CN107058852B - A method of residual ferrite in refinement oxide dispersion intensifying martensite steel - Google Patents
A method of residual ferrite in refinement oxide dispersion intensifying martensite steel Download PDFInfo
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- CN107058852B CN107058852B CN201710090256.XA CN201710090256A CN107058852B CN 107058852 B CN107058852 B CN 107058852B CN 201710090256 A CN201710090256 A CN 201710090256A CN 107058852 B CN107058852 B CN 107058852B
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- 239000010959 steel Substances 0.000 title claims abstract description 73
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 71
- 229910000734 martensite Inorganic materials 0.000 title claims abstract description 64
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000006185 dispersion Substances 0.000 title claims abstract description 9
- 238000010792 warming Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 37
- 238000005245 sintering Methods 0.000 claims description 26
- 238000005275 alloying Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000004615 ingredient Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 17
- 229910001566 austenite Inorganic materials 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 17
- 230000009466 transformation Effects 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004575 stone Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- 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
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- 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
- C21D2211/005—Ferrite
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a kind of methods of residual ferrite size in refinement oxide dispersion intensifying martensite steel, sintered state 9Cr ODS martensite steels are annealed 1~5h at 800 DEG C so that the Y in sintered state 9Cr ODS martensite steels2O3It is fully precipitated, while generating carbide；Obtain the 9Cr ODS martensite steels of annealed state；The 9Cr ODS martensite steels of annealed state are warming up to 1100 DEG C with 10 DEG C/min, 0~5min is kept the temperature, is then cooled to room temperature with the rate of 30~1000 DEG C/min.The annealing of the present invention ensures Y and O atom with more tiny and disperse Y2O3Form is precipitated completely, and the strain energy stored in sintered state 9Cr ODS steel all discharges；It is stronger to the pinning effect of austenite grain boundary；Obtain tiny residual ferrite crystal grain, the slow rate of heat addition of 10 DEG C/min can promote the dissolving of carbide in heating process, promote austenite phase transformation, further refine residual ferrite size, it is simple for process, purpose is strong, and the elevated temperature strength to further increasing ODS martensite steels is of great significance.
Description
Technical field
The invention belongs to oxide dispersion intensifying martensite steel preparing technical fields, and it is strong to be related to a kind of refinement dispersed oxide
Change the heat treatment process of residual ferrite in martensite steel.
Background technology
The extremely harsh Service Environment of nuclear reactor core requires structural material that can be subjected to high temperature, high pressure, coolant
Chemical attack and strong irradiation stream.Ferrite/martensite heat resisting steel is considered as advanced fission-type reactor fuel jacket pipe and future
Nuclear fusion stack cladding structure candidate material.High heat-intensity oxide dispersion intensifying (ODS) ferrite/martensite steel Europe,
The U.S., Japan and Russia's more than ten years of development.The oxide of addition has Ti2O3And Y2O3.The commercialization preparation of ODS steel is related to fast
Mechanical alloying and subsequent hot extrusion or the hip moulding of alloy powder and superfine oxide powder are consolidated in rapid hardening.Oxygen
The main function of compound additive is the recrystallization process of material after slowing down cold forming or hot-working.The tiny Y of Dispersed precipitate2O3
(and Y-Ti-O) oxide can hinder dislocation motion, improve elevated temperature strength, capture at the same time as defect trap and lured by irradiation displacement
The point defect of hair reduces void swelling.
According to the difference of chromium content and carbon content, the matrix of ODS steel mainly has 9%Cr systems martensite steel and 12~22%Cr
It is ferritic steel, the main distinction is in heating process (complete) austenite phase transformation whether can occur.For inversion of phases ODS
Steel, the Y added in its preparation process2O3Nail can be played to the austenite grain boundary of generation during austenite phase transformation to ferrite
Bundle acts on, and hinders the movement of austenite grain boundary, so that transformation of the ferrite to austenite is obstructed, forms a certain amount of remnants
Ferrite.The concentration of excess of oxygen and the content of Ti, Al alloying element are in oxide dispersion intensifying martensite steel in sintering powder
The generation of residual ferrite has a major impact.Studies have shown that the position difference of martensite-residual ferrite boundary is larger, these
High-angle boundary being capable of Anticrack.The collocation of residual ferrite and this hard and soft tissue of martensite more can effectively be alleviated
Stress concentration and inhibition strain, to improve the creep-resistant property of steel.With increasing for residual ferrite content, 9Cr-ODS
Steel is improved in 700 DEG C of creep strength, but the ductility reduction of steel.It is strong that refined crystalline strengthening mechanism is that one kind can improve steel simultaneously
Degree and plasticity strengthening mechanism, if residual ferrite size can be refined, can improve simultaneously 9Cr-ODS steel creep strength and
Plasticity.However the alloying component for being based primarily upon 9Cr-ODS steel to the control of the content of residual ferrite at present controls, to remainder fe element
The research of body size Control is not yet seen in report.Preparation and subsequent heat treatment work of applicant's early period by control 9Cr-ODS steel
Skill realizes the control to residual ferrite content.But the size of obtained residual ferrite is larger.How by new
Heat treatment process refines residual ferrite size, pair improves the elevated temperature strength of 9Cr-ODS steel and plasticity is of great significance simultaneously.
Invention content
The present invention passes through intermediate annealing process so that in the oxide dispersion intensifying martensite steel of discharge plasma sintering state
Abundant precipitated oxide and carbide refine original austenite grain and residual ferrite using oxide to the pinning effect of crystal boundary
Crystal grain promotes austenite phase transformation, further realizes refinement residual ferrite using the abundant dissolving of carbide under the slow rate of heat addition
The purpose of size.
Specific technical solution is as follows：
A method of residual ferrite size in refinement oxide dispersion intensifying martensite steel, its step are as follows：
1) by pre-alloying powder and nanoscale Y2O3By 99.65:0.35 mass ratio is mixed, pre-alloying powder
Mass component is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C；Mechanical ball mill is carried out in the ball mill, is protected using argon gas；Profit
Ball-milled powder is heated to 800 DEG C with discharge plasma sintering, keeps the temperature 5~10min, it is further heated up to 1100 DEG C, heat preservation 10
~15min, sintering pressure are 40~50MP, cool to room temperature with the furnace, obtain sintered state of the molding consistency 99% or more
9Cr-ODS martensite steels；
2) anneal sintered state 9Cr-ODS martensite steels at 800 DEG C 1~5h so that in sintered state 9Cr-ODS martensite steels
Y2O3It is fully precipitated, while generating carbide；Obtain the 9Cr-ODS martensite steels of annealed state；
3) the 9Cr-ODS martensite steels of annealed state are warming up to 1100 DEG C with 10 DEG C/min, keep the temperature 0~5min, then with
The rate of 30~1000 DEG C/min is cooled to room temperature.
It is preferred that ratio of grinding media to material is 15 in the ball mill:1.
It is preferred that rotational speed of ball-mill is 400r/min in the ball mill.
It is preferred that Ball-milling Time is 45h in the ball mill.
Crystal grain is in growth process, and by the pinning effect of second phase particles, crystallite dimension will be refined significantly.Applicant early period
9Cr-ODS martensite steels have been prepared using discharge plasma sintering technique, and by the release of controlled strain energy, have been realized
The wherein control of residual ferrite content.As a kind of rapid shaping technique, the Y that is decomposed in mechanical milling process2O3It can not discharge
It is all precipitated during plasma agglomeration, if annealing process can be passed through so that still undecomposed Y atoms and O atom are with Y2O3Shape
Formula is precipitated, in follow-up residual ferrite generating process, tiny Y2O3The pinning effect that particle grows residual ferrite is further
Enhancing, then may be implemented the refinement of residual ferrite crystallite dimension.It is worth noting that, after annealing, the matrix of 9Cr-ODS
Tissue is tempered martensite by martensite transfor mation, and the microstructure of annealed state 9Cr-ODS is ferrite+carbide+Y2O3, moving back
In the austenitization of fiery state 9Cr-ODS, the dissolving of carbide has a major impact austenite phase transformation, and carbide dissolution more fills
Point, austenite phase transformation driving force is bigger, and the size of residual ferrite is smaller.
The key of the present invention be the composition design of pre-alloying powder, quick shaping process, 800 DEG C of annealing heat-treats and
Subsequent heat treatment technique.The alloying component of pre-alloying powder is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C (wt.%), certainly
The intrinsic driving force of 9Cr-ODS martensite steel austenite phase transformations is determined；A certain amount of Y in mechanical milling process2O3It decomposes；Due to using
Discharge plasma sintering process carries out rapid shaping, and the Y and O atom of decomposition can not be precipitated completely；800 DEG C of annealing process can be with
Ensure Y and O atom with more tiny and disperse Y2O3Form is precipitated completely, generates a certain amount of carbide, while sintered state
The strain energy stored in 9Cr-ODS steel all discharges；In subsequent heat treatment technique, due to Y2O3Size is more tiny, and distribution is more
Disperse, it is stronger to the pinning effect of austenite grain boundary, tiny original austenite and residual ferrite crystal grain can be obtained；Due to Austria
The phase transformation of family name's body is related with the dissolving of carbide, under the slow rate of heat addition of 10 DEG C/min, can promote carbide in heating process
Dissolving, promote austenite phase transformation, further refine residual ferrite size.
Advantage of the present invention：
Certain composition design is carried out to 9Cr-ODS martensite steels by early period and preparation process adjusts, to being prepared
9Cr-ODS martensite steels use simple annealing process and 10 DEG C/min slow heating rate, you can in subsequent heat treatment mistake
Tiny residual ferrite crystal grain is obtained in journey, simple for process, purpose is strong, to further increasing the high temperature of ODS- martensite steels
Intensity is of great significance.
Description of the drawings
Fig. 1 (a) is the differential scanning calorimetric curve of sintered state and annealed state 9Cr-ODS martensite steels in embodiment 1；
Fig. 1 (b) is that the transmission electron microscope (TEM) of annealed state in embodiment 1 (800 DEG C of annealing 1h) 9Cr-ODS martensite steels shines
Piece；
Fig. 2 (a) is to be heated to annealed state (800 DEG C of annealing 1h) 9Cr-ODS martensite steels with 10 DEG C/min in embodiment 1
1100 DEG C, keep the temperature 5min, light microscopic (OM) photo being then cooled to room temperature with the rate of 30 DEG C/min；
Fig. 2 (b) is to be heated to annealed state (800 DEG C of annealing 1h) 9Cr-ODS martensite steels with 10 DEG C/min in embodiment 1
1100 DEG C, keep the temperature 5min, scanning electron microscope (SEM) photo being then cooled to room temperature with the rate of 30 DEG C/min；
Fig. 3 (a) is that sintered state 9Cr-ODS martensite steels are heated to 1100 DEG C by comparative example 1 with 10 DEG C/min, heat preservation
5min, light microscopic (OM) photo being then cooled to room temperature with the rate of 30 DEG C/min；
Fig. 3 (b) is that sintered state 9Cr-ODS martensite steels are heated to 1100 DEG C by comparative example 1 with 10 DEG C/min, heat preservation
5min, scanning electron microscope (SEM) photo being then cooled to room temperature with the rate of 30 DEG C/min；
Fig. 4 (a) is that annealed state (800 DEG C of annealing 1h) 9Cr-ODS martensite steels are heated to by comparative example 2 with 40 DEG C/min
1100 DEG C, keep the temperature 5min, light microscopic (OM) photo being then cooled to room temperature with the rate of 30 DEG C/min；
Fig. 4 (b) is that annealed state (800 DEG C of annealing 1h) 9Cr-ODS martensite steels are heated to by comparative example 2 with 40 DEG C/min
1100 DEG C, keep the temperature 5min, scanning electron microscope (SEM) photo being then cooled to room temperature with the rate of 30 DEG C/min.
Specific implementation mode
The present invention is described in further detail With reference to embodiment.
Pre-alloying powder of the present invention is made of the following components according to mass percent tool：C=0.1%, Cr=
9%, W=1.5%, V=0.2%, Ta=0.07%, remaining is Fe.Y of the present invention2O3Powder size is distributed as 30~
50nm。
To refining the heat treatment process of residual ferrite size in 9Cr-ODS martensite steels in the present invention, step is：
1. it is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C's (wt.%) to obtain alloying component by powder by atomization technique
Pre-alloying powder, by pre-alloying powder and nanoscale Y2O3By 99.65:0.35 mass ratio is mixed, in planetary ball
Mechanical ball mill, ratio of grinding media to material 15 are carried out in grinding machine:1, rotational speed of ball-mill 400r/min, Ball-milling Time 45h are protected using argon gas
Shield；Ball-milled powder is heated to 800 DEG C using discharge plasma sintering process, keeps the temperature 5~10min, it is further heated up to 1100
DEG C, 10~15min is kept the temperature, sintering pressure is 40~50MP, cools to room temperature with the furnace, obtains molding consistency 99% or more
9Cr-ODS martensite steels.
2. the obtained 9Cr-ODS martensite steels of sintering are annealed 1~5h at 800 DEG C so that sintered state 9Cr-ODS martensites
Y in steel2O3It is fully precipitated, generates a certain amount of carbide.
3. the 9Cr-ODS martensite steels that pair annealing obtains carry out subsequent heat treatment, heated up with the rate of heat addition of 10 DEG C/min
To 1100 DEG C, 0~5min is kept the temperature, is then cooled to room temperature with the rate of 30~1000 DEG C/min.
The following is specific embodiments of the present invention, but the present invention is not limited to following embodiments.
Embodiment 1：
It is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C that the ingredient of 1 pre-alloying powder of embodiment, which is shown in Table as ingredient,
(wt.%).By pre-alloying powder and Y2O3Powder presses 99.65：0.35 mass ratio is mixed, in planetary ball mill
Carry out mechanical ball mill, ratio of grinding media to material 15:1, rotational speed of ball-mill 400r/min, Ball-milling Time 45h are protected using argon gas；In stone
It after being packed into suitable ball-milled powder in black mold, is put into discharge plasma sintering stove and carries out curing molding, with 100 DEG C/min's
The rate of heat addition is warming up to 800 DEG C, keeps the temperature 5min, then be warming up to 1100 DEG C at the same rate, keeps the temperature 10min, and sintering pressure is
40MP cools to room temperature with the furnace.
The obtained 9Cr-ODS martensite steels of sintering are annealed 1h at 800 DEG C, to the 9Cr-ODS martensite steels of annealed state into
Row subsequent heat treatment is warming up to 1100 DEG C with the rate of heat addition of 10 DEG C/min, keeps the temperature 5min, then cold with the rate of 30 DEG C/min
But to room temperature.
Fig. 1 (a) is the differential scanning calorimetric curve of sintered state and annealed state 9Cr-ODS martensite steels, can from figure
Go out sintered state 9Cr-ODS martensite steels at 660 DEG C nearby there are one exothermic peak, the precipitation of corresponding yttrium oxide illustrates mechanical milling process
The Y and O atom of middle dissolving are not precipitated in the discharge plasma sintering stage.After 800 DEG C are annealed 1h, what yttrium oxide was precipitated puts
Thermal spike disappears, and illustrates Y2O3It is fully precipitated in 800 DEG C of annealing processes.Fig. 1 (b) is the TEM of annealed state 9Cr-ODS martensite steels
Photo, it can be seen that the yttrium oxide being precipitated in annealed state 9Cr-ODS martensites more disperse, tiny.
Fig. 2 (a) and (b) are respectively that annealed state 9Cr-ODS martensite steels are heated to 1100 DEG C with 10 DEG C/min, heat preservation
5min, the light microscopic (OM) and scanning electron microscope (SEM) photo being then cooled to room temperature with the rate of 30 DEG C/min, in martensitic matrix
In be uniform-distribution with tiny residual ferrite, residual ferrite average grain size is 2.2 μm.
Embodiment 2：
It is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C that the ingredient of 2 pre-alloying powder of embodiment, which is shown in Table as ingredient,
(wt.%).By pre-alloying powder and Y2O3Powder presses 99.65：0.35 mass ratio is mixed, in planetary ball mill
Carry out mechanical ball mill, ratio of grinding media to material 15:1, rotational speed of ball-mill 400r/min, Ball-milling Time 45h are protected using argon gas；In stone
It after being packed into suitable ball-milled powder in black mold, is put into discharge plasma sintering stove and carries out curing molding, with 100 DEG C/min's
The rate of heat addition is warming up to 800 DEG C, keeps the temperature 10min, then be warming up to 1100 DEG C at the same rate, keeps the temperature 15min, and sintering pressure is
45MP cools to room temperature with the furnace.
The obtained 9Cr-ODS martensite steels of sintering are annealed 3h at 800 DEG C, to the 9Cr-ODS martensite steels of annealed state into
Row subsequent heat treatment is warming up to 1100 DEG C with the rate of heat addition of 10 DEG C/min, 3min is kept the temperature, then with the rate of 600 DEG C/min
It is cooled to room temperature.
Embodiment 3：
It is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C that the ingredient of 3 pre-alloying powder of embodiment, which is shown in Table as ingredient,
(wt.%).By pre-alloying powder and Y2O3Powder presses 99.65：0.35 mass ratio is mixed, in planetary ball mill
Carry out mechanical ball mill, ratio of grinding media to material 15:1, rotational speed of ball-mill 400r/min, Ball-milling Time 45h are protected using argon gas；In stone
It after being packed into suitable ball-milled powder in black mold, is put into discharge plasma sintering stove and carries out curing molding, with 100 DEG C/min's
The rate of heat addition is warming up to 800 DEG C, keeps the temperature 10min, then be warming up to 1100 DEG C at the same rate, keeps the temperature 15min, and sintering pressure is
50MP cools to room temperature with the furnace.
The obtained 9Cr-ODS martensite steels of sintering are annealed 5h at 800 DEG C, to the 9Cr-ODS martensite steels of annealed state into
Row subsequent heat treatment is warming up to 1100 DEG C with the rate of heat addition of 10 DEG C/min, 5min is kept the temperature, then with the rate of 1000 DEG C/min
It is cooled to room temperature.
Comparative example 1：
It is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C that the ingredient of pre-alloying powder, which is shown in Table as ingredient, in comparative example 1
(wt.%).By pre-alloying powder and Y2O3Powder presses 99.65：0.35 mass ratio is mixed, in planetary ball mill
Carry out mechanical ball mill, ratio of grinding media to material 15:1, rotational speed of ball-mill 400r/min, Ball-milling Time 45h are protected using argon gas；In stone
It after being packed into suitable ball-milled powder in black mold, is put into discharge plasma sintering stove and carries out curing molding, with 100 DEG C/min's
The rate of heat addition is warming up to 800 DEG C, keeps the temperature 5min, then be warming up to 1100 DEG C at the same rate, keeps the temperature 10min, and sintering pressure is
40MP cools to room temperature with the furnace.The 9Cr-ODS martensite steels that sintering obtains are warming up to 1100 with the rate of heat addition of 10 DEG C/min
DEG C, 5min is kept the temperature, is then cooled to room temperature with the rate of 200 DEG C/min.
Fig. 3 (a) and (b) are respectively that sintered state 9Cr-ODS martensite steels are directly heated to 1100 DEG C with 10 DEG C/min, heat preservation
5min, the light microscopic (OM) and scanning electron microscope (SEM) photo being then cooled to room temperature with the rate of 30 DEG C/min, can from figure
Go out, the crystallite dimension of residual ferrite is larger, and residual ferrite average grain size is 5.2 μm.By being done pair with embodiment 1
Than, it can be seen that annealing process ensures Y2O3Fully be precipitated, can by the size of residual ferrite in 9Cr-ODS martensite steels by
5.2 μm are refined to 2.2 μm.
Comparative example 2：
It is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C that the ingredient of pre-alloying powder, which is shown in Table as ingredient, in comparative example 2
(wt.%).By pre-alloying powder and Y2O3Powder presses 99.65：0.35 mass ratio is mixed, in planetary ball mill
Carry out mechanical ball mill, ratio of grinding media to material 15:1, rotational speed of ball-mill 400r/min, Ball-milling Time 45h are protected using argon gas；In stone
It after being packed into suitable ball-milled powder in black mold, is put into discharge plasma sintering stove and carries out curing molding, with 100 DEG C/min's
The rate of heat addition is warming up to 800 DEG C, keeps the temperature 5min, then be warming up to 1100 DEG C at the same rate, keeps the temperature 10min, and sintering pressure is
40MP cools to room temperature with the furnace.The obtained 9Cr-ODS martensite steels of sintering are annealed 1h at 800 DEG C, to the 9Cr- of annealed state
ODS martensite steels carry out subsequent heat treatment, are warming up to 1100 DEG C with the rate of heat addition of 40 DEG C/min, 5min are kept the temperature, then with 30
DEG C/rate of min is cooled to room temperature.
Fig. 4 (a) and (b) are respectively to be by annealed state (800 DEG C of annealing 1h) 9Cr-ODS martensite steels in the present invention with 40
DEG C/min is heated to 1100 DEG C, keeps the temperature 5min, the light microscopic (OM) and scanning being then cooled to room temperature with the rate of 30 DEG C/min are electric
Mirror (SEM) photo, residual ferrite average grain size are 3.2 μm.By being compared with embodiment 1, it can be seen that even if through
Annealing process processing is crossed, subsequent heat rate still has an impact the size of residual ferrite, when the rate of heat addition is 10 DEG C/min,
Carbide dissolution is more abundant, and austenite phase transformation carries out more complete, and residual ferrite is smaller (2.2 μm)；Heating speed
When rate is 40 DEG C/min, carbide dissolution is insufficient, and austenite phase transformation driving force is smaller, larger (3.2 μ of residual ferrite size
m)。
Although above in conjunction with figure, invention has been described, and the invention is not limited in above-mentioned specific embodiment parties
Formula, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are in this hair
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the guarantor of the present invention
Within shield.
Claims (4)
1. a kind of method of residual ferrite size in refinement oxide dispersion intensifying martensite steel, it is characterized in that steps are as follows：
1) by pre-alloying powder and nanoscale Y2O3By 99.65:0.35 mass ratio is mixed, pre-alloying powder quality
Ingredient is Fe-9Cr-1.5W-0.2V-0.07Ta-0.1C；Mechanical ball mill is carried out in the ball mill, is protected using argon gas；Using putting
Ball-milled powder is heated to 800 DEG C by electric plasma agglomeration, keeps the temperature 5~10min, it is further heated up to 1100 DEG C, heat preservation 10~
15min, sintering pressure are 40~50MP, cool to room temperature with the furnace, obtain sintered state 9Cr- of the molding consistency 99% or more
ODS martensite steels；
2) anneal sintered state 9Cr-ODS martensite steels at 800 DEG C 1~5h so that in sintered state 9Cr-ODS martensite steels
Y2O3It is fully precipitated, while generating carbide；Obtain the 9Cr-ODS martensite steels of annealed state；
3) the 9Cr-ODS martensite steels of annealed state are warming up to 1100 DEG C with 10 DEG C/min, keep the temperature 0~5min, then with 30~
The rate of 1000 DEG C/min is cooled to room temperature.
2. the method as described in claim 1, it is characterized in that ratio of grinding media to material is 15 in the ball mill in step 1):1.
3. the method as described in claim 1, it is characterized in that rotational speed of ball-mill is 400r/min in the ball mill in step 1).
4. the method as described in claim 1, it is characterized in that Ball-milling Time is 45h in the ball mill in step 1).
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| 机械合金化和SPS工艺制备9CrWTi-Y2O3/铁素体-马氏体钢;杨剑 等;《复合材料学报》;20130630;第30卷(第3期);第143-145、147页 * |
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