CN102560170B - WC-Fe-Y2O3 (Sc2O3) nano-cladded alloy and preparation method capable of inhibiting Eta phase in mechanical activation process - Google Patents

WC-Fe-Y2O3 (Sc2O3) nano-cladded alloy and preparation method capable of inhibiting Eta phase in mechanical activation process Download PDF

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CN102560170B
CN102560170B CN201210046589.XA CN201210046589A CN102560170B CN 102560170 B CN102560170 B CN 102560170B CN 201210046589 A CN201210046589 A CN 201210046589A CN 102560170 B CN102560170 B CN 102560170B
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nanometer
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alloy
mechanical activation
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CN102560170A (en
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徐培全
杨尚磊
卢庆华
任江伟
邓沛然
闫华
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Shanghai University of Engineering Science
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Shanghai University of Engineering Science
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Abstract

The invention discloses a WC-Fe-Y2O3 (Sc2O3) nano-cladded alloy. The WC-Fe-Y2O3 (Sc2O3) nano-cladded alloy is prepared from the mixture of the following materials by weight percent: 48-62 percent of nano-WC powder, 33-49 percent of nano-Fe powder, 2-8 percent of nano-Y2O3 powder, and 1-3 percent of nano-Sc2O3 powder. By adding nano-Y2O3 rare earth and nano-Sc2O3 rare earth, an Eta phase which is easily formed in a high-energy ball milling process of the nano-WC powder and the nano-Fe powder can be inhibited in a combined way. The WC-Fe-Y2O3 (Sc2O3) nano-cladded alloy can be applied to laser repair of surfaces of a thick steel plate and an invar and is applied to production and repair of a ship, a valve and other products.

Description

A kind of WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy and can suppress the preparation method of the η phase in mechanical activation process
Technical field
The present invention relates to a kind of nano surface cladding alloy, specifically, is a kind of WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy and can suppress the preparation method of the η phase in mixed powder mechanical activation process, can be used for the laser repairing on thick plate steel and Invar alloy surface.
Background technology
Slab steel and Invar alloy are to manufacture hull, the isostructural critical material of valve, and the destructions such as fatigue, wearing and tearing occur in process under arms, have a strong impact on the use properties of product.On the other hand, in the manufacturing processed of hull, valve, laser melting coating manufacturing technology is more and more ripe, can prepare one deck on steel or Invar alloy surface and there is high temperature resistant, wear-resistant and corrosion resistant structure, make product both there is the performance of anti-corrosion, the easy shaping of steel or Invar alloy, there is high temperature resistant, the wear-resistant and corrosion resistant performance that cladding layer possesses simultaneously.At shipbuilding industry and oil gas carrier, stainless steel, Invar alloy, Wimet are the important materials of producing key components and parts.The reparation of key components and parts and to manufacture be all to extend product service life, energy-saving and cost-reducing key issue again.And be that exploitation is mature and stable and have a cladding alloy of excellent properties by laser melting and coating technique for one of key issue of high-end product manufacture.
In various cladding alloys, the alloy that contains transition element (Fe, Co, Ni) is widely applicable a kind of material, particularly Fe base alloy material, owing to having good economy performance, with the good and widespread use of steel, Invar alloy fusion character.Secondly, WC is a kind of conventional strengthening element, has the advantages that wear resisting property and corrosion resisting property are good, high-temperature behavior is excellent.The particularly application of nanometer WC, is used for developing cladding alloy by nanometer WC, not only has the performance that micron WC has, and significantly improves the fracture property of WC, has important effect for the toughness that improves cladding layer.Therefore, nanometer WC is mixed to use with nanometer Fe, make full use of the effect of Binder Phase and the strengthening phase of nanometer WC and Fe, significant for the high-end cladding alloy of exploitation.In the process of preparing at WC-Fe alloy, because W-C-Fe system is under activation condition, sufficient energy will make WC decompose, active large nanometer Fe is by the diffusion occurring to WC, WC forms η phase owing to losing carbon and transition element to matrix diffusion, and the formation of η phase can reduce the over-all properties of cladding alloy.
For micron-sized WC-Fe alloy system, propose under equilibrium conditions by regulating C, rare earth, Cr 3c 2, the composition means control interface η phase such as the poor Co of poor C/, M/C formation and form; Or suppress by controlling synthesis temperature the formation that η equates middle phase, experimental results show that it is effective.Through the literature search of prior art is found, W Barona Mercado etc. are at magazine Hyperfine Interact, paper " the Sythesis and characterization of Fe that deliver 2007,175:49～54 6w 6c by mechanical alIoying " in, propose to utilize method mechanical activation W, C, the Fe mixed powder of mechanical alloying, carry out respectively the ball milling of 1h, 3h, 5h, 10h, 15h, 30h; along with the carrying out of time; three kinds of powder mix gradually, but in mixing process, have formed Fe 3w 3c, Fe 6w 6the η phases such as C.The generation of these non-equilibrium products easily reduces the toughness of cladding layer, reduces surperficial mechanical property.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, developed a kind of WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy.
The present invention also provides above-mentioned WC-Fe-Y 2o 3(Sc 2o 3) preparation method of nanometer cladding alloy, and η phase control method in nanometer cladding alloy preparation process.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy, prepare this alloy material used by nanometer WC powder, Fe Nano-Powders, nanometer Y 2o 3powder, nanometer Sc 2o 3powder composition, in mixture, each components based on weight percentage is respectively: WC powder 48～62%, Fe Nano-Powders 33～49%, nanometer Y 2o 3powder 2～8%, nanometer Sc 2o 3powder 1～3%.
A preparation method who suppresses the η phase in mixed powder mechanical activation process, prepares this WC-Fe-Y 2o 3(Sc 2o 3) method of nanometer cladding alloy, comprise the steps:
(1) weigh each raw material by above-mentioned content, by nanometer WC powder, Fe Nano-Powders, nanometer Y after weighing 2o 3powder, nanometer Sc 2o 3powder mixed grinding in mortar is even, and the time is unsuitable long, prevents oxidation of iron powder;
(2) adopt mechanical activation technique, the mixed powder of step (1), by mechanical activation, is obtained to WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy.
Described mechanical activation technique is: ball material weight ratio is that 15: 1, the rotating speed of main shaft are 400 revs/min, countershaft rotating speed-400 rev/min, Ball-milling Time 15h; Grinding ball material can be selected carbon tungsten alloy (WC), ball radius 5～10mm.
For preventing, in mechanical milling process, metal-powder oxidation occurs, in ball grinder, fill sample and sample and all in the glove box under atmosphere protection, carry out; Shielding gas is argon gas or helium.
WC, Sc described in step (1) 2o 3the particle diameter of powder particle is 100nm, Fe, Y 2o 3the particle diameter of powder particle is 50nm.
The present invention is by adding rare earth nano Y 2o 3, nanometer Sc 2o 3, combine and suppress the easy η phase forming in nanometer WC and Fe powder Process During High Energy Ball Milling.
WC-Fe-Y of the present invention 2o 3(Sc 2o 3) nanometer cladding alloy can be applicable to the laser repairing on thick plate steel and Invar alloy surface, for production and the reparation of the product such as hull, valve.
Brief description of the drawings
Fig. 1 is WC-Fe-Y after mechanical activation 2o 3(Sc 2o 3) nanometer cladding alloy XRD phase composite;
Fig. 2 is WC-Fe-Y 2o 3(Sc 2o 3) scanning pattern and the back scattering figure of nanometer cladding alloy;
Wherein, (a) SEM phase; (b) become phase-splitting for the corresponding back scattering in this visual field;
Fig. 3 is TEM, SEAD diffraction pattern and the HRTEM figure of nano particle;
Wherein, (a) be the nanoparticle transmission electron microscope pattern after mechanical activation; (b) be the high resolution shape appearance figure of nanoparticle.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail and completely:
Embodiment 1
Described preparation WC-Fe-Y 2o 3(Sc 2o 3) the mechanical activation step of nanometer cladding alloy is as follows,
(1) first by the nanometer WC powder, Fe Nano-Powders, the nanometer Y that are scattered in alcohol 2o 3powder, nanometer Sc 2o 3powder is drying for standby in vacuum drying oven, after taking-up, weighs, and weight percent is respectively 57.6%, 33.4%, 8%, 1%; In mortar mixed grinding evenly after, argon gas atmosphere condition lower seal is preserved;
(2) adopt mechanical activation technique, step (1) mixed powder is carried out to mechanical activation, obtain WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy.Mechanical activation technique is: ball material weight ratio is that 15: 1, the rotating speed of main shaft are 400 revs/min, 400 revs/min of countershaft rotating speeds, Ball-milling Time 15h; Grinding ball material can be selected carbon tungsten alloy (WC), ball radius 5mm;
(3) sampling analysis.After 15h, in the ball grinder under argon gas atmosphere protection, in glove box, take out sample, in alcohol, distributed and saved is for subsequent use.
WC, Sc described in step (1) 2o 3the particle diameter of powder particle is 100nm, Fe, Y 2o 3the particle diameter of powder particle is 50nm.
Embodiment 2
Described preparation WC-Fe-Y 2o 3(Sc 2o 3) the mechanical activation step of nanometer cladding alloy is as follows,
(1) first by the nanometer WC powder, Fe Nano-Powders, the nanometer Y that are scattered in alcohol 2o 3powder, nanometer Sc 2o 3powder is drying for standby in vacuum drying oven, after taking-up, weighs, and weight percent is respectively: WC powder 58%, Fe Nano-Powders 33%, nanometer Y 2o 3powder 8%, nanometer Sc 2o 3powder 1%.; In mortar mixed grinding evenly after, argon gas atmosphere condition lower seal is preserved;
(2) adopt mechanical activation technique, step (1) mixed powder is carried out to mechanical activation, obtain WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy.Mechanical activation technique is: ball material weight ratio is that 15: 1, the rotating speed of main shaft are 400 revs/min, 400 revs/min of countershaft rotating speeds, Ball-milling Time 15h; Grinding ball material can be selected carbon tungsten alloy (WC), ball radius 5mm;
(3) sampling analysis.After 15h, in the ball grinder under argon gas atmosphere protection, in glove box, take out sample, in alcohol, distributed and saved is for subsequent use.
Embodiment 3
Described preparation WC-Fe-Y 2o 3(Sc 2o 3) the mechanical activation step of nanometer cladding alloy is as follows,
(1) first by the nanometer WC powder, Fe Nano-Powders, the nanometer Y that are scattered in alcohol 2o 3powder, nanometer Sc 2o 3powder is drying for standby in vacuum drying oven, after taking-up, weighs, and weight percent is respectively: WC powder 62%, Fe Nano-Powders 35%, nanometer Y 2o 3powder 2%, nanometer Sc 2o 3powder 1%; In mortar mixed grinding evenly after, argon gas atmosphere condition lower seal is preserved;
(2) adopt mechanical activation technique, step (1) mixed powder is carried out to mechanical activation, obtain WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy.Mechanical activation technique is: ball material weight ratio is that 15: 1, the rotating speed of main shaft are 400 revs/min, 400 revs/min of countershaft rotating speeds, Ball-milling Time 15h; Grinding ball material can be selected carbon tungsten alloy (WC), ball radius 5mm;
(3) sampling analysis.After 15h, in the ball grinder under argon gas atmosphere protection, in glove box, take out sample, in alcohol, distributed and saved is for subsequent use.
Embodiment 4
Described preparation WC-Fe-Y 2o 3(Sc 2o 3) the mechanical activation step of nanometer cladding alloy is as follows,
(1) first by the nanometer WC powder, Fe Nano-Powders, the nanometer Y that are scattered in alcohol 2o 3powder, nanometer Sc 2o 3powder is drying for standby in vacuum drying oven, after taking-up, weighs, and weight percent is respectively WC powder 60%, Fe Nano-Powders 34%, nanometer Y 2o 3powder 4%, nanometer Sc 2o 3powder 2%; In mortar mixed grinding evenly after, argon gas atmosphere condition lower seal is preserved;
(2) adopt mechanical activation technique, step (1) mixed powder is carried out to mechanical activation, obtain WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy.Mechanical activation technique is: ball material weight ratio is that 15: 1, the rotating speed of main shaft are 400 revs/min, 400 revs/min of countershaft rotating speeds, Ball-milling Time 15h; Grinding ball material can be selected carbon tungsten alloy (WC), ball radius 5mm;
(3) sampling analysis.After 15h, in the ball grinder under argon gas atmosphere protection, in glove box, take out sample, in alcohol, distributed and saved is for subsequent use.
After testing, mixed powder after mechanical activation, WC-Fe-Y 2o 3(Sc 2o 3) nanometer cladding alloy XRD facies analysis result as shown in Figure 1, as can be known from the results, at mechanical activation after 15 hours, the transition phase of main phase place WC, Fe and a small amount of WC-η phase, does not have η to form mutually, Rare Earth Y 2o 3and Sc 2o 3add, suppressed the formation of η phase.
WC-Fe-Y 2o 3(Sc 2o 3) the SEM phase of nanometer cladding alloy and backscatter images are as shown in Figure 2, Fig. 2 (a) is SEM phase, Fig. 2 (b) becomes phase-splitting for the corresponding back scattering in this visual field, the pixel grey scale of black and white represents different compositions, known, main component is white WC and the Fe of grey, and there is certain transition phase centre, does not have η to form mutually.
Test-results adopts transmission electron microscope structural characterization verification experimental verification, as shown in Figure 3, Fig. 3 (a) is the nanoparticle transmission electron microscope pattern after mechanical activation, the embedded figure in the upper left corner is that electron diffraction pattern (SAED is chosen in the transmission of nanoparticle, Selected Area Electron Diffraction), show that this nano particle structure has not been single WC or Fe structure, but a kind of mixed structure, but do not comprise η phase structure, Fig. 3 (b) is the high resolution shape appearance figure of nanoparticle, visible obvious lattice (amplifying lattice as shown in embedded figure), as shown in fourier transformation (Fourier Transform) figure as embedded in the upper right corner of edge lattice.Therefore,, according to XRD test-results, SEM and back scattering test and transmission electron microscope high resolution analysis structure, can judge: WC-Fe-Y of the present invention 2o 3(Sc 2o 3) nanometer cladding alloy is a kind of evenly to mix with WC and Fe, nanoparticle is reunited on a small quantity, the alloy that does not have η to form mutually.The Rare Earth Y proposing 2o 3and Sc 2o 3add, suppressed the formation of η phase.

Claims (6)

1. a WC-Fe-Y 2o 3-Sc 2o 3nanometer cladding alloy, is characterized in that: prepare this alloy material used by nanometer WC powder, Fe Nano-Powders, nanometer Y 2o 3powder, nanometer Sc 2o 3powder composition, in mixture, each components based on weight percentage is respectively: WC powder 48～62%, Fe Nano-Powders 33～49%, nanometer Y 2o 3powder 2～8%, nanometer Sc 2o 3powder 1～3%.
2. WC-Fe-Y according to claim 1 2o 3-Sc 2o 3nanometer cladding alloy, is characterized in that: the laser repairing that can be applicable to thick plate steel and Invar alloy surface.
3. WC-Fe-Y according to claim 1 2o 3-Sc 2o 3the preparation method of nanometer cladding alloy, is characterized in that: can suppress the η phase in mixed powder mechanical activation process, this preparation method comprises the steps:
(1) press WC powder 48～62%, Fe Nano-Powders 33～49%, nanometer Y 2o 3powder 2～8%, nanometer Sc 2o 3the proportioning of powder 1～3% weighs each raw material, by nanometer WC powder, Fe Nano-Powders, nanometer Y after weighing 2o 3powder, nanometer Sc 2o 3powder mixed grinding in mortar is even, and the time is unsuitable long, prevents oxidation of iron powder;
(2) adopt mechanical activation technique, the mixed powder of step (1), by mechanical activation, is obtained to WC-Fe-Y 2o 3-Sc 2o 3nanometer cladding alloy.
4. preparation method according to claim 3, is characterized in that: described mechanical activation technique is: ball material weight ratio is that the rotating speed of 15:1, main shaft is 400 revs/min, 400 revs/min of countershaft rotating speeds, Ball-milling Time 15h; Grinding ball material is selected carbon tungsten alloy (WC), ball radius 5～10mm.
5. preparation method according to claim 4, is characterized in that: in ball grinder, fill sample and sample and all in the glove box under atmosphere protection, carry out; Shielding gas is argon gas or helium.
6. preparation method according to claim 3, is characterized in that: WC, Sc described in step (1) 2o 3the particle diameter of powder particle is 100nm, Fe, Y 2o 3the particle diameter of powder particle is 50nm.
CN201210046589.XA 2012-02-27 2012-02-27 WC-Fe-Y2O3 (Sc2O3) nano-cladded alloy and preparation method capable of inhibiting Eta phase in mechanical activation process Expired - Fee Related CN102560170B (en)

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