CN101892402A - Titanium alloy material and structural member and container for radioactive waste - Google Patents
Titanium alloy material and structural member and container for radioactive waste Download PDFInfo
- Publication number
- CN101892402A CN101892402A CN201010180682.0A CN201010180682A CN101892402A CN 101892402 A CN101892402 A CN 101892402A CN 201010180682 A CN201010180682 A CN 201010180682A CN 101892402 A CN101892402 A CN 101892402A
- Authority
- CN
- China
- Prior art keywords
- quality
- titanium alloy
- alloy material
- environment
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F5/00—Transportable or portable shielded containers
-
- 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
Abstract
Provide a kind of at the neutral chloride environment of sulphuric acid environment, high temperature or contain in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical, low-cost and given play to the titanium alloy material of excellent erosion resistance, with the structural member that uses this titanium alloy material, and the container for radioactive waste that uses this titanium alloy material.A kind of titanium alloy material wherein, contains Ru:0.005～0.10 quality %, Pd:0.005～0.10 quality %, Ni:0.01～2.0 quality %, Cr:0.01～2.0 quality %, V:0.01～2.0 quality %, and surplus is made of Ti and unavoidable impurities.In addition, structural member and container for radioactive waste use this titanium alloy material.
Description
Technical field
The present invention relates to the titanium alloy material of low-cost excellent corrosion resistance, particularly be adapted at the neutral chloride environment of sulphuric acid environment, high temperature or contain the titanium alloy material that uses in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical, with the structural member that uses this titanium alloy material, and the container for radioactive waste that uses this titanium alloy material.
Background technology
Because the titanium excellent corrosion resistance, so in the chemical plant, various fields such as marine structure, building materials are used.The erosion resistance of titanium largely exists with ... in environment for use the stability of formed passive state epithelium on the surface.Titanium forms stable passive state epithelium, thereby has given play to excellent corrodibility in the normal temperature chloride environment of the oxidizing acid of nitric acid etc. and seawater etc. on the surface.But non-oxidizing environment (sulfuric acid, high density salt solution etc.) is because oxidizing power is little, thus insufficient based on the formation of the stable passive state epithelium of titanium oxide, the so not good situation of erosion resistance is arranged.
In order to tackle the problem of the erosion resistance in so non-oxidizable environment, develop and a kind ofly in titanium, add various alloying elements and further improve the alloy of erosion resistance.For example, the Ti-Pd alloy is the also excellent alloy of erosion resistance in non-oxidizable environment, and this is that the passive state epithelium is in more stable status because Pd shuffles the current potential of titanium.Industrial Ti-0.15 quality %Pd alloy is turned to Grade7 or the Grade11 of ASTM by specification, uses in the field of petroleum refining that requires high erosion resistance and petroleum chemical plant etc.But Ti-0.15 quality %Pd alloy causes the such problem of material cost rising owing to will add the Pd of high price comparatively in large quantities so have.
As more cheap and given play to the titanium alloy of excellent erosion resistance, develop a kind of Ti alloy, its compound interpolation is identical with Pd, bringing into play by the current potential platinum group metal element of the corrosion-resistant raising effect brought of shuffling, and is added with other alloying elements in addition.For example exploitation has Ti-0.05 quality %Pd-0.3 quality %Co alloy, is turned to Grade30, the Grade31 of ASTM by specification.In patent documentation 1, disclose a kind of titanium alloy that is added with platinum group metal element, Cr, Ni in addition, in patent documentation 2, disclosed a kind of titanium alloy that improves erosion resistance by suitableization of ratio that makes Pd and Pd platinum group metal element in addition.
[patent documentation 1] spy opens flat 4-308051 communique
[patent documentation 2] spy opens the 2000-248324 communique
Yet there are the following problems in existing titanium alloy material.
Usually, when using titanium alloy as the building materials in atmospheric environment, though there are not problems such as significant spot corrosion and crevice corrosion, but exist because the situation that the surface discolouration that corrosion causes occurs as the problem points on the view, countermeasure as at the acid rain environment that exposes industrial belt in sulfuric acid etc. to the open air also requires low-cost erosion resistance down further to improve.
In addition, the demand height of titanium alloy in the neutral chloride environment of the pyritous such as heat-transfer pipe in the condenser of firepower, atomic power plant and seawater fresh water chemical plant, and its environment for use is harsh, requires erosion resistance further to improve.Muriate particularly takes place under the dirt settling of structural slit formation portion and titanium alloy surface concentrate, thereby it is a lot of that the such situation of crevice corrosion takes place, this just requires the raising of slit and corrosion resistant.
In addition, be used for transporting or handle by nuclear fuel manufacturing facility, atomic power plant, the nuclear fuel container of the radioactive waste that produces of the nuclear power related facility of treatment facility etc. again, because the heating of radioactive waste, the metallic surface temperature that causes container is up to the situation more than 100 ℃.So can envision, when transportation or processing, along with moisture evaporation, vessel surface can form as spissated highly concentrated solutions such as the muriate of the corrosion promotion factor and fluorochemicals, thereby becomes harsh corrosive environment.In addition, known fluorochemical is that acidic region below 6 makes the titanium corrosion at pH, and also there is problem in the erosion resistance that contains under the acid chlorization substance environment of fluorochemical.
Summary of the invention
The present invention does in view of problem point, its purpose is, provide a kind of at the neutral chloride environment of sulphuric acid environment, high temperature or contain in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical, low-cost and given play to the titanium alloy material of excellent erosion resistance, with the structural member that uses this titanium alloy material, and the container for radioactive waste that uses this titanium alloy material.
Present inventors improve for the erosion resistance in the non-oxidizable environment and study, and found that as the platinum group metal element, the compound interpolation of Ru and Pd is the most effective, in addition by add Ni, Cr, V makes erosion resistance reach best.Concrete situation is as follows.
The compound interpolation of Ru and Pd, its effect that has shuffle the current potential of titanium as described above, form the stable passive state epithelium based on titanium oxide on the surface.At this moment, with compound interpolation Ni of Ru, Pd while, Cr, V, the Ru of the titanium alloy surface in the non-oxidizable environment and the surface of Pd concentrate and are promoted that even Ru and Pd are after a little while, the formation effect of stable passive state epithelium also will be brought into play significantly.Also having, even Ni also can form stable oxide under non-oxide generation environment, is the element that helps erosion resistance to improve.In addition, Ni, Cr, V form the protection epithelium of stable complex fluoride at titanium alloy surface in containing the environment of fluorochemical, help erosion resistance to improve.By above such synergy that respectively adds element, think to show excellent erosion resistance.
Also find in addition, except aforesaid element, add Al, Si in right amount, Fe improves effectively for the erosion resistance of fluorochemical, in addition, by an amount of interpolation Os, Rh, Ir, Pt, can access more excellent erosion resistance.
Promptly, titanium alloy material of the present invention, wherein, contain Ru:0.005～0.10 quality %, Pd:0.005～0.10 quality %, Ni:0.01～2.0 quality %, Cr:0.01～2.0 quality %, V:0.01～2.0 quality %, surplus is made of Ti and unavoidable impurities.
According to such formation, titanium alloy material contains Ru and Pb with specified amount, and the current potential of titanium is shuffled, and forms on the surface based on the stable passive state epithelium of titanium oxide.In addition, contain Ni, Cr, V, in non-oxidizable environment by specified amount; the Ru of titanium alloy surface and the surface of Pd concentrate and obtain promoting; the formation of stable passive state epithelium is promoted, in containing the environment of fluorochemical, forms the protection epithelium of stable complex fluoride at titanium alloy surface in addition.In addition, contain Ni by specified amount, titanium alloy surface forms stable oxide in non-oxidizable environment.
Titanium alloy material of the present invention preferably also contains select at least a from Al:0.005～2.0 quality %, Si:0.005～2.0 quality % and Fe:0.005～2.0 quality %.
According to such formation, titanium alloy material is by optionally further containing Al, Si, Fe with specified amount, further improves for the erosion resistance of fluorochemical, and intensity also improves in addition.
Titanium alloy material of the present invention preferably also contains select among Os:0.005～0.10 quality %, Rh:0.005～0.10 quality %, Ir:0.005～0.10 quality % and the Pt:0.005～0.10 quality % at least a.
According to such formation, titanium alloy material is by optionally containing Os, Rh, Ir, Pt again with specified amount, and the current potential of titanium is shuffled, and forms on the surface based on the stable passive state epithelium of titanium oxide.Thus, the erosion resistance in the non-oxidizable environment further improves.
Structural member of the present invention uses aforesaid titanium alloy material.
According to such formation, because that uses is at sulphuric acid environment, the neutral chloride environment of high temperature or contains the titanium alloy material of the excellent corrosion resistance in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical, so can become the structural member of the excellent corrosion resistance in the non-oxidizable environment.
Container for radioactive waste of the present invention uses aforesaid titanium alloy material.
According to such formation, because that uses is at sulphuric acid environment, the neutral chloride environment of high temperature or contains the titanium alloy material of the excellent corrosion resistance in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical, so can become the container for radioactive waste that also can adapt in the harsh corrosive environment that radioactive waste forms.
Titanium alloy material of the present invention is at the neutral chloride environment of sulphuric acid environment, high temperature or contain in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical and still given play to excellent erosion resistance.In addition, cost is low, and economy is also excellent.
Structural member of the present invention can be applicable to the parts of the petroleum refining that exposes to the open air in non-oxidizable environment and petroleum chemical plant, marine structure, building materials etc., for example the heat-transfer pipe in the condenser of firepower, atomic power plant and seawater fresh water chemical plant etc.
Container for radioactive waste of the present invention even also can adapt to, therefore is suitable as the container of transportation and processing radioactive waste in the harsh corrosive environment that radioactive waste forms.
Description of drawings
Fig. 1 (a)～(d) is the mode chart that expression is used for the test film of embodiment.
[nomenclature]
A test film (TP-A)
B test film (TP-B)
C crevice corrosion test sheet
Embodiment
Next, be described in detail for titanium alloy material of the present invention and structural member and container for radioactive waste.
(titanium alloy material)
Titanium alloy material of the present invention, Ru:0.005～0.10 quality %, Pd:0.005～0.10 quality %, Ni:0.01～2.0 quality %, Cr:0.01～2.0 quality %, V:0.01～2.0 quality %, surplus is made of Ti and unavoidable impurities.
Titanium alloy also can be further contains select among Al, Si and the Fe at least a with specified amount, in addition also can contain select at least a again from Os, Rh, Ir and Pt with specified amount.
Below, describe for the qualification reason of composition.
(Ru:0.005～0.10 quality %)
Ru makes the current potential of titanium shuffle in non-oxygenated environment, is effectively to add element for the stable passive state epithelium that forms based on titanium oxide at titanium alloy surface.In order to bring into play such effect, need make it to contain more than the 0.005 quality %.On the other hand, if Ru content surpasses 0.10 quality %, then this effect is saturated, because Ru is the element of high price, is not preferred for the cost this point therefore.Therefore, Ru content is 0.005～0.10 quality %.Also have, Ru content is preferably more than the 0.008 quality %, more preferably more than the 0.010 quality %.In addition, be preferably below the 0.095 quality %, more preferably below the 0.090 quality %.
(Pd:0.005～0.10 quality %)
It is effectively to add element for the stable passive state epithelium that forms based on titanium oxide at titanium alloy surface that Pd makes the current potential of titanium shuffle in non-oxidizable environment, and particularly by making it the coexistence with Ru, this effect is remarkable.In order to bring into play the effect like this of Pd, need make it to contain more than the 0.005 quality %.On the other hand, if Pd content surpasses 0.10 quality %, then this effect is saturated, because Pd is the element of high price, is not preferred for the cost this point therefore.Therefore, Pd content is 0.005～0.10 quality %.Also have, Pd content is preferably more than the 0.008 quality %, more preferably more than the 0.010 quality %.In addition, be preferably below the 0.095 quality %, more preferably below the 0.090 quality %.
(Ni:0.01～2.0 quality %)
Ni be by with the coexistence of Cr and V, in non-oxidizable environment, promote the surperficial spissated element of Ru and Pd.Ni is the element that forms stable oxide in non-oxidizable environment at titanium alloy surface in addition, and this is external to contain in the environment of fluorochemical, and it forms the protection epithelium of stable complex fluoride at titanium alloy surface, is the element that helps erosion resistance to improve.In order to bring into play such effect, need make it to contain more than the 0.01 quality %.Yet, if the addition surplus, weldability and hot workability deterioration, so Ni content is below the 2.0 quality %.Therefore, Ni content is 0.01～2.0 quality %.Also have, Ni content is preferably more than the 0.03 quality %, more preferably more than the 0.05 quality %.In addition, be preferably below the 1.95 quality %, more preferably below the 1.90 quality %.
(Cr:0.01～2.0 quality %)
Cr be by with the coexistence of Ni and V, in non-oxidizable environment, promote the surperficial spissated element of Ru and Pd.This is external to contain in the environment of fluorochemical, and it forms the protection epithelium of stable complex fluoride at titanium alloy surface, is the element that helps erosion resistance to improve.In order to bring into play such effect, need make it to contain more than the 0.01 quality %.Yet, if the addition surplus, weldability and hot workability deterioration, so Cr content is below the 2.0 quality %.Therefore, Cr content is 0.01～2.0 quality %.Also have, Cr content is preferably more than the 0.03 quality %, more preferably more than the 0.05 quality %.In addition, be preferably below the 1.95 quality %, more preferably below the 1.90 quality %.
(V:0.01～2.0 quality %)
V be by with the coexistence of Ni and C, in non-oxidizable environment, promote the surperficial spissated element of Ru and Pd.This is external to contain in the environment of fluorochemical, and it forms the protection epithelium of stable complex fluoride at titanium alloy surface, is the element that helps erosion resistance to improve.In order to bring into play such effect, need make it to contain more than the 0.01 quality %.Yet, if the addition surplus, weldability and hot workability deterioration, so V content is below the 2.0 quality %.Therefore, V content is 0.0l～2.0 quality %.Also have, V content is preferably more than the 0.03 quality %, more preferably more than the 0.05 quality %.In addition, be preferably below the 1.95 quality %, more preferably below the 1.90 quality %.
(that selects from Al:0.005～2.0 quality %, Si:0.005～2.0 quality % and Fe:0.005～2.0 quality % is at least a)
Though Al, Si and Fe are not at hydrochloric acid and vitriolic erosion resistance effective elements, add by trace, be erosion resistance raising effective elements for fluorochemical, improving for intensity also is effective elements.In order to bring into play such effect, need make it respectively to contain more than the 0.005 quality %.But if exceedingly add, then the erosion resistance under making sour environment the deterioration, also can make processibility deterioration greatly, so its content is the upper limit with 2.0 quality % greatly.Therefore, when adding Al, Si and Fe, be respectively 0.005～2.0 quality %.Also have, Al, Si and Fe content are preferably respectively more than the 0.008 quality %, more preferably more than the 0.010 quality %.Be preferably respectively in addition below the 1.95 quality %, more preferably below the 1.90 quality %.
(that selects among Os:0.005～0.10 quality %, Rh:0.005～0.10 quality %, Ir:0.005～0.10 quality % and the Pt:0.005～0.10 quality % is at least a)
Os, Rh, Ir and Pt shuffle the current potential of titanium, promote stable passive state epithelium to form, and are the elements that helps erosion resistance to improve.In order to bring into play such effect, need make it respectively to contain more than the 0.005 quality %.But, when excessively adding, then make processibility deterioration greatly, so its content is the upper limit with 0.10 quality %.Therefore, when adding Os, Rh, Ir and Pt, be respectively 0.005～0.10 quality %.Also have, Os, Rh, Ir and Pt content are preferably respectively more than the 0.008 quality %, more preferably more than the 0.010 quality %.Os, Rh, Ir and Pt are preferably respectively below the 0.095 quality % in addition, more preferably below the 0.090 quality %.
(surplus: Ti and unavoidable impurities)
The composition of titanium alloy material as described above, surplus is made of Ti and unavoidable impurities.Unavoidable impurities can allow in the scope of all characteristics of not damaging titanium alloy material.For example, if N by about 0.03 quality %, C by about 0.08 quality %, H by about 0.02 quality %, O by about 0.3 quality %, then these elements contain no problemly, still can obtain erosion resistance of the present invention and improve effect.
(manufacture method)
Next, the example for the manufacture method of titanium alloy material of the present invention describes.
At first, fuse various metals and alloy, make titanium alloy ingot bar with aforementioned component.After the ingot bar that obtains forged with 950～1050 ℃ Heating temperature,, reach the thickness of slab of regulation with 800～900 ℃ the hot rolling of carrying out.Then, after 10～60 minutes annealing of 700～900 ℃ of enforcement, by the titanium alloy material of cold rolling making specific thickness.
(structural member)
Structural member of the present invention uses aforesaid titanium alloy material.
As described above, titanium alloy material of the present invention is at the neutral chloride environment of sulphuric acid environment, high temperature or contain excellent corrosion resistance in the non-oxidizable environment of the neutral chloride environment of high temperature etc. of fluorochemical.Can use as the parts that expose petroleum refining in this environment and petroleum chemical plant, marine structure, building materials etc. to the open air.For example, can be used in the condenser of firepower, atomic power plant and the heat-transfer pipe in seawater fresh water chemical plant etc.
(container for radioactive waste)
Container for radioactive waste of the present invention uses aforesaid titanium alloy material.
As described above, be used for transporting or handle by nuclear fuel manufacturing facility, atomic power plant, the nuclear fuel container of the radioactive waste that produces of the nuclear power related facility of treatment facility etc. again, because the heating of radioactive waste, cause the metallic surface temperature of container to reach a high temperature, form as spissated highly concentrated solutions such as muriate that corrodes the promotion factor and fluorochemicals, thereby become harsh corrosive environment.
Therefore, use titanium alloy material of the present invention, even can become the container for radioactive waste that under this harsh corrosive environment, also can adapt to.
[embodiment]
Then down, with regard to titanium alloy material of the present invention and structural member and container for radioactive waste, the comparative example that satisfies the important document of the embodiment of important document of the present invention and the invention of discontented unabridged version is compared and specifically described.
(for the making of examination material)
Use the vacuum arc melting furnace, the various metals and the alloy total of fusing raw material is about the 500g fusion, make various titanium alloy ingot bars.Chemical constitution (surplus is Ti and unavoidable impurities) as shown in table 1.After forging resulting ingot bar with 1000 ℃ Heating temperature, carry out hot rolling with 870 ℃, reach thickness of slab 5mm.Then, after 20 minutes annealing of 750 ℃ of enforcement, by the former material of titanium alloy sheet of the thick 3mm of cold rolling making.From the former material of the titanium alloy sheet that obtains downcut vertical 50mm * horizontal 30mm * thick 2mm test film A (Fig. 1 (a), TP-A), and the test film B of vertical 30mm * horizontal 30mm * thick 2mm (Fig. 1 (b), TP-B).
In addition, for trapeze test sheet when the corrosion test, open in the end of TP-A
The hole of 3mm.In addition in order to investigate the crevice corrosion characteristic, also make identical materials TP-A and TP-B are overlapped each other and with screw fastening crevice corrosion test sheet (for the examination material) C (Fig. 1 (c), (d)).Also have, in crevice corrosion test sheet C, face (slit), infiltration test solution that TP-A and TP-B are engaged, thereby salinity takes place to be concentrated and the reduction of pH value, the harsher etching condition in outside, constituent ratio slit, according to the kind of crevice corrosion test sheet, (crevice corrosion) carried out in corrosion.Crevice corrosion test sheet C is that the central authorities at TP-A and TP-B have
The hole of 5mm, and with the screw and nut fastening test film of pure titanium system.At this moment, lashing force makes the spire lining silicone tube of pure titanium screw-making apart from being 8.5Nm, presss from both sides the packing ring (PTFE packing ring) every polytetrafluoroethylene (PTFE) system again, prevents that TP-A from contacting with the dissimilar metal of screw, nut with TP-B.Also have, whole TP-A and TP-B grind whole face until SiC#600 with the wet spin grinding machine, wash with acetone and clean the back for test.
(corrosion test method)
As corrosive environment, implement the erosion resistance evaluation in following three kinds of non-oxidizable solution: (1) aqueous sulfuric acid; (2) salt solution; (3) contain the salt solution of fluorochemical.In corrosive environment (1), 5%H seethes with excitement
2SO
4Dip etching test in the aqueous solution is estimated according to the corrosion decrement of being tried to achieve by the quality change before and after the dip test.Dipping time is 72 hours.At first, in the round-bottomed flask of capacity 1L, pour testing liquid into, make it boiling with the mantle heater heating.After the solution boiling, use the silk thread suspention of PTFE system to make it dipping as test film A (TP-A) for the examination material.At this moment, cooling tube is set in flask, prevents the evaporation of solution.The liquid measure ratio of testing liquid is 1 test film (for the examination material) 1L.In this test, each 5 of the titanium alloy material of the No.1 shown in the table 1～40 difference are to calculate 5 mean value for trying, corroding decrement.Also have, the quality after the test is to wash with acetone for the test film A behind the dipping to clean, and makes it to measure after the drying again.
In corrosive environment (2), crevice corrosion test sheet (for the examination material) is immersed in the boiling 20%NaCl aqueous solution, the junction surface of investigation crevice corrosion test sheet has or not the generation crevice corrosion.At first, same with aforementioned (1), in the round-bottomed flask of capacity 1L, pour testing liquid into, make it boiling with the mantle heater heating.After the solution boiling, use the silk thread suspention of PTFE system to make it dipping as crevice corrosion test sheet C for the examination material.Dipping time is 30 days.At this moment, cooling tube is set in flask, prevents the evaporation of solution.The liquid measure ratio of testing liquid is 1 test film (for the examination material) 1L.In this test, the titanium alloy material of the No.1 shown in the table 1～40 respectively each 5 for examination, try to achieve crevice corrosion incidence (=taken place number/5 * 100 (%) of the test film of crevice corrosion).Also have, crevice corrosion has or not generation, is the crevice corrosion test sheet C after the off-test is disintegrated, cleans, and the situation of the corrosion hole that the dark 10 μ m that confirm are above is judged to be crevice corrosion and takes place.
In corrosive environment (3), carry out pH is adjusted to dip etching test in 4.0 the boiling 20%NaCl+0.01%NaF aqueous solution, estimate according to the corrosion decrement of trying to achieve by the quality change before and after the dip test.Dipping time is 30 days.At first, with room temperature an amount of HCl that adds in the 20%NaCl+0.01%NaF aqueous solution, the pH of solution is adjusted to 4.0.Then, in the round-bottomed flask of capacity 1L, pour testing liquid into, make it boiling with the mantle heater heating.After the solution boiling, use the silk thread suspention of PTFE system to make it dipping as test film A (TP-A) for the examination material.At this moment, cooling tube is set in flask, prevents the evaporation of solution.The liquid measure ratio of testing liquid is 1 test film (for the examination material) 1L.In this test, each 5 of the titanium alloy material of the No.1 shown in the table 1～40 difference are to calculate 5 mean value for trying, corroding decrement.Also have, the quality after the test is to wash with acetone for the test film A behind the dipping to clean, and makes it to measure after the drying again.
In corrosion test in these two kinds of non-oxidizable solution of salt solution of fluorochemical was contained in this (1) aqueous sulfuric acid, (3), each was that 100 o'clock relative value is represented for the corrosion decrement of examination material with the corrosion decrement of establishing No.35 (pure titanium).Then, as comprehensive evaluation, in the salt solution of (2), generation to crevice corrosion unconfirmed (the crevice corrosion probability of occurrence is 0), and aforementioned (1), (3) the corrosion decrement relative value in each acid solution is all in (corrosion decrement be below 1/50 of No.35) below 2, be erosion resistance extremely good (◎ ◎), any one is above to surpass 2 and in that (the corrosion decrement is above 1/50 of No.35 5 below, below 1/20), and be good (◎) below 5 all, any one is above to surpass 5 and in (the corrosion decrement surpasses 1/20 of No.35, below 1/10) 10 below and below 10 be better (zero) all.In addition, confirm crevice corrosion (the crevice corrosion probability of occurrence is more than 20) takes place, and in the corrosion decrement relative value in each acid solution of aforementioned (1), (3), any one above 10 (the corrosion decrement is above 1/10 of No.35) that surpass, be lower than 100 for erosion resistance bad (△), the corrosion decrement (100) of No.35 (pure titanium) is for extremely bad.
Chemical constitution for the examination material is presented in the table 1, and corrosion test result is presented in the table 2.Also have, in table 1, the underscore of drawing under numerical value of discontented unabridged version scope of invention represents that the composition that does not comprise is represented with "-".
[table 1]
[table 2]
Shown in table 1,2, the titanium alloy material of No.1～34 satisfies scope of the present invention, therefore all unconfirmed to the crevice corrosion that takes place in the salt solution, and aqueous sulfuric acid and the corrosion decrement that contains in the salt solution of fluorochemical be below 1/10 of pure titanium of No.35, obtains the result of excellent corrosion resistance.Its erosion resistance is by the compound interpolation of Ru, Pd, Ni, Cr, V and manifest.
On the other hand, the unabridged version scope of invention is discontented with in No.35～40, therefore becomes following result.
No.35 is because be pure titanium, so corrosion-resistant.
If the titanium alloy of No.36～No.40 compares with the titanium alloy of No.35, then erosion resistance improves, but confirms the generation of the crevice corrosion in the salt solution, and the reduction of corrosion decrement is also insufficient.
No.36 and No.37 are respectively that the content of Ru and Pd is lower than lower value, so how the current potential of titanium do not shuffle, and stable passive state epithelium generates insufficient, corrosion-resistant.
No.38 and No.39 and No.40 are respectively that the content of Ni, Cr and V is lower than lower value, so the surface of Ru and Pd concentrates and can not get promoting how the current potential of titanium is not shuffled that stable passive state epithelium generation is insufficient, corrosion-resistant.In addition, in containing the salt solution of fluorochemical, the generation of the complex fluoride epithelium of the Ni of protectiveness, Cr and V is insufficient, corrosion-resistant.Also have, No.38 is because the content of Ni is lower than lower value, so also do not generate stable oxide.
As above, titanium alloy material of the present invention all has excellent erosion resistance in non-oxidizable environment, be suitable as structural member.Particularly contain the erosion resistance in the salt solution of fluorochemical, (excellence of No.36～No.40) therefore is suitable as and is used for transporting or handling the container for radioactive waste that exposes to the open air at the radioactive waste that concentrates the highly concentrated solution environment that muriate and fluorochemical etc. are arranged to add titanium alloy material than existing micro-platinum group metal.
More than, with regard to titanium alloy material of the present invention and structural member and container for radioactive waste, mode of show implementing and embodiment and explain, but aim of the present invention is not limited by foregoing.Also have, content of the present invention can change widely based on aforesaid record certainly, change etc.
Claims (6)
1. titanium alloy material, it is characterized in that, contain Ru:0.005～0.10 quality %, Pd:0.005～0.10 quality %, Ni:0.01～2.0 quality %, Cr:0.01～2.0 quality %, V:0.01～2.0 quality %, surplus is Ti and unavoidable impurities.
2. titanium alloy material according to claim 1 is characterized in that, also contains at least a element of selecting from Al:0.005～2.0 quality %, Si:0.005～2.0 quality % and Fe:0.005～2.0 quality %.
3. titanium alloy material according to claim 1, it is characterized in that, also contain at least a element of from Os:0.005～0.10 quality %, Rh:0.005～0.10 quality %, Ir:0.005～0.10 quality % and Pt:0.005～0.10 quality %, selecting.
4. titanium alloy material according to claim 2, it is characterized in that, also contain at least a element of from Os:0.005～0.10 quality %, Rh:0.005～0.10 quality %, Ir:0.005～0.10 quality % and Pt:0.005～0.10 quality %, selecting.
5. a structural member is characterized in that, uses each described titanium alloy material in the claim 1～4.
6. a container for radioactive waste is characterized in that, uses each described titanium alloy material in the claim 1～4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-122409 | 2009-05-20 | ||
| JP2009122409A JP5390934B2 (en) | 2009-05-20 | 2009-05-20 | Titanium alloy material and structural member, and radioactive waste container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101892402A true CN101892402A (en) | 2010-11-24 |
| CN101892402B CN101892402B (en) | 2012-07-11 |
Family
ID=43064520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010180682.0A Expired - Fee Related CN101892402B (en) | 2009-05-20 | 2010-05-14 | Titanium alloy material, structural member, and container for radioactive waste |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20100322817A1 (en) |
| JP (1) | JP5390934B2 (en) |
| KR (1) | KR101218858B1 (en) |
| CN (1) | CN101892402B (en) |
| FR (1) | FR2945822B1 (en) |
| RU (1) | RU2452785C2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152744A (en) * | 2014-07-08 | 2014-11-19 | 宁夏东方钽业股份有限公司 | Low-cost medium-high-strength corrosion-resistant titanium alloy and processing method thereof |
| CN104520456A (en) * | 2012-08-10 | 2015-04-15 | 新日铁住金株式会社 | Titanium alloy material |
| CN105349808A (en) * | 2015-11-13 | 2016-02-24 | 无锡清杨机械制造有限公司 | Preparing method for titanium alloy panel |
| CN105551557A (en) * | 2013-07-02 | 2016-05-04 | 中科华核电技术研究院有限公司 | Middle-low-radioactivity nuclear waste treatment device |
| CN108467970A (en) * | 2018-03-23 | 2018-08-31 | 中国石油天然气集团公司管材研究所 | A kind of iron content titanium alloy tube and preparation method thereof for highly corrosive oil and gas development |
| CN108998696A (en) * | 2018-07-20 | 2018-12-14 | 中国航发北京航空材料研究院 | A kind of marine engineering equipment use in strong corrosion resistant titanium alloy |
| CN109022914A (en) * | 2018-10-09 | 2018-12-18 | 广州宇智科技有限公司 | A kind of corrosion-resistant high heat-transfer performance chemical field titanium alloy and its technique |
| CN111430057A (en) * | 2020-03-18 | 2020-07-17 | 张云逢 | High radioactive nuclear waste container |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5556585B2 (en) * | 2010-10-26 | 2014-07-23 | 株式会社Ｉｈｉ | Corrosion test apparatus and corrosion test method |
| 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 |
| US10023942B2 (en) | 2014-04-28 | 2018-07-17 | Arconic Inc. | Titanium alloy, parts made thereof and method of use |
| US20180087131A1 (en) * | 2015-03-18 | 2018-03-29 | Nippon Steel & Sumitomo Metal Corporation | Titanium alloy, separator, and polymer electrolyte fuel cell |
| RU2614229C1 (en) * | 2016-03-01 | 2017-03-23 | Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") | Titanium-based alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04365828A (en) * | 1990-07-06 | 1992-12-17 | Nikko Kyodo Co Ltd | Titanium alloy for anode |
| US5316722A (en) * | 1992-07-09 | 1994-05-31 | Kabushiki Kaisha Kobe Seiko Sho | Corrosion resistant Ti-Cr-Ni alloy containing a platinum group metal |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62107040A (en) * | 1985-11-05 | 1987-05-18 | Sumitomo Metal Ind Ltd | Titanium alloy excellent in crevice corrosion resistance |
| JPH0689423B2 (en) * | 1985-11-05 | 1994-11-09 | 住友金属工業株式会社 | Titanium alloy with excellent corrosion resistance |
| JPH0436445A (en) * | 1990-05-31 | 1992-02-06 | Sumitomo Metal Ind Ltd | Production of corrosion resisting seamless titanium alloy tube |
| JP2871867B2 (en) * | 1991-01-16 | 1999-03-17 | 株式会社神戸製鋼所 | Corrosion resistant Ti-based alloy |
| US5478524A (en) * | 1992-08-24 | 1995-12-26 | Nissan Motor Co., Ltd. | Super high vacuum vessel |
| RU2039113C1 (en) * | 1992-12-30 | 1995-07-09 | Всероссийский научно-исследовательский институт авиационных материалов | Titanium-base alloy |
| DE19962585C2 (en) * | 1998-12-28 | 2003-06-26 | Kobe Steel Ltd | Corrosion-resistant titanium alloy and components made from it |
| JP4877185B2 (en) * | 2007-10-05 | 2012-02-15 | 株式会社Ｉｈｉ | Radioactive waste disposal container and manufacturing method thereof, and radioactive waste disposal container manufacturing apparatus |
-
2009
- 2009-05-20 JP JP2009122409A patent/JP5390934B2/en not_active Expired - Fee Related
-
2010
- 2010-04-30 US US12/771,147 patent/US20100322817A1/en not_active Abandoned
- 2010-05-11 FR FR1053699A patent/FR2945822B1/en not_active Expired - Fee Related
- 2010-05-14 CN CN201010180682.0A patent/CN101892402B/en not_active Expired - Fee Related
- 2010-05-19 RU RU2010120135/02A patent/RU2452785C2/en not_active IP Right Cessation
- 2010-05-19 KR KR1020100046701A patent/KR101218858B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04365828A (en) * | 1990-07-06 | 1992-12-17 | Nikko Kyodo Co Ltd | Titanium alloy for anode |
| US5316722A (en) * | 1992-07-09 | 1994-05-31 | Kabushiki Kaisha Kobe Seiko Sho | Corrosion resistant Ti-Cr-Ni alloy containing a platinum group metal |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520456A (en) * | 2012-08-10 | 2015-04-15 | 新日铁住金株式会社 | Titanium alloy material |
| CN107746996A (en) * | 2012-08-10 | 2018-03-02 | 新日铁住金株式会社 | Titanium alloy material |
| CN105551557A (en) * | 2013-07-02 | 2016-05-04 | 中科华核电技术研究院有限公司 | Middle-low-radioactivity nuclear waste treatment device |
| CN104152744A (en) * | 2014-07-08 | 2014-11-19 | 宁夏东方钽业股份有限公司 | Low-cost medium-high-strength corrosion-resistant titanium alloy and processing method thereof |
| CN105349808A (en) * | 2015-11-13 | 2016-02-24 | 无锡清杨机械制造有限公司 | Preparing method for titanium alloy panel |
| CN108467970A (en) * | 2018-03-23 | 2018-08-31 | 中国石油天然气集团公司管材研究所 | A kind of iron content titanium alloy tube and preparation method thereof for highly corrosive oil and gas development |
| CN108998696A (en) * | 2018-07-20 | 2018-12-14 | 中国航发北京航空材料研究院 | A kind of marine engineering equipment use in strong corrosion resistant titanium alloy |
| CN109022914A (en) * | 2018-10-09 | 2018-12-18 | 广州宇智科技有限公司 | A kind of corrosion-resistant high heat-transfer performance chemical field titanium alloy and its technique |
| CN111430057A (en) * | 2020-03-18 | 2020-07-17 | 张云逢 | High radioactive nuclear waste container |
Also Published As
| Publication number | Publication date |
|---|---|
| US20100322817A1 (en) | 2010-12-23 |
| CN101892402B (en) | 2012-07-11 |
| JP5390934B2 (en) | 2014-01-15 |
| FR2945822A1 (en) | 2010-11-26 |
| JP2010270360A (en) | 2010-12-02 |
| RU2452785C2 (en) | 2012-06-10 |
| RU2010120135A (en) | 2011-11-27 |
| KR20100125189A (en) | 2010-11-30 |
| KR101218858B1 (en) | 2013-01-07 |
| FR2945822B1 (en) | 2014-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101892402B (en) | Titanium alloy material, structural member, and container for radioactive waste | |
| CN106536777B (en) | Ferrite-group stainless steel and its manufacturing method and using ferrite-group stainless steel as the heat exchanger of component | |
| JP5379752B2 (en) | Titanium alloy with excellent intergranular corrosion resistance | |
| KR101707284B1 (en) | Titanium alloy | |
| JP5660253B2 (en) | Titanium alloy with excellent corrosion resistance in environments containing bromine ions | |
| Pavlik et al. | Corrosion behavior of Incoloy 800H/HT in the fluoride molten salt FLiNaK+ MF x (MF x= CrF 3, FeF 2, FeF 3 and NiF 2) | |
| Jayaraj et al. | Electrochemical and passive characterization of a beta type Ti45Zr38Al17 cast rod in nitric acid medium | |
| EP2546376B1 (en) | Ferritic stainless steel having excellent corrosion resistance in condensed water environment produced by exhaust gas from hydrocarbon combustion | |
| CN105463306B (en) | A kind of fluoride molten salt and/or molten chloride corrosion protection method | |
| JP2003535973A (en) | Cold rolled steel sheet with excellent corrosion resistance to sulfuric acid | |
| CN105980613B (en) | Ferrite-group stainless steel and its manufacturing method | |
| Zhang et al. | Hot corrosion of an electrodeposited Ni-11 wt% Cr nanocomposite under molten Na2SO4–K2SO4–NaCl | |
| WO2016147858A1 (en) | Titanium alloy, separator, and solid polymer fuel cell | |
| EP1941070A2 (en) | Austenitic stainless steel | |
| US20050260433A1 (en) | Titanium alloys excellent in hydrogen absorption-resistance | |
| JP2012052213A (en) | High corrosion-resistance titanium alloy large in 0.2%-proof stress in rolling direction, and its manufacturing method | |
| Crook | Corrosion characteristics of the wrought Ni‐Cr‐Mo alloys | |
| US4744878A (en) | Anode material for electrolytic manganese dioxide cell | |
| WO2018025942A1 (en) | Austenitic stainless steel | |
| Mahajan et al. | Elevated temperature molten salt corrosion study of SS304L austenitic boiler steel | |
| JPS63121641A (en) | External coating of sheathed heater made of austenitic stainless steel | |
| Wang et al. | Corrosion of Zr-xTi-yNb alloys in concentrated nitric acid at elevated temperature | |
| JP3878376B2 (en) | Corrosion resistant Ti alloy | |
| KR101471889B1 (en) | Oxidation resistant ferritic stainless steel, method of manufacturing the steel, and fuel cell interconnect using the steel | |
| JP7333399B2 (en) | Steel sheet having corrosion resistance in sulfuric acid and sulfuric acid/hydrochloric acid complex condensed environment and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120711 Termination date: 20200514 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |