CN101210320A - Method for preparing silver-nickel core-shell particles - Google Patents
Method for preparing silver-nickel core-shell particles Download PDFInfo
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- CN101210320A CN101210320A CNA2007101591719A CN200710159171A CN101210320A CN 101210320 A CN101210320 A CN 101210320A CN A2007101591719 A CNA2007101591719 A CN A2007101591719A CN 200710159171 A CN200710159171 A CN 200710159171A CN 101210320 A CN101210320 A CN 101210320A
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Abstract
The invention relates to a preparation method of Ag-Ni core-shell particles. The adopted technical scheme comprises the following steps of: mixing OP-4 polyoxyethylene (4) nonylphenyl ether, OP-7 polyoxyethylene (7) nonylphenyl ether and paraffin hydrocarbon uniformly to obtain an oil phase; dissolving nickel nitrate or nickel acetate and silver nitrate in secondary water, adding 10% NaOH solution to precipitate, adding 30% ammonia water to dissolve the precipitate to obtain an oxidant-containing water phase; preparing NaBH4 to 1 to 5% water solution to obtain a reducer-containing water phase; mixing 100 to 150 parts of the oil phase with one part of the oxidant-containing water phase to obtain an oxidant-containing inverse microemulsion; mixing 100 to 150 parts of the oil phase with one part of the reducer-containing water phase to obtain a reducer-containing inverse microemulsion; and adding the oxidant-containing inverse microemulsion into the reducer-containing inverse microemulsion dropwise, mechanically stirring at 20 to 40 DEG C, centrifuging, cleaning and drying. The invention has simple method, and the prepared shell has strong bonding force, good dispersity, good cladding uniformity and compact cladding.
Description
Technical field: the present invention relates to a kind of method for preparing silver-nickel core-shell particles field, particularly a kind ofly prepare the silver-nickel core-shell particles field with the reverse micro emulsion one-step synthesis.
Background technology: the core-shell structure magnetic material is a kind of functional composite material with special construction, because they have the performance of outer shell and inner nuclear material concurrently, simultaneously have many special physics, chemical property that are different from nuclear, shell material again, wide application prospect is arranged in fields such as biological medicine, electromagnetism, chemical catalysis and micromechanics effects.Because silver has good electrical conductivity, the metallic nickel coating layer have good erosion resistance, wear resistance, good toughness, low-stress, good with most powder wettabilitys, with substrate metal bonding strength advantages of higher, so nickel cladded type silver is used very extensive in fields such as thermospray, biological medicine, electromagnetism and micromechanics effects.
The existing method for preparing core-shell material mainly contains: 1. ball milled; 2. chemical reduction sedimentation; 3. sol-gel; 4. substitution method; 5. electroless plating; 6. electrodeposition; 7. thermolysis-reduction method etc.The ball milled method is simple, and the thickness of coating layer is controlled easily, but the difficult composite powder that forms cladded type; Sol-gel method prepares good dispersity, and the thickness of coating layer is even relatively, but coating layer mostly is metal oxide, need just can obtain metal simple-substance through processes such as high temperature reduction processing, so the kind of coating is restricted; The displacement reduction method has advantages such as technology is simple, speed of response is fast, with low cost, is a kind of method for preparing the nucleocapsid bimetallic material of excellence.It is fewer that but this legal system is equipped with the kind of bimetallic material, generally only is confined to the preparation of strong oxidizing property metallic cover strong reducing property metal; It is actually rare to utilize the electrodeposition legal system to be equipped with the bimetallic report of nucleocapsid structure at present; Thermolysis-reduction method is considered the influence factor of metal carbonyl coat and core, is total to capacitive (chemical reaction, solubleness), compossibility and wettability etc. such as alternate thermodynamics, and reaction conditions is comparatively harsh; Though electroless plating is one of more sophisticated method, before the plating, must carry out sensitization and activation treatment to it, need washing repeatedly after handling, pretreatment process is many, and complicated operation adopts precious metal to make activator cost height, and the plating bath instability.
At present, the method for preparing silver-nickel core-shell particles mainly is the chemical reduction sedimentation, has at first prepared the Nano silver grain with monodispersity in ethylene glycol; Then the above-mentioned Nano silver grain that has prepared being dispersed in the ethylene glycol, is that reductive agent has prepared the silver-nickel core-shell nanoparticle with the hydrazine.Not only method complexity, and cost height, and needed for two steps carried out.And can't see the nucleocapsid structure of complete display from TEM figure (Fig. 2), silver (nuclear) size of particles is 9.5nm, and the core-shell particles form is irregular and coating layer is inhomogeneous, and more serious clustering phenomena is arranged.Particle size distribution figure shows single core-shell particles size distribution between 10-30nm, the size-grade distribution inequality.Because the form of particle is irregular, coating layer is inhomogeneous and serious gathering, has seriously limited the application of silver-nickel core-shell particles on above-mentioned field.
Summary of the invention:, the invention provides a kind of method for preparing silver-nickel core-shell particles in order to address the above problem.The inventive method is simple, constructs that the shell bonding force is strong, good dispersity, cladding uniformity is good and coat densification.
The technical solution used in the present invention is: method for preparing silver-nickel core-shell particles,
1) preparation of oil phase: OP-4 Nonyl pheno (4) ether, OP-7 Nonyl pheno (7) ether and a kind of normal alkane of containing 7-10 C atom are mixed; Wherein, the weight ratio of OP-4 Nonyl pheno (4) ether and OP-7 Nonyl pheno (7) ether is 1: 0.1～1, and OP-4 Nonyl pheno (4) ether and OP-7 Nonyl pheno (7) ether account for 10～25% of oil phase mixing solutions gross weight;
2) contain the preparation of oxygenant water: get nickel salt and Silver Nitrate and be dissolved in the secondary water and make solution, add 10%NaOH solution, precipitation occurs, add 30% ammoniacal liquor to solution again and clarify, the mol ratio of nickel salt and Silver Nitrate is 1～5: 1;
3) contain the preparation of reductive agent water: with NaBH
4Be made into 1～5% the aqueous solution;
4) contain the preparation of oxygenant reverse micro emulsion
Get 100～150 parts of oil phases and 1 part and contain the oxygenant water, under the room temperature, mechanical stirring 30～50 minutes;
5) contain the preparation of reductive agent reverse micro emulsion
Get 100～150 parts of oil phases and 1 part and contain the reductive agent water, under the room temperature, mechanical stirring 30～50 minutes;
6) will contain the oxygenant reverse micro emulsion and dropwise join and contain in the reductive agent reverse micro emulsion, under 20-40 ℃, mechanical stirring reaction 1～2 hour, centrifugal, use secondary water and absolute ethanol washing respectively, vacuum-drying.
Described nickel salt is nickelous nitrate or nickel acetate.
The invention has the beneficial effects as follows: the present invention utilizes the reaction micelle as microreactor by the reverse micro emulsion one-step synthesis, the preparation core-shell particles, and the preparation method is simple.Core-shell particles by present method preparation can be clear that from TEM figure particle has obviously complete nucleocapsid structure and is shaped as regular spheroid.Single core-shell particles size distribution is between 80-130nm, and most particles are between 110-120nm.For the size of particles of nuclear between 40-70nm, shell thickness is between 10-12nm, good dispersity, cladding uniformity is good and coat densification.And the core-shell particles of traditional method preparation be can't see the nucleocapsid structure of complete display from TEM figure (Fig. 2), and silver (nuclear) size of particles is 9.5nm, and the core-shell particles form is irregular and coating layer is inhomogeneous, and more serious clustering phenomena is arranged.Particle size distribution figure shows single core-shell particles size distribution between 10-30nm, the size-grade distribution inequality.
Description of drawings:
Fig. 1 is the TEM figure of the embodiment of the invention 1;
Fig. 2 is the TEM figure of the silver-nickel core-shell nanoparticle of chemical reduction sedimentation preparation.
Embodiment
Material: secondary water or distilled water
OP-4 Nonyl pheno (4) ether Liaoyang gram difficult to understand polyethers company limited
OP-7 Nonyl pheno (7) ether Liaoyang gram difficult to understand polyethers company limited;
Embodiment 1
1) preparation of oil phase: in two Erlenmeyer flasks, each mixes 1.75g OP-4 Nonyl pheno (4) ether, 0.70g OP-7 Nonyl pheno (7) ether and 11.00g normal heptane;
2) contain the preparation of oxygenant water
Claim 0.0698g (0.24mmol) Ni (NO
3)
26H
2O and 0.0204g (0.12mmol) AgNO
3Be dissolved in 0.80g secondary water and be mixed with solution, add 10%NaOH solution, precipitation occurs, add 30% ammoniacal liquor to solution again and clarify;
3) contain the preparation of reductive agent water
With NaBH
4Be made into 2.5% the aqueous solution;
4) contain the preparation of oxygenant reverse micro emulsion
Get oil phase 13.45g and contain oxygenant water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 30 minutes;
5) contain the preparation of reductive agent reverse micro emulsion
Get oil phase 13.45g and contain reductive agent water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 30 minutes;
6) will contain the oxygenant reverse micro emulsion and dropwise join and contain in the reductive agent reverse micro emulsion, under 20-40 ℃, mechanical stirring reaction 1 hour, centrifugal black solid is used secondary water and absolute ethanol washing respectively, vacuum-drying.
7) adopt magnetic separation to separate and to obtain silver-nickel core-shell particles
The gained silver-nickel core-shell particles detects through JEM-100SX type transmission electron microscope, and the figure of TEM as a result of gained is as Fig. 1.
From Fig. 1, can be clear that particle has obviously complete nucleocapsid structure.Single core-shell particles size distribution is between 80-130nm, and most particles are between 110-120nm.For the silver particles size of nuclear between 40-70nm, the nickel shell thickness is between 10-12nm, good dispersity, cladding uniformity is good and coat densification.
Embodiment 2
1) preparation of oil phase: in two Erlenmeyer flasks, each mixes 1.75g OP-4 Nonyl pheno (4) ether, 1.75g OP-7 Nonyl pheno (7) ether and 10.50g octane;
2) contain the preparation of oxygenant water
Claim 0.1245g (0.5mmol) C
4H
6NiO
44H
2O and 0.0204g (0.1mmol) AgNO
3Be dissolved in 0.80g secondary water and be mixed with solution, add 10%NaOH solution, precipitation occurs, add 30% ammoniacal liquor to solution again and clarify;
3) contain the preparation of reductive agent water
With NaBH
4Be made into 1% the aqueous solution.
4) contain the preparation of oxygenant reverse micro emulsion
Get oil phase 14.00g and contain oxygenant water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 50 minutes;
5) contain the preparation of reductive agent reverse micro emulsion
Get oil phase 14.00g and contain reductive agent water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 50 minutes;
6) will contain the oxygenant reverse micro emulsion and dropwise join and contain in the reductive agent reverse micro emulsion, under 20-40 ℃, mechanical stirring reaction 1 hour, centrifugal black solid is used secondary water and absolute ethanol washing respectively, and vacuum-drying promptly gets silver-nickel core-shell particles.
The gained silver-nickel core-shell particles detects through JEM-100SX type transmission electron microscope, has obviously complete nucleocapsid structure.Single core-shell particles size distribution is between 73-110nm, and most particles are between 87-93nm.For the silver particles size of nuclear between 30-35nm, the nickel shell thickness is between 15-20nm, good dispersity, cladding uniformity is good and coat densification.
Embodiment 3
1) preparation of oil phase: in two Erlenmeyer flasks, each mixes 0.90g OP-4 Nonyl pheno (4) ether, 0.10g OP-7 Nonyl pheno (7) ether and the positive nonane of 9.00g;
2) contain the preparation of oxygenant water
Claim 0.0249g (0.10mmol) Ni (NO
3)
26H
2O and 0.0204g (0.10mmol) AgNO
3Be dissolved in 0.80g secondary water and be mixed with solution, add 10%NaOH solution, precipitation occurs, add 30% ammoniacal liquor to solution again and clarify;
3) contain the preparation of reductive agent water
With NaBH
4Be made into 5% the aqueous solution.
4) contain the preparation of oxygenant reverse micro emulsion
Get oil phase 10.00g and contain oxygenant water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 40 minutes;
5) contain the preparation of reductive agent reverse micro emulsion
Get oil phase 10.00g and contain reductive agent water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 30 minutes;
6) will contain the oxygenant reverse micro emulsion and dropwise join and contain in the reductive agent reverse micro emulsion, under 20-40 ℃, mechanical stirring reaction 1 hour, centrifugal black solid is used secondary water and absolute ethanol washing respectively, vacuum-drying.
7) adopt magnetic separation to separate and to obtain silver-nickel core-shell particles.
The gained silver-nickel core-shell particles detects through JEM-100SX type transmission electron microscope, can be clear that particle has obviously complete nucleocapsid structure.Single core-shell particles size distribution is between 65-120nm, and most particles are between 80-90nm.For the silver particles size of nuclear between 30-45nm, the nickel shell thickness is between 7-10nm, good dispersity, cladding uniformity is good and coat densification.
Embodiment 4
1) preparation of oil phase: in two Erlenmeyer flasks, each mixes 1.85g OP-4 Nonyl pheno (4) ether, 1.15g OP-7 Nonyl pheno (7) ether and 12.00g n-decane;
2) contain the preparation of oxygenant water
Claim 0.0747g (0.3mmol) Ni (NO
3)
26H
2O and 0.0204g (0.1mmol) AgNO
3Be dissolved in 0.80g secondary water and be mixed with solution, add 10%NaOH solution, precipitation occurs, add 30% ammoniacal liquor to solution again and clarify;
3) contain the preparation of reductive agent water
With NaBH
4Be made into 3.0% the aqueous solution.
4) contain the preparation of oxygenant reverse micro emulsion
Get oil phase 15.00g and contain oxygenant water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 30 minutes;
5) contain the preparation of reductive agent reverse micro emulsion
Get oil phase 15.00g and contain reductive agent water 0.10g, place the 50ml Erlenmeyer flask, under the room temperature, mechanical stirring 30 minutes;
6) will contain the oxygenant reverse micro emulsion and dropwise join and contain in the reductive agent reverse micro emulsion, under 20-40 ℃, mechanical stirring reaction 1 hour, centrifugal black solid is used secondary water and absolute ethanol washing respectively, and vacuum-drying promptly gets silver-nickel core-shell particles.
The gained silver-nickel core-shell particles detects through JEM-100SX type transmission electron microscope, can be clear that particle has obviously complete nucleocapsid structure.Single core-shell particles size distribution is between 85-120nm, and most particles are between 100-108nm.For the silver particles size of nuclear between 32-40nm, the nickel shell thickness is between 12-16nm, good dispersity, cladding uniformity is good and coat densification.
Claims (2)
1. method for preparing silver-nickel core-shell particles is characterized in that the preparation method is as follows:
1) preparation of oil phase: OP-4 Nonyl pheno (4) ether, OP-7 Nonyl pheno (7) ether and a kind of normal alkane of containing 7-10 C atom are mixed; Wherein, the weight ratio of OP-4 Nonyl pheno (4) ether and OP-7 Nonyl pheno (7) ether is 1: 0.1～1, and OP-4 Nonyl pheno (4) ether and OP-7 Nonyl pheno (7) ether account for 10～25% of oil phase mixing solutions gross weight;
2) contain the preparation of oxygenant water: get nickel salt and Silver Nitrate and be dissolved in the secondary water and make solution, add 10%NaOH solution, precipitation occurs, add 30% ammoniacal liquor to solution again and clarify, the mol ratio of nickel salt and Silver Nitrate is 1～5: 1;
3) contain the preparation of reductive agent water: with NaBH
4Be made into 1～5% the aqueous solution;
4) contain the preparation of oxygenant reverse micro emulsion
Get 100～150 parts of oil phases and 1 part and contain the oxygenant water, under the room temperature, mechanical stirring 30～50 minutes;
5) contain the preparation of reductive agent reverse micro emulsion
Get 100～150 parts of oil phases and 1 part and contain the reductive agent water, under the room temperature, mechanical stirring 30～50 minutes;
6) will contain the oxygenant reverse micro emulsion and dropwise join and contain in the reductive agent reverse micro emulsion, under 20-40 ℃, mechanical stirring reaction 1～2 hour, centrifugal, use secondary water and absolute ethanol washing respectively, vacuum-drying.
2. method for preparing silver-nickel core-shell particles according to claim 1 is characterized in that described nickel salt is nickelous nitrate or nickel acetate.
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| CNB2007101591719A CN100564596C (en) | 2007-12-25 | 2007-12-25 | Method for preparing silver-nickel core-shell particles |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588679A (en) * | 2015-01-15 | 2015-05-06 | 黑龙江大学 | Preparation method of nano silver-nickel alloy powder |
| CN109535809A (en) * | 2017-08-18 | 2019-03-29 | 上海沪正实业有限公司 | A kind of luminous paint and preparation method thereof |
| CN111468739A (en) * | 2020-03-26 | 2020-07-31 | 浙江师范大学 | Magnetic recyclable Ni-coated Ag core-shell structure composite nanoparticle, preparation method thereof and dye degradation method |
-
2007
- 2007-12-25 CN CNB2007101591719A patent/CN100564596C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588679A (en) * | 2015-01-15 | 2015-05-06 | 黑龙江大学 | Preparation method of nano silver-nickel alloy powder |
| CN109535809A (en) * | 2017-08-18 | 2019-03-29 | 上海沪正实业有限公司 | A kind of luminous paint and preparation method thereof |
| CN111468739A (en) * | 2020-03-26 | 2020-07-31 | 浙江师范大学 | Magnetic recyclable Ni-coated Ag core-shell structure composite nanoparticle, preparation method thereof and dye degradation method |
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| CN100564596C (en) | 2009-12-02 |
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