CN106399806B - A kind of batch preparation of nano-structure oxide dispersion strengthened steel - Google Patents
A kind of batch preparation of nano-structure oxide dispersion strengthened steel Download PDFInfo
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Abstract
The present invention provides a kind of batch preparation of nano-structure oxide dispersion strengthened steel：The supersaturated powder alloy prepared using atomization is raw material, with mechanical alloying ball milling, hot solids processing and the Subsequent thermomechanical treatment process in the conventional fabrication process flow of powder alloy hot rolling substitution nanostructured ODS steel, nano-structure oxide dispersion strengthened steel is directly prepared.The powder alloy hot rolling is divided to breaking down and finish to gauge two steps, and it is that nanometer mutually separates out offer forming core site that breaking down, which makes powder alloy preliminary solids be melted into shape with high density dislocation is formed, and finish to gauge completes the solidification of alloy and is densified and separates out high density nano-strengthening phase.Prepared by the batch that this method is suitable for nanostructured ODS steel, and improve intensity while the holding excellent Flouride-resistani acid phesphatase of material anti-helium brittleness energy and improve toughness plasticity.
Description
Technical field
The present invention relates to the core component cladding nuclear fuels/covering high temperature resistant, high intensity, Flouride-resistani acid phesphatase alloy of nuclear reactor
Technology of preparing, the batch system of high performance and nano structure oxide dispersion intensifying steel (nanostructured ODS steel) a kind of is especially provided
Preparation Method.
Background technology
Cladding nuclear fuels are the critical structural components that operating mode is most harsh in reactor, its effect is to prevent radioactive fission thing
Matter enters primary cooling system, and Fukushima, Japan Nuclear Power Accident is the thing caused by cooling system failure causes fuel sheath failure
Therefore U.S. Department of Energy starts the research of the new nuclear fuel of light water reactor and new cladding materials to increase security immediately after occurring.It is existing
The advanced nuclear reactors such as fast reactor and fusion reactor are being greatly developed in the world, and the working environment of its fuel can/covering is very
It is harsh：High temperature, continually changing huge stress, strong chemical reaction environment, long-term neutron irradiation and high He amounts etc., cause bag
The change and physics of a series of microstructures of shell/clad material and mi-crochemistry, the notable deterioration of chemistry and mechanical property, therefore
High requirement is proposed to material.As one of most important safety curtain of nuclear reactor, fuel can/covering research has become
The hot spot of international nuclear material research.People gradually recognize in long-term R＆D process, in order to meet Advanced Reactor to involucrum/bag
The key structure material at high temperature creep strengths such as layer and Flouride-resistani acid phesphatase, the requirement of anti-He brittleness energy, material must have highdensity receive
Metrical scale (several nanometers) strengthens precipitated phase, and only passes through solid solution/super saturated solid solution of respective alloy element and separate out again,
It can realize the formation of the nanoscale hardening constituent of highly dispersed distribution, thus develop nano-structure oxide dispersion strengthened steel
(nanostructured ODS steel), the ultra high density of its characteristic is (up to 1023—1024/m3, it is higher by than ordinary oxide dispersion-strengthened steel
3-4 orders of magnitude), nanoscale (2-5nm), highly dispersed distribution it is nonequilibrium it is non-chemical than rich Y-Ti-O reinforcing precipitation
Phase, is the enormous amount Dispersed precipitate of the point defect (room and interstitial atom) that capture irradiation produces and the He that nuclear reaction generates
Site, makes point defect and He are evenly distributed on respectively in the form of extremely fine point defect group and He bubbles in material matrix, so that
Effectively reduce void swelling and He is crisp, avoid generating macroscopic void on crystal boundary and big He bubbles cause material creep intensity decreases and material
It is brittle；In addition, the effectively pin of the excellent high-temperature stability shape paired dislocation of the dispersion-strengtherning precipitated phase of ultra high density and crystal boundary,
Significantly improve the intensity and high temperature creep strength of material.Now, nanostructured ODS steel is because of its excellent Flouride-resistani acid phesphatase and the crisp energy of anti-helium
The leading candidate material and international research of power and excellent elevated temperature strength with creep strength and as Advanced Reactor fuel can/covering
Hot spot.For performance, nanostructured ODS steel has possessed involucrum/clad material application prospect substantially, but due to existing system
Its preparative capacibility of standby technology restriction is only feather weight, seriously constrains it as the practical of nuclear reactor cladding materials, solves
Its batch preparative capacibility becomes the key technology bottleneck for the new involucrum of the restriction/clad material development for being badly in need of solving at present then.Cause
This development nanostructured ODS steel batch preparation makes system to substitute the complicated technology link of existing conventional formulation techniques
Standby material still possesses the characteristic microstructure of nanostructured ODS steel, particularly to the vital high density nanometer of performance
Precipitated phase, becomes the key problem of development nanostructured ODS steel.
The performances such as the excellent Flouride-resistani acid phesphatase of nanostructured ODS steel, high temperature resistant are superelevation first from its unique microstructure
The nanometer precipitated phase of density.To form this microstructure characteristic, the following processing steps used in conventional formulation techniques are led
The low of preparation efficiency is caused：
1., prolonged mechanical alloying：Purpose is to form the powder alloy of super saturated solid solution and mutually separate out for nanometer to make group
Knit preparation.It is with high pure metal powder or atomization foundry alloy powder and yttria nanopowders through a long time high energy in customary preparation methods
Ball milling forms high density dislocation and is mutually analysed for follow-up nanometer to obtain the powder alloy of Y super saturated solid solutions, other element solid solutions
Go out to provide forming core site.Y is the key element to form high density nanometer phase, and the oxide precipitated phase of rich Y has excellent heat surely
Qualitative and irradiation stability, but room temperature solubilities of the Y in steel is extremely low, it is difficult to it is allowed to have in the alloy by ordinary metallurgical method
Enough solid solutions, therefore mechanical alloying ball milling becomes the main means for realizing Y super saturated solid solutions.It is but several often to be needed up to this purpose
Ten to hundreds of hours (energy for depending on equipment), long-time ball milling is also difficult to avoid that oxygen and grinding medium in milling atmosphere
The pollution of matter (mill ball and tank body), causes material property to decline.Mechanical alloying ball milling, which becomes, causes ODS steel preparative capacibilities low
Under (be only feather weight) and be difficult to one of the main reason for practical；
2. hot solids：Purpose is to realize high density nanometer mutually precipitation, powder alloy from super saturated solid solution powder alloy
Solidification and densification.Conventional hot solids main means are high temperature insostatic pressing (HIP) and hot extrusion.The former the advantages of is not produce
The anisotropy of obvious tissue and performance, shortcoming are that required temperature is high, the time is long, crystal grain is thicker, of high cost, and need to be into one
Hot rolling is walked to increase consistency and improve performance.The advantages of hot extrusion is that required temperature is relatively low, the time is short, crystal grain is tiny, but is deposited
In the anisotropy of obvious organization and performance, (draw ratio of crystal grain is up to 10：1), it is necessary to which complicated Subsequent thermomechanical is handled,
After preparation i.e. in nanostructured ODS steel is basically completed (nanometer precipitated phase forms and complete solidification), to eliminate crystal grain in heat
The direction of extrusion too elongates that (draw ratio of crystal grain is remote>1) high temperature and thermo-mechanical processi carried out, will pass through recrystallization and heat engine
The draw ratio of tool processing adjustment crystal grain this not only adds the complexity of preparation process, and is likely to result in nanometer analysis to ≈ 1
Go out phase scale grow up, density reduce and grain coarsening and reduce material property.Carrying out solidified technique using hot extrusion also makes
Preparative capacibility is limited.
The content of the invention
In order to solve the problems, such as that the existing conventional fabrication process preparation efficiency of nanostructured ODS steel and preparative capacibility are low, this
Invention provides a kind of batch preparation of nanostructured ODS steel, and this method is using powder alloy hot-rolling method substitution nano junction
The conventional fabrication process flow of structure ODS steel (is prepared at foundry alloy → mechanical alloying ball milling → hot solids processing → subsequent thermal
Reason), so as to fast and efficiently prepare the nanostructured ODS steel for possessing higher elevated temperature strength and toughness plasticity.
Technical solution of the present invention is as follows：
A kind of batch preparation of nano-structure oxide dispersion strengthened steel, it is characterised in that：With atomization (specific side
Method see another patent application " a kind of high efficiency preparation method of nano-structure oxide dispersion strengthened steel " of present invention applicant,
Patent No. ZL201210513997.1) prepare supersaturated powder alloy be raw material, it is hot rolled directly to prepare with nanometer
The nano-structure oxide dispersion strengthened steel of structure ODS steel characteristic microstructures.
Wherein, supersaturated powder alloy prepared by atomization is full of jacket (being made of pure iron or mild steel) before hot rolling,
Powder alloy hot rolling is carried out after 400 DEG C are heated degasification sealing.
The batch preparation of nano-structure oxide dispersion strengthened steel of the present invention, it is characterised in that the hot rolling
It is divided into two steps：Breaking down and finish to gauge, wherein, breaking down temperature TBreaking down=T0- Δ TBreaking down,ΔTBreaking down=20~80 DEG C；Finishing temperature
TFinish to gauge=T0+ΔTFinish to gauge, Δ TFinish to gauge=90~300 DEG C；Wherein T0Be the alloying element of solid solution/super saturated solid solution in powder alloy again
The start temperature substantially separated out, can be determined by experiment.Breaking down is different with the rolling temperature of finish to gauge, thus rolls to alloy knot
Structure has different influences：Breaking down makes powder alloy preliminary solids, and generates the crystal defects such as high density dislocation in the alloy, is
Thereafter nanometer mutually separates out the forming core site needed for providing during finish to gauge；Finish to gauge forms the precipitation of high density nanoscale in steel
Phase, and complete the solidification and densification of alloy.If breaking down temperature TBreaking down≥T0It can then cause because lacking forming core site in steel
Nanometer precipitated phase in nanostructured ODS steel does not reach due high density, Δ TBreaking downThe deformation of alloy when crossing conference increase rolling
Resistance, the defects of may causing to produce macroscopic cracking in the operation of rolling.TFinish to gauge＜ T0High density will not be formed and strengthen precipitated phase, Δ
TFinish to gauge>=90 DEG C are to make material full densification, but Δ TFinish to gaugeCrossing senior general makes precipitated phase roughening and penalty, causes nanometer
The standby failure of structure ODS steels.
The batch preparation of nano-structure oxide dispersion strengthened steel of the present invention, it is characterised in that：1. breaking down
Rolling is than (total deformation of breaking down, powder original depth during being full of powder alloy in jacket on the basis of) εBreaking down>=70%；②
The rolling of finish to gauge is than (total deformation of finish to gauge, on the basis of the alloy thickness after the completion of breaking down) εFinish to gauge>=70%；3. breaking down and end
Roll should all shunting time carry out, bloom pass quantity NBreaking downWith last pass quantity NFinish to gaugeThe size of power, workpiece depending on milling train
Situation is reduced with the temperature in the workpiece operation of rolling, the temperature of workpiece must be maintained at foregoing in the operation of rolling of every a time
The breaking down of defined and rolling temperature control range；4. the rolling direction of neighboring track time changes 90 ° during rolling, to mitigate and avoid
Rolling causes the anisotropy (texture) for occurring alloy grain orientation and performance in nanostructured ODS steel；
The batch preparation of nano-structure oxide dispersion strengthened steel of the present invention, it is characterised in that：Total finish to gauge
Time tFinish to gauge=∑ ti≤t0[1-0.25 (Δ TFinish to gauge/ 300)], i.e., total finish to gauge time tFinish to gauge≤t0, and with finishing temperature TFinish to gauge
Rise and shortened, wherein t0For in temperature T0Shi Gangzhong forms the time needed for the nanometer precipitated phase of maximal density, that is, exists
In T in conventional fabrication process0Soaking time during hot solidsization processing is carried out, can be determined by experiment；TFinish to gaugeFor finishing temperature；
Corner brace i=1,2 ..., tN finish to gaugesFor last pass sequence number, tI=t1,t2... tN finish to gaugesFor finish to gauge the 1st, 2 ... NFinish to gaugeWorkpiece temperature in passage
Degree reaches TFinish to gaugeThe sum of rear insulation and mill operation time.After the completion of finish to gauge, by controlling the type of cooling to obtain corresponding crystal knot
The nanostructured ODS steel of structure, the type of cooling is furnace cooling, air-cooled, oil cooling or water cooling.
The batch preparation of nano-structure oxide dispersion strengthened steel of the present invention, it is characterised in that：The nanometer
Structure oxide dispersion-strengthened steel is nanostructured ODS martensite steels, nanostructured ODS ferrite/martensites dual phase steel or receives
Rice structure ODS ferritic steels；Wherein the component of martensite steel and ferrite/martensite dual phase steel is mass percent wt%：Cr
7-12, W 1-5, Ti 0.1-1.0, Y 0.1-1.0, Al 0.1-5.0, contain or not contain Mn, Ta of total amount≤1wt%, V,
C, N, remaining is Fe；The component of ferritic steel is mass percent wt%：Cr 13-20, W 1-5, Ti 0.1-1.0, Y 0.1-
1.0, Al 0.1-5.0, contain or not contain Mn, Ta, V, C, N of total amount≤0.8wt%, remaining is Fe.
Since powder alloy forms and phase in the mechanical alloying mechanical milling process in customary preparation methods in breaking down process
As high density nanometer mutually form site, finish to gauge provides the thermodynamics bar that the nanometer similar to hot solidsization processing mutually separates out
Part, therefore provide by supersaturated powder alloy hot rolling the necessary bar for the characteristic microstructure to form nanostructured ODS steel
Part.Compared with customary preparation methods, the hot rolling of powder alloy can realize a nanometer batch production for ODS steel, be its practical offer skill
Art approach.Hot rolling makes nanostructured ODS crystalline grain of steel more refine the elevated temperature strength and creep strength for being conducive to improve alloy, hot rolling
The defects of improving consistency, reducing microfissure is conducive to improve the toughness plasticity of material.
The invention key technical problem to be solved：
The maximum feature that nanostructured ODS steel is different from other materials is the nanometer precipitated phase for having very high-density, it is
The most important microstructure characteristic of nanostructured ODS steel, and can be with good elevated temperature strength with the anti-helium brittleness of excellent Flouride-resistani acid phesphatase
Deciding factor.The microstructure of nanostructured ODS steel characteristics, particularly nanometer precipitated phase, bag are formed during finish to gauge
The scale and density of precipitated phase are included, is the key technical problem of this invention.
Crystal structure types of this invention according to nanostructured ODS steel and its nanometer precipitated phase in preparation process for this
Formation condition, it is specified that breaking down temperature TBreaking down, finishing temperature TFinish to gaugeThe heating time t total with finish to gaugeFinish to gaugeDeng control condition, really
Protect after the completion of the hot rolling of powder alloy, while Alloy Forming is with densification, form the distinctive feature of nanostructured ODS steel
Property microstructure.
The beneficial effects of the invention are as follows：
1., the present invention prepare nano-structure oxide dispersion strengthened steel for batch and provide technological approaches, preparation efficiency and
Conventional method compared to greatly improving, efficiently solve customary preparation methods inefficiency, single can prepare quantity it is too low (kilogram
Level), product degree of purity fluctuation big (cause performance inconsistency big) the shortcomings of, be nanostructured ODS steel as cladding nuclear fuels/covering
The batch of material prepares and practical offer technical foundation；
2., the nanostructured ODS steel that is prepared using the method for the invention, alloy grain degree ratio using high temperature insostatic pressing (HIP) etc. often
Rule method substantially refines (average crystal grain scale is reduced to about 0.5 μm from about 1~2 μm), and material density is improved to >=99% reason
By density.Therefore compared with the nanostructured ODS steel routinely prepared, its elevated temperature strength of alloy and toughness plasticity prepared by the present invention is equal
Increase；
3., using preparation method of the present invention, be not in obvious texture in alloy, grain form is not obvious
Anisotropy, therefore the performance of material does not have obvious directionality, it is no longer necessary to Subsequent thermomechanical processing.
Embodiment
Embodiment 1
Nanostructured oxide dispersion-strengtherning martensite steel is prepared, alloy composition is (mass percent wt%, similarly hereinafter) Fe-
9Cr-1W-0.3Ti-0.3Y-0.1Al-0.2Ta。
The atomization powder alloy of alloying element whole solid solution/super saturated solid solution is prepared by alloy composition.(atomization powder alloy
Preparation referring to applicant another authorized patent " efficient preparation side of one kind of nano-structure oxide dispersion strengthened steel
Method ", patent No. ZL201210513997.1, similarly hereinafter).Through Analyzer testing result atomization powder alloy average grain diameter~110 μm.
Detected through X- diffraction and show that powder alloy only has the diffraction maximum of Fe, show whole alloying elements include Y and Ti be dissolved completely/
Super saturated solid solution.Atomized alloy powder encloses jacket and is heated to sealing after 400 DEG C of pumpings.According to experimental studies results and common process
Prepare the technical data of nanostructured ODS martensite steels, the T of corresponding component0=850 DEG C, to=60 minutes.The present embodiment uses
TBreaking down=800 DEG C (correspond to Δ TBreaking down=50 DEG C), NBreaking down=4, εBreaking down=20% × NBreaking down=80%；TFinish to gauge=1100 DEG C (correspond to
ΔTFinish to gauge=250 DEG C), NFinish to gauge=3, εFinish to gauge=25% × NFinish to gauge=75%, tFinish to gauge=15 minutes/passage × NFinish to gauge=45 minutes.Finish to gauge
Water cooling afterwards.Sampling shows that the alloy after hot rolling is martensitic structure through Electronic Speculum detection, crystal particle scale is average~and 0.52 μm, it is fine and close
~99.3% solid density is spent, precipitated phase is mainly the rich Y-Ti-O precipitated phases of scale 2-5nm, separates out phase density~2 × 1024/
m3.Room-temperature yield strength reaches 1180MPa, elongation percentage 15%, and the ODS steel room temperatures of the same sample ingredient prepared with conventional method are bent
It is 1050MPa to take intensity, elongation percentage 10% (see comparative example 1).
Embodiment 2
Nanostructured oxide dispersion-strengtherning martensite steel is prepared, alloy composition is Fe-8Cr-2W-0.9Ti-0.4Y-
0.1Al-0.2Ta-0.1V-0.1Mn-0.1C。
The atomization powder alloy of alloying element whole solid solution/super saturated solid solution is prepared by alloy composition.Through Particle Size Analyzer
Detection atomization powder alloy average grain diameter~105 μm.The diffraction maximum for showing that powder alloy only has Fe is detected through X- diffraction, is shown complete
Portion's alloying element complete solid solution/super saturated solid solution.Atomized alloy powder encloses jacket and is heated to sealing after 400 DEG C of pumpings.Root
Result of study and common process prepare the technical data of nanostructured ODS martensite steels, the T of corresponding component according to the experiment0=860
DEG C, to=60 minutes.The present embodiment uses TBreaking down=780 DEG C (correspond to Δ TBreaking down=80 DEG C), NBreaking down=4, εBreaking down=20% × NBreaking down
=80%；TFinish to gauge=1100 DEG C (correspond to Δ TFinish to gauge=240 DEG C), NFinish to gauge=3, εFinish to gauge=25% × NFinish to gauge=75%, tFinish to gauge=15 points
Clock/passage × NFinish to gauge=45 minutes.Water cooling after finish to gauge.Sampling shows that the alloy after hot rolling is martensitic structure through Electronic Speculum detection,
Average~0.61 μm of crystal particle scale, the solid density of consistency~99.2%, precipitated phase is mainly the rich Y-Ti-O analysis of scale 2-5nm
Go out phase, separate out phase density~1.9 × 1024/m3。
Embodiment 3
Nanostructured oxide dispersion-strengtherning martensite/ferrite dual phase steel is prepared, alloy composition is Fe-12Cr-2W-
0.3Ti-0.8Y-4Al-0.3V-0.1Ta-0.4Mn-0.1N。
The atomization powder alloy of alloying element whole solid solution/super saturated solid solution is prepared by alloy composition.Through Particle Size Analyzer
Detection atomization powder alloy average grain diameter~99.3 μm.The diffraction maximum for showing that powder alloy only has Fe is detected through X- diffraction, is shown
Whole alloying elements complete solid solution/super saturated solid solution.Atomized alloy powder encloses jacket and is heated to sealing after 400 DEG C of pumpings.
The technical data of nanostructured ODS martensite steels, the T of corresponding component are prepared according to experimental studies results and common process0=910
DEG C, to=54 minutes.The present embodiment uses TBreaking down=860 DEG C (correspond to Δ TBreaking down=50 DEG C), NBreaking down=3, εBreaking down=25% × NBreaking down
=75%；TFinish to gauge=1000 DEG C (correspond to Δ TFinish to gauge=90 DEG C), NFinish to gauge=3, εFinish to gauge=25% × NFinish to gauge=75%, tFinish to gauge=16 points
Clock/passage × NFinish to gauge=48 minutes.It is air-cooled after finish to gauge.Sampling shows that the alloy after hot rolling is martensite/iron element through Electronic Speculum detection
Body duplex structure, crystal particle scale is average~0.64 μm, and the solid density of consistency~99.1%, precipitated phase is mainly scale 2-5nm
Rich Y-Ti-O precipitated phases, separate out phase density~2.5 × 1024/m3。
Embodiment 4
Nanostructured oxide dispersion-strengtherning martensite/ferrite dual phase steel is prepared, alloy composition is：Fe-11Cr-4W-
0.5Ti-0.5Y-2Al-0.2Ta-0.1Mn-0.5V-0.1N。
The atomization powder alloy of alloying element whole solid solution/super saturated solid solution is prepared by alloy composition.Through Particle Size Analyzer
Detect atomized alloy powder average grain diameter~106.3 μm.The diffracted ray for showing that powder alloy only has Fe is detected through X- diffraction, is shown complete
Portion's alloying element whole solid solution/super saturated solid solutions.Atomized alloy powder encloses jacket and is heated to sealing after 400 DEG C of pumpings.Root
Result of study and common process prepare the technical data of nanostructured ODS martensite steels/ferrite dual phase steel according to the experiment, accordingly into
The T divided0=840 DEG C, to=57 minutes.The present embodiment uses TBreaking down=780 DEG C (correspond to Δ TBreaking down=60 DEG C), NBreaking down=3, εBreaking down
=25% × NBreaking down=75%；TFinish to gauge=1140 DEG C (correspond to Δ TFinish to gauge=200 DEG C), NFinish to gauge=3, εFinish to gauge=25% × NFinish to gauge=
75%, tFinish to gauge=15 minutes/passage × NFinish to gauge=45 minutes.It is air-cooled after finish to gauge.Sampling is detected through Electronic Speculum to be shown, the alloy after hot rolling
It is martensite/ferrite dual phase tissue, crystal particle scale is average~0.67 μm, the solid density of consistency~99.2%, precipitated phase master
If the rich Y-Ti-O precipitated phases of scale 2-5nm, phase density~9.9 × 10 are separated out23/m3。
Embodiment 5
Prepare nanostructured oxide dispersion strengthening ferrite steel, alloying component Fe-14Cr-2W-0.3Ti-0.3Y-
0.1Al-0.2OTa。
The atomization powder alloy of alloying element whole solid solution/super saturated solid solution is prepared by alloy composition.Through Particle Size Analyzer
Detect atomized alloy powder average grain diameter~113.3 μm.The diffraction maximum for showing that powder alloy only has Fe is detected through X- diffraction, is shown complete
Portion's alloying element whole solid solution/super saturated solid solutions.Atomized alloy powder encloses jacket and is heated to sealing after 400 DEG C of pumpings.Root
Result of study and common process prepare the technical data of nanostructured ODS ferritic steels, the T of corresponding component according to the experiment0=850
DEG C, to=54 minutes.The present embodiment uses TBreaking down=770 DEG C (correspond to Δ TBreaking down=80 DEG C), NBreaking down=5, εBreaking down=15% × NBreaking down
=75%；TFinish to gauge=1150 DEG C (correspond to Δ TFinish to gauge=300 DEG C), NFinish to gauge=3, εFinish to gauge=25% × NFinish to gauge=75%, tFinish to gauge=13 points
Clock/passage × NFinish to gauge=39 minutes.It is air-cooled after finish to gauge.Sampling shows that the alloy after hot rolling is ferritic structure through Electronic Speculum detection,
Average~0.53 μm of crystal particle scale, the solid density of consistency~99.3%, precipitated phase is mainly the rich Y-Ti-O analysis of scale 2-5nm
Go out phase, separate out phase density~9.9 × 1023/m3。
Embodiment 6
Prepare nanostructured oxide dispersion strengthening ferrite steel, alloying component Fe-19Cr-1W-0.5Ti-0.5Y-
0.4Al-0.2Ta-0.3V-0.1C-0.1N。
The atomization powder alloy of alloying element whole solid solution/super saturated solid solution is prepared by alloy composition.Through Particle Size Analyzer
Detect atomized alloy powder average grain diameter~114.3 μm.The diffracted ray for showing that powder alloy only has Fe is detected through X- diffraction, is shown complete
Portion's alloying element whole solid solution/super saturated solid solution.Atomized alloy powder encloses jacket and is heated to sealing after 400 DEG C of pumpings.According to
Experimental studies results and common process prepare the technical data of nanostructured ODS ferritic steels, the T of corresponding component0=830 DEG C, to
=54 minutes.The present embodiment uses TBreaking down=750 DEG C (correspond to Δ TBreaking down=80 DEG C), NBreaking down=4, εBreaking down=20% × NBreaking down=
80%；TFinish to gauge=950 DEG C (correspond to Δ TFinish to gauge=120 DEG C), NFinish to gauge=3, εFinish to gauge=25% × NFinish to gauge=75%, tFinish to gauge=16 minutes/
Passage × NFinish to gauge=48 minutes.It is air-cooled after finish to gauge.Sampling shows that the alloy after hot rolling is martensitic structure, crystal grain through Electronic Speculum detection
Average~0.42 μm of scale, the solid density of consistency~99.1%, precipitated phase is mainly that the rich Y-Ti-O of scale 2-5nm is separated out
Phase, separates out phase density~9.5 × 1023/m3。
Comparative example 1：
Nanostructured oxide dispersion-strengtherning martensite steel is prepared according to existing conventional method.Alloying component is the same as embodiment 1.
With foundry alloy of the vaccum sensitive stove refining without Ti and Y；Foundry alloy is inserted into powder by atomization device, is evacuated to 6.6 × 10- 1Pa, is then charged with argon gas, heats and carries out powder by atomization after opening electromagnetic agitation to alloy raw material all fusing.Atomization gas
For argon gas, pressure 3.0MPa, alloy flow quantity 0.22kg/s.140 μm of alloyed powder average grain diameter.By atomized alloy powder and quality hundred
Divide the Ti powder and 0.3 Y than 0.32O3Powder mixing is placed in planetary high-energy ball mill, when ball milling 70 is small under Ar protections, ball milling
Alloyed powder afterwards encloses jacket, into 1100 DEG C of trip temperature, the soaking time powder alloy thermosetting of 60 minutes in hot isostatic press
Bodyization is handled, hot-rolled temperature t used by above-mentioned hot solids technological parameter and embodiment 1oIt is identical, heat is carried out after high temperature insostatic pressing (HIP)
Processing, normalizing/quenching+tempering processing, the solid density of consistency~98%.Sampling shows through Electronic Speculum detection, is organized as martensite,
Crystal particle scale is~1.5 μm average, has highly dispersed, scale 2-5nm rich Y-Ti-O precipitated phases, density 3.2 × 1023/m3。
It is also observed that scale arrives the thick oxides of hundreds of nanometers richness Cr/Ti for tens nanometers, room-temperature yield strength is
1050MPa, elongation percentage 10%.
Comparative example 2：
Nanostructured oxide dispersion strengthening ferrite steel is prepared according to existing conventional method.Alloying component is the same as embodiment 6.
With foundry alloy of the vaccum sensitive stove refining without Ti and Y；Foundry alloy is inserted into powder by atomization device, is evacuated to 6.7 × 10- 1Pa, is then charged with argon gas, heats and carries out powder by atomization after opening electromagnetic agitation to alloy raw material all fusing.Atomization gas
For argon gas, pressure 3.0MPa, alloy flow quantity 0.22kg/s.134 μm of alloyed powder average grain diameter.By atomized alloy powder and quality hundred
Divide the Ti powder and 0.5 Y than 0.52O3Powder mixing is placed in planetary high-energy ball mill, when ball milling 75 is small under Ar protections, ball milling
Alloyed powder afterwards encloses jacket, and hot extrusion, soaking time t are carried out at 950 DEG Co=50, above-mentioned Hot Extrusion Parameters are with implementing
Hot-rolled temperature t used by example 6oIt is identical, the solid density of consistency~98.6%.Electronic Speculum detection shows that alloy is after solidification
Ferritic structure, crystal particle scale is average~and 0.88 μm, but crystal grain elongates in hot extrusion direction, and the aspect ratio of crystal grain is more 3:1 to
4:1, there is highly dispersed, scale 2-5nm rich Y-Ti-O precipitated phases, density 8.0 × 10 in alloy23/m3.Additionally observe
To scale the thick oxides of hundreds of nanometers richness Cr/Ti are arrived for tens nanometers.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (7)
- A kind of 1. batch preparation of nano-structure oxide dispersion strengthened steel, it is characterised in that：The mistake prepared with atomization Saturation powder alloy is raw material, hot rolled directly to prepare the nanostructured with nanostructured ODS steel characteristic microstructures Oxide dispersion intensifying steel；The hot rolling is divided into two steps：Breaking down and finish to gauge, wherein, breaking down temperature TBreaking down=T0- Δ TBreaking down,ΔTBreaking down=20~80 ℃；Finishing temperature TFinish to gauge=T0+ΔTFinish to gauge, Δ TFinish to gauge=90~300 DEG C；Wherein T0It is solid solution/super saturated solid solution in powder alloy The start temperature that alloying element separates out.
- 2. according to the batch preparation of nano-structure oxide dispersion strengthened steel described in claim 1, it is characterised in that：Hot rolling The preceding supersaturated powder alloy for preparing atomization is full of jacket, and powder alloy hot rolling is carried out after 400 DEG C are heated degasification sealing, Wherein jacket is made of pure iron or mild steel.
- 3. according to the batch preparation of nano-structure oxide dispersion strengthened steel described in claim 1, it is characterised in that：Breaking down Rolling compare εBreaking down>=70%；ε is compared in the rolling of finish to gaugeFinish to gauge>=70%.
- 4. according to the batch preparation of nano-structure oxide dispersion strengthened steel described in claim 3, it is characterised in that：Breaking down Divide equally passage with finish to gauge to carry out, the rolling direction of neighboring track time changes 90 ° during rolling.
- 5. according to the batch preparation of any nano-structure oxide dispersion strengthened steel of Claims 1 to 4, its feature exists In：Total finish to gauge time tFinish to gauge=∑ ti≤t0[1-0.25 (Δ TFinish to gauge/ 300)], wherein t0For in temperature T0Shi Gangzhong is formed most Time needed for the nanometer precipitated phase of big density, i.e., in T in conventional fabrication process0When carrying out insulation when hot solidsization are handled Between；TFinish to gaugeFor finishing temperature；Corner brace i=1,2 ..., tN finish to gaugesFor last pass sequence number, ti=t1,t2... tN finish to gaugesFor finish to gauge the 1st, 2 ... NFinish to gaugeWorkpiece temperature reaches T in passageFinish to gaugeThe sum of rear insulation and mill operation time.
- 6. according to the batch preparation of any nano-structure oxide dispersion strengthened steel of Claims 1 to 4, its feature exists In：After the completion of finish to gauge, by controlling the type of cooling, the nanostructured ODS steel of corresponding crystal structure is obtained, the type of cooling is Furnace cooling, air-cooled, oil cooling or water cooling.
- 7. according to the batch preparation of nano-structure oxide dispersion strengthened steel described in claim 1, it is characterised in that：It is described Nano-structure oxide dispersion strengthened steel is nanostructured ODS martensite steels, nanostructured ODS ferrite/martensite dual phase steels Or nanostructured ODS ferritic steels；Wherein the component of martensite steel and ferrite/martensite dual phase steel is mass percent Wt%：Cr 7-12, W 1-5, Ti 0.1-1.0, Y 0.1-1.0, Al 0.1-5.0, contain or not contain total amount≤1wt%'s Mn, Ta, V, C, N, remaining is Fe；The component of ferritic steel is mass percent wt%：Cr 13-20, W 1-5, Ti 0.1-1.0, Y 0.1-1.0, Al 0.1-5.0, contain or not contain Mn, Ta, V, C, N of total amount≤0.8wt%, remaining is Fe.
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