CN106001596A - Preparation method for spherical-phase dispersion strengthened metal base composite - Google Patents
Preparation method for spherical-phase dispersion strengthened metal base composite Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 239000006185 dispersion Substances 0.000 title abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 239000002738 chelating agent Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 8
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 7
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 29
- 239000010949 copper Substances 0.000 abstract description 25
- 239000000047 product Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000002244 precipitate Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 25
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 22
- 239000000843 powder Substances 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 14
- 229920002689 polyvinyl acetate Polymers 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- 229910016287 MxOy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B22F1/0003—
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a spherical-phase dispersion strengthened metal base composite. A preparation method for the spherical-phase dispersion strengthened metal base composite includes the steps that firstly, soluble Cu salt or soluble Fe salt and soluble salt corresponding to oxide dispersion are made into an aqueous solution, and a metal salt solution is obtained after uniform mixing; secondly, a complexing agent is added to the metal salt solution, the pH value of the solution is controlled to range from 3 to 5 after dissolution is completed, a reaction is conducted, and a complex reaction solution is obtained; thirdly, a surfactant aqueous solution is added to the complex reaction solution, and uniform mixing is conducted; then ammonia water is added, stirring and a reaction are conducted till the solution is neutral, and precipitate is obtained; fourthly, calcination is conducted after the obtained precipitate is cleaned, and a calcined product is obtained; and fifthly, reduction is conducted on the calcinaed product, and the composite can be obtained. By the adoption of the preparation method, superfine dispersion strengthened copper powder and dispersion strengthened iron powder which are uniform in grain size can be prepared, besides contained dispersion phases are subsphaeroidal and uniformly distributed, and the preparation method and the composite have the beneficial effects that product performance is stable, the cost is low and the process is controllable.
Description
Technical field
The present invention relates to the preparation method of a kind of composite, the preparation method of a kind of spherical phase dispersion-strengthened metal based composites.
Background technology
Dispersion-strengtherning is to introduce stable, uniform, tiny Second Phase Particles in metallic matrix, the motion of obstruction dislocation, thus the method for strengthening material.So the intensity of dispersion-strengthened material is high.The most valuable is when disperse phase fusing point is high, at high temperature stable, still plays invigoration effect at high temperature so that material can work at a temperature of fusing point (0.8～0.9T fusing point).
Dispersion-strengthened Cu has the combination property that high intensity, high rigidity, high softening temperature, high-termal conductivity and high conductivity etc. are excellent, is widely used in fields such as welding, electronics, electrical equipment, metallurgy.At present, the preparation of dispersion-strengtherning copper product mainly by powder metallurgic method, is first to prepare dispersion-strengtherning copper powder, then uses the technique of compacting-sintering to prepare dispersion-strengtherning copper product.The research of dispersion-strengthened Cu is started late by China, and the problem in producing it is grasped the most completely, and product exists the weak points such as machining property is poor, mechanical property is unstable；In addition production cost is too high, also has certain distance away from industrialization.
Oxide dispersion intensifying (ODS) high temperature alloy has good heat stability and chemical stability, can work under the melting temperature of alloy, succeeds application in stator blade and some rings and turbo blade；And oxide dispersion intensifying (ODS) material has excellent Flouride-resistani acid phesphatase and elevated temperature strength, it it is preferable nuclear reactor cladding materials.Oxide dispersion intensifying iron material mainly uses the process route of mechanical alloying now, but the disperse phase size prepared in this way is the most tiny, skewness.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of even-grained spherical phase dispersion-strengthened metal based composites.
For solving above-mentioned technical problem, the method step that the present invention is taked is: soluble-salt corresponding with dispersed oxide to soluble Cu salt or Dissolvable Fe salt is configured to aqueous solution by (1), obtains metal salt solution after mix homogeneously；
(2) being joined by chelating agent in above-mentioned metal salt solution, the pH value controlling solution after dissolving reacts in 3～5, obtains complex reaction liquid；
(3) in above-mentioned complex reaction liquid, aqueous surfactant solution, mix homogeneously are added；Then add ammonia, stirring reaction, be precipitated thing；
(4) by calcining after gained sediment undergoes washing, calcined product is obtained；
(5) above-mentioned calcined product is reduced, i.e. available described composite.
In step of the present invention (1), the concentration of metal salt solution is 1～10mol/L.In described step (1), dispersed oxide is Al mutually2O3、Y2O3Or ZrO2, the mass fraction of dispersed oxide phase is 0.1～10%.
In step of the present invention (2), the chelating agent that soluble Cu salt is corresponding is EDTA-2Na or sodium potassium tartrate tetrahydrate, and the chelating agent that Dissolvable Fe salt is corresponding is citric acid；The addition of its complexing agent is according to metal ion: the mol ratio of chelating agent is 1:10～10:1 adds.In described step (2), reaction temperature is 30～70 DEG C.
In step of the present invention (3), add ammonia to the aobvious neutrality of solution.
In step of the present invention (3), surfactant is polyvinyl alcohol, and addition is according to polyvinyl alcohol: metal ion mol ratio is 0.1:1～10:1 adds.
In step of the present invention (4), calcining heat is 200～700 DEG C.
In step of the present invention (5), using hydrogen reducing, reduction temperature is 400～900 DEG C, the time is 0.5～4 hour.
Use and have the beneficial effects that produced by technique scheme: the present invention uses complexation-coprecipitation method, fully ensure that powdered ingredients is uniform by adding chelating agent, add surfactant and control coprecipitation process, even-grained ultra-fine dispersion-strengtherning copper powder, dispersion strengthened iron powder can be prepared, and the disperse phase contained is subsphaeroidal, be evenly distributed, have the advantages that properties of product are stable, low cost, technique are controlled.
The present invention uses complexation-coprecipitation method, is simultaneously suitable for dispersion-strengthened Cu, the preparation of two kinds of powder of dispersion strengthened iron；Have an advantage that (1) ensure that the powder of preparation full and uniformization on composition by complex reaction, it is ensured that disperse phase ion and parent metal ion are in strict accordance with calculating homogeneous precipitation；(2) can directly use industry cupric, the waste liquid of ferrum is raw material, it is possible to achieve the high added value of copper recycles；(3) employing the method can be with multiple spherical disperse phase, including Al2O3、Y2O3、ZrO2；(4) not only can control the granularity of hardening constituent, pattern and dispersion in disperse powder by the addition of dispersant (surfactant) especially PVAC polyvinylalcohol, and can ensure that disperse powder size uniformity；(5) present invention is simple to operate, low cost, the cycle is short, stability is high, provides one stablize route for realizing industrialization.
Detailed description of the invention
The preparation method following processing step of employing of this spherical phase dispersion-strengthened metal based composites:
(1) preparation of soluble-salt: soluble-salt corresponding with dispersed oxide phase (MxOy) to soluble Cu salt or Dissolvable Fe salt is configured to aqueous solution, obtains metal salt solution after mix homogeneously；In described metal salt solution, the concentration of Cu salt (Fe salt) is 1～10mol/L；Described soluble copper salt can be CuSO4、CuCl2Or Cu (NO3)2, soluble ferric iron salt can be FeSO4、FeCl2Or Fe (NO3)3；Described dispersed oxide is Al mutually2O3、Y2O3Or ZrO2, corresponding soluble-salt can be Al (NO3)3Or Al2(SO4)3、YCl3、Zr(NO3)4；The mass fraction of dispersed oxide phase is 0.1～10%.
(2) preparation of complex coacervation: joined by chelating agent in above-mentioned metal salt solution, reacts in 3～5 with the pH value of ammonia control solution after dissolving, reaction temperature 30～70 DEG C, obtains complex reaction liquid；The chelating agent that copper ion (soluble Cu salt) is corresponding is EDTA-2Na or sodium potassium tartrate tetrahydrate, and the chelating agent that iron ion (Dissolvable Fe salt) is corresponding is citric acid, and the addition of its complexing agent is according to metal ion: the mol ratio of chelating agent is 1:10～10:1 adds.
(3) interpolation of surfactant: add aqueous surfactant solution, mix homogeneously in above-mentioned complex reaction liquid；Surfactant is preferably mass fraction 5～the PVAC polyvinylalcohol aqueous solution of 30%, addition is according to PVA: metal ion mol ratio is 0.1:1～10:1 adds, the addition of PVAC polyvinylalcohol is to control hardening constituent MxOy pattern and the key of disperse powder size, and can decompose removing completely in the follow-up high temperature reduction stage.
(4) preparation of precursor powder: compound concentration be the ammonia spirit of 5～30wt% as precipitant, above-mentioned solution adds this ammonia until solution display neutrality, stirring reaction, is precipitated thing, after 5～10 minutes, reaction is thoroughly, without bulk precipitation granule existence.
(5) calcining: gained precipitate deionized water is cleaned, until the deionized water after cleaning is transparent, then calcines, calcining heat 200～700 DEG C, obtain calcined product；
(6) hydrogen reducing: the powder after calcining being put into reduction in hydrogen reducing furnace and obtains dispersion-strengthened Cu or dispersion-strengtherning iron composite powder, wherein reduction temperature is at 400～900 DEG C, and insulation (reduction) time is 0.5～4 hour.
Below in conjunction with specific embodiment, the present invention is further detailed explanation.
Embodiment 1: with Al2O3As a example by the dispersion strengthened iron powder of content 2wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first ferric nitrate and aluminum nitrate being configured to aqueous solution, in solution, iron nitrate concentration is
1mol/L；When raw material is converted into the quality of aluminium oxide and ferrum, the mass fraction that aluminium oxide accounts for is 2%.
(2) take chelating agent citric acid the most fully to dissolve, citric acid solution is joined in above-mentioned solution, wherein the content of citric acid is according to metal ion: mole ratio 2:1 of citric acid calculates, it is thoroughly mixed uniformly, the pH value controlling solution with ammonia is 3, and reaction temperature controls at 50 DEG C.
(3) taking the PVAC polyvinylalcohol solution that concentration is 10wt%, add in above-mentioned solution, be thoroughly mixed uniformly, wherein the addition of PVA is according to PVA: the mole ratio of metal ion is that 0.2:1 calculates.
(4) compound concentration be the ammonia spirit of 10wt% as precipitant, join under the effect of agitator in above-mentioned solution, control pH=7, after predetermined pH value, being further continued for stirring 5 minutes so that react thoroughly, precipitating granule existence without bulk.
(5) after solution layering, pouring out supernatant liquid, and repeatedly clean precipitation with deionized water, go the removal of impurity, then calcine at Muffle furnace, temperature controls at 550 DEG C.
(6) hydrogen reducing: being put in hydrogen reducing furnace by the composite powder drying preparation and reduce, obtain dispersion strengthened iron powder, wherein reduction temperature is at 900 DEG C, and temperature retention time is 1 hour.
The present embodiment gained dispersion iron powder end granularity is less than 1.5 μm, narrower particle size distribution, Al2O3Disperse phase is subsphaeroidal structure, and granularity is less than 100nm, and disperse phase is evenly distributed in the matrix of copper, interparticle distance 100～200nm.
Embodiment 2: with Al2O3As a example by the dispersion-strengtherning copper powder of content 2wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first copper sulfate and aluminum nitrate being configured to aqueous solution, in solution, concentration of copper sulfate is at 1mol/L；When raw material is converted into the quality of aluminium oxide and copper, the mass fraction that aluminium oxide accounts for is at 2wt%.
(2) take chelating agent sodium potassium tartrate tetrahydrate the most fully to dissolve, potassium sodium tartrate solution is joined in above-mentioned solution, wherein the content of sodium potassium tartrate tetrahydrate is according to metal ion: the mole ratio of sodium potassium tartrate tetrahydrate is that 1:1 calculates, it is thoroughly mixed uniformly, the pH value controlling solution with ammonia is 3, and reaction temperature controls at 60 DEG C.
(3) taking the PVAC polyvinylalcohol solution that concentration is 15wt%, add in above-mentioned solution, be thoroughly mixed uniformly, wherein the addition of PVA is according to PVA: the mole ratio of metal ion is that 0.4:1 calculates.
(4) compound concentration be the ammonia spirit of 15wt% as precipitant, join under the effect of agitator in above-mentioned solution, control pH=7, after predetermined pH value, being further continued for stirring 5 minutes so that react thoroughly, precipitating granule existence without bulk.
(5) after solution layering, pouring out supernatant liquid, and repeatedly clean precipitation with deionized water, go the removal of impurity, calcine the most in an oven, temperature controls at 500 DEG C.
(6) composite powder drying preparation being put into reduction in hydrogen reducing furnace, obtain dispersion-strengtherning copper powder, wherein reduction temperature is at 550 DEG C, and temperature retention time is 1 hour.
The present embodiment gained dispersion copper powder size is less than 1 μm, narrower particle size distribution, Al2O3Disperse phase is subsphaeroidal structure, and granularity is less than 70nm, and disperse phase is evenly distributed in the matrix of copper, interparticle distance 100～150nm.
Embodiment 3: with ZrO2As a example by the dispersion-strengtherning copper powder of content 3wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first copper nitrate and zirconium nitrate being configured to aqueous solution, in solution, copper nitrate concentration is at 2mol/L；When raw material is converted into the quality of zirconium oxide and copper, the mass fraction that zirconium oxide accounts for is at 3wt%.
(2) EDTA-2Na(disodiumedetate is taken) solution joins in above-mentioned solution, wherein copper ion: EDTA-2Na=2:1 mole, adjusts pH=4, reaction temperature to control at 50 DEG C with ammonia after mixing.
(3) take the PVAC polyvinylalcohol solution that concentration is 20wt% and add in above-mentioned solution, mix homogeneously, wherein PVA: metal ion=1:1 mole.
(4) ammonia spirit that concentration is 20wt% is joined in above-mentioned solution, control pH=7, stir 8 minutes.
(5), after solution layering, separation, precipitation is carried out, 600 DEG C of calcinings.
(6) composite powder of calcining preparation being put into reduction in hydrogen reducing furnace, obtain dispersion-strengtherning copper powder, wherein reduction temperature is at 560 DEG C, and temperature retention time is 0.5 hour.
The present embodiment gained dispersion copper powder size is less than 2 μm, narrower particle size distribution, ZrO2Disperse phase is subsphaeroidal structure, and granularity is less than 100nm, and disperse phase is evenly distributed in the matrix of copper, about interparticle distance 100nm.
Embodiment 4: with Y2O3As a example by the dispersion strengthened iron powder of content 5wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first iron sulfate and Yttrium chloride(Y2Cl6) being configured to aqueous solution, iron sulfate concentration is at 3mol/L；When raw material is converted into the quality of yittrium oxide and ferrum, the mass fraction that yittrium oxide accounts for is at 5wt%.
(2) take citric acid solution and join in above-mentioned solution, wherein metal ion: citric acid=0.5:1 mol ratio, adjust pH=4 with ammonia after mixing, 50 DEG C are reacted.
(3) taking concentration is that 10wt% PVAC polyvinylalcohol solution adds in above-mentioned solution, mix homogeneously, wherein PVA: metal ion=3:1 mole.
(4) ammonia spirit that concentration is 30wt% is joined in above-mentioned solution, control pH=7, stir 10 minutes.
(5), after solution layering, separation, precipitation is carried out, 480 DEG C of calcinings.
(6) composite powder of calcining preparation being put into reduction in hydrogen reducing furnace, obtain dispersion strengthened iron powder, wherein reduction temperature is at 900 DEG C, and temperature retention time is 4 hours.
The present embodiment gained dispersion iron powder end granularity is less than 1 μm, narrower particle size distribution, ZrO2Disperse phase is subsphaeroidal structure, and granularity is less than 80nm, and disperse phase is evenly distributed in the matrix of copper, about interparticle distance 100nm.
Embodiment 5: with Al2O3As a example by the dispersion-strengtherning copper powder of content 0.1wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first copper chloride and aluminum sulfate being configured to aqueous solution, copper chloride concentration is at 10mol/L；When raw material is converted into the quality of aluminium oxide and copper, the mass fraction that aluminium oxide accounts for is at 0.1wt%.
(2) take potassium sodium tartrate solution and join in above-mentioned solution, wherein metal ion: sodium potassium tartrate tetrahydrate=2:1 mole, adjust pH=3 with ammonia after mixing, 40 DEG C are reacted.
(3) take the PVAC polyvinylalcohol solution that concentration is 15wt% and add in above-mentioned solution, mix homogeneously, wherein PVA: metal ion=0.1:1 mole.
(4) ammonia spirit that concentration is 5wt% is joined in above-mentioned solution, control pH=7, stir 7 minutes.
(5), after solution layering, separation, precipitation is carried out, 520 DEG C of calcinings.
(6) composite powder of calcining preparation being put into reduction in hydrogen reducing furnace, obtain dispersion-strengtherning copper powder, wherein reduction temperature is at 560 DEG C, and temperature retention time is 2 hours.
The present embodiment gained dispersion copper powder size is less than 1 μm, narrower particle size distribution, Al2O3Disperse phase is subsphaeroidal structure, and granularity is less than 50nm, and disperse phase is evenly distributed in the matrix of copper, interparticle distance 100～150nm.
Embodiment 6: with Y2O3As a example by the dispersion-strengtherning copper powder of content 7wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first copper sulfate and Yttrium chloride(Y2Cl6) being configured to aqueous solution, in solution, concentration of copper sulfate is at 10mol/L；When raw material is converted into the quality of yittrium oxide and copper, the mass fraction that yittrium oxide accounts for is at 7wt%.
(2) take EDTA-2Na solution and join in above-mentioned solution, wherein copper ion: EDTA-2Na=0.1:1 mole, adjust pH=5, reaction temperature to control at 70 DEG C with ammonia after mixing.
(3) take the PVAC polyvinylalcohol solution that concentration is 5wt% and add in above-mentioned solution, mix homogeneously, wherein PVA: metal ion=5:1 mole.
(4) ammonia spirit that concentration is 20wt% is joined in above-mentioned solution, control pH=7, stir 8 minutes.
(5), after solution layering, separation, precipitation is carried out, 200 DEG C of calcinings.
(6) composite powder of calcining preparation being put into reduction in hydrogen reducing furnace, obtain dispersion-strengtherning copper powder, wherein reduction temperature is at 400 DEG C, and temperature retention time is 1.5 hours.
The present embodiment gained dispersion copper powder size is less than 2 μm, narrower particle size distribution, Y2O3Disperse phase is subsphaeroidal structure, and granularity is less than 100nm, and disperse phase is evenly distributed in the matrix of copper, interparticle distance about 100 ~ 150nm.
Embodiment 7: with ZrO2As a example by the dispersion strengthened iron powder of content 10wt%, the concrete technology of the preparation method of this spherical phase dispersion-strengthened metal based composites is as described below.
(1) first iron chloride and zirconium nitrate being configured to aqueous solution, ferric chloride concn is at 5mol/L；When raw material is converted into the quality of zirconium oxide and ferrum, the mass fraction that zirconium oxide accounts for is at 10wt%.
(2) take citric acid solution and join in above-mentioned solution, wherein metal ion: citric acid=10:1 mol ratio, adjust pH=4 with ammonia after mixing, 30 DEG C are reacted.
(3) taking concentration is that 30wt% PVAC polyvinylalcohol solution adds in above-mentioned solution, mix homogeneously, wherein PVA: metal ion=10:1 mole.
(4) ammonia spirit that concentration is 25wt% is joined in above-mentioned solution, control pH=7, stir 6 minutes.
(5), after solution layering, separation, precipitation is carried out, 700 DEG C of calcinings.
(6) composite powder of calcining preparation being put into reduction in hydrogen reducing furnace, obtain dispersion strengthened iron powder, wherein reduction temperature is at 700 DEG C, and temperature retention time is 3 hours.
The present embodiment gained dispersion iron powder end granularity is less than 5 μm, narrower particle size distribution, ZrO2Disperse phase is subsphaeroidal structure, and granularity is less than 100nm, and disperse phase is evenly distributed in the matrix of copper, about interparticle distance 100nm.
Claims (9)
1. the preparation method of a spherical phase dispersion-strengthened metal based composites, it is characterized in that, its method step is: soluble-salt corresponding with dispersed oxide to soluble Cu salt or Dissolvable Fe salt is configured to aqueous solution by (1), obtains metal salt solution after mix homogeneously；
(2) being joined by chelating agent in above-mentioned metal salt solution, the pH value controlling solution after dissolving reacts in 3～5, obtains complex reaction liquid；
(3) in above-mentioned complex reaction liquid, aqueous surfactant solution, mix homogeneously are added；Then add ammonia, stirring reaction, be precipitated thing；
(4) by calcining after gained sediment undergoes washing, calcined product is obtained；
(5) above-mentioned calcined product is reduced, i.e. available described composite.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterised in that: in described step (1), the concentration of soluble Cu salt or Dissolvable Fe salt is 1～10mol/L.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterised in that: in described step (1), dispersed oxide is Al mutually2O3、Y2O3Or ZrO2, the mass fraction of dispersed oxide phase is 0.1～10%.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterized in that: in described step (2), the chelating agent that soluble Cu salt is corresponding is EDTA-2Na or sodium potassium tartrate tetrahydrate, and the chelating agent that Dissolvable Fe salt is corresponding is citric acid；The addition of its complexing agent is according to metal ion: the mol ratio of chelating agent is 1:10～10:1 adds.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterised in that: in described step (2), reaction temperature is 30～70 DEG C.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterised in that: in described step (3), add ammonia to the aobvious neutrality of solution.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterised in that: in described step (3), surfactant is polyvinyl alcohol, and addition is according to polyvinyl alcohol: metal ion mol ratio is 0.1:1～10:1 adds.
The preparation method of spherical phase dispersion-strengthened metal based composites the most according to claim 1, it is characterised in that: in described step (4), calcining heat is 200～700 DEG C.
9. according to the preparation method of the spherical phase dispersion-strengthened metal based composites described in claim 1-8 any one, it is characterised in that: in described step (5), using hydrogen reducing, reduction temperature is 400～900 DEG C, the time is 0.5～4 hour.
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