CN109160532B - Water-soluble copper sulfide nano particle, preparation method thereof and application of water-soluble copper sulfide nano particle as water-based lubricating additive - Google Patents
Water-soluble copper sulfide nano particle, preparation method thereof and application of water-soluble copper sulfide nano particle as water-based lubricating additive Download PDFInfo
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Abstract
The invention relates to a preparation method of water-soluble copper sulfide nano particles, which comprises the following steps: 1) under the condition of ice-water bath, mixing an absolute ethyl alcohol solution containing diethanol amine and an absolute ethyl alcohol solution containing carbon disulfide, heating to room temperature, stirring for reaction for 0.5-2 h, and performing rotary evaporation to obtain dihydroxyhexyl dithiocarbamic acid; 2) dissolving cetyl trimethyl ammonium bromide in a copper nitrate aqueous solution to obtain a light blue transparent solution, adding ammonia water, and uniformly stirring; 3) dissolving dihydroxyhexyl dithiocarbamic acid in polyethylene glycol-400, adding the product obtained in the step 2), stirring for 5-30 min at room temperature, reacting for 1-3 h at 110-170 ℃, cooling to room temperature after the reaction is finished, centrifuging, drying and collecting to obtain the dihydroxyhexyl dithiocarbamic acid. The copper sulfide nanometer particles have high purity and uniform particle size distribution, the friction coefficient and the wear rate of the copper sulfide nanometer particles are respectively reduced by 78.3 percent and 93.7 percent compared with distilled water, and the copper sulfide nanometer particles have good tribological performance and good application prospect in a water lubricating system.
Description
Technical Field
The invention belongs to the technical field of preparation of novel functional nano materials, and particularly relates to a water-soluble copper sulfide nano particle, a preparation method thereof and application of the water-soluble copper sulfide nano particle as a water-based lubricating additive.
Background
The copper sulfide has various different lattice structures, so that the copper sulfide has a plurality of special physicochemical properties, wide sources, no toxicity and multiple functions, and has potential application values in different fields. At present, the preparation method comprises the steps of adding sulfide into a copper salt solution to prepare copper sulfide nano particles; secondly, processing the precursor at high temperature and high pressure to generate the copper sulfide nanometer particles. However, the preparation and modification processes of these copper sulfide nanoparticles have the defects of complicated reaction, harsh conditions, long reaction period and the like. In addition, at present, the research on copper sulfide nano materials as lubricating additives is mostly focused on the application of the copper sulfide nano materials as oil-soluble lubricating additives, and the technical bottleneck restricting the application of copper sulfide nano particles in water is the dispersion stability of the copper sulfide nano particles, and the copper sulfide nano particles are difficult to stably disperse in a water phase due to the high specific surface and surface energy of the nano particles and the difference of the composition and microstructure of the particles. Therefore, there is a need to research and develop new copper sulfide nanoparticles so that they can be used as water-based lubricant additives.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the water-soluble copper sulfide nano particles which have high purity, uniform particle size distribution, friction coefficient and wear rate which are respectively reduced by 78.3 percent and 93.7 percent compared with distilled water, good tribological performance and good application prospect in a water lubricating system.
The invention also provides a preparation method of the water-soluble copper sulfide nano particles and application of the water-soluble copper sulfide nano particles as a water-based lubricating additive.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of water-soluble copper sulfide nanoparticles specifically comprises the following steps:
1) under the condition of ice-water bath, mixing an absolute ethyl alcohol solution containing diethanol amine and an absolute ethyl alcohol solution containing carbon disulfide, heating to room temperature, stirring for reaction for 0.5-2 h, and performing rotary evaporation to obtain dihydroxyhexyl dithiocarbamic acid;
2) dissolving cetyl trimethyl ammonium bromide in a copper nitrate aqueous solution to obtain a light blue transparent solution, adding ammonia water, and uniformly stirring;
3) dissolving dihydroxyhexyl dithiocarbamic acid in polyethylene glycol-400, adding the product obtained in the step 2), stirring at room temperature for 5-30 min, reacting at 110-170 ℃ for 1-3 h, cooling to room temperature after the reaction is finished, and centrifuging, drying and collecting the reaction product to obtain the dihydroxyhexyl dithiocarbamic acid.
In the preparation method of the water-soluble copper sulfide nanoparticles, in the step 1), 2-10 mL of diethanolamine is dissolved in 10-30 mL of absolute ethanol to obtain absolute ethanol solution containing diethanolamine; dissolving 10-30 mL of carbon disulfide in 10-50 mL of absolute ethanol to obtain an absolute ethanol solution containing carbon disulfide.
In the preparation method of the water-soluble copper sulfide nanoparticles, in the step 2), 1-3 mmol of hexadecyl trimethyl ammonium bromide is dissolved in 10-70 mL of 0.02-0.4 mol/L copper nitrate aqueous solution; the adding amount of ammonia water (25-28%) is 1-5 mL.
In the preparation method of the water-soluble copper sulfide nanoparticles, in the step 3), 3-20 mmol of dihydroxyhexyldithiocarbamic acid is dissolved in 10-50 mL of polyethylene glycol-400.
The invention provides the water-soluble copper sulfide nano particles prepared by the preparation method.
The water-soluble copper sulfide nano particles prepared by the invention are added into distilled water, and the tribology and the heat conductivity of the water-soluble copper sulfide nano particles as a distilled water additive are tested. The test shows that: the water-soluble copper sulfide nano particles have good tribological property and heat conductivity, and can be used as a water-based lubricating additive.
In the preparation reaction of the water-soluble copper sulfide nano particles, dihydroxyhexyl dithiocarbamic acid is used as a reactant to provide a sulfur source and also used as a modifier to keep good dispersion stability of the nano particles by adopting an in-situ surface modification technology; the prepared copper sulfide nanoparticles have high purity and uniform particle size distribution, the friction coefficient and the wear rate of the copper sulfide nanoparticles are respectively reduced by 78.3 percent and 93.7 percent compared with those of distilled water, and the copper sulfide nanoparticles have good tribological performance; the heat conductivity coefficient is improved by 3 percent compared with that of distilled water, thereby being beneficial to the heat loss of a friction contact area, reducing the friction wear caused by local overheating and having good application prospect in a water lubricating system.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention uses self-made dihydroxyhexyl dithiocarbamic acid to react with copper ions to generate a copper sulfide precursor, and the precursor is decomposed at high temperature to obtain surface-modified water-soluble copper sulfide nanoparticles;
2) in the preparation process, the dihydroxyhexyl dithiocarbamic acid is used as a reactant to provide a sulfur source, hydrogen sulfide gas is not introduced, and impurities and environmental pollution in a system are reduced; in the growth process of the copper sulfide nano particles, the surface of the copper sulfide can be modified to inhibit the growth of the copper sulfide; the hydrophilic group on the surface of the modifier provides good water solubility for the prepared copper sulfide nano particles, so that the copper sulfide nano particles can be stably dispersed in water;
3) the water-soluble copper sulfide nano particles prepared by the method have small particle size and uniform distribution; the preparation process is easy to operate and is beneficial to large-scale industrial production;
4) the water-soluble copper sulfide nano particles prepared by the invention are added into distilled water, and the friction coefficient is reduced from 0.56 to 0.12; the wear rate is 99.2 multiplied by 10-6mm3·Nm-1Reduced to 6.24 × 10-6mm3·Nm-1(ii) a The heat conductivity coefficient is improved by 3 percent, and the lubricant has wide application prospect in the aspect of water-based lubricants.
Drawings
FIG. 1 is a schematic diagram of a process for preparing water-soluble copper sulfide according to the present invention;
FIG. 2 is an XRD pattern of water-soluble copper sulfide nanoparticles prepared in example 1;
FIG. 3 is a TEM image of the water-soluble copper sulfide nanoparticles obtained in example 1;
FIG. 4 is a graph of the coefficient of friction and rate of wear as a function of concentration for water-soluble copper sulfide nanoparticles prepared in example 1;
FIG. 5 is a graph showing the thermal conductivity of the water-soluble copper sulfide nanoparticles prepared in example 1 as a function of concentration.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, the mass fraction of ammonia water used is 25 to 28%.
Example 1
A preparation method of water-soluble copper sulfide nanoparticles (a process route is shown in figure 1) specifically comprises the following steps:
(1) mixing 4 mL of diethanolamine and 20 mL of absolute ethanol in a 250 mL three-neck flask, and uniformly stirring under the condition of ice-water bath;
(2) mixing 10 mL of carbon disulfide and 20 mL of absolute ethyl alcohol in a beaker, and uniformly stirring;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under the conditions of ice-water bath and magnetic stirring; after the dropwise addition, heating the reaction solution to the room temperature of 25 ℃, and stirring for 1 h to obtain a yellow transparent solution;
(4) after the reaction is finished, removing the solvent ethanol and excessive reaction substances in the product obtained in the step (3) through rotary evaporation to finally obtain light yellow transparent dihydroxyhexyl dithiocarbamate viscous liquid;
(5) 2 mL of 0.5M Cu (NO)3)2·3H2Mixing O and 10 mL of distilled water in a 50 mL three-neck flask uniformly;
(6) adding 1 mmol of hexadecyl trimethyl ammonium bromide into the copper nitrate aqueous solution obtained in the step (5), fully stirring at room temperature until the hexadecyl trimethyl ammonium bromide is completely dissolved to obtain a light blue transparent solution, adding 1 mL of ammonia water into the solution, and uniformly stirring;
(7) weighing 5 mmol of dihydroxyhexyl dithiocarbamic acid obtained in the step (4), dissolving the dihydroxyhexyl dithiocarbamic acid in 10 mL of polyethylene glycol-400, and uniformly stirring;
(8) adding the mixed solution obtained in the step (7) into the mixed solution obtained in the step (6), magnetically stirring at room temperature for 10 min, transferring into an oil bath kettle at 170 ℃, and reacting for 1 h to obtain a black solution;
(9) after the reaction is finished, cooling to room temperature, centrifuging and drying the reaction solution, and collecting to obtain the surface-modified water-soluble copper sulfide nano particles.
The XRD pattern of the water-soluble copper sulfide nanoparticles prepared above is shown in FIG. 2. As can be seen from fig. 2: consistent with standard card (PDF # 060464), the successful preparation of copper sulfide nanomaterials was demonstrated.
A TEM image of the water-soluble copper sulfide nanoparticles prepared above is shown in fig. 3. As can be seen from FIG. 3, the prepared water-soluble copper sulfide nanoparticles have uniform particle size, an average particle size of about 4 nm, and no obvious agglomeration phenomenon.
The graph of the relationship between the friction coefficient and the wear rate of the water-soluble copper sulfide nanoparticles prepared in the above manner as a function of the concentration is shown in FIG. 4. As can be seen from FIG. 4, the coefficient of friction and the wear rate were significantly reduced compared to distilled water after adding the water-soluble copper sulfide nanoparticles to distilled water. When 0.8wt% of water-soluble copper sulfide nanoparticles are added into distilled water, the friction coefficient and the wear rate are respectively reduced by 78.3% and 93.7% compared with the distilled water, which shows that the water-soluble copper sulfide nanoparticles have good tribological performance.
The graph of the relationship between the thermal conductivity of the water-soluble copper sulfide nanoparticles prepared in the above manner and the concentration is shown in FIG. 5. As can be seen from FIG. 5, the thermal conductivity was significantly improved as compared with distilled water after adding the water-soluble copper sulfide nanoparticles to distilled water, and when 0.8wt% of the water-soluble copper sulfide nanoparticles were added to distilled water, the thermal conductivity was improved by 3% as compared with distilled water, indicating that the heat conductive properties were good.
Example 2
A preparation method of water-soluble copper sulfide nanoparticles specifically comprises the following steps:
(1) mixing 6 mL of diethanolamine and 20 mL of absolute ethanol in a 250 mL three-neck flask, and uniformly stirring under the condition of ice-water bath;
(2) mixing 15 mL of carbon disulfide and 20 mL of absolute ethyl alcohol in a beaker, and uniformly stirring;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under the conditions of ice-water bath and magnetic stirring; after the dropwise addition, heating the reaction solution to the room temperature of 25 ℃, and stirring for 1 h to obtain a yellow transparent solution;
(4) after the reaction is finished, removing the solvent ethanol and excessive reaction substances in the product obtained in the step (3) through rotary evaporation to finally obtain light yellow transparent dihydroxyhexyl dithiocarbamate viscous liquid;
(5) 6 mL of 0.5M Cu (NO)3)2·3H2O and 30 mL of distilled water are uniformly mixed in a 100 mL three-neck flask;
(6) adding 2 mmol of hexadecyl trimethyl ammonium bromide into the solution obtained in the step (5), fully stirring at room temperature until the hexadecyl trimethyl ammonium bromide is completely dissolved to obtain a light blue transparent solution, adding 2 mL of ammonia water, and uniformly stirring by magnetic force;
(7) weighing 15 mmol of dihydroxyhexyl dithiocarbamic acid obtained in the step (4), adding the weighed dihydroxyhexyl dithiocarbamic acid into 20 mL of polyethylene glycol-400, and uniformly stirring by magnetic force;
(8) adding the mixed solution obtained in the step (7) into the mixed solution obtained in the step (6), magnetically stirring for 30 min at room temperature, transferring into an oil bath kettle at 150 ℃, and reacting for 2 h to obtain a black reaction solution;
(9) and after the reaction is finished, cooling to room temperature, centrifuging and drying the reaction solution, and collecting to obtain the surface-modified water-soluble copper sulfide nano particles.
Example 3
A preparation method of water-soluble copper sulfide nanoparticles specifically comprises the following steps:
(1) mixing 8 mL of diethanolamine and 25 mL of absolute ethanol in a 250 mL three-neck flask, and uniformly stirring under the condition of ice-water bath;
(2) mixing 20 mL of carbon disulfide and 50 mL of absolute ethyl alcohol in a beaker, and uniformly stirring;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under the conditions of ice-water bath and magnetic stirring; after the dropwise addition, heating the reaction solution to the room temperature of 25 ℃, and stirring for 1 h to obtain a yellow transparent solution;
(4) after the reaction is finished, removing the solvent ethanol and excessive reaction substances in the product obtained in the step (3) through rotary evaporation to finally obtain light yellow transparent dihydroxyhexyl dithiocarbamate viscous liquid;
(5) 8 mL of 0.5M Cu (NO)3)2·3H2Mixing O and 10 mL of distilled water in a 250 mL three-neck flask uniformly;
(6) adding 3mmol of hexadecyl trimethyl ammonium bromide into the copper nitrate aqueous solution obtained in the step (5), fully stirring at room temperature until the hexadecyl trimethyl ammonium bromide is completely dissolved to obtain a light blue transparent solution, adding 2 mL of ammonia water into the solution, and uniformly stirring;
(7) weighing 20 mmol of dihydroxyhexyl dithiocarbamic acid obtained in the step (4), dissolving in 50 mL of polyethylene glycol-400, and uniformly stirring;
(8) adding the mixed solution obtained in the step (7) into the mixed solution obtained in the step (6), magnetically stirring at room temperature for 20 min, transferring into an oil bath kettle at 130 ℃, and reacting for 2 h to obtain a black solution;
(9) and after the reaction is finished, cooling to room temperature, centrifuging and drying the reaction solution, and collecting to obtain the surface-modified water-soluble copper sulfide nano particles.
Example 4
A preparation method of water-soluble copper sulfide nano particles specifically comprises the following steps:
(1) mixing 10 mL of diethanolamine and 30 mL of absolute ethanol in a 250 mL three-neck flask, and uniformly stirring under the condition of ice-water bath;
(2) mixing 30 mL of carbon disulfide and 50 mL of absolute ethyl alcohol in a beaker, and uniformly stirring;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under the conditions of ice-water bath and magnetic stirring; after the dropwise addition, heating the reaction solution to the room temperature of 25 ℃, and stirring for 1 h to obtain a yellow transparent solution;
(4) after the reaction is finished, removing the solvent ethanol and excessive reaction substances in the product obtained in the step (3) through rotary evaporation to finally obtain light yellow transparent dihydroxyhexyl dithiocarbamate viscous liquid;
(5) 8 mL of 0.5M Cu (NO)3)2·3H2Mixing O and 10 mL of distilled water in a 250 mL three-neck flask uniformly;
(6) adding 3mmol of hexadecyl trimethyl ammonium bromide into the copper nitrate aqueous solution obtained in the step (5), fully stirring at room temperature until the hexadecyl trimethyl ammonium bromide is completely dissolved to obtain a light blue transparent solution, adding 2 mL of ammonia water into the solution, and uniformly stirring;
(7) weighing 20 mmol of dihydroxyhexyl dithiocarbamic acid obtained in the step (4), dissolving in 50 mL of polyethylene glycol-400, and uniformly stirring;
(8) adding the mixed solution obtained in the step (7) into the mixed solution obtained in the step (6), magnetically stirring at room temperature for 30 min, transferring into an oil bath kettle at 110 ℃, and reacting for 3 h to obtain a black solution;
(9) and after the reaction is finished, cooling to room temperature, centrifuging and drying the reaction solution, and collecting to obtain the surface-modified water-soluble copper sulfide nano particles.
Example 5
A preparation method of water-soluble copper sulfide nanoparticles specifically comprises the following steps:
(1) mixing 6 mL of diethanolamine and 20 mL of absolute ethanol in a 250 mL three-neck flask, and uniformly stirring under the condition of ice-water bath;
(2) mixing 15 mL of carbon disulfide and 20 mL of absolute ethyl alcohol in a beaker, and uniformly stirring;
(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under the conditions of ice-water bath and magnetic stirring; after the dropwise addition, heating the reaction solution to the room temperature of 25 ℃, and stirring for 1 h to obtain a yellow transparent solution;
(4) after the reaction is finished, removing the solvent ethanol and excessive reaction substances in the product obtained in the step (3) through rotary evaporation to finally obtain light yellow transparent dihydroxyhexyl dithiocarbamate viscous liquid;
(5) 2 mL of 0.5M Cu (NO)3)2·3H2O and 10 mL of distilled water are dissolved in a 100 mL three-neck flask;
(6) adding 1 mmol of hexadecyl trimethyl ammonium bromide into the copper nitrate aqueous solution obtained in the step (5), fully stirring at room temperature until the hexadecyl trimethyl ammonium bromide is completely dissolved to obtain a light blue transparent solution, adding 1 mL of ammonia water into the solution, and uniformly stirring;
(7) weighing 6 mmol of dihydroxyhexyl dithiocarbamic acid obtained in the step (3), dissolving in 10 mL of polyethylene glycol-400, and uniformly stirring;
(8) adding the mixed solution obtained in the step (7) into the mixed solution obtained in the step (6), magnetically stirring at room temperature for 10 min, transferring into an oil bath kettle at 110 ℃, and reacting for 1 h to obtain a black solution;
(9) and after the reaction is finished, cooling to room temperature, centrifuging and drying the reaction solution, and collecting to obtain the surface-modified water-soluble copper sulfide nano particles.
The water-soluble copper sulfide particles obtained in the above examples 2 to 5 were detected by XRD and TEM to find that: the obtained product is copper sulfide nanometer particles, has narrow particle size distribution, and has good water solubility when being added into distilled water.
In conclusion, it can be found that: the water-soluble copper sulfide nano particles have good tribological property and heat conductivity, and can be widely applied as a water-based lubricating additive.
Finally, it should be noted that: the above embodiments are merely illustrative and not restrictive of the technical solutions of the present invention, and any equivalent substitutions and modifications or partial substitutions made without departing from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.
Claims (6)
1. A preparation method of water-soluble copper sulfide nano particles is characterized by comprising the following steps:
1) under the condition of ice-water bath, mixing an absolute ethyl alcohol solution containing diethanol amine and an absolute ethyl alcohol solution containing carbon disulfide, heating to room temperature, stirring for reaction for 0.5-2 h, and performing rotary evaporation to obtain dihydroxyhexyl dithiocarbamic acid;
2) dissolving cetyl trimethyl ammonium bromide in a copper nitrate aqueous solution to obtain a light blue transparent solution, adding ammonia water, and uniformly stirring;
3) dissolving dihydroxyhexyl dithiocarbamic acid in polyethylene glycol-400, adding the product obtained in the step 2), stirring at room temperature for 5-30 min, reacting at 110-170 ℃ for 1-3 h, cooling to room temperature after the reaction is finished, and centrifuging, drying and collecting the reaction product to obtain the dihydroxyhexyl dithiocarbamic acid.
2. The method for preparing water-soluble copper sulfide nanoparticles as claimed in claim 1, wherein in step 1), 2-10 mL of diethanolamine is dissolved in 10-30 mL of absolute ethanol to obtain an absolute ethanol solution containing diethanolamine; dissolving 10-30 mL of carbon disulfide in 10-50 mL of absolute ethanol to obtain an absolute ethanol solution containing carbon disulfide.
3. The method for preparing water-soluble copper sulfide nanoparticles as claimed in claim 1, wherein in the step 2), 1 to 3mmol of cetyltrimethylammonium bromide is dissolved in 10 to 70 mL of 0.02 to 0.4 mol/L aqueous solution of copper nitrate; the adding amount of the ammonia water is 1-5 mL.
4. The method for preparing water-soluble copper sulfide nanoparticles according to claim 1, wherein in the step 3), 3 to 20 mmol of dihydroxyhexyldithiocarbamic acid is dissolved in 10 to 50 mL of polyethylene glycol-400.
5. The water-soluble copper sulfide nanoparticles obtained by the production method according to any one of claims 1 to 4.
6. Use of the water-soluble copper sulphide nanoparticles as claimed in claim 5 as a water-based lubricant additive.
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| CN101544394A (en) * | 2008-03-25 | 2009-09-30 | 大同股份有限公司 | Porous copper sulfide nano-micron hollow sphere and preparation method thereof |
| CN108314075A (en) * | 2018-02-06 | 2018-07-24 | 肇庆千江高新材料科技股份公司 | Flakes copper sulphide nano slurries, the water transparent heat insulation paint based on copper sulphide nano snowflake and preparation method and application method |
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