CN104028778B - A kind of method of preparing fast nanometer copper particle - Google Patents
A kind of method of preparing fast nanometer copper particle Download PDFInfo
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Abstract
Prepare fast a method for nanometer copper particle, belong to material technology field, carry out according to the following steps: (1) makes ethanol water; (2) reducing agent is dissolved in ethanol water, makes reductant solution; (3) under stirring condition, mantoquita and dispersant are dissolved in the ethanol water of step (1), make mantoquita dispersant solution; (4) reductant solution is heated to 25 ~ 85 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 25 ~ 85 DEG C of temperature; (5) be heated to 25 ~ 85 DEG C, reaction 2 ~ 4h; (6) filter to isolate solid phase precipitation, be placed in centrifuge centrifugation, the dry moisture of removing under vacuum condition, obtaining surface coverage has the nanometer copper particle of dispersant. Method of the present invention has been saved the reaction time, has improved productive rate, and the nanometer copper particle of preparation can be used as additive application having antiwear and antifriction, self-repair function and repeatedly in reusable lubricating oil.
Description
Technical field
The invention belongs to material technology field, particularly a kind of method of preparing fast nanometer copper particle.
Background technology
Friction loss has very large impact for the economy of society, and over a little years, people hanker after the research to lube oil additive now, and all kinds of anti-extreme pressure agents, antiwear agents are added in lubricating oil to improve its greasy property. The physicochemical property of quantum size effect, skin effect, macro quanta tunnel effect and copper that nanometer copper particle has as nano material self uniqueness, add the effect that there is anti-extreme pressure in lubricant, independently repairs metal surface to, can improve greasy property and reduce friction loss.
At present, researcher both domestic and external has attempted inorganic nano-particle and organic-inorganic composite nano particle to add in lubricating oil, mainly comprises some inorganic simple substance nano particles (copper powder, nickel powder, graphite, diamond etc.), nano boric acid salt (nano-zinc borate, nano boric acid titanium etc.), nano-oxide and hydroxide (ZrO2、SiO2、ZnO、TiO2、MoO2、Fe2O3、Ni(OH)2、Mn(OH)2、La(OH)3Deng), nanometer sulfide (MoS2、WS2, ZnS etc.) and other compound (CeF3、LaF3、CaCO3Deng); The frictional behaviour of test lubricating oil, finds that they all have good antiwear and friction reduction property; And because nano metal powder preparation is simple, there is good compatibility with friction pair material again, also just more and more deep to its research, there is good application prospect; Patent CN101818364A, CN101607313A, CN102586800A, CN102198513A have all introduced the preparation method of nanometer copper particle, comprise electrolysis, Detonation Process, liquid phase two step reduction method etc.; The shortcomings such as then said method all has preparation process long, requires temperature high, and size distribution is inhomogeneous.
Summary of the invention
The problems referred to above that exist in technology of preparing for existing nanometer copper particle, the invention provides a kind of method of preparing fast nanometer copper particle, the mode that adopts ultrasonic promotion to disperse, and by dispersant covering copper particle, reach low-temp reaction and the effect of the time of minimizing, prepare well behaved nanometer copper particle.
The method of preparing fast nanometer copper particle of the present invention is carried out according to the following steps:
1, second alcohol and water is mixed and made into ethanol water, wherein the volume ratio of water and ethanol is 2:(1 ~ 2);
2, reducing agent is dissolved in the ethanol water of step 1, makes reductant solution; Described reducing agent is inferior sodium phosphate and citric acid, and wherein the mol ratio of citric acid and inferior sodium phosphate is 1:(2 ~ 9); The concentration of reducing agent in ethanol water is 5.20 × 10-3~12.90×10-3g/mL；
3, under stirring condition, mantoquita and dispersant are dissolved in the ethanol water of step 1, make mantoquita dispersant solution; Described dispersant is oleic acid or polyvinylpyrrolidone; The mass ratio of dispersant and mantoquita is 1:(10 ~ 30); The concentration of mantoquita in ethanol water is 0.003 ~ 0.05g/ml;
4, reductant solution is heated to 25 ~ 85 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 25 ~ 85 DEG C of temperature, the volume ratio that dripping quantity is pressed mantoquita dispersant solution and reductant solution is (1 ~ 2): 2; Time for adding is 2 ~ 6min;
5, under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 25 ~ 85 DEG C, reaction 2 ~ 4h, reaction finishes rear generation solid phase precipitation; The surface coverage of the nanometer copper particle in solid phase precipitation has dispersant;
6, the material filtering after reaction is finished is isolated solid phase precipitation, and solid phase precipitation washing is placed on to centrifugation in centrifuge, removes the dispersant that does not cover copper particle surface; After centrifugation, obtain centrifugal solid phase; By centrifugal solid phase dry moisture of removing under vacuum condition, obtaining surface coverage has the nanometer copper particle of dispersant.
It is 100 ~ 220nm that above-mentioned surface coverage has the average grain diameter of the nanometer copper particle of dispersant.
Stirring condition in above-mentioned step 3,4 and 5 is 500 ~ 1500rpm.
In Ultrasonic Conditions in above-mentioned step 4 and 5, hyperacoustic frequency is 20 ~ 40Hz.
Solid phase washing is referred to the water washing of solid phase same volume 3 ~ 5 times in above-mentioned step 6.
Centrifugal rotational speed when above-mentioned centrifugation is 2000 ~ 4000rpm.
The above-mentioned dry moisture of removing under vacuum condition refers under vacuum≤5000Pa condition, is incubated at least 12h at 50 ~ 70 DEG C.
Above-mentioned mantoquita is selected cupric sulfate pentahydrate.
Method of the present invention adopts ultrasonic original position to synthesize and modifies, not only save the reaction time but also improved productive rate, the surface coverage of preparation has the nanometer copper particle of dispersant, can be used as additive application having antiwear and antifriction, self-repair function and repeatedly in reusable lubricating oil.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
1, whole reaction system, in ultrasonic system, makes solute (mantoquita) in solvent (ethanol water), well be disperseed and collide effect by hyperacoustic effect, has greatly improved reaction rate;
2, in the mixed solution system of water and ethanol, react, heating, meets low-carbon green environmental requirement at low temperatures;
3, use organic surface active agent as dispersant and covering, the agglomeration between the nanometer copper particle that can effectively prevent from preparing, and make nanometer copper particle there is non-oxidizability.
Adopt method of the present invention, make the preparation of nanometer copper particle be expected to realize large-scale industrialization production, can prepare the different nanometer copper particle of particle diameter by changing mantoquita from ratio, adjustment temperature, the change supersonic frequency of reducing agent, thereby there is different anti-extreme pressure abilities, prepare the lube product of different model, be applied in different working environments; Nanometer copper particle material prepared by method of the present invention can be used as nano-lubricating material becomes the required new material of OIL IN LUBRICATING OIL PRODUCTION.
Brief description of the drawings
Fig. 1 is the Fourier transform infrared spectroscopy figure that the surface coverage prepared taking oleic acid as dispersant in the embodiment of the present invention 1 has the nanometer copper particle of dispersant;
Fig. 2 is the Fourier transform infrared spectroscopy figure that the surface coverage prepared taking polyvinylpyrrolidone as dispersant in the embodiment of the present invention 2 has the nanometer copper particle of dispersant;
Fig. 3 is that the EDS of the surface coverage prepared taking oleic acid as dispersant in the embodiment of the present invention 1 nanometer copper particle that has dispersant can spectrogram;
Fig. 4 is that the EDS of the surface coverage prepared taking polyvinylpyrrolidone as dispersant in the embodiment of the present invention 2 nanometer copper particle that has dispersant can spectrogram;
Fig. 5 is the SEM electron scanning micrograph figure that the surface coverage of preparation in the embodiment of the present invention 1 has the nanometer copper particle of dispersant;
Fig. 6 is the particle size distribution figure that the surface coverage of preparation in the embodiment of the present invention 1 has the nanometer copper particle of dispersant;
Fig. 7 is that the surface coverage of preparing taking oleic acid as dispersant in the embodiment of the present invention 1 has the TG of the nanometer copper particle of dispersant to scheme, and is used for characterizing its decomposition temperature;
Fig. 8 is the UV absorption spectrogram that the surface coverage prepared taking oleic acid as dispersant in the embodiment of the present invention 1 has the nanometer copper particle of dispersant;
Fig. 9 is the UV absorption spectrogram that the surface coverage prepared taking polyvinylpyrrolidone as dispersant in the embodiment of the present invention 2 has the nanometer copper particle of dispersant;
Figure 10 is frequency condition in the embodiment of the present invention 3 and the graph of a relation of average grain diameter;
Figure 11 is the additive capacity of nanometer copper particle and the wear scar diameter curve map of crude oil percentage that the surface coverage of preparing taking oleic acid as dispersant in the embodiment of the present invention 1 has dispersant;
Figure 12 is the additive capacity of nanometer copper particle and the wear scar diameter curve map of crude oil percentage that the surface coverage of preparing taking polyvinylpyrrolidone as dispersant in the embodiment of the present invention 2 has dispersant.
Detailed description of the invention
The heat reduction agent solution adopting in the embodiment of the present invention is to adopt water-bath to heat.
The water adopting in the embodiment of the present invention is deionized water.
The ethanol adopting in the embodiment of the present invention is AR.
The inferior sodium phosphate, citric acid, the anhydrous cupric sulfate (CuSO that in the embodiment of the present invention, adopt4·5H2O), oleic acid and polyvinylpyrrolidone are commercial AR.
In the embodiment of the present invention, employing applies the KQ-250DE type numerical control ultrasonic cleaner that the equipment of ultrasonic wave employing is Kunshan Ultrasonic Instruments Co., Ltd..
The centrifuge adopting in the embodiment of the present invention is 800 type centrifuges of high honour instrument manufacturing Co., Ltd.
In the embodiment of the present invention, under vacuum condition, the dry equipment adopting is the infrared Quick drying box of GQ7EH of instrument manufacturing Co., Ltd of county of Fengcheng City, and the equipment that vacuumizes employing is the Shanghai XZ-1 of Hui Tong vacuum equipment Co., Ltd type rotary-vane vaccum pump.
The equipment that in the embodiment of the present invention, copper test distribution of particles adopts is the Nano-S90ZETASIZER of Ma Erwen instrument company.
The equipment that in the embodiment of the present invention, thermogravimetric analysis adopts is the Q5000SA type TG(TA of TA company of the U.S.).
The TU-1901 type dual-beam ultraviolet-uisible spectrophotometer that the equipment of testing absorbance employing in the embodiment of the present invention is Beijing Puxi General Instrument Co., Ltd.
The equipment that electron microscopic in the embodiment of the present invention and EDS power spectrum adopt is the ZEISSULTRA field emission scanning electron microscope of encouraging smart scientific and technological (Shanghai) Co., Ltd..
The equipment that in the embodiment of the present invention, ftir analysis adopts is the PERKINELMERFT-IR infrared spectrometric analyzer of PERKINELMER company of the U.S..
In the embodiment of the present invention, test wear scar diameter and last non seizure load (PB) equipment that adopts of the value omnipotent friction wear testing machine of MMW-2A that is Jinan Yihua Tribology Testing Technology Co., Ltd.; The experiment condition of test wear scar diameter is: load 200N, rotating speed 600r/min, time 15min.
Embodiment 1
(1) second alcohol and water is mixed and made into ethanol water, wherein the volume ratio of water and ethanol is 2:1;
(2) reducing agent is dissolved in the ethanol water of step (1), makes reductant solution; Described reducing agent is inferior sodium phosphate and citric acid, and wherein the mol ratio of citric acid and inferior sodium phosphate is 1:2; The concentration of reducing agent in ethanol water is 5.20 × 10-3g/mL；
(3) under stirring condition, mantoquita and dispersant are dissolved in the ethanol water of step (1), make mantoquita dispersant solution; Described dispersant is oleic acid; The mass ratio of dispersant and mantoquita is 1:10; The concentration of mantoquita in ethanol water is 0.003g/ml; Described mantoquita is cupric sulfate pentahydrate;
(4) reductant solution is heated to 85 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 85 DEG C of temperature, dripping quantity is 1:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 2min;
(5) under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 85 DEG C, reaction 2h, reaction finishes rear generation solid phase precipitation; The surface coverage of the nanometer copper particle in solid phase precipitation has dispersant;
(6) material filtering after reaction is finished is isolated solid phase precipitation, and solid phase precipitation washing is placed on to centrifugation in centrifuge, removes the dispersant that does not cover copper particle surface; After centrifugation, obtain centrifugal solid phase; By centrifugal solid phase dry moisture of removing under vacuum condition, obtaining surface coverage has the nanometer copper particle of dispersant, and average grain diameter is 220nm;
Stirring condition in step (3), (4) and (5) is 500rpm;
In Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is 20Hz;
Solid phase washing is referred to the water washing of solid phase same volume 5 times in step (6);
Centrifugal rotational speed when centrifugation is 2000rpm;
Under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, at 50 ~ 70 DEG C of insulation 12h;
As shown in Figure 1, as seen from the figure, the surface of nanometer copper particle has been coated with oleic acid dispersant to Fourier transform infrared spectroscopy; EDS power spectrum as shown in Figure 3, as seen from the figure, except containing Cu element, also contains the element such as C, O, shows that its surface coverage has oleic acid dispersant; SEM electron scanning micrograph as shown in Figure 5; As shown in Figure 6, particle diameter is at 100 ~ 220nm for size distribution; Thermogravimetric analysis (TG) result as shown in Figure 7; Ultraviolet absorption spectrum as shown in Figure 8;
Adopt above-mentioned surface coverage to have the nanometer copper particle of dispersant as additive, join in crude oil and test wear scar diameter curve, result as shown in figure 11; When addition is 0.2%, last non seizure load (PB) be worth for 310N; That crude oil adopts is KM22, the cycloalkyl Dormant oils that a kind of viscosity is 22cst, PBValue is 250N; After adding additive, last non seizure load has improved 24%; Visible added nanometer copper particle all has anti-extreme pressure energy, all makes the P of crude oilBValue is improved, and the nanometer copper particle of oleic acid modified is high compared with the anti-extreme pressure of the nanometer copper particle of PVP modification, and this may be relatively large relevant with the particle diameter of the nanometer copper particle of oleic acid modified.
Embodiment 2
Method is with embodiment 1, and difference is:
(1) dispersant is polyvinylpyrrolidone;
(2) it is 210nm that the surface coverage obtaining has the average grain diameter of the nanometer copper particle of dispersant;
Fourier transform infrared spectroscopy as shown in Figure 2; EDS power spectrum as shown in Figure 4, as seen from the figure, except containing Cu element, also contains the element such as C, O, shows that its surface coverage has oleic acid dispersant; Ultraviolet absorption spectrum as shown in Figure 9;
Adopt above-mentioned surface coverage to have the nanometer copper particle of dispersant as additive, join in crude oil and test wear scar diameter curve, result as shown in figure 12; When addition is 0.2%, last non seizure load (PB) be worth for 280N; After adding additive, last non seizure load has improved 12%.
Embodiment 3
Carry out respectively 4 groups of tests and 5 groups of contrast tests, the numbering of 5 groups of contrast tests is respectively 1#, 2#, 3#, 4# and 5#; The numbering of 4 groups of tests is respectively 6#, 7#, 8# and 9#; Method is with embodiment 1, and difference is:
(1) in ethanol water, the volume ratio of water and ethanol is 2:2;
(2) in reductant solution, the mol ratio of citric acid and inferior sodium phosphate is 1:4; The concentration of reducing agent in ethanol water is 6.80 × 10-3g/mL；
(3) in mantoquita dispersant solution, the mass ratio of dispersant and mantoquita is 1:15; The concentration of mantoquita in ethanol water is 0.01g/ml;
(4) reductant solution is heated to 65 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 65 DEG C of temperature, dripping quantity is 1.5:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 3min;
(5), under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 65 DEG C, reaction 3h;
(6) surface coverage obtaining have dispersant nanometer copper particle average grain diameter by the order of 1 ~ 9# be respectively 460,360,340,290,260,220,200,150,150nm;
(7) stirring condition in step (3), (4) and (5) is 800rpm;
(8) in the Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is respectively 0,4,8,12,16,20,24,28,32,36 and 40Hz;
(9) solid phase washing is referred to the water washing of solid phase same volume 4 times in step (6);
(10) centrifugal rotational speed when centrifugation is 3000rpm;
(11) under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 16h at 50 ~ 70 DEG C;
Different rows ultrasonic frequency obtain surface coverage have dispersant nanometer copper particle average grain diameter result as shown in figure 10.
Embodiment 4
Method is with embodiment 2, and difference is:
(1) in ethanol water, the volume ratio of water and ethanol is 2:2;
(2) in reductant solution, the mol ratio of citric acid and inferior sodium phosphate is 1:4; The concentration of reducing agent in ethanol water is 6.80 × 10-3g/mL；
(3) in mantoquita dispersant solution, the mass ratio of dispersant and mantoquita is 1:15; The concentration of mantoquita in ethanol water is 0.01g/ml;
(4) reductant solution is heated to 65 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 65 DEG C of temperature, dripping quantity is 1.5:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 3min;
(5), under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 65 DEG C, reaction 3h;
(6) it is 200nm that the surface coverage obtaining has the average grain diameter of the nanometer copper particle of dispersant;
(7) stirring condition in step (3), (4) and (5) is 800rpm;
(8) in the Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is 24Hz;
(9) solid phase washing is referred to the water washing of solid phase same volume 4 times in step (6);
(10) centrifugal rotational speed when centrifugation is 3000rpm;
(11) under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 16h at 50 ~ 70 DEG C.
Embodiment 5
Method is with embodiment 1, and difference is:
(1) in ethanol water, the volume ratio of water and ethanol is 2:1.5;
(2) in reductant solution, the mol ratio of citric acid and inferior sodium phosphate is 1:6; The concentration of reducing agent in ethanol water is 9.40 × 10-3g/mL；
(3) in mantoquita dispersant solution, the mass ratio of dispersant and mantoquita is 1:20; The concentration of mantoquita in ethanol water is 0.03g/ml;
(4) reductant solution is heated to 45 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of temperature 45 C, dripping quantity is 1.8:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 4min;
(5), under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 45 DEG C, reaction 3h;
(6) it is 190nm that the surface coverage obtaining has the average grain diameter of the nanometer copper particle of dispersant;
(7) stirring condition in step (3), (4) and (5) is 1000rpm;
(8) in the Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is 28Hz;
(9) solid phase washing is referred to the water washing of solid phase same volume 3 times in step (6);
(10) centrifugal rotational speed when centrifugation is 4000rpm;
(11) under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 20h at 50 ~ 70 DEG C.
Embodiment 6
Method is with embodiment 2, and difference is:
(1) in ethanol water, the volume ratio of water and ethanol is 2:1.5;
(2) in reductant solution, the mol ratio of citric acid and inferior sodium phosphate is 1:6; The concentration of reducing agent in ethanol water is 9.40 × 10-3g/mL；
(3) in mantoquita dispersant solution, the mass ratio of dispersant and mantoquita is 1:20; The concentration of mantoquita in ethanol water is 0.03g/ml;
(4) reductant solution is heated to 45 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of temperature 45 C, dripping quantity is 1.8:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 4min;
(5), under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 45 DEG C, reaction 3h;
(6) it is 170nm that the surface coverage obtaining has the average grain diameter of the nanometer copper particle of dispersant;
(7) stirring condition in step (3), (4) and (5) is 1000rpm;
(8) in the Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is 28Hz;
(9) solid phase washing is referred to the water washing of solid phase same volume 3 times in step (6);
(10) centrifugal rotational speed when centrifugation is 4000rpm;
(11) under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 20h at 50 ~ 70 DEG C.
Embodiment 7
Method is with embodiment 1, and difference is:
(1) in ethanol water, the volume ratio of water and ethanol is 2:1.8;
(2) in reductant solution, the mol ratio of citric acid and inferior sodium phosphate is 1:9; The concentration of reducing agent in ethanol water is 12.90 × 10-3g/mL；
(3) in mantoquita dispersant solution, the mass ratio of dispersant and mantoquita is 1:30; The concentration of mantoquita in ethanol water is 0.05g/ml;
(4) reductant solution is heated to 25 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 25 DEG C of temperature, dripping quantity is 2:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 6min;
(5), under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 25 DEG C, reaction 4h;
(6) it is 120nm that the surface coverage obtaining has the average grain diameter of the nanometer copper particle of dispersant;
(7) stirring condition in step (3), (4) and (5) is 1500rpm;
(8) in the Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is 40Hz;
(9) solid phase washing is referred to the water washing of solid phase same volume 3 times in step (6);
(10) centrifugal rotational speed when centrifugation is 4000rpm;
(11) under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 16h at 50 ~ 70 DEG C.
Embodiment 8
Method is with embodiment 2, and difference is:
(1) in ethanol water, the volume ratio of water and ethanol is 2:1.8;
(2) in reductant solution, the mol ratio of citric acid and inferior sodium phosphate is 1:9; The concentration of reducing agent in ethanol water is 12.90 × 10-3g/mL；
(3) in mantoquita dispersant solution, the mass ratio of dispersant and mantoquita is 1:30; The concentration of mantoquita in ethanol water is 0.05g/ml;
(4) reductant solution is heated to 25 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 25 DEG C of temperature, dripping quantity is 2:2 by the volume ratio of mantoquita dispersant solution and reductant solution; Time for adding is 6min;
(5), under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 25 DEG C, reaction 4h;
(6) it is 100nm that the surface coverage obtaining has the average grain diameter of the nanometer copper particle of dispersant;
(7) stirring condition in step (3), (4) and (5) is 1500rpm;
(8) in the Ultrasonic Conditions in step (4) and (5), hyperacoustic frequency is 40Hz;
(9) solid phase washing is referred to the water washing of solid phase same volume 3 times in step (6);
(10) centrifugal rotational speed when centrifugation is 4000rpm;
(11) under vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 16h at 50 ~ 70 DEG C.
Claims (4)
1. prepare fast a method for nanometer copper particle, it is characterized in that carrying out according to the following steps:
(1) second alcohol and water is mixed and made into ethanol water, wherein the volume ratio of water and ethanol is 2:(1 ~ 2);
(2) reducing agent is dissolved in the ethanol water of step (1), makes reductant solution; Described reducing agent is inferior sodium phosphate and citric acid, and wherein the mol ratio of citric acid and inferior sodium phosphate is 1:(2 ~ 9); The concentration of reducing agent in ethanol water is 5.20 × 10-3~12.90×10-3g/mL；
(3) under stirring condition, mantoquita and dispersant are dissolved in the ethanol water of step (1), make mantoquita dispersant solution; Described dispersant is oleic acid or polyvinylpyrrolidone; The mass ratio of dispersant and mantoquita is 1:(10 ~ 30); The concentration of mantoquita in ethanol water is 0.003 ~ 0.05g/ml; Described mantoquita is selected cupric sulfate pentahydrate;
(4) reductant solution is heated to 25 ~ 85 DEG C; Under stirring condition and Ultrasonic Conditions, mantoquita dispersant solution is added drop-wise in the reductant solution of 25 ~ 85 DEG C of temperature, the volume ratio that dripping quantity is pressed mantoquita dispersant solution and reductant solution is (1 ~ 2): 2; Time for adding is 2 ~ 6min;
(5) under stirring condition and Ultrasonic Conditions, the mixed solution that is added dropwise to complete rear acquisition is heated to 25 ~ 85 DEG C, reaction 2 ~ 4h, reaction finishes rear generation solid phase precipitation; The surface coverage of the nanometer copper particle in solid phase precipitation has dispersant;
(6) material filtering after reaction is finished is isolated solid phase precipitation, and solid phase precipitation washing is placed on to centrifugation in centrifuge, removes the dispersant that does not cover copper particle surface; After centrifugation, obtain centrifugal solid phase; By centrifugal solid phase dry moisture of removing under vacuum condition, obtaining surface coverage has the nanometer copper particle of dispersant, and average grain diameter is 100 ~ 220nm.
2. a kind of method of preparing fast nanometer copper particle according to claim 1, is characterized in that the stirring condition in described step (3), (4) and (5) is 500 ~ 1500rpm.
3. a kind of method of preparing fast nanometer copper particle according to claim 1, is characterized in that in the Ultrasonic Conditions in described step (4) and (5), hyperacoustic frequency is 20 ~ 40Hz.
4. a kind of method of preparing fast nanometer copper particle according to claim 1, is characterized in that under described vacuum condition, the dry moisture of removing refers under vacuum≤5000Pa condition, is incubated at least 12h at 50 ~ 70 DEG C.
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| GB2548084A (en) | 2016-02-26 | 2017-09-13 | Midatech Ltd | Nanoparticle production |
| CN107020389A (en) * | 2017-04-06 | 2017-08-08 | 江苏大学 | A kind of preparation method of high-dispersion nano copper |
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| CN112296345B (en) * | 2019-07-23 | 2022-02-18 | 富兰克科技（深圳）股份有限公司 | Preparation method of self-dispersible nano-copper with long organic carbon chain, nano-copper preparation and application thereof |
| CN110744068B (en) * | 2019-10-21 | 2021-01-26 | 河南大学 | Oil-soluble nano copper and preparation method thereof |
| CN114535863B (en) * | 2022-03-25 | 2024-01-16 | 重庆平创半导体研究院有限责任公司 | Self-sintered nano copper soldering paste, preparation method and use method thereof |
| CN114749677B (en) * | 2022-04-26 | 2023-04-11 | 苏州星翰新材料科技有限公司 | Preparation method and application of micron copper powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1442260A (en) * | 2002-03-01 | 2003-09-17 | 中国科学院理化技术研究所 | Preparation method of metallic nano powder |
| CN101274367A (en) * | 2007-03-26 | 2008-10-01 | 中南大学 | Surface modification method of copper powder for conductive paste |
| CN102151823A (en) * | 2011-01-26 | 2011-08-17 | 宁波广博纳米材料有限公司 | Antioxidation method of nano copper powder |
| CN102896322A (en) * | 2012-11-01 | 2013-01-30 | 广东东硕科技有限公司 | Preparation method for nano-copper with oxidation resistance and dispersibility |
| CN103464774A (en) * | 2012-06-07 | 2013-12-25 | 荆门市格林美新材料有限公司 | Preparation method for low-agglomeration antioxidant copper nanoparticle powder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101375403B1 (en) * | 2006-07-28 | 2014-03-17 | 후루카와 덴키 고교 가부시키가이샤 | Method for producing fine particle dispersion and fine particle dispersion |
| JP4330024B2 (en) * | 2007-07-25 | 2009-09-09 | 古河電気工業株式会社 | Method for producing fine particle dispersion, and fine particle dispersion |
-
2014
- 2014-06-25 CN CN201410289710.0A patent/CN104028778B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1442260A (en) * | 2002-03-01 | 2003-09-17 | 中国科学院理化技术研究所 | Preparation method of metallic nano powder |
| CN101274367A (en) * | 2007-03-26 | 2008-10-01 | 中南大学 | Surface modification method of copper powder for conductive paste |
| CN102151823A (en) * | 2011-01-26 | 2011-08-17 | 宁波广博纳米材料有限公司 | Antioxidation method of nano copper powder |
| CN103464774A (en) * | 2012-06-07 | 2013-12-25 | 荆门市格林美新材料有限公司 | Preparation method for low-agglomeration antioxidant copper nanoparticle powder |
| CN102896322A (en) * | 2012-11-01 | 2013-01-30 | 广东东硕科技有限公司 | Preparation method for nano-copper with oxidation resistance and dispersibility |
Non-Patent Citations (4)
| Title |
|---|
| 液相化学还原法制备分散稳定的纳米铜溶胶;杨海军等;《材料导报》;20130430;第27卷(第4期);第32-35页 * |
| 超声条件下表面活性剂对水合肼还原制备纳米铜粉的影响;王玉棉等;《粉末冶金技术》;20080831;第26卷(第4期);第296-298、303页 * |
| 超声电解法制备纳米铜粉的研究;朱协彬等;《上海有色金属》;20040930;第25卷(第3期);第97-99页 * |
| 铜纳米粒子的形状控制合成;杨玉娟等;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130315;第30-37页 * |
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