CN101161379A - A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle - Google Patents
A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle Download PDFInfo
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Abstract
The present invention belongs to the material technique field, specifically relates to a method for preparing a Co-Ni-Cu system amorphous alloy monodisperse nano-particles. The reacted precursor chooses the soluble metal salt as the metal ion source, the clear transparent positive phase micromulsion is configured by controlling the water, oil, surfactant and cosurfactant with a definite ratio, then the micro-reactor provided by the configured microemulsion is used to realize the control of the crystal system and appearance, the Co-Ni-Cu system amorphous alloy monodisperse nano-particles with good monodispersity and uniform grain diameter are prepared, the grain diameter range of the nano-particle is 4 to 20nm, and the nano-particles have excellent physicochemical property and have excellent capability and wide application on the aspects of magnetism, catalyzing property, hydrogen-storing property and wave-absorbing property, etc.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of Co-Ni-Cu system amorphous alloy monodispersity nanometer particle process method.
Background technology
Amorphous alloy is because characteristics such as its magnetic characteristic is good, hardness is high, resistance to corrosion is strong, chemism is good, absorption and anti-irradiation ability are strong have caused that people study interest greatly.Amorphous alloy has entered application, and the application aspect magnetic material mainly is as transformer material, magnetic head material, magnetic shielding material, magnetostriction materials and magnetic bubble material etc., especially as soft magnetic materials great application prospect is arranged.At present, the amorphous soft magnetic alloy of comparative maturity mainly contains iron-based, Fe-Ni based and cobalt-based three major types.
The nanometer of amorphous alloy material structure is the new direction of magnetic material development.Nano material has the not available physics of traditional material, chemical characteristic, can produce four big effects: small-size effect, quantum effect (containing macro quanta tunnel effect), skin effect and interfacial effect.The amorphous nano magnetic material not only has the excellent magnetism energy, also has the chemical property of favorable mechanical performance, excellence.Non-crystalline material generally adopts alloy melt or the preparation of gas rapid condensation method, and can only form banded amorphous alloy thin slice, people have opened up the new method of multiple preparation superfines in recent years, as mechanical alloying method, sol-gel process, hydro-thermal method, vapour deposition process, microemulsion method etc., also the preparation for non-crystalline material provides new way.At present, nano material has obtained using widely in fields such as catalysis, luminous, magnetic, semiconductor and fine ceramics materials, promoted the research of people to the preparation ultrafine particle, one of difficult problem wherein is the nanoparticle that how to obtain controllable size, high dispersive and stable uniform.Because microemulsion method reaction condition gentleness, the control particle size had special advantages, and it is simple to have experimental provision, easy to operate, advantages such as application is wide and cause gradually people's attention and very big interest, its operational simplification and the applicability of using also provide a simple and easy preparation approach for the preparation of amorphous alloy nano particulate.
Summary of the invention
The objective of the invention is to propose that controllable granularity under a kind of room temperature, decrystallized state are controlled, good stability, easy to operate, be easy to industrialized Co-Ni-Cu system amorphous alloy monodispersity nanometer particle process method.
The present invention adopts the method for the positive microemulsion of surfactant compound, realizes the preparation of amorphous alloy nano particle with reducing agent reduction soluble metal salt.Microemulsion method is a kind of heterogeneous liquid phase synthesizing method, be two kinds of immiscible solvents, under Action of Surfactant, form emulsion, in microvesicle through nucleation, condense, reunite, obtain nanoparticle after the heat treatment, with sol-gal process, coprecipitation, other wet chemical method such as hydro-thermal method is compared, it has particulate and is difficult for coalescent, controlled amount, good dispersion, narrow particle size distribution, easy to operate, the characteristics that do not need specific conditions such as HTHP have been widely used in elemental metals and alloy nano particles, the catalyst nano particulate, the semiconductor nano particulate, magnetic Nano material, biomaterial, the organic/inorganic composite nanoparticle, the self assembly of nano particle in the preparation of ceramic powder and the microemulsion.
It is metal ion source that the presoma of the present invention's reaction is selected soluble metallic salt, the amount of the water by controlling certain proportioning, oil, surfactant, cosurfactant, configure the positive microemulsion of clear, the microreactor that utilizes the microemulsion configure to provide is then prepared the nanometer amorphous alloying pellet with regular morphology and crystal formation, and then realizes the control to crystal formation and pattern.
The preparation method of the Co-Ni-Cu system amorphous alloy nano particle that the present invention proposes, concrete steps are as follows:
(1) mixed liquor with 200-400mg NaOH (guaranteeing pH value＞7 of solution), 17-20ml deionized water and 25-30ml ethanol stirs, then add 8ml by oleic acid and Tween-80 compounded surfactant, 2ml n-hexane, stir, form lurid positive microemulsion solution;
(2) with the 5ml molar concentration be the M of 0.5mmol
2+The inorganic salts deionized water solution add in the microemulsion solution of step (1) gained, stir, form and have M
2+And the positive microemulsion of characteristic color;
(3) with the 5ml molar concentration be the KBH of 10-20mmol
4Perhaps NaBH
4Deionized water solution be added drop-wise in the microemulsion of step (2) gained, stir while dripping, after dropwising, continue to stir 5-10min, drip the moment microemulsion and promptly become black, and produce precipitated product;
(4) in the solution of step (3) gained, add the 20-25ml n-hexane and carry out breakdown of emulsion, solution transferred in the separatory funnel fully shake up, leave standstill, solution is divided into two-layer, upper oil phase is mainly n-hexane, part ethanol, oleic acid and Tween-80, and lower floor's water is mainly water, reacts remaining M
2+With residue ethanol; Because the colloidal particle surface that generates is coating surfactant, hydrophobic group C-H chain outwardly, so colloidal particle almost completely is extracted in the upper oil phase; Extract upper solution then, upper solution is adopted absolute ethyl alcohol and stirring, washing synthetic product (generally washing 3-6 time), with 4000-5000 rev/min rotating speed centrifugation, promptly get required product then, products obtained therefrom is dissolved in the 15ml n-hexane, and sealing is deposited;
Wherein, the described M that contains
2+Inorganic salts be the metal inorganic salt of the divalence of all solubilities, purity is not less than chemical pure.
Among the present invention, the volume ratio of described oleic acid and Tween-80 is 1: 3-19: 1.
Among the present invention, the purity of described n-hexane, oleic acid, Tween-80 and absolute ethyl alcohol is not less than chemical pure.
Among the present invention, described KBH
4, NaBH
4Be not less than chemical pure with the purity of NaOH.
Among the present invention, stir described in step (1), (2), (3), (4) and can be undertaken by modes such as mechanical agitation or vibration, magnetic agitation, sonic oscillations.
Among the present invention, the described sonic oscillation time can suitably be adjusted according to the power of ultrasonic generating means, and ultrasonic time is 10-30 minute usually.
Among the present invention, step (1) and (2) described mixing time are good for making microemulsion reach transparent and homogeneous.
Among the present invention, KBH described in the step (3)
4Perhaps NaBH
4The speed that is added drop-wise in the microemulsion of deionized water solution drip for per minute 10-30.
Among the present invention, after each washing is finished, with wash again after the whizzer separation next time.
Among the present invention, KBH
4Perhaps NaBH
4Addition look metal M
2+The kind of inorganic salts and deciding, addition is generally at 10-20mmol, and the needs that this scope can either satisfy reduction can not cause the wasting of resources again.
Structure, pattern, composition to the inventive method products therefrom characterize, can select X-ray powder diffraction (XRD), SEM (SEM), fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), x-ray photoelectron spectroscopy (XPS), transmission electricity border (TEM) etc. respectively for use, XRD result shows crystal formation, size distribution and the main component of product, SEM, TEM shows particle diameter and whole pattern, the result of FTIR checking XRD and the kind and the content of particle surface bag addendum.XPS detects the microcell element and forms, the result of evidence XRD.
The invention has the advantages that:
1. the present invention has realized utilizing slaine soluble in water under the normal temperature presoma for reduction reaction, preparation metal and alloy in the positive microemulsion of surfactant compound, break through the synthetic classical mode of reverse micro emulsion in the past, inorganic synthetic a kind of new route of synthesis that provides is provided.
2. the particle surface that generates of this method coats the layer of surface activating agent, is difficult for coalescently, and the collosol stability that obtains is good, but the long period stores.
3. the present invention adopts simple inorganic salts as reactant respectively, has very strong versatility.
4. the present invention is that the positive microemulsion of employing surfactant compound is the method for soft template, be different from reverse microemulsion process, continuous phase in the microemulsion is water, decentralized photo is an oil phase, the amount of used organic solvent is far smaller than reverse microemulsion process, has avoided a large amount of uses of organic solvent, has reduced the content of organic solvent in the waste discharge, making whole process of production more meet the sustainable development requirement, is a kind of environment-friendly type synthesis technique.
5. the positive microemulsion method that method used in the present invention is a surfactant compound, use equipment is simple, and operation is convenient, and testing required temperature is room temperature, is convenient to industry and transforms, and realizes large-scale production.
6. the present invention is applied widely, can be used for the synthetic of multiple transition metal oxide and alloy crystal or noncrystal nano/micron level powder, by changing reducing agent, kinds of surfactants and consumption, size to the crystal formation of product, pattern, particle is regulated and control, thereby obtains nanometer-size die different crystal forms, different-shape.
7. utilize the inventive method to prepare that monodispersity is good, the Co-Ni-Cu system monodisperse amorphous state alloy nano particle of uniform particle diameter, the nano particle diameter scope is 4-20nm, thereby has excellent physicochemical property.For example at magnetic, catalytic, there is excellent performance aspects such as storage hydrogen and absorbing material and uses widely.
8. the product prepared of the inventive method can be by further becoming membrane operations, prepares alloy firm as LB, method such as lift.
9. the portion of product of the present invention's preparation has good magnetic performance, can be used as the powder or the bulk material of magnetic head material, piezomagnetic material, magnetic recording material, and comparatively vast potential for future development and application space are arranged.
10. technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is easily controlled, and is with low cost, and product pattern, size are easily controlled, the purity height, and the product processing is convenient succinct, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is among the embodiment 1--embodiment 4, the XRD spectra of the product that application compounded surfactant oleic acid and Tween-80 prepare under the condition of different volumes ratio.Wherein:
Figure (a) is for using the XRD spectra of the synthetic amorphous alloy nano particle of positive microemulsion method; The S1 curve is the XRD spectra of NiCu, and the S2 curve is the XRD spectra of CoCu, and the S3 curve is the XRD spectra of CoNiCu, and the S4 curve is the XRD spectra of CoNi;
The XRD spectra that figure (b) records after half an hour through 650 ℃ of high temperings in nitrogen atmosphere for the amorphous alloy nano particle, the S1 curve is the XRD spectra of NiCu, the S2 curve is the XRD spectra of CoCu, and the S3 curve is the XRD spectra of CoNiCu, and the S4 curve is the XRD spectra of CoNi.
Fig. 2 is among the embodiment 1, uses the product S 1 for preparing under the condition of compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 1: 3): the TEM photo of NiCu and electron diffraction diagram thereof (upper left corner illustration).
Fig. 3 is among the embodiment 2, uses the product S 2 for preparing under the condition of compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 3: 5): the TEM photo of CoCu and electron diffraction diagram thereof (upper left corner illustration).
Fig. 4 is among the embodiment 3, uses the product S 3 for preparing under the condition of compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 1: 1): the TEM photo of CoNiCu and electron diffraction diagram thereof (upper left corner illustration).
Fig. 5 is among the embodiment 4, uses the product S 4 for preparing under the condition of compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 5: 3): the TEM photo of CoNi and electron diffraction diagram thereof (upper left corner illustration).
Fig. 6 is the TEM photo of the resulting product C uNi of preparation under the condition of using compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 3: 1) among the embodiment 5.
Fig. 7 is the TEM photo of the resulting product C oCu of preparation under the condition of using compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 7: 1) among the embodiment 6.
Fig. 8 is the TEM photo of the resulting product C oNiCu of preparation under the condition of using compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 9: 1) among the embodiment 7.
Fig. 9 is the TEM photo of the resulting product C oNi of preparation under the condition of using compounded surfactant oleic acid and Tween-80 (volume ratio of oleic acid and Tween-80 is 19: 1) among the embodiment 8.
The specific embodiment
Further describe the present invention below by examples of implementation.
Embodiment 1:NiCu amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 1: 3)
The first step, take by weighing 400mgNaOH and place beaker, the mixed liquor stirring a period of time that adds 20ml deionized water and 30ml ethanol makes its dissolving, adds 2ml oleic acid, 6ml Tween-80 and 2ml n-hexane more successively, fully stirs and forms lurid positive microemulsion solution.
Second step, accurately weighing 0.0594gNiCl
26H
2O and 0.0624gCuSO
45H
2O is dissolved in the 5ml deionized water, solution joined in the resulting system of the first step, and ultrasonic agitation 10 minutes, formation has M
2+And the positive microemulsion of characteristic color, and transfer in the three-necked bottle.
The 3rd step, accurately weighing 0.5394gKBH
4, be dissolved in the deionized water, solution is added drop-wise in the microemulsion that second step obtained stirring reaction 30 minutes with the speed of 30 of per minutes.
In the 4th step, after reaction finishes, in solution, add 25ml n-hexane breakdown of emulsion.Stir after 10 minutes, leave standstill a moment, solution is divided into two-layer.Separatory is transferred to upper solution in the dry beaker, add the 20ml absolute ethyl alcohol, supersound washing 10 minutes, the rotating speed centrifugation of transferring to then in the centrifuge tube with 4000rpm/min goes out precipitation, discard centrifugate, promptly get required product, products obtained therefrom partly is dispersed in the n-hexane, carry out electron microscopic observation; Remainder alternately washs with ethanol and deionized water, centrifugation, and XRD analysis is carried out in the product vacuum drying that obtains.
Fig. 1 (a) and (b) in provided products obtained therefrom S1 respectively: the X-ray powder diffraction figure after the X-ray powder diffraction collection of illustrative plates of NiCu amorphous alloy nano particle and its tempering.Can see the diffraction maximum of NiCu amorphous alloy nano particle broadening from Fig. 1 (a), prove that it is in amorphous state, the electron diffraction diagram among Fig. 2 has further proved this result.Sample is converted into the crystal alloy with FCC structure through after the tempering by amorphous state.From TEM electromicroscopic photograph shown in Figure 2 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 2:CoCu amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 3: 5)
Get 400mgNaOH, 20ml deionized water, 30ml ethanol, 3ml oleic acid, 5ml Tween-80,2ml n-hexane, 0.0594gCoCl respectively
26H
2O, 0.0624gCuSO
45H
2O and 0.5394gKBH
4Press embodiment 1 described step, make required product.Fig. 1 (a) and (b) in provided products obtained therefrom S2 respectively: the X-ray powder diffraction collection of illustrative plates of CoCu amorphous alloy nano particle and the X-ray powder diffraction figure after the tempering.Can see the diffraction maximum of NiCu amorphous alloy nano particle broadening from Fig. 1 (a), prove that it is in amorphous state, the electron diffraction diagram among Fig. 3 has further proved this result.Sample is converted into the crystal alloy with FCC structure through after the tempering by amorphous state.From TEM electromicroscopic photograph shown in Figure 3 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 3:CoNiCu amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 1: 1)
Get 400mgNaOH, 20ml deionized water, 30ml ethanol, 4ml oleic acid, 4ml Tween-80,2ml n-hexane, 0.0397gCoCl respectively
26H
2O, 0.0396gNiCl
26H
2O, 0.0416gCuSO
45H
2O and 0.8091gKBH
4Press embodiment 1 described step, the reaction time is 1 hour, makes required product.Fig. 1 (a) and (b) in provided products obtained therefrom S3 respectively: the X-ray powder diffraction collection of illustrative plates of CoNiCu amorphous alloy nano particle and the X-ray powder diffraction figure after the tempering.Can see the diffraction maximum of CoNiCu amorphous alloy nano particle broadening from Fig. 1 (a), prove that it is in amorphous state, the electron diffraction diagram among Fig. 4 has further proved this result.Sample is converted into the crystal alloy with FCC structure through after the tempering by amorphous state.From TEM electromicroscopic photograph shown in Figure 4 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 4:CoNi amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 5: 3)
Get 400mgNaOH, 20ml deionized water, 30ml ethanol, 5ml oleic acid, 3ml Tween-80,2ml n-hexane, 0.0594gCoCl respectively
26H
2O, 0.0594gNiCl
26H
2O and 0.8091gKBH
4Press embodiment 1 described step, the reaction time is 15 minutes, makes required product.Fig. 1 (a) and (b) in provided products obtained therefrom S4 respectively: the X-ray powder diffraction collection of illustrative plates of CoNi amorphous alloy nano particle and the X-ray powder diffraction figure after the tempering.Can see the diffraction maximum of CoNi amorphous alloy nano particle broadening from Fig. 1 (a), prove that it is in amorphous state, the electron diffraction diagram among Fig. 5 has further proved this result.Sample is converted into the crystal alloy with FCC structure through after the tempering by amorphous state.From TEM electromicroscopic photograph shown in Figure 5 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 5:CuNi amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 3: 1)
Get 200mgNaOH, 17ml deionized water, 25ml ethanol, 6ml oleic acid, 2ml Tween-80,2ml n-hexane, 0.0594gNiCl respectively
26H
2O, 0.0624gCuSO
45H
2O and 0.5394gKBH
4Press embodiment 1 described step, the reaction time is 25 minutes, makes required product.From TEM electromicroscopic photograph shown in Figure 6 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 6:CoCu amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 7: 1)
Get 200mgNaOH, 17ml deionized water, 25ml ethanol, 7ml oleic acid, 1ml Tween-80,2ml n-hexane, 0.0594gCoCl respectively
26H
2O, 0.0624gCuSO
45H
2O and 0.5394gKBH
4Press embodiment 1 described step, the reaction time is 50 minutes, makes required product.From TEM electromicroscopic photograph shown in Figure 7 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 7:CoNiCu amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 9: 1)
Get 200mgNaOH, 17ml deionized water, 25ml ethanol, 7.2ml oleic acid, 0.8ml Tween-80,2ml n-hexane, 0.0397gCoCl respectively
26H
2O, 0.0396gNiCl
26H
2O, 0.0416gCuSO
45H
2O and 0.8091gKBH
4Press embodiment 1 described step, the reaction time is 35 minutes, makes required product.From TEM electromicroscopic photograph shown in Figure 8 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Embodiment 8:CoNi amorphous alloy nano particle (volume ratio of oleic acid and Tween-80 is 19: 1)
Get 200mgNaOH, 17ml deionized water, 25ml ethanol, 7.6ml oleic acid, 0.4ml Tween-80,2ml n-hexane, 0.0594gCoCl respectively
26H
2O, 0.0594gNiCl
26H
2O and 0.8091gKBH
4Press embodiment 1 described step, the reaction time is 35 minutes, makes required product.From TEM electromicroscopic photograph shown in Figure 9 as can be seen, product is the nano level particle of amorphous state, and particle diameter is little and have a monodispersity.
Claims (9)
1. the preparation method of a Co-Ni-Cu system amorphous alloy nano particle is characterized in that concrete steps are as follows:
(1) mixed liquor with NaOH, 17-20ml deionized water and the 25-30ml ethanol of 200-400mg pH value＞7 stirs, then add 8ml by oleic acid and Tween-80 compounded surfactant, 2ml n-hexane, stir, form lurid positive microemulsion solution;
(2) with the 5ml molar concentration be the M of 0.5mmol
2+The inorganic salts deionized water solution add in the microemulsion solution of step (1) gained, stir, form and have M
2+And the positive microemulsion of characteristic color;
(3) with the 5ml molar concentration be the KBH of 10-20mmol
4Perhaps NaBH
4Deionized water solution drip in the microemulsion of step (2) gained, stir while dripping, after dropwising, continue to stir 5-10min, drip the moment microemulsion and promptly become black, and the generation precipitated product;
(4) in the solution of step (3) gained, add the 20-25ml n-hexane and carry out breakdown of emulsion, solution transferred in the separatory funnel fully shake up, leave standstill, solution is divided into two-layer, and the extraction upper solution adopts absolute ethyl alcohol and stirring, washing synthetic product then, then with 4000-5000 rev/min rotating speed centrifugation, promptly get required product, products obtained therefrom is dissolved in the n-hexane, and sealing is deposited;
Wherein, the described M that contains
2+Inorganic salts be the metal inorganic salt of the divalence of all solubilities, purity is not less than chemical pure.
2. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1, the volume ratio that it is characterized in that described oleic acid and Tween-80 is 1: 3-19: 1.
3. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1 is characterized in that the purity of described n-hexane, oleic acid, Tween-80 and absolute ethyl alcohol is not less than chemical pure.
4. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1 is characterized in that described KBH
4, NaBH
4Be not less than chemical pure with the purity of NaOH.
5. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1 is characterized in that described in step (1), (2), (3), (4) stirring by mechanical agitation or vibration, magnetic agitation, sonic oscillation mode and is undertaken.
6. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 5 is characterized in that the described sonic oscillation time is 10-30 minute.
7. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1 is characterized in that step (1) and (2) described mixing time get final product for making microemulsion reach transparent and homogeneous.
8. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1 is characterized in that KBH described in the step (3)
4Perhaps NaBH
4The speed that is added drop-wise in the microemulsion of deionized water solution drip for per minute 10-30.
9. the preparation method of Co-Ni-Cu system amorphous alloy nano particle according to claim 1 is characterized in that after each washing is finished, and washs after separating with whizzer next time again.
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| CN100372968C (en) * | 2003-04-03 | 2008-03-05 | 南开大学 | NiP amorphous alloy and prep. thereof |
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| CN105880625A (en) * | 2016-05-04 | 2016-08-24 | 四川大学 | Liquid-liquid two-phase method for preparing nano cobalt powder |
| CN108052794A (en) * | 2018-01-16 | 2018-05-18 | 桂林电子科技大学 | The Forecasting Methodology of the eutectic temperature of various sizes of nanometer Ag-Cu alloy systems |
| CN108052794B (en) * | 2018-01-16 | 2022-01-28 | 桂林电子科技大学 | Method for predicting eutectic temperature of nano Ag-Cu alloy systems with different sizes |
| JP2019178385A (en) * | 2018-03-30 | 2019-10-17 | 日揮触媒化成株式会社 | Method for producing alloy particle dispersion liquid |
| JP2019178386A (en) * | 2018-03-30 | 2019-10-17 | 日揮触媒化成株式会社 | Alloy particle dispersion liquid and method for producing the same |
| JP7014663B2 (en) | 2018-03-30 | 2022-02-01 | 日揮触媒化成株式会社 | Method for manufacturing alloy particle dispersion |
| JP7014664B2 (en) | 2018-03-30 | 2022-02-01 | 日揮触媒化成株式会社 | Alloy particle dispersion and its manufacturing method |
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