, Mm, a didymium alloy, Y (Y is particularly preferable), which are easily obtained and relatively inexpensive among rare earth elements.
  • Any Mm and didymium alloy that are commercially available can be used for the present invention regardless of the component ratio of rare earth element(s).
  • the range of the content of the rare earth element(s) in the titanium alloy according to the present invention is greater than or equal to 0.001 and less than 0.02 mass%.
  • the content of the rare earth element(s) is 0.001 mass% or more, in a passivation area of a Ti- alloy, it is possible to melt Ti, the platinum group element, and the rare earth element(s) simultaneously in a chloride aqueous solution, and to obtain a sufficient effect of promoting the precipitation of the platinum group element on the surface of the alloy.
  • the upper limit of the content of the rare earth element(s) is set to less than 0.02 mass% because the content of the rare earth element(s) being more than this limit does not increase the above effect, and in addition, a compound that is not produced in a case of not adding the rare earth element(s) may be produced in the Ti alloy. This compound is melted preferentially in a chloride aqueous solution, and generates pit-like corrosion in the Ti-platinum group element. Accordingly, the Ti-platinum group element alloy in which this compound is produced has lower corrosion resistance than in a case of not adding the rare earth element(s).
  • the content of the rare earth element(s) in the Ti-platinum group element alloy is preferably set to the solid solubility limit or less in ⁇ -Ti, the solid solubility limit being shown in a phase diagram or the like.
  • the solid solubility limit of Y in ⁇ -Ti is 0.02 mass% (0.01 at%). Accordingly, it is preferable that the content of Y is less than 0.02 mass% in a case of adding Y.
  • the solid solubility of La in ⁇ -Ti is extremely high, which is 2.84 mass% (1 at%) according to Non-Patent Document 4 above.
  • the content of La is set to less than 0.02 mass%.
  • the titanium alloy according to the present invention contains O in less than 0.1 mass%.
  • the content of O is set to less than 0.1 mass% because corrosion resistance and favorable processability are secured.
  • Ti has high solid solubility of oxygen, so that Ti having high solid solubility of oxygen (JIS type-2 to type-4 titanium) is intentionally used for a usage for which high strength is required. Indeed the solid solution of oxygen is effective in increasing the strength, but it may degrade processability. Accordingly, considering processability in addition to corrosion resistance and economic efficiently, the upper limit of the content of O is set to 0.1 mass%. For a usage that does not need high strength or a usage that puts much value on processability, the content of O is preferably set to less than 0.05 mass%.
  • the titanium alloy according to the present invention may contain, instead of part of Ti, one or more of Ni, Co, Mo, V, Cr, and W.
  • the titanium alloy in combination with the effects of the platinum group element and the rare earth element(s), the titanium alloy can have higher corrosion resistance in a bromine-ion-containing environment.
  • the contents thereof are as follows: Ni: 1.0 mass% or less, Co: 1.0 mass% or less, Mo: 0.5 mass% or less, V: 0.5 mass% or less, Cr: 0.5 mass% or less, and W: 0.5 mass% or less.
  • impurities in the titanium alloy include Fe, O, C, H, N, Al, Zr, Nb, Si, Sn, Mn, and Cu.
  • Fe, O, C, H, and N are mixed from a raw material, a melting electrode, and an environment, and Al, Zr, Nb, Si, Sn, Mn, and Cu are mixed in a case of using scrap as a raw material.
  • These impurities may be mixed without any problem as long as the amount thereof is as small as not to impede the effects of the present invention seriously.
  • the amounts of the impurities being as small as not to impede the effects of the present invention seriously are as follows: Fe: 0.3 mass% or less, O: less than 0.1 mass%, C: 0.18 mass% or less, H: 0.015 mass% or less, N: 0.03 mass% or less, Al: 0.3 mass% or less, Zr: 0.2 mass% or less, Nb: 0.2 mass% or less, Si: 0.02 mass% or less, Sn: 0.2 mass% or less, Mn: 0.01 mass% or less, and Cu: 0.1 mass% or less.
  • the total amount of these elements is 0.6 mass% or less.
  • Table 1 shows samples that were used for the tests and composition thereof (analytical values are shown for elements other than Ti, and Ti is the balance (bal.)).
  • Comparative material 1 1 0.14 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.109 0.006 0.0018 0.0077 0.073 - - Bal.
  • Comparative material 2 2 0.06 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.07 0.006 0.0042 0.005 0.036 - - Bal.
  • Comparative material 3 3 - 0.054 0.52 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.004 0.001 0.003 0.03 - - Bal.
  • Comparative material 4 4 - 0.052 0.01 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.06 0.006 0.0022 0.005 0.04 - - Bal.
  • Present invention example 1 (claim 1) 5 - 0.042 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.005 0.0021 0.006 0.03 0.005 - Bal.
  • Present invention example 2 (claim 1) 6 - 0.049 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.08 0.006 0.0032 0.004 0.03 0.004 - Bal.
  • Present invention example 3 (claim 1) 7 - 0.087 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.005 0.0022 0.006 0.04 - 0.01 Bal.
  • Present invention example 4 (claim 1) 8 - 0.013 ⁇ 0.01 ⁇ 0.01 ⁇ 0.03 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.007 0.0028 0.006 0.03 0.01 - Bal.
  • Example beyond invention range 1 9 - 0.048 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.12* 0.007 0.0033 0.004 0.03 0.01 - Bal.
  • Example beyond invention range 2 10 - 0.004* ⁇ 0.01 ⁇ 0.01 ⁇ 0.03 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.006 0.0034 0.006 0.04 0.01 - Bal.
  • Example beyond invention range 3 11 - 0.043 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.007 0.0044 0.005 0.04 - 0.12* Bal.
  • Present invention examples 5 (claim 2) 12 - 0.025 0.12 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.03 0.008 0.002 0.005 0.02 0.01 - Bal.
  • Present invention example 6 (claim 2) 13 - 0.027 ⁇ 0.01 ⁇ 0.01 0.18 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.007 0.003 0.006 0.03 0.01 - Bal.
  • Present invention example 7 (claims 2) 14 - 0.028 ⁇ 0.01 0.18 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.04 0.008 0.003 0.006 0.04 - 0.01 Bal.
  • Present invention example 8 (claim 2) 15 - 0.029 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.11 ⁇ 0.01 ⁇ 0.01 0.03 0.006 0.004 0.005 0.03 0.01 - Bal.
  • Present invention example 9 (claims 2) 16 - 0.028 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.14 ⁇ 0.01 0.04 0.006 0.005 0.006 0.03 0.015 - Bal.
  • Present invention example 10 (claim 2) 17 - 0.027 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 0.19 0.03 0.007 0.004 0.005 0.03 0.01 - Bal.
  • Comparative materials which are conventional materials (sample numbers 1 to 4); Present invention examples (sample numbers 5 to 8 each corresponding to claim 1, and sample numbers 12 to 18 each corresponding to claim 2); Examples beyond the range of the present invention, which are not conventional materials (hereinafter simply referred to as “Examples beyond invention range", sample numbers 9 to 12).
  • Comparative materials 1 to 3 were obtained from the market, and the other samples (including Comparative material 4) were fabricated in a laboratory.
  • Comparative material 4 was obtained by employing the composition of the Ti-Ru alloy disclosed in Patent Document 3 above, which is described as "having high crevice corrosion resistance and bendability".
  • Comparative material 1 is Gr. 7
  • Comparative material 2 is Gr. 17
  • Comparative material 3 is Gr. 13.
  • Each of Comparative materials 1 to 4 is an alloy that does not contain a rare earth element.
  • the content of the rare earth element(s) is less than 0.02 %.
  • Example beyond invention range 1 being beyond the range of the present invention in that the O content exceeds 0.10 mass%.
  • Example beyond invention range 2 being beyond the range of the present invention in that the Ru content is less than 0.01 mass%.
  • Example beyond invention range 3 being beyond the range of the present invention in that the content of the rare earth element(s) is 0.02 mass% or more.
  • Raw materials used for the fabrication of the titanium alloys were commercially available pure Ti sponge (JIS type-1) for industrial use, ruthenium (Ru) powder (purity 99.9 mass%) produced by Kishida chemical Co., Ltd., turning yttrium (Y) (purity 99.9 mass%) produced by Kishida chemical Co., Ltd., and a massive form Mm (mixed rare earth elements).
  • the ratio of rare earth elements in Mm was as follows: La: 28.6 mass%, Ce: 48.8 mass%, Pr: 6.4 mass%, and Nd: 16.2 mass%.
  • the raw materials were measured to be in the predetermined ratio for each sample to be fabricated, and were melted (molten) in an argon atmosphere by an arc melting furnace to fabricate five ingots (each of which weighs 80 g). Then, all the five ingots were re-melted together to fabricate square ingots each having a thickness of 15 mm. Each of the square ingots was re-melted for homogenization to fabricate square ingots each having a thickness of 15 mm again. That is, melting was performed three times in total.
  • the square ingot subjected to heat treatment was rolled under the following conditions to obtain a sheet material having a thickness of 2.5 mm.
  • ⁇ -phase region hot rolling rolling was performed with a heating temperature of 1000 °C to reduce the thickness from 15 mm to 9 mm.
  • ⁇ + ⁇ -phase region hot rolling rolling was performed on the sheet material, subjected to the ⁇ -phase region hot rolling, with a heating temperature of 875 °C to reduce the thickness from 9 mm to 2.5 mm.
  • the sheet material obtained by rolling was annealed in vacuum at 750 °C for 30 minutes to remove strain.
  • test pieces to be used for the following tests were obtained by machining.
  • FIG. 2 is schematic diagrams showing a test piece for a crevice corrosion resistance tests, and (a) shows a plan view and (b) shows a side view. As shown in the figures, this test piece haf a thickness of 2 mm, a width of 30 mm, and a length of 30 mm. A hole having a diameter of 7 mm was formed in the center of the test piece. Further, on one surface (front surface) of the test piece was polished using an emery paper with a grit of 600.
  • FIG. 3 is a schematic diagram showing a state of a test piece used in a crevice corrosion resistance test.
  • a test piece 1 was interposed between clevises (spacers) 2 formed of poly-trifluoroethylene.
  • a hole was formed in the center of each of the clevises so as to correspond to the hole in the test piece 1.
  • On one surface of the clevis 2 a plurality of trenches were formed, and the surface including the trenches were made to be in contact with the test piece 1. The trench formed a crevice between the test piece 1 and the clevis 2.
  • a bolt 3 was inserted into the hole of the test piece 1 and the clevis 2, and a nut 4 was attached to the bolt 3, so that the test piece 1 and the clevises 2 were tightened.
  • the bolt 3 and the nut 4 were obtained by oxidizing the surface of a bolt and a nut which were made of pure titanium, by heat treatment in air.
  • the torque at the time of tightening was 40 kgf ⁇ cm.
  • the weight per test piece before the test was about 7 g.
  • the processability of a material was evaluated by bending tests and tension tests.
  • the test conditions were as follows.
  • the test piece was obtained in the following manner.
  • a sheet material having a thickness of 2.0 mm to 2.5 mm was extended to a thickness of 0.5 mm by rolling and then was annealed.
  • a fragment having a size and a shape which are based on JIS Z 2204 (a width of 20 mm and a length of 60 mm) was cut out, and a surface of the fragment was polished by an emery paper with a grit of 600 in the rolling direction and the perpendicular direction.
  • the bending tests were performed by a method based on JIS Z 2248, and T-direction adhesion bendability was evaluated.
  • test pieces 1 for the above crevice corrosion resistance tests which were not used in the crevice corrosion resistance tests, two test pieces each having half the size of ASTM with a thickness of 2 mm were cut out in a direction parallel to the rolling longitudinal direction.
  • the cut out test pieces were subjected to tension tests by using an autograph tension tester manufactured by Shimadzu Cooperation.
  • the tension rate was 0.5%/min up to the bearing force, and was 5 mm/min thereafter.
  • An average value of breaking extension measured for the two test pieces was set as a stretch of that test piece in an L direction.
  • Table 2 shows results of the crevice corrosion resistance tests.
  • Present invention examples have high corrosion resistance (crevice corrosion resistance) both in a chloride environment that does not contain bromine ions substantially and a chloride environment containing bromine ions.
  • Table 3 shows results of bendability tests (sealing-bending) and tension tests.
  • Comparative materials 1 and 3 breaks were generated by sealing-bending in the T-direction and stretches in the L-direction were small. That is, the bendability of Comparative materials 1 and 3 was low.
  • Comparative material 2 a break was not seen in sealing-bending in the T-direction and the stretch in the L-direction was as large as that of a JIS type-1 material.
  • Comparative material 4 although the stretch in the L-direction was as high as that of a JIS type-1 material, a fine break was seen on the surface of the test piece in sealing-bending in the T-direction.
  • Example beyond invention range 1 the stretch in the L-direction was poor and a break was generated in sealing-bending in the T-direction.
  • Example beyond invention range 2 both results of sealing-bending in the T-direction and the stretch in the L-direction were favorable.
  • Example beyond invention range 3 although the stretch in the L-direction was large, a break was generated in sealing-bending in the T-direction.
  • the processability tends to increase as the O content is lower and the contents of Ni, Cr, Co, Mo, W, and V are lower.
  • Each of Present invention examples 1, 3, and 4 has more favorable processability than Present invention example 2 possibly because the O content of Present invention examples 1,3, and 4 was less than 0.05 mass% whereas the O content of Present invention example 2 was 0.05 mass% or more (however, the O content is less than 0.1 mass% and is within the region of the present invention).
  • Each of Present invention examples 5 to 11 has lower processability than Present invention examples 1, 3, and 4 possibly because each of Present invention examples 5 to 11 contains any of Ni, Cr, Co, Mo, W, and V.
  • Example beyond invention range 3 exceeded the range of the content of the rare earth element(s) in the present invention (0.01 to 0.10 mass%), and a compound containing a rare earth element was produced in this sample.
  • the break generated by sealing-bending in the T-direction of Example beyond invention range 3 was assumed to have started from this compound.
  • Table 4 shows calculation results of cost of a platinum group element in the price of row materials, based on the ratio of the platinum group element contained in the samples.
  • the price of the bare metal of the platinum group element was set to ⁇ 1905/g for Pd and ⁇ 300/g for Ru.
  • Cost of platinum group element means the cost ( ⁇ ) of the platinum group element in 1 kg of the titanium alloy
  • Relative cost of platinum group element means the cost ratio of the platinum group element in each sample when the cost of the platinum group element of Comparative material 1 is set to 100.
  • the cost of the platinum group element of each Present invention example is 1/10 or less of the cost of the platinum group element of Comparative material 1, and is 1/4 or less of the cost of the platinum group element of Comparative material 2.
  • Table 5 shows results of the overall evaluation of Comparative materials and Present invention examples.
  • Crevice corrosion resistance Processability Economic efficiency Overall evaluation Environment not containing bromine ions substantially Environment containing bromine ions Comparative material 1 A C C C - Comparative material 2 A C A C - Comparative material 3 A C C A - Comparative material 4 C C B A - Present invention examples A A A to B A A
  • the processability of the present invention may become relatively poor in some cases (such as in Present invention example 2). Further, the processability is considered to become poor in a case in which the content of O is 0.05 mass% or more or in a case in which Ni, Cr, Co, Mo, W, or V is contained. Accordingly, in a case of being used in a usage that puts much value on processability, the titanium alloy according to the present invention has the O content of less than 0.05 mass% and does not contain Ni, Cr, Co, Mo, W, and V substantially.
  • the present invention is excellent in all the items.
  • Comparative materials are poor in any of the evaluation items.
  • none of Comparative materials has crevice corrosion resistance that is high enough to be used substantially in a bromine-ion-containing environment.
  • Table 6 shows compositions of titanium alloys used in Example 2. In accordance with the method for manufacturing the samples shown in Example 1, alloys having the compositions shown in Table 6 were obtained. [Table 6] Type Rare earth element Platinum group element Ni Cr Co Mo W V O C H N Fe Bal.
  • Comparative materials 5 and 6 contain a rare earth element in less than 0.001 %, and is beyond the range of the present invention. From the materials shown in Table 6, a titanium alloy sheet for crevice corrosion tests in FIG. 2 was obtained by machining, and using the test piece, the crevice corrosion test piece shown in FIG. 3 was formed. Note that the torque at the time of tightening was 40 kgf ⁇ cm. This crevice corrosion test piece was used in each crevice corrosion test in a bromine-ion-containing environment described in 1-2-3.
  • Table 7 shows results obtained by performing 500-hour crevice corrosion tests.
  • Comparative material 5 which does not contain a rare earth element, crevice corrosion was seen in a large number of portions, and the decrease due to corrosion was 325 mg.
  • Comparative material 6 which does not contain a sufficient rare earth element, crevice corrosion was also seen, and the decrease due to corrosion was 32 mg.
  • a desirable content of rare earth element(s) is 200 ppm or less in a bromide-ion-containing environment.
  • the content of the rare earth element in each of Present invention examples 12 to 15 was within the range of the present invention, and accordingly, crevice corrosion did not occur, and the decrease in weight thereof due to corrosion was small.
  • crevice corrosion test pieces of materials of Present invention examples 16 to 19 having different contents of Ru were used in crevice corrosion tests in the bromine-ion-containing environment shown in 1-2-3. Further, Eriksen tests based on JIS Z 2247 were performed to investigate the press formability of the materials.
  • the titanium alloy used in the present invention can be applied to equipment, apparatuses, and the like that are to be used in an environment that requires corrosion resistance in a bromine-ion-containing environment (in particular, a high-temperature and high-concentration chloride environment).

Claims (6)

  1. Utilisation d'un alliage de titane, dans laquelle l'alliage de titane consiste, en % massique, en
    un élément du groupe du platine : supérieur ou égal à 0,01 % et inférieur ou égal à 0,10%,
    un élément des terres rares : supérieur ou égal à 0,001 % et inférieur à 0,02 %,
    O : supérieur ou égal à 0 % et inférieur à 0,1 %, et contient éventuellement, à la place d'une part de Ti, un ou plusieurs choisis dans le groupe constitué par Ni, Co, Mo, V, Cr et W,
    dans laquelle
    la teneur en Ni est inférieure ou égale à 1,0 % massique,
    la teneur en Co est inférieure ou égale à 1,0 % massique,
    la teneur en Mo est inférieure ou égale à 0,5 % massique,
    la teneur en V est inférieure ou égale à 0,5 % massique,
    la teneur en Cr est inférieure ou égale à 0,5 % massique, et
    la teneur en W est inférieure ou égale à 0,5 % massique, et
    le reste : du Ti et des impuretés, pour conférer une résistance à la corrosion dans un environnement contenant des ions brome.
  2. Utilisation selon la revendication 1, dans laquelle, en % massique,
    l'élément du groupe du platine est supérieur ou égal à 0,01 % et inférieur ou égal à 0,05%.
  3. Utilisation selon l'une quelconque des revendications 1 et 2, dans laquelle l'élément du groupe du platine est Ru.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle l'élément des terres rares est Y.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, dans laquelle la teneur en O est inférieure à 0,05 % massique.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, dans laquelle l'alliage de titane est utilisé dans un dispositif d'usine chimique.
EP14743073.0A 2013-01-25 2014-01-24 Alliage de titane possédant une excellente résistance à la corrosion dans un environnement contenant des ions bromure Active EP2889386B1 (fr)

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PCT/JP2014/051550 WO2014115845A1 (fr) 2013-01-25 2014-01-24 Alliage de titane possédant une excellente résistance à la corrosion dans un environnement contenant des ions bromure

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CN108467970B (zh) * 2018-03-23 2020-12-25 中国石油天然气集团公司管材研究所 一种用于高腐蚀性油气开发的含铁钛合金管及其制备方法
CN108893651A (zh) * 2018-07-25 2018-11-27 中南大学 一种高强高韧耐蚀性钛合金及其制备方法
CN110747372B (zh) * 2019-09-04 2021-03-12 宝钛集团有限公司 100％返回炉料制备低成本高强度钛合金板材及其制备方法
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US20150240332A1 (en) 2015-08-27
CN104955970B (zh) 2017-03-08
JPWO2014115845A1 (ja) 2017-01-26
WO2014115845A1 (fr) 2014-07-31
JP5660253B2 (ja) 2015-01-28
EP2889386A1 (fr) 2015-07-01
EP2889386A4 (fr) 2016-04-20
CN104955970A (zh) 2015-09-30

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