CN101214554A - One-step method preparing nano copper colloid water solution under ultrasonic field - Google Patents
One-step method preparing nano copper colloid water solution under ultrasonic field Download PDFInfo
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- CN101214554A CN101214554A CNA2008100327234A CN200810032723A CN101214554A CN 101214554 A CN101214554 A CN 101214554A CN A2008100327234 A CNA2008100327234 A CN A2008100327234A CN 200810032723 A CN200810032723 A CN 200810032723A CN 101214554 A CN101214554 A CN 101214554A
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Abstract
A one-step method for preparing nanometer copper colloid water liquor under an ultrasonic field is characterized in that the invention carries out according to the following steps: A) dissolving the prepared cupric salt and water-solubility macromolecule surface activator in water and transferring into a three mouth flank to heat for 60 to 100 DEG C and stirring mechanically and mixing uniformly; B) putting the three mouth flank into an ultrasonator with a frequency of 20 to 50KHz and a power of 200 to 350W; C) dripping the water liquor containing reducing agent slowly into the three mouth blank and removing heating and stirring after the reaction is finished; D) ultrasonically oscillating continuously for 30 minutes and being able to acquire stable nanometer copper colloid water liquor. The invention adopts a wet chemistry method to directly prepare the nanometer copper colloid in the water liquor with no need of pumping protection gas in the ultrasonic field; the grain diameter of a copper particle is distributed between 15 to 35mm; the anti-oxidizing capacity of the nanometer copper is higher and the dispersing performance of the particle is good; the distribution of the grain diameter is narrow and the technique is simple.
Description
Technical field
The present invention relates to a kind of preparation method of nano copper colloid water solution, specifically adopt the method for wet chemistry, directly prepare nano copper colloid water solution in next footwork of ultrasonic field effect.
Background technology
In recent years, nano copper colloid had caused many field scientists' very big interest, became the instrument and the object of nano material theoretical and experimental study, and obtained to use widely at numerous areas.Be used for the research of spectroscopy as nanometer copper glue, they are widely used in SERS (SERS) research.Studies show that of the electrochemical properties of copper glue, copper nano particles have good electrochemical properties, and utilize it successfully to measure the coulomb ladder that single electron transmits.The copper nano-colloid also is applied to material science, and suitably the copper doped nano particle can improve the character of material body.In addition, copper glue is at optics, electronics (comprising nanoelectronics) and biologically also have a wide range of applications.
Production technology along with nanometer copper particle is ripe gradually at present, and its application also enlarges thereupon.In its application process, than distinct issues is that nanometer copper particle is because surface area is big and the surface can be high, the particle oxidation very easily taking place in preparation, post processing and application process, condense, reunite, form offspring, makes grain diameter become big, thereby lose the performance that is possessed.Researchers have proposed some valid approach in order to improve the dispersed and stable of nanometer copper particle, are mainly following two kinds of methods:
A kind of method is to adopt two-step method to prepare nano copper colloid solution.In two-step method, the first step is preparation nanometer copper particle (comprising in the synthetic and storage process of nanometer copper anti-oxidant etc.); Second step was that nanometer copper particle is scattered in the water, by adding suitable surfactant, and cooperate with physical means such as stirring, sonic oscillation or glue mills, be beneficial to stable (be as the application number 00135329.2 and 01813035.6 Chinese patent) of the dispersion of nano particle and system.Though the two-step method program is comparatively simple, cost is few, applicable surface is wider, but because copper nanoparticle has huge specific area, and it is active higher, the existence of Van der Waals force makes and is easy between nano particle reunite, particularly copper powder very easily oxidation in storage process, so the difficult nano copper colloid of preparing single dispersion, high stable of two-step method.
Another kind method is an one-step method, promptly directly prepares the method for nano copper colloid solution.One-step method can adopt physical method, prepares nano copper colloid as vapour deposition process, can stablize about several days to a week; See Choi U.S.et al.Appl.Phys.Lett. (2001) 79:2252, but this method is to the having relatively high expectations of equipment, output is little, and the expense height is not easy to industrialization promotion; One-step method also can adopt the method preparation of wet chemistry.As Materials Science and Engineering journal (2005), 23:598; Yangzhou University's journal: natural science edition (2002), 5:27; Its major defect is that size distribution is wide, the poor stability of nano copper colloid water solution, and copper particle precipitates easily.
Summary of the invention
The present invention discloses a kind of one-step method preparation of nano copper colloid water solution under ultrasonic field, and its purpose is to overcome two-step method and prepares the nano copper colloid water solution poor stability, and nanometer copper particle is easily oxidation in preparation, storing process, and hard aggregation is more in the dispersion process; Vapour deposition process prepares the requirement harshness of nano copper colloid to equipment, and output is little, the expense height, and single employing wet chemistry methods to prepare the nano copper colloid water solution size distribution wide, poor stability, copper particle is problem such as precipitation easily.
The present invention proposes to adopt the method for wet chemistry in the aqueous solution, in heating and churned mechanically while, adds the ultrasonic field peptizaiton, and one-step method directly prepares the stabilized nano copper colloid water solution.Preparation technology is simple for this method, avoids the reunion of copper powder and grows up the narrow diameter distribution of nano particle, the good stability of colloid.
The one-step method preparation of nano copper colloid water solution under ultrasonic field is characterized in that carrying out as follows:
A) proportioning is good cupric salt and water soluble polymer surfactant are soluble in water, and are transferred in the there-necked flask, are heated to 60-100 ℃, and mechanical agitation, mix;
B) there-necked flask is placed ultrasonator, the frequency of ultrasonic field is at 20-50KHz, and power is at 200-350W;
C) in there-necked flask, slowly drip the aqueous solution that contains reducing agent, after reaction finishes, remove heating and stirring;
D) continue sonic oscillation 30 minutes, can obtain the stabilized nano copper colloid water solution.
Described water soluble polymer surfactant is a kind of or compound in polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol or the ammonium polymethacrylate.
For the high nano copper colloid water solution of concentration, drip reducing agent and adopt two-step method, promptly drip weak reductant earlier, be used for the nucleation stage of nanometer copper particle, the back drips strong reductant, so that the copper ion reduction is fully.
Cupric salt is a copper chloride, copper sulphate, copper nitrate or copper acetate; Reducing agent is one or both in potassium borohydride, trisodium citrate, ascorbic acid or the inferior sodium phosphate.
This method can prepare stabilized nano copper colloid under the condition of not logical inert gas shielding, applicable surface is extensive.
The present invention introduces wet chemistry colloid for preparing process with the effect of ultrasonic field, ultrasonic wave in reaction solution density interphase to previous irradiation, make liquid flow and produce micro-bubble, these bubbles form at the negative pressuren zone of ultrasonic wave longitudinal propagation, growth, and at the zone of positive pressure rapid closing, in the process of this being referred to as " cavitation " effect, the bubble closure can form the high temperature of several Baidu and surpass the instantaneous pressure of 1000 air pressure.Ultrasonic field formed " cavitation " effect can be the energy that provides of reduction reaction on the one hand, make the quick nucleation of copper particle, can control the growth process after the copper particle nucleation in the solution simultaneously, reduce and reunite, it is comparatively narrow that particle diameter is distributed, and Zhi Bei nano copper colloid water solution system is stable simultaneously.
Advantage of the present invention and good effect are: adopt wet chemistry methods; need not in the aqueous solution of logical protective gas directly preparation nano copper colloid in ultrasonic field; storage stability is good; the copper particle particle diameter is distributed in 15-35nm; the oxidation resistance of nanometer copper is stronger; and dispersion of nano-particles is good, narrow diameter distribution, and technology is simple.
Description of drawings
Fig. 1 is the transmission electron microscope photo of nanometer copper particle;
Fig. 2 is that the particle diameter of nanometer copper particle distributes;
Fig. 3 is the high-resolution-ration transmission electric-lens photo of nanometer copper crystal lattice.
By Fig. 1 and Fig. 2 explanation: copper particle dispersed fine, do not have adhesion phenomenon, and be evenly distributed, particle diameter is distributed in 15-35nm.Fig. 3 illustrates that the crystallinity of copper particle is better, and spacing of lattice is 0.21nm, and crystal is a face-centred cubic structure.
The specific embodiment
Embodiment 1:
0.025g cupric sulfate pentahydrate and polyvinylpyrrolidone PVP K-30 0.2g (mean molecule quantity 40,000) are dissolved in the 100ml water, and are transferred in the there-necked flask, mix, add 40KHz simultaneously, the 200W ultrasonic field slowly drips and contains NaH
2PO
2H
2The aqueous solution of O (0.04g) is heated to 85 ℃, reacts after 2 hours, removes heating and stirring, continues ultrasonic 30 minutes, can obtain stable light yellow nano copper colloid water solution.
Embodiment 2:
0.20g one hydrated copper acetate and sodium polymethacrylate 0.3g (mean molecule quantity 30,000,000) are dissolved in the 100ml water, and be transferred in the there-necked flask, mix, add 60KHz simultaneously, the 250W ultrasonic field, slowly drip the aqueous solution that contains ascorbic acid (1.41g), be heated to 60 ℃, react after 4 hours, remove heating and stirring, continued ultrasonic 30 minutes, and can obtain stable red nano copper colloid water solution.
Embodiment 3:
With 1g cupric sulfate pentahydrate and polyvinylpyrrolidone PVP K-30 1g (mean molecule quantity 40,000) is dissolved in the 100ml water, and be transferred in the there-necked flask, mix, add 40KHz simultaneously, the 200W ultrasonic field, normal temperature slowly drips the aqueous solution that contains ascorbic acid (5.64g) down, and back flow reaction removed and stirs and heater after 6 hours, continued ultrasonic 30 minutes, and can obtain stable black nano copper colloid water solution.
Embodiment 4:
0.25g cupric sulfate pentahydrate and polyvinylpyrrolidone PVP K-30 0.5g (mean molecule quantity 40,000) are dissolved in the 100ml water, and are transferred in the there-necked flask, mix, add 40KHz simultaneously, the 200W ultrasonic field, normal temperature slowly drips down and contains KBH
4The aqueous solution (0.21g) reacted after 1 hour, removed stirring, continued ultrasonic 30 minutes, can obtain stable red nano copper colloid water solution.
Embodiment 5:
With 0.17g Copper dichloride dihydrate and polyacrylamide (mean molecule quantity 3,000,000) 0.5g is dissolved in the 100ml water, and is transferred in the there-necked flask, mix, add 40KHz simultaneously, the 600W ultrasonic field, refluxing slowly drips the aqueous solution that contains two hydration trisodium citrates (1.18g) down, react after 4 hours, remove heating and stirring, continued ultrasonic 30 minutes, can obtain stable red nano copper colloid water solution.
Embodiment 6:
With 0.25g cupric sulfate pentahydrate and polyacrylamide (mean molecule quantity 3,000,000) 0.5g is dissolved in the 100ml water, and is transferred in the there-necked flask, mixes, add 40KHz simultaneously, the 200W ultrasonic field, 60 ℃ of slow down droppings are contained ascorbic acid (0.71g), react after 1 hour, remove heating, normal temperature drips down and contains KBH
4The aqueous solution (0.11g) reacted after 1 hour, removed stirring, continued ultrasonic 30 minutes, can obtain stable red nano copper colloid water solution.
Claims (3)
1. the one-step method of nano copper colloid water solution under ultrasonic field preparation is characterized in that carrying out as follows:
A) proportioning is good cupric salt and water soluble polymer surfactant are soluble in water, and are transferred in the there-necked flask, are heated to 60-100 ℃, and mechanical agitation, mix;
B) there-necked flask is placed ultrasonator, the frequency of ultrasonic field is at 20-50KHz, and power is at 200-350W;
C) in there-necked flask, slowly drip the aqueous solution that contains reducing agent, after reaction finishes, remove heating and stirring;
D) continue sonic oscillation 30 minutes, can obtain the stabilized nano copper colloid water solution.
2. the one-step method of nano copper colloid water solution under ultrasonic field according to claim 1 preparation, it is characterized in that: described water soluble polymer surfactant is polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol or ammonium polymethacrylate.
3. the one-step method of nano copper colloid water solution under ultrasonic field according to claim 1 preparation, it is characterized in that: for the high nano copper colloid water solution of concentration, drip reducing agent and adopt two-step method, promptly drip weak reductant earlier, the nucleation stage that is used for nanometer copper particle, the back drips strong reductant, so that the copper ion reduction fully.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464778A (en) * | 2013-09-05 | 2013-12-25 | 江苏大学 | Synthetic method of nanometer copper particles different in particle size under irradiation of microwave and ultraviolet |
| CN105127441A (en) * | 2015-08-18 | 2015-12-09 | 昆明理工大学 | Preparation method of platinum nanocrystalline dispersion system |
| CN108941605A (en) * | 2018-08-02 | 2018-12-07 | 西安雷晶新材料科技有限公司 | A kind of preparation method of superfine cupper powder |
| CN110385443A (en) * | 2019-07-28 | 2019-10-29 | 长春黄金研究院烟台贵金属材料研究所有限公司 | A kind of preparation method of acid system Nanometer Copper colloidal sol |
| CN111496266A (en) * | 2020-05-09 | 2020-08-07 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Environment-friendly conductive nano copper ink and preparation method thereof |
| CN111618314A (en) * | 2020-05-15 | 2020-09-04 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
-
2008
- 2008-01-16 CN CNA2008100327234A patent/CN101214554A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464778A (en) * | 2013-09-05 | 2013-12-25 | 江苏大学 | Synthetic method of nanometer copper particles different in particle size under irradiation of microwave and ultraviolet |
| CN103464778B (en) * | 2013-09-05 | 2017-03-01 | 江苏大学 | The synthetic method of different-grain diameter Nanometer Copper under microwave or ultraviolet irradiation |
| CN105127441A (en) * | 2015-08-18 | 2015-12-09 | 昆明理工大学 | Preparation method of platinum nanocrystalline dispersion system |
| CN108941605A (en) * | 2018-08-02 | 2018-12-07 | 西安雷晶新材料科技有限公司 | A kind of preparation method of superfine cupper powder |
| CN110385443A (en) * | 2019-07-28 | 2019-10-29 | 长春黄金研究院烟台贵金属材料研究所有限公司 | A kind of preparation method of acid system Nanometer Copper colloidal sol |
| CN111496266A (en) * | 2020-05-09 | 2020-08-07 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Environment-friendly conductive nano copper ink and preparation method thereof |
| CN111618314A (en) * | 2020-05-15 | 2020-09-04 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
| CN111618314B (en) * | 2020-05-15 | 2023-01-03 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
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