CN106041352B - A kind of organic acid silver cladding nano-Ag particles and its preparation method and application - Google Patents
A kind of organic acid silver cladding nano-Ag particles and its preparation method and application Download PDFInfo
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- CN106041352B CN106041352B CN201610686226.0A CN201610686226A CN106041352B CN 106041352 B CN106041352 B CN 106041352B CN 201610686226 A CN201610686226 A CN 201610686226A CN 106041352 B CN106041352 B CN 106041352B
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- organic acid
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- acid silver
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- 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
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
Abstract
The invention discloses a kind of organic acid silver cladding nano-Ag particles and its preparation method and application.The organic acid silver cladding nano-Ag particles are characterized in that the nano-Ag particles are coated by organic acid silver, and the mean particle size being wrapped by is 6~12nm, and is uniformly dispersed.The preparation method of the organic acid silver cladding nano-Ag particles is as follows：(1) NaOH, organic acid and deionized water are mixed, is heated to certain temperature, adds silver nitrate immediately, stirred, stratification, take the waxy substance of upper strata white；(2) whiteness in above-mentioned steps (1) is centrifuged, washed, drying, is then heated to 220~280 DEG C in nitrogen, keeps the temperature 80~100min, and organic acid silver cladding nano-Ag particles are made.Preparation method of the present invention is easy to operate, and securely and reliably, of low cost, prospects for commercial application is wide, and obtained machine acid silver cladding nano-Ag particles can be used for Electronic Packaging as solder.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to for a kind of organic acid silver cladding nano-Ag particles and its preparation side
Method and application, the reunion of nano-Ag particles prepared by this method by Coated with Organic Matter to avoid nano particle, can be directly as pricker
Material is applied to Electronic Packaging field.
Background technology
In microelectronics industry, leaded solder due to have the advantages that disposable, wetability it is good and it is cheap once
Through being widely deployed.But lead and its compound are noxious materials, long-time service can damage environment and the mankind, institute
Gradually forbid using by every country with solder containing pb.At present using relatively broad lead-free brazing have Sn-Bi, Sn-Ag-Cu and
Sn-Cu etc., these solders have the characteristics that low-melting.But when electronic package material needs high temperature resistant, this kind of solder is with regard to nothing
Method meets needs.Silver has higher electrical conductivity, thermal conductivity and thermal fatigue resistance, in addition, silver point is higher (960 DEG C),
Therefore silver is appropriate high temperature resistant electronic package material.When size reduction to the Nano grade of Argent grain, since size is imitated
Its fusing point should can be caused to significantly reduce, therefore nano silver can be used for Electronic Packaging field as solder, it is relatively low to reach connection temperature,
And the purpose that temperature in use is higher.
Nano silver preparation method is more, including liquid chemical method, ionising radiation reduction, laser ablation, vacuum evaporation and light
Electrochemical reducing etc., liquid chemical method have the advantages that of low cost and technique is simple compared with other methods.Cao Yang et al.
Solution phase chemical reduction is used to prepare nano-Ag particles of the average grain diameter for 20~30nm；Zou Gui lifes et al. equally use liquid phase
Chemical reduction method, is that raw material prepares nano-Ag particles of the average grain diameter as 40nm using PVP and silver nitrate.Due to nano particle table
Face can be higher, and agglomeration easily occurs, and therefore, it is electricity to prepare good dispersion and the small Coated with Organic Matter nanometer silver solder of size
One of key technology of sub- encapsulation field.
The content of the invention
The problem of preparing reunion involved in nano silver and larger particle diameter for liquid chemical method in the prior art, this hair
Bright purpose is to provide a kind of organic acid silver cladding nano-Ag particles and its preparation method and application.Organic acid produced by the present invention
Silver cladding dispersed nano-silver particles it is good, do not reunite, particle diameter it is smaller, Electronic Packaging can be used for directly as solder.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of organic acid silver cladding nano-Ag particles, it is characterised in that the nano-Ag particles are coated by organic acid silver, quilt
The mean particle size of cladding is 6~12nm, and is uniformly dispersed.The structure diagram of the organic acid silver cladding nano-Ag particles
As shown in Figure 1.
By such scheme, it is preferable that the organic acid silver is laurate silver or ascorbic acid silver.
A kind of preparation method of organic acid silver cladding nano-Ag particles, it is characterised in that comprise the following steps：
(1) NaOH, organic acid and deionized water are mixed, is heated to certain temperature, adds silver nitrate immediately, stirred, it is quiet
Layering is put, takes the waxy substance of upper strata white；
(2) by whiteness centrifuge washing in above-mentioned steps (1), drying, is then heated to 220~280 DEG C in nitrogen,
80~100min is kept the temperature, organic acid silver cladding nano-Ag particles are made.
By such scheme, it is preferable that the NaOH, organic acid, the molar ratio of deionized water and silver nitrate are：1：1~
1.1：2000~2500：1~2.
By such scheme, it is preferable that the organic acid is laurate or ascorbic acid.
By such scheme, it is preferable that heating-up temperature described in step (1) is 75~85 DEG C.
By such scheme, it is preferable that mixing time described in step (1) is 1.5h.
By such scheme, it is preferable that centrifuge washing is specially described in step (2)：In the centrifugal rotational speed of 7000r/min
Under, washed respectively for several times with deionized water and alcohol, each wash time is 10min, it is therefore an objective to removes impurity.
By such scheme, it is preferable that drying temperature described in step (2) is 70~80 DEG C, and the time is 6~8h.
The present invention also provides above-mentioned organic acid silver cladding nano-Ag particles as application of the solder in Electronic Packaging field.
The basic principle of the present invention is as follows：
First pass through liquid chemical method and organic acid silver is first made, then obtaining organic acid silver cladding by organic acid silver decomposition receives
Rice Argent grain.Due to the active aldehyde radical of organic acid silver, the reduction and metal cluster that reproducibility aldehyde radical can be as metal ion
The place of nucleation；Organic acid silver has long linear molecular structure, and intermolecular and intramolecular hydrogen bond effect forms molecular level
On separate space, provide good template for the growth of nanoparticle, which hinders particle and further grow up, and plays
Cladding nano-Ag particles simultaneously prevent its effect reunited.
Compared with the prior art, the beneficial effects of the present invention are：
(1) the obtained organic acid silver cladding dispersed nano-silver particles of the present invention are uniform, soilless sticking phenomenon；
(2) the obtained organic acid silver cladding nano-Ag particles size of the present invention is small, and average grain diameter only has 6~12nm,
It is with good stability under room temperature；
(3) preparation method of the present invention is easy to operate, securely and reliably, of low cost, and easy to implement, prospects for commercial application is wide
It is wealthy.
Brief description of the drawings
Fig. 1 is the structure diagram of organic acid silver cladding nano-Ag particles of the present invention.
Fig. 2 is embodiment 1 using the laurate silver cladding nano-Ag particles TEM figures prepared by laurate.
Fig. 3 is embodiment 2 using the ascorbic acid silver cladding nano-Ag particles TEM figures prepared by ascorbic acid.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
Organic acid silver cladding nano-Ag particles are prepared for raw material using laurate etc., are comprised the following steps that：
(1) deionized water of the laurate of NaOH, 0.016mol of 0.015mol and 600ml are mixed, and is heated to 80
DEG C, the silver nitrate of 0.015mol is added immediately, after stirring 1.5h, is layered after standing, and the waxy substance for taking out upper strata white wraps
Laurate silver containing a small amount of impurity；
(2) White waxy material deionized water in above-mentioned steps (1) and alcohol are distinguished into eccentric cleaning 3 times, 1 time, from
Heart speed is 7000r/min, and each scavenging period is 10min, it is therefore an objective to removes impurity；Then it is baked to, temperature is 80 DEG C,
Drying time is 6h；Finally, 250 DEG C are heated in nitrogen, keeps the temperature 90min, obtains powdered laurate silver cladding nano silver
Grain.
Fig. 2 is the TEM photos of laurate silver cladding nano-Ag particles made from the present embodiment.It can be seen that nano-Ag particles
It is uniformly dispersed, soilless sticking phenomenon, particle diameter is smaller, and average grain diameter is about 6.5nm.
Embodiment 2
Organic acid silver cladding nano-Ag particles are prepared for raw material using ascorbic acid etc., are comprised the following steps that：
(1) deionized water of the ascorbic acid of NaOH, 0.015mol of 0.014mol and 550ml are mixed, and are heated to
80 DEG C, the silver nitrate of 0.02mol is added immediately, after stirring 1.5h, is layered after standing, is taken the waxy substance of upper strata white to include
The ascorbic acid silver of a small amount of impurity；
(2) White waxy material deionized water in above-mentioned steps (1) and alcohol are distinguished into eccentric cleaning 4 times, 1 time, from
Heart speed is 7000r/min, and each scavenging period is 10min, it is therefore an objective to removes impurity；Then it is baked to, temperature is 75 DEG C,
Drying time is 8h；Finally, 230 DEG C are heated in nitrogen, keeps the temperature 100min, obtains powdered ascorbic acid silver cladding nano silver
Particle.
Fig. 3 is the TEM photos of ascorbic acid silver cladding nano-Ag particles made from the present embodiment.Receive as can be seen from this figure
Rice Argent grain is uniformly dispersed, and soilless sticking phenomenon, particle diameter is small, and average grain diameter is about 11.7nm.
Claims (9)
1. a kind of organic acid silver cladding nano-Ag particles, the nano-Ag particles are coated by organic acid silver, the particle being wrapped by is put down
Equal particle diameter is 6~12nm, and is uniformly dispersed, it is characterised in that is prepared by following methods：
(1) NaOH, organic acid and deionized water are mixed, is heated to certain temperature, adds silver nitrate immediately, stirred, stood and divide
Layer, takes the waxy substance of upper strata white；The NaOH, organic acid, the molar ratio of deionized water and silver nitrate are：1：1~1.1：
2000~2500：1~2；
(2) by whiteness centrifuge washing in above-mentioned steps (1), drying, is then heated to 220~280 DEG C, insulation in nitrogen
80~100min, is made organic acid silver cladding nano-Ag particles.
2. organic acid silver cladding nano-Ag particles according to claim 1, it is characterised in that the organic acid silver is bay
Sour silver or ascorbic acid silver.
3. a kind of preparation method of organic acid silver cladding nano-Ag particles, it is characterised in that comprise the following steps：
(1) NaOH, organic acid and deionized water are mixed, is heated to certain temperature, adds silver nitrate immediately, stirred, stood and divide
Layer, takes the waxy substance of upper strata white；The NaOH, organic acid, the molar ratio of deionized water and silver nitrate are：1：1~1.1：
2000~2500：1~2；
(2) by whiteness centrifuge washing in above-mentioned steps (1), drying, is then heated to 220~280 DEG C, insulation in nitrogen
80~100min, is made organic acid silver cladding nano-Ag particles.
4. the preparation method of organic acid silver cladding nano-Ag particles according to claim 3, it is characterised in that described organic
Acid is laurate or ascorbic acid.
5. the preparation method of organic acid silver cladding nano-Ag particles according to claim 3, it is characterised in that step (1)
Described in heating-up temperature be 75~85 DEG C.
6. the preparation method of organic acid silver cladding nano-Ag particles according to claim 3, it is characterised in that step (1)
Described in mixing time be 1.5h.
7. the preparation method of organic acid silver cladding nano-Ag particles according to claim 3, it is characterised in that step (2)
Described in centrifuge washing be specially：Under the centrifugal rotational speed of 7000r/min, washed respectively for several times, often with deionized water and alcohol
Secondary wash time is 10min.
8. the preparation method of organic acid silver cladding nano-Ag particles according to claim 3, it is characterised in that step (2)
Described in drying temperature be 70~80 DEG C, the time is 6~8h.
9. the silver cladding nano-Ag particles of organic acid described in claim 1 or 2 are as application of the solder in Electronic Packaging field.
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| CN107282918B (en) * | 2017-05-17 | 2019-01-22 | 宁波大学 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
| CN107511602B (en) * | 2017-08-14 | 2019-12-17 | 武汉工程大学 | nano Ag-Cu soldering paste and preparation method and application thereof |
| CN111812163B (en) * | 2020-06-23 | 2022-11-29 | 武汉工程大学 | Semiconductor resistor type ethanol gas sensor and preparation method thereof |
| CN113385688B (en) * | 2021-05-27 | 2023-03-24 | 湖南中伟新银材料科技有限公司 | Preparation method and application of silver powder |
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