CN105965026A - Method for preparing nanometer MeC-W powder through sol-heterogeneous precipitation-spray drying - Google Patents
Method for preparing nanometer MeC-W powder through sol-heterogeneous precipitation-spray drying Download PDFInfo
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Abstract
The invention relates to a method for preparing nanometer carbide/tungsten composite powder. The method comprises the steps that firstly, carbide particles are subjected to ball milling and modification to obtain nanometer carbide particles with the good dispersity and uniform granularity, then, the nanometer carbide particles are added into a tungsten salt solution, pH of the solution is adjusted to enable some nanometer tungsten to form heterogeneous precipitation on the surfaces of the carbide particles, a dispersing agent and a thickening agent are added, sedimentation and agglomeration of the carbide particles are effectively avoided, and a suspension sol with the nanometer carbide being uniformly dispersed into liquid is formed; then, rapid spraying and drying are performed to manufacture a composite precursor, then, precursor powder is calcined in non-oxidizing atmosphere, and reduction is performed in the hydrogen atmosphere. According to the composite powder manufactured through the method, the carbide can be one or more of ZrC, TiC and HfC, and the content is 0.01-10%; the nanometer carbide particles are evenly dispersed into nanometer tungsten, the size of the carbide is 10-50 nm, the size of tungsten is 30-100 nm, and the good sintering activity is achieved.
Description
Technical field
The present invention relates to the preparation method of powdered metallurgical material, especially with the method for powder modification-colloidal sol-non-homogeneous phase deposition-spray drying preparation nanometer MeC-W composite powder.
Background technology
Tungsten has the excellent properties such as high-melting-point, high heat conductance, low thermal coefficient of expansion, high anti-neutron irradiation ability and low sputtering raste, as a kind of critically important high-temperature material, is widely used in the field such as nuclear energy, Aero-Space.But utilize pure tungsten material prepared by tradition micron powder after 2700 DEG C are sintered, and consistency is only 93 ~ 95%, and grain structure thick (> 100 μm), performance extreme difference.For eliminating high temperature sintering tungsten residual porosity, at present business pure tungsten material typically uses forging, rolls and the large deformation strengthening means such as extruding, but the pure tungsten material after large deformation still suffer from organizing the thickest, in threadiness orientation, ductile-brittle transition temperature height, the defect such as recrystallization temperature is low, fragility is big.
In order to improve the performance of pure tungsten, research worker overcomes the black brittleness of tungsten by adding the modes such as a small amount of carbide particle (MeC, HfC, ZrC etc.) crystal grain thinning, reduces the ductile-brittle transition temperature of tungsten, achieved with preferable effect.Japanese scholars uses high-energy ball milling+high temperature insostatic pressing (HIP)+high temperature forging to prepare W-(0.25 ~ 0.8%) MeC(mass fraction) material, after result shows to add MeC, tungsten grain significantly refines, ductile-brittle transition temperature reduces, room temperature and elevated temperature strength, recrystallization temperature are significantly improved, simulation neutron irradiation environment simultaneously, at 4He+In irradiation reaction device 600 DEG C, 3MeV, He particle flux is 2 × 1024n/m2Under the conditions of tested, result shows the 1/3 ~ 1/4 of its vacancy defect concentration only tradition pure tungsten, demonstrates good anti-neutron irradiation ability.Therefore, add carbide second phase dispersion-strengtherning carefully brilliant tungsten material and have become as an important directions of current high temperature tungsten material.But, mechanical alloying/high-energy ball milling method is prepared composite powder and be there are some problems: can introduce foreign peoples's impurity in mechanical alloying, Process During High Energy Ball Milling, and in composite powder, second phase particles is easily formed at alloy grain boundaries and reunites, and weakens material property；Meanwhile, the powder of mechanical alloying is lamellar, and crystallized ability is very poor, it is difficult to prepare the exemplar of large-size.
For solving problem above, we utilize colloidal sol-spray drying-thermal reduction to be prepared for ultra-fine/nanometer activation tungsten powder, compared with mechanical alloying powder, powder purity prepared by the method is high, composition is uniform and sphericity is high, good moldability, simultaneously because powder with the addition of the active elements such as trace Ni, Co, Fe, there is good sintering activity.The method applied for a patent " a kind of ultra-fine or preparation method of nanometer activation tungsten powder " (patent No.: ZL201010049432.3) in 2010.But owing to active element Ni embrittlement can reduce material property under neutron irradiation effect, pure tungsten powder also exists, when sintering, the problem that crystal grain is grown up, and its grain size is more than more than 20 μm, it is difficult to preparation grain size is less than the thin brilliant tungsten material of 10 μm simultaneously.Carbide particle is added in tungsten preferably to play the effect of refinement tungsten grain, improve the anti-neutron irradiation ability of tungsten simultaneously, we add ZrC/TiC particle in tungsten salt at early stage, prepare ZrC/TiC by the method for colloidal sol-spray drying-thermal reduction and strengthen thin brilliant tungsten material, and at Journal of
Publish an article on Nuclear Materials " Micro/nano
composited tungsten material and its high thermal loading behavior”.By adding ZrC/TiC particle phase, the crystal grain of tungsten is refined to below 10 μm, and its anti-high heat load ability increases substantially simultaneously.But, the electric double layer that common dispersants produces in saline solution is compressed, and does not has dispersion effect, and carbide particle easily produces reunion, segregation and sinking, causes carbide to produce segregation at alloy grain boundaries so that it is unstable properties.
Summary of the invention
For solving the problems referred to above, the present invention, first by Nano-Scaled Carbide particle homogeneous for carbide particle ball milling modification prepared sizes, improves its dispersibility in the solution；Regulation solution ph makes nanometer tungsten precipitate at carbide surface, improves the interfacial combined function of W Yu MeC；Add dispersant further and be simultaneously introduced haloduric thickener, dispersant is utilized to change the surface potential of MeC particle, salt ion in thickening agent chelate solution, the two synergy prevents carbide particle sedimentation and reunites, forming the suspension colloid that nano-carbide disperse is dispersed in liquid.
The nanometer MeC-W composite powder composition of the present invention is by mass percentage: MeC content is 0.01-10%, and surplus is W.MeC can be ZrC, TiC, HfC etc..
For reaching above-mentioned purpose, concrete scheme of the present invention is as follows:
(1) initially with ball milling method, MeC powder carried out powder modification process, ball milling modification technique be ratio of grinding media to material be 1:1 ~ 5:1, rotating speed is 100 ~ 300rad/s, and Ball-milling Time is 1 ~ 10h.
(2) in deionized water, solubility tungsten salt is added, controlling its concentration is 10 ~ 80mmol/L, it is added thereto to modified nanometer MeC subsequently, the PH of regulation solution is 10 ~ 12, the dispersant accounting for overall solution volume 0.01 ~ 10% is added after stirring, add solution gross mass 0.1 ~ 2% thickening agent, form stable sol.
(3) colloidal sol is spray-dried, the composite precursor powder obtained.
(4) by composite precursor powder at 150 ~ 500 DEG C, the nonoxidizing atmosphere environment such as hydrogen, nitrogen, cracked ammonium, argon is calcined 1-5h.
(5) powder after calcining is placed in reduction furnace and carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is 450 ~ 650 DEG C, and temperature retention time is 2h；Second step hydrogen reduction temperature is 680 ~ 900 DEG C, and temperature retention time is 2 ~ 6h.
Advantages of the present invention and good effect are embodied in:
(1) present invention adds dispersant and thickening agent in tungsten salt solution, by dispersant change TiC particle surface current potential, thickening agent, salt ion is carried out chelation, it is achieved the even dispersion dispersion in saline solution of the TiC granule.
(2) the MeC-W composite powder distributed components that prepared by the present invention: nanometer MeC granule even dispersion is distributed in nano-tungsten powder, wherein nano-carbide particle size is 10 ~ 50nm, and the size of nano-tungsten powder is 30 ~ 100nm.
(3) the MeC-W composite powder that prepared by the present invention has good sintering activity: the granularity of composite powder is tiny homogeneous, regulation solution ph makes nanometer tungsten precipitate at carbide surface, forms carbide particle during special nucleocapsid structure can effectively stop follow-up sintering and grows up.This powder is especially suitable for preparing carbide dispersion-strengthened carefully brilliant tungsten material.
(4) the MeC-W composite powder that prepared by the present invention is spherical in shape, has good mouldability.
Detailed description of the invention
Example 1:
As a example by preparing nano 0.01wt%TiC-W composite powder.
(1) take 0.009g nano TiC powder, by ratio of grinding media to material be 1:1, TiC is modified processing by the ball-milling technology of rotating speed 100r/min, time 3h.
(2) measuring 1L deionized water, be added thereto to 121.9g ammonium metatungstate, stirring, to dissolving, with adding 0.009gTiC in backward solution, is added dropwise over ammonia, stirs.
(3) adding 0.1g sodium carboxymethyl cellulose in above-mentioned suspension, 0.01ml tween 80, stir formation stable colloid.
(4) being spray-dried at 250 DEG C by above-mentioned colloidal sol, wherein shower nozzle rotating speed is 25000 revs/min, obtains precursor powder.
(5) by precursor powder at 150 DEG C, hydrogen environment is calcined 4h.
(6) powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is 550 DEG C, and temperature retention time is 2h；Second step hydrogen reduction temperature is 740 DEG C, and temperature retention time is 6h, obtains 0.01wt%MeC-W composite powder, and oxygen content in power is 0.24%, and powder size is 55nm.
Example 2:
As a example by preparing nano 0.1wt%Ti-W composite powder.
(1) take 0.09g nano TiC, by ratio of grinding media to material be 2:1, TiC is modified processing by the ball-milling technology of rotating speed 100r/min, time 5h.
(2) measure 1L deionized water, be added thereto to 121.9g ammonium metatungstate, stir to dissolving addition 0.09gTiC in backward above-mentioned mixed solution, be added dropwise over ammonia, stir.
(3) entering to add 5g Dodecyl trimethyl ammonium chloride (CTAB), 0.5g sodium hydroxyethlcellulose in above-mentioned suspension, stir formation stable colloid.
(4) being spray-dried at 250 DEG C by above-mentioned colloidal sol, wherein shower nozzle rotating speed is 25000 revs/min.
(5) by precursor powder at 250 DEG C, hydrogen environment is calcined 4h.
(6) powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.In the range of first step hydrogen reduction reduction temperature is 500 DEG C, temperature retention time is 2h；Second step hydrogen reduction temperature is 780 DEG C, and temperature retention time is 4h.Obtaining 0. 1wt%TiC-W composite powder, oxygen content in power is 0.14%, and powder size is 80nm.
Example 3:
As a example by preparing nano 0.5wt%ZrC-W composite powder.
(1) take 0.44g nanometer ZrC, by ratio of grinding media to material be 1:1, ZrC is modified processing by the ball-milling technology of rotating speed 300r/min, time 10h.
(2) measure 1L deionized water, be added thereto to 136.3g ammonium paratungstate, stir to dissolving addition 0.44g in backward above-mentioned mixed solution
ZrC, is added dropwise over ammonia, stirs.
(3) in above-mentioned suspension, drip 10mlPEG400,1g sodium carboxymethyl cellulose, be mixing uniformly to form stable colloid.
(4) being spray-dried at 250 DEG C by above-mentioned colloidal sol, wherein shower nozzle rotating speed is 25000 revs/min.
(5) by precursor powder at 300 DEG C, hydrogen environment is calcined 4h.
(6) powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature controls in the range of 600 DEG C, and temperature retention time is 2h；Second step hydrogen reduction temperature controls at 780 DEG C, and temperature retention time is 2.5h.Obtaining 0. 1wt% ZrC-W composite powder, oxygen content in power is 0.19%, and powder size is 45nm.
Example 4:
As a example by preparing nano 1wt% ZrC-W composite powder.
(1) take 0.89g nanometer ZrC, by ratio of grinding media to material be 3:1, rotating speed 200r/min, time 5h, liquid-solid ratio 2；The ball-milling technology of 1 carries out high-energy ball milling de-agglomerated to ZrC, is placed in vacuum drying oven by powder and is dried after ball milling.
(2) measuring 1L deionized water, be added thereto to 136.3g ammonium paratungstate, stirring, to dissolving, adds 0.89g subsequently in above-mentioned mixed solution
ZrC, is added dropwise over ammonia, stirs.
(3) in above-mentioned suspension, add 0.15g carboxymethyl cellulose, 20mlPEG400, be mixing uniformly to form stable colloid.
(4) being spray-dried at 250 DEG C by above-mentioned colloidal sol, wherein shower nozzle rotating speed is 25000 revs/min.
(5) by precursor powder at 400 DEG C, hydrogen environment is calcined 4h.
(5) powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.In the range of first step hydrogen reduction reduction temperature is 650 DEG C, temperature retention time is 2h；Second step hydrogen reduction temperature is 820 DEG C, and temperature retention time is 2h.Obtaining 1wt% ZrC-W composite powder, oxygen content in power is 0.23%, and powder size is 45nm.
Example 5:
As a example by preparing nano 5wt%HfC-W composite powder.
(1) take 4.65 g nanometers HfC, by ratio of grinding media to material be 3:1, rotating speed 300r/min, time 10h, liquid-solid ratio 3；The ball-milling technology of 1 carries out high-energy ball milling de-agglomerated to HfC, is placed in vacuum drying oven by powder and is dried after ball milling.
(2) measuring 1L deionized water, be added thereto to 158.33g sodium tungstate, stirring, to dissolving, adds 4.65 subsequently in above-mentioned mixed solution
HfC, is added dropwise over ammonia, stirs.
(3) in above-mentioned suspension, drip 50ml tween 80,2 carboxymethyl celluloses, be mixing uniformly to form stable colloid.
(4) being spray-dried at 250 DEG C by above-mentioned colloidal sol, wherein shower nozzle rotating speed is 25000 revs/min.
(5) by precursor powder at 350 DEG C, hydrogen environment is calcined 4h.
(6) powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.In the range of first step hydrogen reduction reduction temperature is 600 DEG C, temperature retention time is 2h；Second step hydrogen reduction temperature is 860 DEG C, and temperature retention time is 2.5h.Obtaining 5wt% HfC-W composite powder, oxygen content in power is 0.19%, and powder size is 55nm.
Example 6:
As a example by preparing nano 10wt% HfC-W composite powder.
(1) take 9.3 g nanometers HfC, by ratio of grinding media to material be 3:1, rotating speed 200r/min, time 10h, liquid-solid ratio 4；The ball-milling technology of 1 carries out high-energy ball milling de-agglomerated to HfC, is placed in vacuum drying oven by powder and is dried after ball milling.
(2) measuring 1L deionized water, be added thereto to 158.33g sodium tungstate, stirring, to dissolving, adds 9.3 subsequently in above-mentioned mixed solution
HfC, is added dropwise over ammonia, stirs.
(3) in above-mentioned suspension, drip 100ml tween 80,2g carboxymethyl cellulose, be mixing uniformly to form stable colloid.
(4) being spray-dried at 250 DEG C by above-mentioned colloidal sol, wherein shower nozzle rotating speed is 25000 revs/min.
(5) by precursor powder at 400 DEG C, hydrogen environment is calcined 4h.
(6) powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.In the range of first step hydrogen reduction reduction temperature is 600 DEG C, temperature retention time is 2h；Second step hydrogen reduction temperature is 900 DEG C, and temperature retention time is 2.5h.Obtaining 10wt% HfC-W composite powder, oxygen content in power is 0.14%, and powder size is 75nm.
Claims (8)
1. the method preparing nanometer MeC-W powder with colloidal sol-non-homogeneous phase deposition-spray drying, it is characterised in that: by mass percentage, MeC content is 0.01-10% to nanometer MeC-W composite powder composition, and surplus is W, and wherein MeC is ZrC, TiC or HfC；First carbide particle ball milling modification is obtained the Nano-Scaled Carbide particle of homogeneous grain diameter, then modified nano-carbide particle is joined in the tungsten salt solution that concentration is 10 ~ 80mmol/L, regulation pH value makes part nanometer tungsten at carbide surface non-homogeneous phase deposition to 10 ~ 12, it is subsequently added dispersant, with the salt-resistant type thickening agent of ehter bond and hydroxyl, nano-carbide carried out surface modification, form the suspension colloid that nano-carbide even dispersion is distributed in liquid；Carrying out colloid preparing, after fast spraying is dried-is calcined-two step hydrogen reductions, the nanometer MeC-W composite powder that nano-carbide even dispersion is distributed in nano-tungsten powder, wherein the particle size of carbide is 10 ~ 50nm, and the particle size of nanometer tungsten is 30 ~ 100nm.
The method that a kind of colloidal sol-non-homogeneous phase deposition-spray drying the most according to claim 1 prepares nanometer MeC-W powder, it is characterized in that: micron order or nanoscale MeC powder are carried out ball milling, Ball-milling Time is 1 ~ 10h, ratio of grinding media to material is 1:1 ~ 5:1, rotating speed is 100 ~ 300rad/s, obtains the nanometer MeC powder of homogeneous grain diameter.
The method that colloidal sol-non-homogeneous phase deposition-spray drying the most according to claim 1 prepares nanometer MeC-W powder, it is characterised in that: described solubility tungsten salt is sodium tungstate, ammonium paratungstate, ammonium metatungstate or sodium tungstate.
The method that colloidal sol-non-homogeneous phase deposition-spray drying the most according to claim 1 prepares nanometer MeC-W powder, it is characterised in that: soda acid used by regulation pH value is one or more in hydrochloric acid, acetic acid, ammonia, sodium hydroxide.
5. according to the method preparing nanometer MeC-W powder with colloidal sol-non-homogeneous phase deposition-spray drying described in claims 1, it is characterized in that: surfactant is one or more in PEG400, tween 80, Dodecyl trimethyl ammonium chloride, account for the 0.01 ~ 10% of overall solution volume.
The method that colloidal sol-non-homogeneous phase deposition-spray drying the most according to claim 1 prepares nanometer MeC-W powder, it is characterized in that: the described salt-resistant type thickening agent with ehter bond and hydroxyl is one or more in methylcellulose, sodium hydroxyethlcellulose, hydroxypropyl methyl cellulose, accounts for the 0.1 ~ 2% of solution gross mass.
7. according to the method preparing nanometer MeC-W powder with colloidal sol-non-homogeneous phase deposition-spray drying described in claims 1, it is characterized in that: described calcining heat is 150 ~ 500 DEG C, temperature retention time is 1 ~ 5h, and calcination atmosphere is nonoxidizing atmosphere, for hydrogen, nitrogen, argon or cracked ammonium atmosphere.
The method that colloidal sol-non-homogeneous phase deposition-spray drying the most according to claim 1 prepares nanometer MeC-W powder, it is characterised in that: in two step hydrogen reductions, the first step also temperature is 450 ~ 650 DEG C, and second step temperature is 680 ~ 900 DEG C, is incubated 2 ~ 6h.
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| CN115323213B (en) * | 2022-09-23 | 2023-02-14 | 西安稀有金属材料研究院有限公司 | Multistage nano-structured carbide dispersion-strengthened molybdenum alloy and preparation method thereof |
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