CN101443469A - Austenitic stainless steel and process for removing hydrogentherefrom - Google Patents
Austenitic stainless steel and process for removing hydrogentherefrom Download PDFInfo
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- CN101443469A CN101443469A CNA2007800172824A CN200780017282A CN101443469A CN 101443469 A CN101443469 A CN 101443469A CN A2007800172824 A CNA2007800172824 A CN A2007800172824A CN 200780017282 A CN200780017282 A CN 200780017282A CN 101443469 A CN101443469 A CN 101443469A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
- C21D3/02—Extraction of non-metals
- C21D3/06—Extraction of hydrogen
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Abstract
By focusing on non-diffusible hydrogen causing hydrogen embrittlement in austenite base stainless steel, it is intended to provide austenite base stainless steel free from the non-diffusible hydrogen by heating austenite base stainless steel at a heating temperature of 200 to 500<o>C for not longer than 460 hours while maintaining it in an evacuated atmosphere of 0.2 Pa or less to thereby eliminate hydrogen (H) contained in the austenite base stainless steel to 0.00007% by mass (0.7 ppm by mass) or less.
Description
Technical field
The present invention relates to reduce the austenite stainless steel and the dehydrogenating process thereof of hydrogen embrittlement.Particularly relate to and reduce austenite stainless steel and the dehydrogenating process thereof that the hydrogen that is present in the austenite stainless steel is given the influence of the fatigue crack growth that takes place in the austenite stainless steel.
Background technology
From global environment problem aspect, receive much concern as the utilization of the hydrogen of energy of future generation, so its research and development are very active.Particularly the fuel-cell vehicle that acts as a fuel with hydrogen, fixation be with the exploitation of fuel cell etc., and its practicality turns into to important topic and receives much concern.Constantly research is as the stainless use (for example, with reference to patent documentation 1) of the material of the high-pressure hydrogen tank in this fuel cell system, various parts, pipe arrangement etc.
Table 1 illustration the composition of typical austenite stainless steel.The 1st row of this table 1 are by the stainless steel of Japanese Industrial Standards' (being designated hereinafter simply as JIS (Japan Industrial Standard) standard) regulation and the title of high temperature steel.Stainless Vickers' hardness (being designated hereinafter simply as HV (Vickers hardness)) is represented in the last guide look of table 1.Other hurdle is the chemical ingredients that contains in the stainless steel, and the unit of composition represents with quality %.Under the situation of hydrogen (H), its content is represented with quality ppm.
Table 1
(unit of composition, quality %,
*Quality ppm)
As everyone knows, hydrogen is invaded the static strength and the fatigue strength (for example, non-patent literature 1,2) that can reduce material in the metallic substance.Remove the method for this hydrogen, the method for influence of prediction hydrogen has all motions.For example, patent documentation 2 keeps carrying out heat treated more than 10 minutes under 270～400 ℃ the temperature after plating is handled austenite stainless steel, is used to prevent the dehydrogenation of hydrogen embrittlement.Patent documentation 3 discloses the hydrogen embrittlement degree methods of judging austenite stainless steel with chemical component prediction.
In addition, delivered and give test film and form the SUS304 of the JIS standard of the micro-holes about 100 μ m, the fatigue test results of SUS316L austenite stainless steel after with prestrain.The FATIGUE CRACK GROWTH velocity ratio of the SUS304 of hydrogenation is not quickened 10 times during hydrogenation.And its fatigue crack growth rate quickens 2 times during SUS316L.
But metastable austenite stainless steel also has because of cold working and repeated stress processes the possibility of bringing out martensitic transformation.About such austenite stainless steels such as SUS316L of JIS standard, so-called hydrogen influences the understanding of FATIGUE CRACK GROWTH speed hardly in the association inside as investigator group, and has been general general knowledge among the practitioner in the art between industrial community.Overthrow the result of this general knowledge with demonstration, apply the circulation loading that causes by the low frequency below the 5Hz and obtain The above results, have meaning very.
In other words, can confirm the propagation rate of the austenite stainless steel of SUS316L etc. crackle because the circulation loading of low frequency can accelerate fatigue.On the other hand, non-patent literature 2 is pointed out " martensitic phase that generates because of phase transformation in (3) austenite stainless steel becomes the passage of the hydrogen that spreads in material, the spread coefficient of hydrogen is risen (with reference to 130 pages) ".
Patent documentation 1: the spy opens the 2004-339569 communique
Patent documentation 2: the spy opens flat 10-199380 communique
Patent documentation 3: the spy opens the 2005-9955 communique
Non-patent literature 1: gold a rugged pretty man of virtue and ability, You rugged thousand are sought, respecting on the ocean, peak two, Song Gang three youths, village should " hydrogen is to the influence of the fatigue crack growth of the austenite stainless steel of giving prestrain " Japanese mechanical subject [No.05-9] M; M2005 mechanics of materials collection of essay lecture collection of thesis (05.11.4-6, Fukuoka city), P86, p.595-596
Non-patent literature 2: gold a rugged pretty man of virtue and ability, You rugged thousand are sought, respect suitable " hydrogen is to the influence and the martensitic transformation of stainless fatigue crack propagation " Japanese mechanics on the ocean, peak two, Song Gang three youths, village can roll up No. 723 (2006-11), p123-130 by collection of thesis (A volumes) 72.(original copy is accepted on May 1st, 2006)
Summary of the invention
But present situation is, can't resolve fully what kind of relation intrinsic non-dispersive hydrogen and above-mentioned FATIGUE CRACK GROWTH speed have in the diffustivity hydrogen that added by the outside in the austenite stainless steel and the crystal.In addition, effect and the fatigue crack growth rate that diffustivity hydrogen and non-dispersive hydrogen quickens the variation of the martensitic phase variable in the material, hydrogen velocity of diffusion that can not fully explain given what kind of influence and relation thereof.
In addition, stainless steel is used for the machine of related hydrogen fuel utilization, when installing, is subjected to all-environment influence according to its environment for use.For example, when in the compressed hydrogen tank of fuel-cell vehicle, pipe arrangement etc., using stainless steel,, carry out loading and release with slow repeat by to the consumption of this compressed hydrogen tank filling hydrogen, hydrogen etc.Yet the fatigue test in past does not have the slow like this circulation of hypothesis.That is to say, consideration be with the fireballing fatigue test of alternation replace such 1 cycling time long by the fatigue test due to the loading.
The circulation loading of the low frequency that causes because of the temperature variation of outer temperature etc. takes place in addition.The contraction of for example, the circulation loading that causes by the outer temperature Change contraction that can think the stainless steel self that causes because of day and night temperature and elongation, the parts that are connected with parts of stainless steel and the thermal stresses that elongation causes.Its frequency, for example temperature head round the clock is several times to more than 10 ℃, 24 hours is 1 cycle.In the equipment of fuel-cell vehicle association, the fuel feed that high-pressure hydrogen tank, fuel cell are used has as described above 1st being that the cycle and the hydrogen loading time of unit is long with equipment etc.In addition, the environment walked of fuel cell garage has several ℃ to tens of ℃ the temperature head and the cycle of submicrosecond～a few hours unit.
The present invention finishes based on technical background as described above, reaches following purpose.
The objective of the invention is to, be provided for reducing the austenite stainless steel and the dehydrogenating process thereof of influence that hydrogen is given the fatigue crack growth rate of austenite stainless steel.
Another object of the present invention is to, be conceived to become the diffustivity hydrogen and the non-dispersive hydrogen of the hydrogen embrittlement reason of austenite stainless steel, austenite stainless steel and the dehydrogenating process thereof of removing both are provided.
The present invention also aims to, be conceived to be present in the austenite stainless steel, become the diffustivity hydrogen and the non-dispersive hydrogen of long circulation loading problem of 1 round-robin time, austenite stainless steel and the dehydrogenating process thereof of removing it are provided.
The present invention also aims to, be provided at and remove the diffustivity hydrogen that exists in the austenite stainless steel and the austenite stainless steel and the dehydrogenating process thereof of non-dispersive hydrogen in the manufacturing process of austenite stainless steel.
The definition of word
The present invention uses following technical terms according to the meaning of following definitions.So-called hydrogenation is meant invades hydrogen in material.The method of so-called hydrogenation is to instigate material to be exposed to method in the compressed hydrogen tank, implement the method for negative electrode hydrogenation and be immersed in method in the chemical solution etc.So-called fatigue crack growth is meant because of crackle takes place for the defective that takes place in the material in manufacturing processed, crackle or the artificial loadings that are subjected to circulating such as hole that import and becomes big.
So-called fatigue crack growth rate is meant the speed of fatigue crack growth.So-called austenite stainless steel is meant the ferrous materials of Cr-Ni system, is to add Cr and Ni in Fe, have the austenite stainless steel mutually that can improve erosion resistance for corrosive environment etc.Table 1 shows this stainless illustration.So-called austenite is the phase of the iron of iron (Fe) in 911～1392 ℃ temperature range of purity 100% mutually, has centroid cubic lattice structure (hereinafter referred to as FCC (FaceCentered Cubic Lattice) structure).
Figure 11 (a) illustrates face-centered cubic lattice.By in iron, adding alloying elements such as Cr, Ni, even at room temperature also can have the austenite phase.Martensitic phase is by making steel from the tissue that the austenite phase chilling of high-temperature stable obtains, having body centered structure structure (hereinafter referred to as BCC (Body Centered Cubic Lattice) structure).Figure 11 (b) illustrates body centered structure.In addition, at normal temperatures, generate martensitic phase by cold working meeting to the stainless steel stress application of austenite phase state etc.
By such cold working, the austenite phase transformation of the martensitic phase of BCC structure in opposite directions by the FCC structure takes place, be called " martensitic transformation is brought out in processing ".So-called diffustivity hydrogen is meant the hydrogen that is present in the material, the at room temperature hydrogen of overflowing in time from material.This diffustivity hydrogen becomes the reason of the hydrogen embrittlement of material.So-called non-dispersive hydrogen is meant the hydrogen that is present in the material, even the hydrogen of also not overflowing from material in time under the temperature about room temperature to 200 ℃.
In order to reach above-mentioned purpose, the present invention adopts following method.
The present inventor etc. have found out the non-dispersive hydrogen in the austenite stainless steel and the relation of fatigue crack growth.
The present invention relates to have austenite stainless steel and the dehydrogenating process thereof that crystalline structure is the austenite phase of centroid cubic lattice structure.The invention is characterized in, remove the diffustivity hydrogen and the non-dispersive hydrogen of the reason of the hydrogen embrittlement that becomes austenite stainless steel, the hydrogen (H) that contains in the austenite stainless steel is removed to 0.00007 quality % (0.7 quality ppm).
Removing of diffustivity hydrogen and non-dispersive hydrogen can be carried out heat treated with austenite stainless steel under the Heating temperature more than 200 ℃.In addition, be preferred for the upper limit of Heating temperature of heat treated of this moment in 500 ℃.The heat treated that is used to remove these diffustivity hydrogen and non-dispersive hydrogen can be carried out under vacuum atmosphere.
Heating temperature is 200～500 ℃ a temperature range, the processing that can remove is present in the austenite stainless steel, is situated between is caused by the circulation loading is brought out martensitic phase and is spread, assembles in the crackle portion that meets with stresses concentrated, the diffustivity hydrogen and the non-dispersive hydrogen of reason of hydrogen embrittlement that becomes austenite stainless steel, makes the hydrogen (H) that contains in the austenite stainless steel become above-mentioned amount.
Heating temperature can be the low temperature of sensitizing temperature that likens the temperature that chromium (Cr) carbide for austenite stainless steel separates out because of heating to.In addition, above-mentioned vacuum atmosphere can be the following environment of 0.2Pa.In addition, heat treated can be in the time that keeps under above-mentioned vacuum atmosphere and the Heating temperature below 460 hours.
The amount of preferably removing the hydrogen (H) that contains in the austenite stainless steel behind diffustivity hydrogen and the non-dispersive hydrogen is below 0.00004 quality % (0.4 quality ppm).The amount of more preferably removing the hydrogen (H) that contains in the austenite stainless steel behind diffustivity hydrogen and the non-dispersive hydrogen is below 0.00001 quality % (0.1 quality ppm).
In the manufacturing process of austenite stainless steel, can carry out heat treated and remove dehydrogenation, hydrogen (H) is become below the 0.00007 quality % (0.7 quality ppm) with the specified time.At this moment, preferred thermal treatment temp is more than 200 ℃ and be lower than stainless melting temperature.Preferred heat-up time for this reason is more than 30 seconds, below tens of hours.This manufacturing process can be an inert gas flow atmosphere.The manufacturing process of austenite stainless steel comprises the solution treatment of using when making stainless steel, the operation of ageing treatment.
The processing of removing of the hydrogen in the manufacturing process can be atmosphere, for example inert atmosphere that vacuum atmosphere or hydrogen branch force down.In addition, the time of preferred heat treated is about several minutes to tens of hours.
The temperature of heat treated, the temperature more than 920 ℃ most preferably when solution treatment.
The temperature of heat treated, the temperature more than 700 ℃ most preferably when ageing treatment.
In addition, preferred austenite stainless steel is the austenite stainless steel or the austenite heat-resistant steel of above-mentioned table 1.
Can obtain following effect according to the present invention.The present invention is the heat treated austenite stainless steel under the temperature more than 200 ℃, can remove non-dispersive hydrogen and diffustivity hydrogen in the austenite stainless steel, the austenite stainless steel that provides resistance to fatigue crack expansibility to improve.
Description of drawings
Fig. 1 is the figure of overview of diagram fatigue test piece, and Fig. 1 (a) is the figure of diagram fatigue test plate shape, and Fig. 1 (b) is the figure of the shape of the artificial micropore that forms on the expression fatigue test piece.
Fig. 2 illustrates the shape of artificial micropore of the overview of test portion of fatigue test piece and importing and the fatigue cracking of being expanded by artificial micropore.
Fig. 3 is the sketch chart that imports the order of prestrain to fatigue test piece.
Fig. 4 is the photo of the fatigue cracking that taken place by artificial micropore after the fatigue test.
Fig. 5 be illustrated in before the fatigue test to test portion surface with after fatigue test to repeated stress failure face with the X-ray examination austenite mutually with the result's of martensitic phase graphic representation, Fig. 5 (a) is the measurement result of SUS304, Fig. 5 (b) is the measurement result of SUS316, and Fig. 5 (c) is the measurement result of SUS316L.
Fig. 6 is the graphic representation of expression by the relation of crack length due to the fatigue test and cycle index.Fig. 6 (a) is the situation of SUS304, and Fig. 6 (b) is the situation of SUS316, and Fig. 6 (c) is the situation of SUS316L.
Fig. 7 is the photo with the fatigue cracking of SUS304, the SUS316 of replica method observation, SUS316L.
Fig. 8 is the result's of diagram SUS316L fatigue test a graphic representation.
Fig. 9 is the result's of diagram SUS316L fatigue test a graphic representation.
Figure 10 is the concept map of expression diffustivity hydrogen and non-dispersive hydrogen Jie mobile main points by martensitic transformation.
Figure 11 is the concept map of the lattice of expression austenite phase and martensitic phase crystalline structure, and Figure 11 (a) is the concept map of the centroid cubic lattice structure (FCC) of austenite phase, and Figure 11 (b) is the concept map of the body centered structure structure (BCC) of martensitic phase.
Figure 12 is the result's of another experimental example 1 of expression a graphic representation.
Figure 13 is the result's of another experimental example 2 of expression a graphic representation.
Embodiment
Below embodiments of the present invention become experimental example describe.Illustrate that at first hydrogen gives the FATIGUE CRACK GROWTH speed that takes place in the austenite stainless steel and with what kind of influence.Even the austenite stainless steel of the SUS304 shown in the table 1, SUS316, SUS316L etc. also contains the non-dispersive hydrogen of 1～4.7 quality ppm after implementing common heat treated (solution treatment).Thought between the practitioner in the art in the past that this non-dispersive hydrogen did not have influence to hydrogen embrittlement.
But, can distinguish that by the fatigue test of following record non-dispersive hydrogen is influential to hydrogen embrittlement.The hydrogen embrittlement that is caused by non-dispersive hydrogen particularly can be identified under the situation of the low cycle fatigue test speed of (1 round-robin alternation time is about 11 minutes) about 0.0015Hz.Inventor of the present invention has carried out following experiment, and non-dispersive hydrogen is observed in what kind of influence has to FATIGUE CRACK GROWTH speed.Show an example of experiment.
Test film
The material that uses is austenite stainless steel SUS304, SUS316 shown in the table 1 and SUS316L (A) (being designated hereinafter simply as SUS316L).Make SUS304, SUS316 and SUS316L carry out using after the solution treatment.Fig. 1 (a) illustrates the shape of fatigue test piece.The test film surface is used after the emery paper of #2000 grinds, and carries out precision work by polishing.
In order easily to observe FATIGUE CRACK GROWTH, at the central part of the length direction of fatigue test piece and along the artificial micropore of opening diameter such shown in Fig. 1 (b) 100 μ m, the degree of depth 100 μ m on the radial direction with the bit drills of its toe angle 120 degree.Central authorities in the test portion of test film import artificial micropore.Test portion is the column part of test film central authorities, and the length of cylinder is about 20mm.Top and the bottom surface of this cylinder parallel and with the axis normal of the length direction of test film.Fig. 2 illustrates the shape of the artificial micropore of the summary of test portion and importing.Under the situation of the fatigue test piece of hydrogenation, after finishing, implements hydrogenation to polish, open again artificial micropore at once.
X-ray diffraction
Measure the martensite volume of the test portion of fatigue test piece with X-ray diffraction for austenite stainless steel.X-ray diffraction carries out with little X ray stress determination device PSPC-RSF/KM of RIGAKU company (Tokyo Zhao Daoshi) system.CrK α line is used in quantitative analysis, and { { the integrated intensity ratio of the diffraction crest of 211} face is obtained for 220} face and martensitic phase by the austenite phase.Martensite volume before the fatigue test that test portion is contained all is about 3% for SUS304, SUS316, SUS316L.
Even under the situation of the test portion of hydrogenation, be about 3% too.Before importing artificial micropore, being determined at of martensite volume carry out at 2 places.The 1st place in this mensuration zone is to be the zone of circle of the diameter 1mm at center with the predetermined position that imports artificial micropore.The 2nd place in this mensuration zone is to be the zone of circle of the diameter 1mm at center with the position that the axle Rotate 180 degree of the length direction that makes test film is worked in the predetermined position that imports artificial micropore.That is to say that the mensuration zone at the 2nd place is positioned at the opposition side of this cylinder in the 1st mensuration zone from the cylinder.
Method of hydrotreating
Hydrogenation carries out with the negative electrode hydrogenation method.The condition of hydrogenation is: the aqueous sulfuric acid of pH=3.5, platinum anode, current density i=27A/m
2When solution temperature is 50 ℃ (323K), carry out the hydrogenation of 672 hours (4 time-of-week), when solution temperature is 80 ℃ (353K), carry out the hydrogenation of 336 hours (2 time-of-week).In order to make because of the variation of sulfuric acid concentration due to the evaporation diminishes, per 1 time-of-week will be changed aqueous sulfuric acid.
The prestrain material
For the acceleration of investigating the fatigue crack growth rate that causes by hydrogen and the relation of martensitic phase variable, prepare to give SUS304, SUS316L with prestrain, the test film of martensitic transformation takes place.Fig. 3 represents to import the sketch chart of prestrain order.In order to promote martensitic transformation, prestrain imports in-70 ℃ ethanol.After importing this prestrain, test film is processed into such shape shown in Fig. 1 (a).For SUS304, give plastix strain (true strain) ε
p=0.28 prestrain for SUS316L, is given plastix strain ε
p=0.35 prestrain.
Mensuration is given the Vickers' hardness after the prestrain (measuring loading 9.8N), the HV=426 of SUS304 (10 average), the HV=351 of SUS316 (10 average).Error is in ± 4%.Behind the grinding test sheet, with the martensite volume of the test portion after the X-ray diffraction mensuration importing prestrain.Martensite volume is 65～69% in volume ratio SUS304, is 26～28% in volume ratio SUS316L.Before importing artificial micropore, being determined at of martensite volume carry out at 2 places.This mensuration zone is that the position with the axle Rotate 180 degree of predetermined position that imports artificial micropore and the length direction that makes test film from the predetermined position that imports artificial micropore is the zone of circle of the diameter 1mm at center.
Fatigue test method
The hydraulic servo Compression and Expansion protracted test machine " Servopulser-EHF-ED30KN " of Shimadzu Scisakusho Ltd (Zhong jing district, capital of a country city) system is used in fatigue test, and alternation speed is 0.0015～5Hz, stress ratio R=-1.Alternation speed is no more than 60 ℃ mode with test portion surface temperature in fatigue test and regulates.Observe fatigue cracking by replica method, measure the length of fatigue cracking simultaneously.
Observing fatigue cracking by replica method carries out according to following.Cellulose acetate film about thickness 0.034mm (hereinafter referred to as the replica film) is immersed in be attached to after for some time in the ritalin liquid will observation place.Wait for 2～3 minutes after pasting the replica film, in case replica film drying is taked the replica film.Gold evaporation on the replica film of taking is used the metal microstructure sem observation, the fatigue cracking of viewing test portion.
Thus, even direct viewing test film not also can be observed the fatigue cracking place of purpose.Under the situation of hydrogenation material, after fatigue test finishes, directly cut out the sample of diameter 7mm, thickness 0.8mm at once, test film is put into vacuum vessel, under the certain condition of heat-up rate, heat from test portion.Pressure in the vacuum vessel is 1 * 10 before heating sample
-7～3 * 10
-7Pa.Be warming up to 800 ℃ with 0.5 ℃/s of heat-up rate.
By the test film in the heating, vacuum container, hydrogen breaks away from from test film, breaks away from the hydrogen amount of analytical equipment (hereinafter referred to as TDS) mensuration disengaging with the intensification of four utmost point mass analysis modes.The TDS that is used to measure is that the intensification of electronics science Co., Ltd. (the wild city of Tokyo Musashi) system breaks away from analytical equipment (hereinafter referred to as TDS) EMD-WA1000S/H.The precision of being measured by TDS is 0.01 quality ppm.
The various characteristics of measuring
Fig. 4 is the photo of the fatigue cracking that produced by the artificial micropore on the SUS304 that imports to hydrogenation not after the fatigue test.Can confirm the fatigue cracking that takes place because of artificial micropore by photo.As can be seen, this fatigue cracking takes place from the both sides of artificial micropore, substantially expansion symmetrically.
Fig. 5 be before fatigue test to test portion surface with after fatigue test to repeated stress failure face with the X-ray examination austenite mutually with the result of martensitic phase.The dotted line of Fig. 5 is represented the result on the preceding determination test portion of fatigue test surface.Solid line is represented the result of the repeated stress failure face of measuring after the fatigue test.Fig. 5 (a) is the measurement result of SUS304, is measured as can be seen by this, compares after the fatigue test with before the fatigue test, and its austenite reduces mutually, and martensitic phase increases.
Fig. 5 (b) is the measurement result of SUS316, is measured as can be seen by this, compares after the fatigue test with before the fatigue test, and its austenite reduces mutually on a small quantity, and martensitic phase increases.Fig. 5 (c) is the measurement result of SUS316L, is measured as can be seen by this, compares after the fatigue test with before the fatigue test, and its martensitic phase increases.Under the situation of SUS316L, the variation of austenite phase almost be can't see.
Fig. 6 is the graphic representation of expression by the relation of crack length due to the fatigue test and cycle index.Fig. 6 (a) is the situation of SUS304, and Fig. 6 (b) is the situation of SUS316, and Fig. 6 (c) is the situation of SUS316L.Each material SUS304, SUS316, SUS316L hydrogenation and the measurement result during hydrogenation have not been represented.Alternation speed is 1.2Hz when SUS304, SUS316, is 5Hz when SUS316L.
By this graphic representation as can be seen, the SUS304 of hydrogenation, SUS316 compare during with hydrogenation not, and the propagation rate of its crackle accelerates.Cycle index N when for example, crack length 2a reaches to 400 μ m is tailing off under the situation than hydrogenation not under the situation of hydrogenation.At this moment, fatigue crack growth rate approximately accelerates under the situation of hydrogenation 2 times.On the other hand, the fatigue crack growth rate during SUS316L, slightly higher under the situation than hydrogenation not under the situation of hydrogenation, but do not see tangible difference.
Fig. 7 is the photo by the fatigue cracking of SUS304, the SUS316 of replica method observation, SUS316L.Because fatigue cracking is substantially expanded as Fig. 4 photo symmetrically, so Fig. 7 has only represented its half photo.Can observe by photo, compare the fatigue cracking of hydrogenation material with hydrogenation material not and expand point-blank.As can be seen, the slip band in the hydrogenation material does not spread generation in the zone of broad, and is relative therewith, and the slip band in the material of hydrogenation is confined near the fatigue cracking.
Fig. 8 is result's the graphic representation of the fatigue test of diagram SUS316L.Hydrogen when the figure shows hydrogenation not is the fatigue test results that the 2 kinds of materials of 0.4 quality ppm, 2.6 quality ppm and the material hydrogenation that makes 2.6 quality ppm become the material of 3.9 quality ppm.Alternation speed was 1.5Hz when its alternation speed reached to 200 μ m in the length of fatigue cracking, and in a single day fatigue crack length becomes 200 μ m, and alternation speed is become 0.0015Hz by 1.5Hz.Hydrogen is the material of 2.6 quality ppm, 3.9 quality ppm, its fatigue crack growth.But when hydrogen was the material of 0.4 quality ppm, fatigue cracking was expanded hardly.
Fig. 9 is the result's of diagram SUS316L fatigue test a graphic representation.Hydrogen when the figure shows hydrogenation not is the fatigue test results that the 2 kinds of materials of 0.4 quality ppm, 2.6 quality ppm and the material hydrogenation that makes 2.6 quality ppm become the material of 3.9 quality ppm, 5.1 quality ppm.Its alternation speed is 1.5Hz and 0.0015Hz2 kind.
By this graphic representation as can be seen, hydrogen is the material of 2.6 quality ppm and when making its hydrogenation become 3.9 quality ppm and 5.1 quality ppm materials, fatigue crack growth.As can be seen, under the situation of 0.0015Hz and low alternation speed, compare its fatigue crack growth rate with 1.5Hz fast.But as can be seen, when hydrogen is 0.4 quality ppm, be that any situation of 0.0015Hz, 1.5Hz is compared with alternation speed, its FATIGUE CRACK GROWTH speed is all slow.Hydrogen in this expression material is when 0.4 quality ppm is following, and fatigue cracking is expanded hardly.
Figure 10 is the concept map of expression diffustivity hydrogen and non-dispersive hydrogen Jie mobile appearance by the martensitic phase of phase transformation.Among the figure, the front end generation martensitic transformation of fatigue cracking, diffustivity hydrogen and non-dispersive hydrogen are situated between and are moved by this martensitic phase.Be that hydrogen moves as path with the fast martensitic phase of velocity of diffusion, concentrate at the front end of fatigue cracking.Be diffusion, traveling time related phenomena with hydrogen.The velocity of diffusion of the hydrogen in the austenite phase (FCC) is than slow 4 figure places of the velocity of diffusion in the martensitic phase (BCC).The periphery generation martensitic transformation of fatigue cracking, its peripheral hydrogen spreads in this martensitic phase, concentrates at the front end of fatigue cracking.
The participation of non-dispersive hydrogen
Thus, according to above-mentioned experiment, not only diffustivity hydrogen but also the non-dispersive hydrogen always do not paid close attention to all demonstrate the intervention hydrogen embrittlement.This relates to the neodoxy of hydrogen embrittlement.By this, influence the martensitic transformation (by the phase transformation of FCC) of fatigue cracking front end to BCC.
The speed of fatigue test and the relation of fatigue crack growth rate
In addition, as above-mentioned experiment as shown in Figure 9, as can be seen, the austenite stainless steel of SUS316L etc. is as long as the speed of fatigue test is slow, and fatigue crack growth rate just accelerates.Equally, as shown in Figure 6, the hydrogenation material that increases the test film etc. of diffustivity hydrogen is compared its fatigue crack growth rate with hydrogenation material not and is accelerated.When hydrogen is the following material of 0.4 quality ppm, shown in Fig. 8,9, like that, almost there is not FATIGUE CRACK GROWTH.According to like this, make the slow-footed effect of fatigue test be and the diffusion of hydrogen, traveling time related phenomena (among the FCC than slow 4 figure places of the velocity of diffusion among the BCC).
Below, alloying constituent, its amount that contains in the austenite stainless steel of the present invention and the manufacture method of stipulating in manufacture method of the present invention etc. are described.
Austenite stainless steel
It is stainless steel that austenite stainless steel is also referred to as Cr-Ni, adds Cr and Ni in Fe.The main component of austenite stainless steel has Fe, Cr, Ni, and the various additives shown in the following table 2 are arranged in addition.
Following table 2 shows the preference of austenite stainless steel of the present invention, but embodiments of the present invention not only are defined in this example.
Table 2
| Composition | Form 1 (mass ratio) | Form 2 (mass ratioes) |
| C | 0.030 below | 0.08 below |
| Si | 1.00 below | 1.50 below |
| Mn | 2.00 below | 2.00 below |
| Ni | 12.00～15.00 | 8.00～27.00 |
| Cr | 16.00～18.00 | 13.50～26.00 |
| Mo | 2.00 below～3.00 | 3.00 below |
| Al | - | 0.35 below |
| N | - | 0.50 below |
| Ti | - | 2.35 below |
| V | - | 0.50 below |
| B | - | 0.010 below |
| H | 0.00007 (0.7ppm) | 0.00007 (0.7ppm) |
| Other | All the other are made of iron and unavoidable impurities. | All the other are made of iron and unavoidable impurities. |
Composition about austenite stainless steel
Cr is used for improving solidity to corrosion and adds Fe to.Ni is in order to increase solidity to corrosion, adds among the Fe and combine with Cr.Ni and Mn guarantee the nonmagnetic element in cold rolling back.In order to keep non magnetic after cold rolling, must contain the above Ni of 10.0 quality %.In addition, must adjust the Ni amount, not generate more than the 1 volume % so that martensitic phase is brought out in processing according to the content of Si, Mn.Mn also has the effect of the solid solubility that improves N.
C is used to form the austenitic element of high strength.In addition, C is the effective element that improves stainless steel intensity.If excessive interpolation C, can separate out thick Cr when then recrystallize is handled is carbide, becomes the reason of anti-grain boundary corrosion, fatigue characteristic reduction.With deoxidation and solution strengthening is that purpose is added Si.So the generation of martensitic phase when promoting cold working owing to the high meeting of content as if Si is preferably micro-the interpolation.N causes solution hardening.
To improve solidity to corrosion is that purpose is added Mo.In addition, when ageing treatment, also play the fine dispersive effect of carbonitride that makes.Ti is to the precipitation hardening effective elements, adds in order to improve by the intensity of ageing treatment.B is the effective alloying constituent that prevents that the limit that takes place that cause is split in that hot processing temperature scope internal cause delta ferrite is different with the resistance to deformation of austenite phase mutually on hot rolled strip.Al is that when steel-making is the element that purpose is added with the deoxidation, and Al and Ti also work to precipitation hardening equally effectively.
Elements such as Nb, Cu can also be added, be used to embodiments of the present invention according to necessity except the described element of above-mentioned table 2.Nb can become the substitute element of Ti.
About the austenite phase
The austenite of preferred austenite stainless steel is 100% of whole volumes mutually substantially.There is not martensitic phase in the preferred austenite stainless steel.
About other character
Preferred average crystal grain diameter is below about 50 μ m.Average crystal grain diameter is about 50 μ m in the existing material, preferably its following average crystal grain diameter.
Handle about dehydrogenation by heating
The narration austenite stainless steel is handled by the dehydrogenation of heating.The present inventor finds out that non-dispersive hydrogen has participated in fatigue crack growth, implements heat treated in the following manner as a setting with this and removes non-dispersive hydrogen and diffustivity hydrogen in the austenite stainless steel.
Removing of diffustivity hydrogen and non-dispersive hydrogen can be carried out heat treated with austenite stainless steel under the Heating temperature more than 200 ℃.Heat treated is carried out under vacuum atmosphere.Vacuum atmosphere is the following environment of 0.2Pa.In addition, heat treated is to be below 460 hours with austenite stainless steel in the time that keeps under vacuum atmosphere and the Heating temperature.Heating temperature is to liken chromium (Cr) carbide for austenite stainless steel to because of the low temperature of sensitizing temperature of the temperature that adds heat evolution.
For example, under the situation of the austenite stainless steel shown in table 1 and the table 2, the upper limit of Heating temperature is 500 ℃ of temperature.Thus, can remove the processing that caused by the circulation loading of being present in the austenite stainless steel, being situated between brings out martensitic phase and spreads, assembles in the crackle portion that meets with stresses concentrated, the diffustivity hydrogen and the non-dispersive hydrogen of hydrogen embrittlement reason that becomes austenite stainless steel.
From austenite stainless steel, remove the diffustivity hydrogen and the non-dispersive hydrogen of the reason of the hydrogen embrittlement that becomes austenite stainless steel by such heat treated, the hydrogen (H) that contains in the austenite stainless steel is become below the 0.00007 quality % (0.7 quality ppm).The amount of the hydrogen (H) that contains in the austenite stainless steel after preferred this heat treated is below 0.00004 quality % (0.4 quality ppm), more preferably below 0.00001 quality % (0.1 quality ppm).
Like this, the amount of the hydrogen that contains in the austenite stainless steel made than amount in the past lack, even the austenite stainless steel that the excellence that fatigue crack growth quickens does not take place under the long circulation loading of a round-robin time yet just can be provided.
Other experimental example 1
The test film that use is made by SUS316 carries out the heat treated experiment.Test film is the pole of diameter 7mm.The circular plate shape that cuts into diameter 7mm, thickness 0.8mm is measured for TDS.Experiment is to put into the test film heat treated 20 minutes in 800 ℃ of temperature.The experiment atmosphere of this moment is in the atmosphere, vacuum atmosphere (about 0.006Pa) and Ar gas atmosphere.Ar gas is supplied with on the limit, and heat treated is carried out on the limit.When TDS measured, the heat-up rate when being heated to 700 ℃ was 0.5 ℃ of a per second.When being heated to 700 ℃, measure the hydrogen of emitting.
(location: the wild city of Tokyo Musashi) the intensification disengaging analytical equipment EMD-WA1000S/H of system carries out mensuration with electronics science Co., Ltd..This measurement result is shown in Figure 12.The transverse axis of the graphic representation among the figure represents to measure temperature, and the longitudinal axis represents that hydrogen emits intensity.The hydrogen concentration of the test film of not heat-treating is 1.5 quality ppm.When it was carried out heat treated in atmosphere, the hydrogen concentration of test film became 0.7 quality ppm.When carrying out heat treated in vacuum atmosphere, the hydrogen concentration of test film becomes 0.4 quality ppm.Under the situation of Ar air-flow, in the enforcement of heat treated, be reduced to 0.4 quality ppm.
Other experimental example 2
The test film that use is made by SUH660 carries out the heat treated experiment.Test film is the pole of diameter 7mm.The circular plate shape that cuts into diameter 7mm, thickness 0.8mm is measured for TDS.Experiment is to put into test film to carry out 16 hours heat treated, carry out ageing treatment in 720 ℃ of temperature.The experiment atmosphere of this moment is vacuum atmosphere (about 0.006Pa).The hydrogen concentration of the test film before the ageing treatment is 1.3ppm.After the ageing treatment, the hydrogen concentration of test film becomes 0.6ppm.
Like this, stainless steel is carried out ageing treatment etc. in its manufacturing process, can remove the hydrogen that wherein contains.When TDS measured, the heat-up rate when being heated to 600 ℃ was 0.33 ℃ of a per second.When being heated to 600 ℃, measure the hydrogen of emitting.The intensification disengaging analytical equipment EMD-WA1000S/H that measures with electronics science Co., Ltd. (the wild city of Tokyo Musashi) system carries out.This measurement result is shown in Figure 13.The transverse axis of the graphic representation among the figure represents to measure temperature, and the longitudinal axis represents that hydrogen emits intensity.
The possibility of utilizing on the industry
The present invention can use in corrosion resistance is utilized the field of High Pressure Hydrogen simultaneously. Particularly can be used in and worry to invade metal sealing sheet that the hydrogen brittleness delayed fracture occurs, automobile with the valve of various valves, spring, steel band, cutter material, fuel cell, the peripheral usefulness of fuel cell system, spring material etc. because of hydrogen.
Claims (12)
1. austenite stainless steel, it is characterized in that, having crystalline structure is the austenite phase of centroid cubic lattice structure, remove the diffustivity hydrogen and the non-dispersive hydrogen that become the hydrogen embrittlement of described austenite stainless steel reason, the hydrogen (H) that contains in the described austenite stainless steel is removed to 0.00007 quality %, that is, below the 0.7 quality ppm.
2. austenite stainless steel according to claim 1 is characterized in that, removes described diffustivity hydrogen and described non-dispersive hydrogen, and described hydrogen (H) is become below the 0.00004 quality %, that is, and and below the 0.4 quality ppm.
3. austenite stainless steel according to claim 2 is characterized in that, removes described diffustivity hydrogen and described non-dispersive hydrogen, and described hydrogen (H) is become below the 0.00001 quality %, that is, and and below the 0.1 quality ppm.
4. according to each described austenite stainless steel in the claim 1～3, it is characterized in that, described austenite stainless steel is carried out heat treated under the Heating temperature more than 200 ℃, removed described diffustivity hydrogen and described non-dispersive hydrogen.
5. austenite stainless steel according to claim 4 is characterized in that, described Heating temperature is 200～500 ℃ a temperature.
6. the dehydrogenating process of an austenite stainless steel, be to be used for heat treated to have the austenite stainless steel that crystalline structure is the austenite phase of centroid cubic lattice structure, remove the heat treating method of the hydrogen that exists in the described austenite stainless steel, it is characterized in that, the described austenite stainless steel of heating under the condition of Heating temperature more than 200 ℃, the diffustivity hydrogen in the described austenite stainless steel and the amount of non-dispersive hydrogen are removed to 0.00007 quality %, that is, and below the 0.7 quality ppm.
7. the dehydrogenating process of austenite stainless steel according to claim 6, it is characterized in that, described Heating temperature is 200～500 ℃ a temperature, remove described diffustivity hydrogen and described non-dispersive hydrogen, the hydrogen (H) that contains in the described austenite stainless steel is become below the 0.00007 quality %, promptly, 0.7 below the quality ppm, described diffustivity hydrogen and described non-dispersive hydrogen are present in the described austenite stainless steel, the processing that Jie is caused by the circulation loading is brought out martensitic phase and is spread, assemble in the crackle portion that meets with stresses concentrated, become the reason of the hydrogen embrittlement of described austenite stainless steel.
8. the dehydrogenating process of austenite stainless steel according to claim 6, it is characterized in that, under 200～500 ℃ the temperature lower, described austenite stainless steel kept the time below 460 hours than sensitizing temperature, described sensitizing temperature is the temperature that chromium (Cr) carbide of described austenite stainless steel is separated out because of heating
Remove the described diffustivity hydrogen and the described non-dispersive hydrogen of the reason of the hydrogen embrittlement that becomes described austenite stainless steel, the described hydrogen (H) that contains in the described austenite stainless steel is become below the 0.00004 quality %, that is, and below the 0.4 quality ppm.
9. according to the dehydrogenating process of claim 7 or 8 described austenite stainless steels, it is characterized in that, the described hydrogen (H) that contains in the described austenite stainless steel is become below the 0.00001 quality %, that is, and below the 0.1 quality ppm.
10. the dehydrogenating process of austenite stainless steel according to claim 6, be used to remove the hydrogen that exists in the austenite stainless steel, it is characterized in that, in the manufacturing process of described austenite stainless steel, in described Heating temperature and be lower than and keep more than 30 seconds in the temperature range of fusing point, the described diffustivity hydrogen that contains in the described austenite stainless steel and the amount of described non-dispersive hydrogen are become below the 0.00007 quality %, that is, and below the 0.7 quality ppm.
11. the dehydrogenating process of austenite stainless steel according to claim 10 is used to remove the hydrogen that exists in the austenite stainless steel, it is characterized in that, described Heating temperature is more than 700 ℃ and be lower than in the temperature range of fusing point of described austenite stainless steel.
12. the dehydrogenating process of austenite stainless steel according to claim 11, be used to remove the hydrogen that exists in the austenite stainless steel, it is characterized in that, described Heating temperature is more than 920 ℃, the described diffustivity hydrogen in the described austenite stainless steel and the amount of described non-dispersive hydrogen are removed to 0.00004 quality %, that is, below the 0.4 quality ppm.
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| JP2007022467 | 2007-01-31 | ||
| JP022467/2007 | 2007-01-31 | ||
| PCT/JP2007/069589 WO2008093453A1 (en) | 2007-01-31 | 2007-10-05 | Austenite based stainless steel and method of dehydrogenating the same |
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| EP (1) | EP2108710A4 (en) |
| JP (1) | JP2008208451A (en) |
| KR (1) | KR20090109466A (en) |
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| JPH0649538A (en) * | 1992-07-29 | 1994-02-22 | Nippon Nuclear Fuel Dev Co Ltd | Method for testing hydrogen embrittlement sensitivity of metallic material |
| JP3542239B2 (en) * | 1996-10-15 | 2004-07-14 | 新日本製鐵株式会社 | High-strength stainless wire with excellent resistance to longitudinal cracking and its wire |
| JP3718308B2 (en) | 1997-01-13 | 2005-11-24 | 株式会社東芝 | Manufacturing method of vacuum valve |
| DE69824702T2 (en) * | 1997-08-19 | 2005-08-04 | Mitsubishi Heavy Industries, Ltd. | AUSTENITIC STAINLESS STEEL WITH RESISTANCE TO INJURY BY NEUTRON RADIATION |
| JPH11181517A (en) * | 1997-12-16 | 1999-07-06 | Nippon Steel Corp | Method for dehydrogenating steel |
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- 2007-10-05 CN CN2007800172824A patent/CN101443469B/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| EP2108710A1 (en) | 2009-10-14 |
| CN101443469B (en) | 2012-10-24 |
| US20090263269A1 (en) | 2009-10-22 |
| WO2008093453A1 (en) | 2008-08-07 |
| EP2108710A4 (en) | 2010-07-14 |
| KR20090109466A (en) | 2009-10-20 |
| US20100154939A1 (en) | 2010-06-24 |
| CA2649355A1 (en) | 2008-08-07 |
| JP2008208451A (en) | 2008-09-11 |
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