CN102198513A - Method for preparing nano copper particle - Google Patents
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- CN102198513A CN102198513A CN 201110140063 CN201110140063A CN102198513A CN 102198513 A CN102198513 A CN 102198513A CN 201110140063 CN201110140063 CN 201110140063 CN 201110140063 A CN201110140063 A CN 201110140063A CN 102198513 A CN102198513 A CN 102198513A
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Abstract
The invention relates to a method for preparing a nano copper particle, in particular to a novel method for preparing a nano copper particle serving as a lubricating oil additive. The synthesis method comprises the following steps of: dissolving water-soluble divalent copper salt into water; adding a proper amount of acid organic extracting agent and coating agent into the solution; extracting divalent copper ions to an organic phase; and then simply and efficiently preparing spherical nano copper particles which have good dispersion, uniform particle size and good oxidation resistance by adopting a two-step liquid phase reduction method. The method provided by the invention has the advantages such as simple process, convenience for operation, low cost, easiness for industrialization and the like; and the prepared nano copper particle has the advantages of good dispersion, uniform particle size, good oxidation resistance, good friction property and the like.
Description
Technical field
The present invention relates to a kind of nano copper particle preparation method, particularly relate to a kind of preparation method who is used for the nano copper particle of lube oil additive.
Background technology
In recent years, nano copper particle replaces noble metal granule can reduce industrial cost greatly at aspects such as making senior lubricant, electrocondution slurry, effective catalyst as the important raw material of industry, has presented extremely important using value in every field.Therefore, in recent years the research of nano copper particle has been caused extensive concern both domestic and external.At present, the method for preparing nano-metal particle is a lot, comprises the gamma-radiation radiation method, physical vaporous deposition, microemulsion method, high-energy ball milling method, hydro-thermal method, sol-gel process, chemical precipitation method, electrolysis etc.But, these method cost height, energy consumption is big, produces complexity, and product is easily reunited, and is mobile poor, is difficult to satisfy the requirement of industries such as electronic conduction slurry, lubricating oil and powder metallurgy.
Liquid phase reduction refers to suitable soluble metallic salt dissolving is made metal ion form in solution by all means and has definite shape and big or small particle, obtains the method for superfine powder particle again through post processing.It has can accurately control chemical composition, mixes quantitatively with the good compound particle of processability; The nano-complex particle surface-active height of preparation, the purity height; Control the shape and the granularity of particle easily; The industrialization low cost and other advantages.Therefore, this technology becomes the most attractive approach of preparation metal nanoparticle.
With respect to gold, silver etc., nano copper particle can not simply directly be reduced by mantoquita, because copper has higher surface active energy, and the existence of a large amount of oxygen is arranged in empty G﹠W, and product copper particle very easily is oxidized to cuprous oxide.And, in the generative process of nano copper particle,, then can cause in the system nucleus concentration to increase until saturated if nucleation rate is too fast, nucleus is collided mutually form the bigger uneven product particle of particle diameter.Therefore, seeking appropriate reductant and surfactant is that preparation has the research emphasis of the nano copper particle of non-oxidizability and good dispersion at present.This method is the extractant covering of holding concurrently with the olefin(e) acid type organic, and bivalent cupric ion is extracted in the organic facies, adopts the liquid phase two step reduction method again, reaction is carried out simultaneously with coating, prepare good dispersion, epigranular has the spherical nano copper particle of good oxidation resistance.This inventive method has superiority such as technical process is simple, easy to operate, cost is low, is easy to industrialization, and prepared nano copper particle has advantages such as good dispersion, epigranular, anti-oxidant, frictional behaviour excellence.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano copper particle especially is suitable for the preparation method of the nano copper particle of lube oil additive; Have the simplification production technology, reduce cost, the product purity height of gained, pattern evenly, controllable granularity, good dispersion and advantage such as anti-oxidant.
The present invention is realized by the following technical programs:
A kind of preparation method of anti-oxidant nano copper particle may further comprise the steps:
(1) forerunner's copper salt solution and the organic solution mixing and stirring that contains oleic acid are extracted to bivalent cupric ion in the organic facies, promptly obtain precursor liquid;
The reduction of (2) two steps
At first D/W is added in the described precursor liquid of step (1), make bivalent cupric ion be reduced to cuprous oxide fully; Then, the ortho phosphorous acid sodium solution is added into above-mentioned solution, cuprous oxide is reduced to elemental copper fully;
(3) vacuum drying
With the centrifugal removal supernatant liquor of product, clean with distilled water and absolute ethyl alcohol again; Last vacuum drying.
The described copper salt solution concentration of step (1) is 0.1～0.5mol/L; The described organic solution concentration that contains oleic acid is 0.1～1.0mol/L; Described mantoquita is the divalence soluble copper salt, Cu in the mantoquita
2+Be controlled at 5: 1～1: 10 with the mol ratio of oleic acid.The described organic solution that contains oleic acid is that oleic acid is dissolved in the solution that obtains in ethanol, acetone or the kerosene.Described mantoquita comprises cupric sulfate pentahydrate, copper chloride or copper nitrate.It is 15～120 minutes that step (1) is mixed the time of stirring.
The molar concentration rate of glucose and mantoquita is 1: 1～5: 1 in the step (2), and mol ratio is 1: 2～5: 1.After adding D/W, under the room temperature, magnetic agitation 10～60 minutes adds the ortho phosphorous acid sodium solution again.The molar concentration rate of inferior sodium phosphate and mantoquita is 2: 1～5: 1, and mol ratio is 1: 2～5: 1.After adding inferior sodium phosphate, under 50～80 ℃ of water-baths, magnetic agitation 30～120 minutes.
The beneficial effect that the present invention obtains is: 1) adopting water-soluble mantoquita is presoma, and by adding extractant and surfactant (being oleic acid), the nano copper particle pattern that finally obtains is even, the nanometer copper that good dispersion and antioxygenic property are good; 2) in extraction bivalent cupric ion process, oleic acid molecular is adsorbed on the copper ion surface, because it has long hydrophobic carbochain, can form polymer protective film in the metal surface, increase space steric effect to reduce interparticle gravitation, improve its stability, prevent nano copper particle oxidation and reunion; Oleic acid has played crucial effect in whole process.It at first is extracted to bivalent cupric ion in the organic solution from the aqueous solution as a kind of extractant; Secondly, oleic acid also carries out finishing as surfactant to the product particle that generates, to avoid its oxidation and reunion.3) adopt two step reduction method reduced nano copper particle, the nucleation rate in the reduction process is slowed down, the collision that has reduced between nucleus is reunited, thereby has avoided the generation of block product.Inferior sodium phosphate can well reduce production costs as a kind of reducing agent of cheapness; 4) adopt the nano copper particle of this technology preparation to add in the 150N base oil, detect through four ball frictional experiments and find, can significantly improve the antiwear and friction reduction property of 150N base oil through the nano copper particle of finishing as additive.
Description of drawings:
The XRD figure of the nano copper particle that Fig. 1 makes for comparative example 1;
The SEM figure of the nano copper particle that Fig. 2 makes for comparative example 1;
The TEM figure of the nano copper particle that Fig. 3 makes for comparative example 1;
The XRD figure of the nano copper particle that Fig. 4 makes for embodiment 2;
The SEM figure of the nano copper particle that Fig. 5 makes for embodiment 2;
The TEM figure of the nano copper particle that Fig. 6 makes for embodiment 2;
The SEM figure of the nano copper particle that Fig. 7 makes for embodiment 3;
(a)C
oleic?acid＝0.1mol/L；(b)C
oleic?acid＝0.2mol/L；(c)C
oleic?acid＝0.4mol/L
The SEM figure of the nano copper particle that Fig. 8 makes for embodiment 4;
(a)t＝60min；(b)t＝90min
The SEM figure of the nano copper particle that Fig. 9 makes for embodiment 5;
(a)T＝50℃；(b)T＝70℃
Figure 10 is the worn steel ball surface topography photo behind the embodiment 6;
Figure 11 is the worn steel ball surface topography photo behind the embodiment 7.
The specific embodiment:
The comparative example 1
1) the 0.2mol/L cupric sulfate pentahydrate is dissolved in the redistilled water, promptly obtains precursor liquid.
2) aqueous solution with an amount of glucose adds in the above-mentioned precursor liquid, and the molar concentration rate of glucose and mantoquita was controlled at 2: 1, and mol ratio was controlled at 2.5: 1; At room temperature, magnetic agitation 10min makes bivalent cupric ion be reduced to cuprous oxide fully.
3) an amount of ortho phosphorous acid sodium solution is added in the above-mentioned mixed solution, the molar concentration rate of inferior sodium phosphate and mantoquita was controlled at 2: 1, and mol ratio was controlled at 2: 1.Under 60 ℃ of water-baths, magnetic agitation 30min makes cuprous oxide be reduced to elemental copper fully.
4) with product high speed (rotating speed is: 1000 rev/mins) centrifugal removal supernatant liquor, clean for several times with distilled water and absolute ethyl alcohol again.In vacuum drying chamber, drying is 6 hours under 60 ℃ of temperature at last.Detect after placing a week.
Embodiment 2
1) with the ethanolic solution of 0.2mol/L cupric sulfate pentahydrate solution and 0.5mol/L oleic acid, prepare by 4: 1 mol ratio, mixed liquor stirs 30min, and bivalent cupric ion is extracted in the organic facies, promptly obtains precursor liquid.
2) an amount of D/W is added in the above-mentioned precursor liquid, the molar concentration rate of glucose and mantoquita was controlled at 2: 1, and mol ratio was controlled at 2.5: 1; At room temperature, magnetic agitation 10min makes bivalent cupric ion be reduced to cuprous oxide fully.
3) an amount of ortho phosphorous acid sodium solution is added in the above-mentioned mixed solution, the molar concentration rate of inferior sodium phosphate and mantoquita is 2: 1, and mol ratio is 2: 1.Under 60 ℃ of water-baths, magnetic agitation 30min makes cuprous oxide be reduced to elemental copper fully.
4) with product high speed (rotating speed is: 1000 rev/mins) centrifugal removal supernatant liquor, clean for several times with distilled water and absolute ethyl alcohol again.In vacuum drying chamber, drying is 6 hours under 60 ℃ of temperature at last.Detect after placing a week.
Embodiment 3
1) (0.1mol/L～1.0mol/L) solution mixes by 1: 2 mol ratio with a certain amount of oleic acid with 0.2mol/L cupric sulfate pentahydrate solution.Mixed liquor stirs 30min, and bivalent cupric ion is extracted in the organic facies, promptly obtains precursor liquid.
2) an amount of D/W is added in the above-mentioned precursor liquid, the molar concentration rate of glucose and mantoquita is 2: 1, and mol ratio was controlled at 1: 2; At room temperature, magnetic agitation 10min makes bivalent cupric ion be reduced to cuprous oxide fully.
3) an amount of ortho phosphorous acid sodium solution is added in the above-mentioned mixed solution, the molar concentration rate of inferior sodium phosphate and mantoquita is 2.5: 1, and mol ratio was controlled at 1: 2.Under 60 ℃ of water-baths, magnetic agitation 30min makes cuprous oxide be reduced to elemental copper fully.
4) with product high speed (rotating speed is: 1000 rev/mins) centrifugal removal supernatant liquor, clean for several times with distilled water and absolute ethyl alcohol again.In vacuum drying chamber, drying is 6 hours under 60 ℃ of temperature at last.Detect after placing a week.
Embodiment 4
1) mixture of configuration 0.5mol/L cupric sulfate pentahydrate solution and 1.0mol/L oleic acid ethanolic solution mixes by 1: 5 mol ratio.Mixture stirs 30min, and bivalent cupric ion is extracted in the organic facies, promptly obtains precursor liquid.
2) an amount of D/W is added in the above-mentioned precursor liquid, the molar concentration rate of glucose and mantoquita is 4: 1, and mol ratio was controlled at 3: 1; At room temperature, magnetic agitation 10min makes bivalent cupric ion be reduced to cuprous oxide fully.
3) an amount of ortho phosphorous acid sodium solution is added in the above-mentioned mixed solution, the molar concentration rate of inferior sodium phosphate and mantoquita is 3: 1, and mol ratio was controlled at 4: 1.Under 60 ℃ of water-baths, magnetic agitation certain hour (60min～90min), make cuprous oxide be reduced to elemental copper fully.
4) with product high speed (rotating speed is: 1000 rev/mins) centrifugal removal supernatant liquor, clean for several times with distilled water and absolute ethyl alcohol again.In vacuum drying chamber, drying is 6 hours under 60 ℃ of temperature at last.Detect after placing a week.
Embodiment 5
1) 0.2mol/L cupric sulfate pentahydrate solution is mixed by 1: 7 mol ratio with 0.5mol/L oleic acid ethanolic solution.Mix and stir 30min, bivalent cupric ion is extracted in the organic facies, promptly obtain precursor liquid.
2) an amount of D/W is added in the above-mentioned precursor liquid, the molar concentration rate of glucose and mantoquita is 2: 1, and mol ratio was controlled at 5: 1; At room temperature, magnetic agitation 10min makes bivalent cupric ion be reduced to cuprous oxide fully.
3) an amount of ortho phosphorous acid sodium solution is added in the above-mentioned mixed solution, the molar concentration rate of inferior sodium phosphate and mantoquita is 2.5: 1; Mol ratio was controlled at 5: 1.Under the uniform temperature water-bath (50 ℃～70 ℃), magnetic agitation 30min makes cuprous oxide be reduced to elemental copper fully.
4) with product high speed (rotating speed is: 1000 rev/mins) centrifugal removal supernatant liquor, clean for several times with distilled water and absolute ethyl alcohol again.In vacuum drying chamber, drying is 6 hours under 60 ℃ of temperature at last.Detect after placing a week.
Embodiment 6
Present embodiment adopts four ball frictiographs that the antiwear and reducing friction performance of the pure base oil of 150N is detected.
Embodiment 7
The product nano copper particle that present embodiment will prepare according to the inventive method is that 4% amount is added in the 150N base oil with mass ratio, adopts four ball frictiographs that the abrasion resistance of this sample oil is detected.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to above-mentioned, those of ordinary skill in the art is to be understood that: still can make amendment or replacement on an equal basis to the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1. the preparation method of an anti-oxidant nano copper particle is characterized in that, may further comprise the steps:
(1) forerunner's copper salt solution and the organic solution mixing and stirring that contains oleic acid are extracted to bivalent cupric ion in the organic facies, promptly obtain precursor liquid;
The reduction of (2) two steps
At first D/W is added in the described precursor liquid of step (1), make bivalent cupric ion be reduced to cuprous oxide fully; Then, the ortho phosphorous acid sodium solution is added into above-mentioned solution, cuprous oxide is reduced to elemental copper fully;
(3) vacuum drying
With the centrifugal removal supernatant liquor of product, clean with distilled water and absolute ethyl alcohol again; Last vacuum drying.
2. preparation method according to claim 1 is characterized in that, the described copper salt solution concentration of step (1) is 0.1～0.5mol/L; The described organic solution concentration that contains oleic acid is 0.1～1.0mol/L; Described mantoquita is the divalence soluble copper salt, Cu in the mantoquita
2+Be controlled at 5: 1～1: 10 with the mol ratio of oleic acid.
3. preparation method according to claim 1 and 2 is characterized in that, the described organic solution that contains oleic acid is that oleic acid is dissolved in the solution that obtains in ethanol, acetone or the kerosene.
4. preparation method according to claim 1 and 2 is characterized in that described mantoquita comprises cupric sulfate pentahydrate, copper chloride or copper nitrate.
5. preparation method according to claim 1 is characterized in that, it is 15～120 minutes that step (1) is mixed the time of stirring.
6. preparation method according to claim 1 is characterized in that, the molar concentration rate of glucose and mantoquita is 1: 1～5: 1 in the step (2), and mol ratio is 1: 2～5: 1.
7. according to claim 1 or 6 described preparation methods, it is characterized in that behind the adding D/W, under the room temperature, magnetic agitation 10～60 minutes adds the ortho phosphorous acid sodium solution again in the step (2).
8. preparation method according to claim 1 is characterized in that, the molar concentration rate of inferior sodium phosphate and mantoquita is 2: 1～5: 1 in the step (2), and mol ratio is 1: 2～5: 1.
9. according to claim 1 or 8 described preparation methods, it is characterized in that, after the middle adding of step (2) inferior sodium phosphate, under 50～80 ℃ of water-baths, magnetic agitation 30～120 minutes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959627A (en) * | 2015-07-20 | 2015-10-07 | 西安工业大学 | Nano copper powder used as lubricating oil additive and preparation method thereof |
| CN106270542A (en) * | 2015-05-19 | 2017-01-04 | 东又悦（苏州）电子科技新材料有限公司 | A kind of vacuum method prepares the method for copper powder |
| CN106818869A (en) * | 2017-01-10 | 2017-06-13 | 南通大学 | A kind of preparation method of carbon-based nano carbon/carbon-copper composite material |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
| CN109622986A (en) * | 2018-12-26 | 2019-04-16 | 天津理工大学 | A kind of preparation method of copper-based modification infusorial earth |
| CN110026560A (en) * | 2018-08-27 | 2019-07-19 | 南方科技大学 | Nano copper particle and its preparation method and application |
| WO2021012754A1 (en) * | 2019-07-23 | 2021-01-28 | 富兰克科技（深圳）股份有限公司 | Preparation method of self-dispersing nano copper with long organice carbon chain, nano copper preparation and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106270542A (en) * | 2015-05-19 | 2017-01-04 | 东又悦（苏州）电子科技新材料有限公司 | A kind of vacuum method prepares the method for copper powder |
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| CN106818869A (en) * | 2017-01-10 | 2017-06-13 | 南通大学 | A kind of preparation method of carbon-based nano carbon/carbon-copper composite material |
| CN106818869B (en) * | 2017-01-10 | 2019-06-21 | 南通大学 | A kind of preparation method of carbon-based nano carbon/carbon-copper composite material |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
| CN110026560A (en) * | 2018-08-27 | 2019-07-19 | 南方科技大学 | Nano copper particle and its preparation method and application |
| CN109622986A (en) * | 2018-12-26 | 2019-04-16 | 天津理工大学 | A kind of preparation method of copper-based modification infusorial earth |
| WO2021012754A1 (en) * | 2019-07-23 | 2021-01-28 | 富兰克科技（深圳）股份有限公司 | Preparation method of self-dispersing nano copper with long organice carbon chain, nano copper preparation and application thereof |
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Application publication date: 20110928 |