CN109537030B - Preparation method of carbon nanoparticle solution and application of carbon nanoparticle solution in nickel coating - Google Patents
Preparation method of carbon nanoparticle solution and application of carbon nanoparticle solution in nickel coating Download PDFInfo
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- CN109537030B CN109537030B CN201811416965.3A CN201811416965A CN109537030B CN 109537030 B CN109537030 B CN 109537030B CN 201811416965 A CN201811416965 A CN 201811416965A CN 109537030 B CN109537030 B CN 109537030B
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Abstract
The invention discloses a preparation method of a carbon nano-particle solution and application of the carbon nano-particle solution in a nickel coating. The preparation method prepares electrolyte, and the electrolyteThe solute is 0.15-0.25 mol/L HNO3，0.08～0.12mol/L(CH2OH)2，0.15～0.25g/L C12H25NaSO4The solvent is deionized water; electrolyzing to obtain a carbon nano-particle solution; adding the carbon nano-particle solution into the nickel plating solution, and depositing to obtain the nickel-carbon nano composite coating. The preparation method of the nickel-carbon nano composite coating is harmless, nontoxic, environment-friendly and convenient, the hardness and the wear resistance of the composite coating are obviously improved, the corrosion resistance is obviously improved, the comprehensive performance of the nickel coating is greatly improved, the industrial application of the nickel coating is expanded, and the nickel-carbon nano composite coating has a good development prospect.
Description
Technical Field
The invention relates to the field of nickel coatings, in particular to a preparation method of a carbon nano-particle solution and application of the carbon nano-particle solution in a nickel coating.
Background
The nickel coating has higher hardness, certain corrosion resistance and friction resistance and beautiful metal luster, so the nickel coating has very wide application in the fields of mechanical parts, electronic products and daily metal products. With the progress of industrial technology and the demand of people for high-performance products, the common nickel coating cannot meet the performance requirements more and more, and the hardness, the wear resistance and the corrosion resistance of the nickel coating need to be further improved. In recent years, researchers have increased research on the performance improvement of nickel coatings, composite coatings formed by co-deposition of nano hard particles and nickel have become a research hotspot in recent years, and the process can improve the performance of nickel coatings, so that the nickel coatings are widely researched by many researchers.
However, the nanoparticles have small size effect and surface effect, so that the nanoparticles have high surface energy, are easy to agglomerate and cannot be fully dispersed in the coating, and the added nanoparticles are agglomerated in the coating matrix, so that the performance of the coating cannot be improved, but the coating generates a loose and porous structure, and the performance of the nickel coating is deteriorated. Therefore, the method for improving the performance of the nickel coating has great limitation.
Application No. 2011104193404, entitled method for preparing titanium diboride/nickel coating with nano-layered structure, which uses TiB2The ceramic target and the metal Ni target are used as raw materials and are prepared by adopting a magnetron sputtering technology to prepare the TiB2The Ni is made of metal Ni and TiB2Formed by in-situ compounding and provided with a plurality of metal Ni layers and TiB2The ceramic layers are mutually superposed to form a nano-layered structure, wherein the thickness of each layer is 6-60nm, and the content of metal Ni is 5-30 at.%; metal Ni layer and TiB2The number of ceramic layers is 20-100000, the thickness of each metal Ni layer is 1-10nm, and each TiB layer2The thickness of the layer is 5-50nm, the toughness is good, the operation is simple, the preparation period is short, the repeatability is strong, and the method can be used for large-scale industrial production. The patent has the defects of high preparation cost, immature technical application and large limitation on the size of the prepared sample.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a carbon nano-particle solution and application thereof in a nickel coating, wherein the carbon nano-particles are added into electroplating solution and are uniformly distributed in nickel after being codeposited with the nickel, so that the carbon nano-particles have higher stability, are not easy to agglomerate, generate a dispersion strengthening effect and lead the crystal grains of the coating to be refined and the structure to be compact, therefore, the coating has high hardness and strong wear resistance and corrosion resistance.
A method of preparing a carbon nanoparticle solution, comprising the steps of:
step 1, preparing electrolyte, wherein the solute of the electrolyte is 0.15-0.25 mol/L HNO3，0.08～0.12mol/L(CH2OH)2，0.15～0.25g/L C12H25NaSO4The solvent is deionized water; step 2, taking two high-purity graphite plates, cleaning the graphite plates by deionized water, fixing the graphite plates by using crocodile clips with copper bars, fixing the crocodile clips on a clamp in parallel and vertically, putting the clamp into a container filled with electrolyte, adjusting the height of the clamp, and immersing the graphite plates into the containerAnd (3) putting the device into an ultrasonic instrument in the electrolyte, fixing, respectively connecting the positive electrode and the negative electrode of a direct current power supply to the copper rod, and carrying out an electrifying reaction to obtain the carbon nanoparticle solution.
As a refinement, the high purity graphite plates in step 2 have a gauge of 100 x 50 x 2 mm.
The improvement is that the vibration frequency of the ultrasonic instrument in the step 2 is 40 KHz; the electrified current density is 6mA/cm2。
Based on the use of a carbon nanoparticle solution for the preparation of nickel coatings.
The application comprises the following steps:
firstly, cutting a brass sheet with a film stuck on both sides and a thickness of 0.2mm into a sample suitable for a plating bath, tearing off a protective film on one side, clamping the middle of a wide edge by using an alligator clip, and then placing the brass sheet in alkaline washing liquid for alkaline washing at 65-80 ℃ for 5 min;
secondly, after the alkali washing is finished, washing a sample with deionized water, then placing the sample in an activation solution for activation for 60-100 seconds at the temperature of 25-35 ℃, taking a stainless steel plate as an anode during the activation, taking the sample after the alkali washing as a cathode, vertically and parallelly placing the cathode and the anode, and then respectively connecting the cathode and the anode with a positive electrode and a negative electrode of a direct-current power supply; thirdly, cleaning the activated sample by using deionized water, clamping the middle part of a wide edge by using an alligator clip with a copper bar, fixing the sample on a clamp, fixing a high-purity nickel plate (length, width and thickness: 40 x 2mm) on the clamp by using the same method, ensuring that the nickel plate is vertically parallel to the brass sample, adjusting the height of the clamp, and completely immersing the sample and the nickel plate into a nickel plating solution containing a carbon nanoparticle solution with the concentration of 5mL/L-50mL/L, wherein the temperature is 50-70 ℃, the pH is 3-5, and the rotation speed of magnetons is as follows: 300-400 rpm, respectively connecting the positive electrode and the negative electrode of a direct current power supply to the two copper rods, and switching on the power supply to carry out electrodeposition when the temperature, the rotating speed and the pH value of the nickel plating solution reach specified values, wherein the deposition time is 20-40 min; and fourthly, taking out the sample after deposition is finished, washing the sample with deionized water, and drying to obtain the nickel-carbon nano composite coating.
As an improvement, the composition and parameters of the alkaline washing solution in the first step are as follows: 30 to 50g/L NaOH、6～15g/L NaH2PO4And the solvent is deionized water.
As an improvement, the composition and parameters of the activating solution in the second step are as follows: 10-20 g/L C6H8O7、50～80g/L C6H5O7(NH4)3And the solvent is deionized water.
The improvement is that the current density of the electro-deposition in the third step is 30-50 mA/cm2。
As an improvement, the composition of the nickel plating solution in the third step is as follows: 100-200 g/L NiSO4·6H2O，10～25g/L NH4Cl，10～30g/L H3BO3，0.01～1g/L C12H25SO4Na。
Has the advantages that:
compared with the prior art, the invention has the advantages that:
1. the composite coating prepared by combining nickel and nano-carbon has good performance. The hardness of the coating is greatly improved: the highest hardness of the prepared nickel/nano carbon composite coating can reach 500HV, while the hardness of the nickel coating without carbon-containing nano particles is only 380 HV. The friction and wear performance is obviously improved: under the same friction condition, the abrasion loss of the nickel/nano carbon composite coating is 3.359 x 10-3mm2And the amount of wear of the coating is 6.040 x 10-3mm2(ii) a Compared with the common nickel coating, the wear amount of the nickel/nano carbon composite coating is reduced by 44.4 percent, which shows that the friction and wear resistance of the coating is obviously improved. The corrosion resistance is obviously improved: by carrying out polarization curve fitting and impedance spectrum analysis on the prepared sample, the corrosion rate of the nickel coating is 0.063636mm/a, and the minimum corrosion rate of the nickel/nano-carbon composite coating is only 0.023763mm/a, which shows that the corrosion resistance of the nickel/nano-carbon composite coating is greatly improved. In conclusion, compared with the existing nickel coating, the hardness, the frictional wear resistance and the corrosion resistance of the nickel coating are greatly improved;
2. because the equipment for preparing the nickel/nano carbon composite coating is simple and has low cost: the method can be completed only by conventional devices such as common chemical reagents, plating bath devices, direct-current power supplies and the like, and has low energy consumption and high feasibility, thereby being suitable for large-scale industrial production;
3. environmental protection and no pollution to the environment: the adopted electrolyte has no volatile acid, the waste liquid treatment process is simpler, and the environment can not be polluted; the nickel plating solution has simple composition and no toxic and harmful substances;
4. the invention adopts the stainless steel plate as the anode material, utilizes the high corrosion potential and corrosion resistance of the stainless steel plate, and can not cause the pollution of the activating solution because of dissolution during activation, so that the activating solution can be repeatedly used, and the cost is reduced.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a high-carbon nanoparticle solution by an electrolytic method;
FIG. 2 is a schematic view of an apparatus for preparing a nickel/nanocarbon composite coating by an electroplating method;
FIG. 3 is SEM morphology of carbon nanoparticles in nickel/nanocarbon composite coatings of different carbon nanoparticle contents, wherein a-nickel coating b-nickel/10 mL/L carbon nanoparticle solution composite coating; c-nickel/50 mL/L carbon nanoparticle solution composite coating;
FIG. 4 is a graph showing the hardness change curves of a pure nickel plating layer and a nickel/nanocarbon composite coating layer of 5 different carbon nanoparticle solution concentrations;
FIG. 5 shows the wear rate variation trends of pure nickel plating and 5 kinds of nickel/nanocarbon composite coatings with different concentrations of carbon nanoparticle solution;
FIG. 6 is a friction profile of nickel/nanocarbon composite coatings with different carbon nanoparticle contents, wherein a-nickel coating b-nickel/10 mL/L carbon nanoparticle solution composite coating; c-nickel/50 mL/L carbon nanoparticle solution composite coating;
FIG. 7 is a Tafel curve for nickel/nanocarbon composite coatings of different carbon nanoparticle content, wherein a-nickel coating b-nickel/10 mL/L carbon nanoparticle solution composite coating; c-nickel/50 mL/L carbon nano particle solution composite coating.
Detailed Description
The process of the present invention is described and illustrated in detail below with reference to specific examples. The content is to explain the invention and not to limit the scope of protection of the invention.
Example 1
A method of preparing a carbon nanoparticle solution, comprising the steps of:
step 1, preparing electrolyte, wherein the solute of the electrolyte is 0.15-0.25 mol/L HNO3，0.08～0.12mol/L(CH2OH)2，0.15～0.25g/L C12H25NaSO4The solvent is deionized water;
wherein, the specification of the high-purity graphite plate in the step 2 is 100 x 50 x 2 mm.
The vibration frequency of the ultrasonic instrument is 40 KHz; the electrified current density is 6mA/cm2。
Respectively 3 groups of electrolytes with different concentrations, wherein the solute in the first group is 0.15mol/L HNO3，0.08mol/L(CH2OH)2，0.15g/L C12H25NaSO4(ii) a The solute in the second group is 0.2mol/L HNO3，0.1mol/L(CH2OH)2，0.18g/L C12H25NaSO4(ii) a The solute in the third group is 0.25mol/L HNO3，0.12mol/L(CH2OH)2，0.25g/L C12H25NaSO4。
Example 2
The carbon nanoparticle solutions with the concentrations of 5mL/L, 10mL/L, 20mL/L, 30mL/L and 50mL/L were added to the nickel plating solution, and the prepared samples were recorded as a second sample, a third sample, a fourth sample, a fifth sample and a sixth sample. The performance of the samples prepared as described above was analyzed to obtain 6 samples, and the 6 samples were compared for performance analysis, and the results are shown in FIGS. 3 to 6.
As can be seen from the figure, when the concentration of the carbon nano-particle solution is 10mL/L, the hardness, the frictional wear resistance and the corrosion resistance of the coating are obviously improved, but when the concentration of the carbon nano-particle solution in the electroplating solution exceeds 10mL/L, the nickel coating generates a loose structure, so that the comprehensive performance of the nickel coating is reduced. When the concentration of the carbon nano particle solution is 50mL/L, the performance of the nickel/carbon nano particle composite coating is poor, and the performance index is lower than that of a pure nickel layer.
Claims (7)
1. A method for preparing a carbon nanoparticle solution, comprising the steps of: step 1, preparing electrolyte, wherein the solute of the electrolyte is 0.15-0.25 mol/L HNO3，0.08~0.12mol/L (CH2OH)2，0.15~0.25g/L C12H25SO4Na and deionized water as a solvent; step 2, cleaning two high-purity graphite plates by using deionized water, fixing the graphite plates by using a crocodile clip with a copper bar, fixing the crocodile clip on a clamp in parallel and vertically, putting the clamp into a container filled with electrolyte, adjusting the height of the clamp to immerse the graphite plates into the electrolyte, putting the device into an ultrasonic instrument, fixing the device, respectively connecting the positive electrode and the negative electrode of a direct-current power supply to the copper bar, and carrying out an electrifying reaction to obtain a carbon nanoparticle solution; in the step 2, the vibration frequency of the ultrasonic instrument is 40 KHz; the electrified current density is 6mA/cm2。
2. The method of claim 1, wherein the high purity graphite plate in step 2 has a gauge of 100 x 50 x 2 mm.
3. Use of a carbon nanoparticle solution prepared according to claim 1 for the preparation of nickel coatings, characterized by the following steps: firstly, cutting a brass sheet with a double-sided film and a thickness of 0.2mm into a sample suitable for a plating bath, tearing off a protective film on one side, clamping the middle of a wide edge by using an alligator clip, and then placing the sample in alkaline washing liquid at 65-80 ℃ for alkaline washing for 5 min; secondly, after the alkali washing is finished, washing a sample with deionized water, then placing the sample in an activation solution for activation for 60-100 seconds at the temperature of 25-35 ℃, taking a stainless steel plate as an anode during the activation, taking the sample after the alkali washing as a cathode, vertically and parallelly placing the cathode and the anode, and then respectively connecting the cathode and the anode with a positive electrode and a negative electrode of a direct-current power supply; thirdly, cleaning the activated sample with deionized water, clamping the middle part of a wide edge with an alligator clip with a copper bar, fixing the sample on a clamp, fixing a high-purity nickel plate on the clamp by the same method, ensuring that the nickel plate is vertically parallel to the brass sample, adjusting the height of the clamp, and completely immersing the sample and the nickel plate into a nickel plating solution containing a carbon nanoparticle solution with the concentration of 5mL/L-30mL/L, wherein the temperature is 50-70 ℃, the pH value is 3-5, and the magneton rotating speed is as follows: 300-400 rpm, respectively connecting the positive electrode and the negative electrode of a direct current power supply to the two copper rods, and switching on the power supply to carry out electrodeposition when the temperature, the rotating speed and the pH value of the nickel plating solution reach specified values, wherein the deposition time is 20-40 min; and fourthly, taking out the sample after deposition is finished, washing the sample with deionized water, and drying to obtain the nickel-carbon nano composite coating.
4. The use according to claim 3, characterized in that the composition and parameters of the alkaline wash in the first step are: 30-50 g/L NaOH, 6-15 g/L NaH2PO4And the solvent is deionized water.
5. Use according to claim 3, characterized in that the composition and parameters of the activation liquid in the second step: 10-20 g/L C6H8O7、50~80g/L C6H5O7 (NH4)3And the solvent is deionized water.
6. The use according to claim 3, wherein the current density of the electrodeposition in the third step is 30 to 50mA/cm2。
7. Use according to claim 3, wherein the composition of the nickel plating solution in the third step is: 100-200 g/L NiSO4•6H2O，10~25g/L NH4Cl，10~30g/L H3BO3，0.01~1g/L C12H25SO4Na。
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Application publication date: 20190329 Assignee: Center for technology transfer Jiangsu University of Science and Technology Assignor: JIANGSU University OF SCIENCE AND TECHNOLOGY Contract record no.: X2021980006173 Denomination of invention: A preparation method of carbon nano particle solution and its application in nickel coating Granted publication date: 20201215 License type: Common License Record date: 20210714 |
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