CN104862676A - Graphene oxide nickel-phosphorus composite plating solution, preparation method and applications thereof - Google Patents
Graphene oxide nickel-phosphorus composite plating solution, preparation method and applications thereof Download PDFInfo
- Publication number
- CN104862676A CN104862676A CN201510133589.7A CN201510133589A CN104862676A CN 104862676 A CN104862676 A CN 104862676A CN 201510133589 A CN201510133589 A CN 201510133589A CN 104862676 A CN104862676 A CN 104862676A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- phosphorus composite
- nickel
- composite plating
- plating bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention discloses a graphene oxide nickel-phosphorus composite plating solution, a preparation method and applications thereof, wherein per liter of the graphene oxide nickel-phosphorus composite plating solution comprises 0.5-1 g of graphene oxide being subjected to reduction treatment, 25-40 g of nickel sulfate, 15-20 g of sodium hypophosphite, 15 g of sodium acetate, 8-10 g of citric acid, 4 ml of lactic acid, 41 mg of a composite stabilizer, and the balance of distilled water. The preparation method comprises preparation of the graphene oxide being subjected to reduction treatment and preparation of the graphene oxide nickel-phosphorus composite plating solution. According to the present invention, the obtained graphene oxide nickel-phosphorus composite plating solution can perform plating on iron and steel at a low temperature of 50-70 DEG C, and the obtained graphene oxide nickel-phosphorus composite plating layer thickness is uniform and the surface is smooth and does not have gap; and the preparation method is simple, and the continuous production can be achieved.
Description
Technical field
The present invention relates to a kind of graphene oxide nickel phosphorus composite plating bath and preparation method thereof and utilize its surface at steel and alloy to carry out electroless plating to form graphene oxide nickel-phosphorus composite deposit.
Technical background
Electroless plating makes metal ion under the self-catalysis of metallic surface, carry out the metal deposition process reduced by reductive agent suitable in solution.Chemical plating can reinforcement material preservative property, wear resistance, is a kind of technique means the most economic extending the materials'use life-span.Along with the development of science and technology, the chemical nickel plating of simplification more and more can not meet the requirement of industrial development.The Ni-P therefore with superperformance just grows up.Composite Coatings is a kind of process of surface treatment developed on the basis of original single electroless plating, and has the over-all properties of matrix metal and composite particles two class material concurrently.Research shows, the composite particles added is conducive to the weave construction and the performance that change coating, and different particle type has different effects to coating.Current people are to various elemental metals or nonmetal, and composite electroless-plating and the coating performance thereof of the various particles such as oxide compound, carbide, nitride, sulfide, diamond or graphite have had certain research.Up-to-date composite deposite research mainly contains graphite, diamond, Al
2o
3, Graphene etc.But the cladding wearability obtained before this is general not high, and its polishing scratch sectional area is at 35-50um
2in scope.
Graphene oxide is powdered graphite through chemical oxidation and the product after peeling off, graphene oxide has the structure of single atomic shell, can expand to some tens of pm at any time on lateral dimension, therefore, and its construct trans typical size of general chemistry and Materials science.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, has the characteristic of amphipathic molecule.Therefore, graphene oxide can as interfacial agent Presence of an interface, and reduce the energy between interface, make metal ion under relatively mild temperature of reaction, evenly, rapidly can deposit subbase surface.Graphene oxide add the wear resisting property that can improve coating, reduce industrial energy consumption with the temperature of reaction of gentleness.
But, not yet have at present about the research containing graphene oxide nickel phosphorus Composite Coatings.
Graphene is joined in chemical plating fluid the report of making composite deposite, as Hu Qinghua adopts chemical nickel plating method, take graphene platelet as matrix, Ni-Graphene has been prepared in nickel sulfate solution, to its characterize rear discovery be deposited on graphene film surface Ni massfraction very high, and there is the dispersiveness of height, but this method does not extend to and is jointly deposited on body material by Ni Graphene; Wu Huihui adopts the method for chemical nickel plating, and in the common deposition in steel substrate surface, prepare Graphene nickel-phosphorus composite deposit, this coating is compared has better properties with nickel-phosphorus coating.But Graphene nickel-phosphorus composite deposit is smooth not, even, and in plating process, temperature of reaction is higher, be generally 80 DEG C-90 DEG C, therefore energy consumption is many.
Summary of the invention
An object of the present invention is to solve temperature of reaction required when above-mentioned Graphene nickel-phosphorus composite deposit Graphene nickel phosphorus composite plating bath used carries out electroless plating high, technical problems such as energy consumption is large and a kind of graphene oxide nickel phosphorus composite plating bath is provided, this graphene oxide nickel phosphorus composite plating bath has selected graphene oxide that is easier and metal co-deposition to be composite particles, temperature of reaction required when therefore utilizing it to carry out electroless plating is low, be only 50-70 DEG C, because the energy consumption of plating process is low, thus reduce electroless plating cost.
Two of object of the present invention is to provide the preparation method of above-mentioned a kind of graphene oxide nickel phosphorus composite plating bath.
Three of object of the present invention is that providing a kind of utilizes above-mentioned a kind of graphene oxide nickel phosphorus composite plating bath to prepare the method for graphene oxide nickel-phosphorus composite deposit, the graphene oxide nickel-phosphorus composite deposit that the method obtains solves above-mentioned Graphene nickel-phosphorus composite deposit problem uniform and smooth not, namely hydrophilic graphene oxide is employed, and pre-treatment is carried out to it, make its surface being deposited on metallic matrix more easily, uniformly thus form the graphene oxide nickel-phosphorus composite deposit with features such as excellent wear resisting property, smooth in appearance are attractive in appearance.
Technical scheme of the present invention
A kind of graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 0.5-1g after reduction treatment
Single nickel salt 25-40g
Inferior sodium phosphate 15-20g
Sodium acetate 15g
Citric acid 8-10g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
The preparation method of above-mentioned a kind of graphene oxide nickel phosphorus composite plating bath, specifically comprises the steps:
(1) preparation of the graphene oxide, after reduction treatment, step is as follows:
1., graphene oxide cleaning
Joined by graphene oxide in scavenging solution, ultrasonic disperse 5-30min, then suction filtration at 40 DEG C, gained filter cake deionized water wash at least three times, obtains through cleaned graphene oxide;
The NaOH aqueous solution of described scavenging solution to be mass percent concentration be 10-40% or mass percent concentration are the KOH aqueous solution of 10-40%;
2., graphene oxide sensitization
To transfer in sensitizing solution through cleaned graphene oxide, ultrasonic disperse 15-30min, then suction filtration under room temperature, gained filter cake deionized water wash at least three times, obtains the graphene oxide after sensitized treatment;
Described sensitizing solution is for containing HCl and SnCl
2the aqueous solution, wherein HCl concentration is 10-30mL/L, SnCl
2concentration is 10-40g/L;
3., graphene oxide activation
Under room temperature, the graphene oxide after sensitized treatment is placed in activation solution, ultrasonic disperse 10-60min, then suction filtration, gained filter cake deionized water wash at least three times, obtains the graphene oxide after activated process;
Described activation solution is for containing HCl and PdCl
2the aqueous solution, wherein HCl concentration is 10-30mL/L, PdCl
2concentration is 0.1-0.5g/L;
4., graphene oxide reduction
Under room temperature, graphene oxide after activated process being joined concentration is in the reductive agent aqueous solution of 20-50g/L, supersound process 20-40min, then suction filtration, gained filter cake is extremely neutral with deionized water wash, control temperature is 20-60 DEG C and carries out vacuum-drying, obtains the graphene oxide after reduction treatment;
Described reductive agent is the mixture of one or more compositions in sodium hypophosphite, sodium borohydride, diethylamine borane;
(2), graphene oxide nickel phosphorus composite plating bath preparation
By often liter of calculating, the distilled water of 20-40g single nickel salt, 15-20g inferior sodium phosphate, 15g sodium acetate, 8-10g citric acid, 4ml lactic acid, 41ml one package stabilizer and surplus is carried out mixing and after dissolving, be that the aqueous sodium hydroxide solution adjust ph of 10% is to 4-6 with mass percent concentration, then control temperature is at 50-70 DEG C, the graphene oxide after reduction treatment of 0.5-1g step (1) gained is added wherein, ultrasonic disperse process 10min, obtains graphene oxide nickel phosphorus composite plating bath.
Above-mentioned graphene oxide nickel phosphorus composite plating bath, preparing the application in graphene oxide nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
By the surface of steel and alloy workpiece successively after 320# and 280# coated abrasive working, first with temperature be 80-100 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 15-20min, distilled water flushing 1min; Then be the aqueous hydrochloric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Be finally the aqueous hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in graphene oxide nickel phosphorus composite plating bath, under agitation condition, control temperature is 50-70 DEG C, insulation 30-90 min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain one deck graphene oxide nickel-phosphorus composite deposit on the surface of iron and steel parts.
The plated surface of above-mentioned gained has the graphene oxide nickel phosphorus Composite Coatings coating on the steel and alloy workpiece of graphene oxide nickel phosphorus Composite Coatings coating, namely in the mode of chemical nickel plating, jointly deposited in coating with nickel-phosphorus alloy by graphene oxide particulate and form graphene oxide nickel-phosphorus composite deposit, the structure of the graphene oxide nickel phosphorus Composite Coatings coating formed is born of the same parents' shape, non-crystal structure.
Beneficial effect of the present invention
The preparation method of a kind of graphene oxide nickel phosphorus composite plating bath of the present invention and coating thereof, owing to carrying out pre-treatment to graphene oxide and steel substrate, then prepares composite plating bath with pretreated amphipathic graphene oxide, reaction is more easily carried out.The preparation of graphene oxide nickel-phosphorus composite deposit can be realized under relatively mild temperature of reaction (50-70 DEG C), thus reduce energy consumption.
A kind of graphene oxide nickel phosphorus composite plating bath of the present invention, owing to adding pretreated graphene oxide in original ni-p electroless plating, prepare graphene oxide nickel phosphorus composite plating bath, then on steel substrate after the pre-treatment, codeposition forms graphene oxide nickel phosphorus Composite Coatings coating.This composite deposite is due to the existence of abrasion-proof particle graphene oxide, and wear resistance strengthens, and polishing scratch sectional area can reach 20-25um after testing
2, solve the problem that nickel-phosphorus chemical plating in prior art wears no resistance.
Further, utilize the preparation method of a kind of graphene oxide nickel-phosphorus composite deposit of the present invention, adopt and pre-treatment is carried out to graphene oxide and steel substrate, then plating.When the plating of steel and alloy workpiece surface, the composite deposite more smooth even of formation, the basis retaining the good wear resistance of coating solves smooth not, the uniform problem of Graphene coating.
Accompanying drawing explanation
The plated surface of Fig. 1 a, Application Example 1 gained has the scanning electron microscope (SEM) photograph of the coating surface of the steel and alloy plating piece A of graphene oxide nickel-phosphorus composite deposit;
The surface of Fig. 1 b, application comparative examples 1 gained is coated with the scanning electron microscope (SEM) photograph of the coating surface of the steel and alloy plating piece B of Graphene nickel-phosphorus composite deposit;
The plated surface of Fig. 2 a, Application Example 2 gained has the scanning electron microscope (SEM) photograph of the coating surface of the steel and alloy plating piece A of graphene oxide nickel-phosphorus composite deposit;
The surface of Fig. 2 b, application comparative examples 2 gained is coated with the scanning electron microscope (SEM) photograph of the coating surface of the steel and alloy plating piece B of Graphene nickel-phosphorus composite deposit.
The plated surface of Fig. 3 a, Application Example 3 gained has the scanning electron microscope (SEM) photograph of the coating surface of the steel and alloy plating piece A of graphene oxide nickel-phosphorus composite deposit;
The surface of Fig. 3 b, application comparative examples 3 gained is coated with the scanning electron microscope (SEM) photograph of the coating surface of the steel and alloy plating piece B of Graphene nickel-phosphorus composite deposit.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described, but the present invention is not limited to following embodiment.
Various raw materials used in various embodiments of the present invention, if no special instructions, are commercially available.
embodiment 1
A kind of graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 0.5g after reduction treatment
Single nickel salt 25g
Inferior sodium phosphate 15g
Sodium acetate 15g
Citric acid 8g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
The preparation method of above-mentioned a kind of graphene oxide nickel phosphorus composite plating bath, specifically comprises the steps:
(1) preparation of the graphene oxide, after reduction treatment, step is as follows:
1., graphene oxide cleaning
Joined by graphene oxide in scavenging solution, ultrasonic disperse 20min, then suction filtration at 40 DEG C, gained filter cake deionized water wash at least three times, obtains through cleaned graphene oxide;
Described scavenging solution to be mass percent concentration be 20% the NaOH aqueous solution;
2., graphene oxide sensitization
To transfer in sensitizing solution through cleaned graphene oxide, ultrasonic disperse 20min, then suction filtration under room temperature, gained filter cake deionized water wash at least three times, obtains the graphene oxide after sensitized treatment;
Described sensitizing solution is for containing HCl and SnCl
2the aqueous solution, wherein HCl concentration is 10mL/L, SnCl
2concentration is 10g/L;
3., graphene oxide activation
Under room temperature, the graphene oxide after sensitized treatment is placed in activation solution, ultrasonic disperse 30min, then suction filtration, gained filter cake deionized water wash at least three times, obtains the graphene oxide after activated process;
Described activation solution is for containing HCl and PdCl
2the aqueous solution, wherein HCl concentration is 10mL/L, PdCl
2concentration is 0.1g/L;
4., graphene oxide reduction
Under room temperature, the graphene oxide after activated process being joined concentration is in the reductive agent aqueous solution of 20 g/L, supersound process 30min, then suction filtration, gained filter cake is with deionized water wash to neutral, and control temperature is 50 DEG C and carries out vacuum-drying, obtains the graphene oxide after reduction treatment;
Described reductive agent is sodium hypophosphite.
(2), graphene oxide nickel phosphorus composite plating bath preparation
By often liter of calculating, the distilled water of 25g single nickel salt, 15g inferior sodium phosphate, 15g sodium acetate, 8g citric acid, 4ml lactic acid, 41ml one package stabilizer and surplus is carried out mixing and after dissolving, by the aqueous sodium hydroxide solution adjust ph to 4.8 that mass percent concentration is 10%, then control temperature is 70 DEG C, the graphene oxide after reduction treatment of 0.5g step (1) gained is added wherein, ultrasonic disperse process 10min, obtains graphene oxide nickel phosphorus composite plating bath.
application Example 1
The graphene oxide nickel phosphorus composite plating bath of embodiment 1 gained, preparing the application in graphene oxide nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
By the surface of steel and alloy workpiece successively after 320# and 280# coated abrasive working, first with temperature be 80 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 20min, distilled water flushing 1min; Then be the aqueous hydrochloric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Be finally the aqueous hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in the graphene oxide nickel phosphorus composite plating bath of embodiment 1 gained, under agitation condition, control temperature is 70 DEG C, insulation 60min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain one deck graphene oxide nickel-phosphorus composite deposit A1 on the surface of iron and steel parts.
Adopt scanning electronic microscope instrument (Hitachi scanning electronic microscope S-3400N) the above-mentioned surface at iron and steel parts to be obtained one deck graphene oxide nickel-phosphorus composite deposit A1 to scan, the scanning electron microscope (SEM) photograph of gained, as shown in 1a, can find out that from Fig. 1 a the black alkene nickel-phosphorus composite deposit surface of oxidation is born of the same parents' shape, non-crystal structure.
application comparative examples 1
A kind of Graphene nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene 0.5g
Single nickel salt 25g
Inferior sodium phosphate 15g
Sodium acetate 15g
Citric acid 8g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
Adopt the Graphene nickel phosphorus composite plating bath of above-mentioned gained, it, preparing the application in Graphene nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
The surface of steel and alloy workpiece is removed through 320# and 280# coated abrasive working successively, first with temperature be 80 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 20min, distilled water flushing 1min; And then be the chlorohydric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Finally, be the hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in Graphene nickel phosphorus composite plating bath, under agitation condition, control temperature is 90 DEG C, insulation 60min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain a layer graphene nickel-phosphorus composite deposit B1 on the surface of iron and steel parts.
Adopt scanning electronic microscope instrument (Hitachi scanning electronic microscope S-3400N) the above-mentioned surface at iron and steel parts to be obtained a layer graphene nickel-phosphorus composite deposit B1 to scan, the scanning electron microscope (SEM) photograph of gained, as shown in 1b, can find out that from Fig. 1 b Graphene nickel-phosphorus composite deposit surface is for particulate state, concavo-convex non-crystal structure.
Comparison diagram 1a and Fig. 1 b, can find out, adopts the graphene oxide nickel phosphorus composite plating bath of embodiment 1 gained to carry out the graphene oxide nickel-phosphorus composite deposit A1 of gained after electroless plating more even, smooth.
The above-mentioned surface at iron and steel parts is obtained the method (Shao Jianbing that one deck graphene oxide nickel-phosphorus composite deposit A1 and Graphene nickel-phosphorus composite deposit B1 adopts contrast polishing scratch sectional area respectively, Zhu Yongwei etc., Ni-P-diamond chemical composite plating Study on Wear-resistance, diamond and grinding materials and grinding tool engineering, 2008), detect at MMD-1 multifunction friction wear trier (Jinan Yihua Tribology Testing Technology Co., Ltd.), its polishing scratch sectional area is respectively at 20-25um
2and 35-40um
2, show thus, the above-mentioned one deck graphene oxide nickel-phosphorus composite deposit A1 obtained at surface of steel workpiece has good wear resistance.
By contrasting the plating process of Application Example 1 and application comparative examples 1, can to find out in Application Example 1 that graphene oxide composite plating bath can at the temperature of gentleness 70 DEG C, form even and that wear resisting property is good composite deposite, and the Graphene composite plating bath applied in comparative examples 1 needs to carry out plating at 90 DEG C, even and that wear resisting property is good composite deposite could be formed.Show thus, utilize a kind of graphene oxide nickel phosphorus composite plating bath of the present invention can prepare even, the better graphene oxide nickel-phosphorus composite deposit of wear resisting property under the condition reducing energy consumption.
embodiment 2
A kind of graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 1g after reduction treatment
Single nickel salt 40g
Inferior sodium phosphate 20g
Sodium acetate 15g
Citric acid 10g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
The preparation method of above-mentioned a kind of graphene oxide nickel phosphorus composite plating bath, specifically comprises the steps:
(1) preparation of the graphene oxide, after reduction treatment, step is as follows:
1., graphene oxide cleaning
Joined by graphene oxide in scavenging solution, ultrasonic disperse 20min, then suction filtration at 40 DEG C, gained filter cake deionized water wash at least three times, obtains through cleaned graphene oxide;
Described scavenging solution to be mass percent concentration be 40% the NaOH aqueous solution;
2., graphene oxide sensitization
To transfer in sensitizing solution through cleaned graphene oxide, ultrasonic disperse 20min, then suction filtration under room temperature, gained filter cake deionized water wash at least three times, obtains the graphene oxide after sensitized treatment;
Described sensitizing solution is for containing HCl and SnCl
2the aqueous solution, wherein HCl concentration is 30mL/L, SnCl
2concentration is 40g/L;
3., graphene oxide activation
Under room temperature, the graphene oxide after sensitized treatment is placed in activation solution, ultrasonic disperse 30min, then suction filtration, gained filter cake deionized water wash at least three times, obtains the graphene oxide after activated process;
Described activation solution is for containing HCl and PdCl
2the aqueous solution, wherein HCl concentration is 30mL/L, PdCl
2concentration is 0.5g/L;
4., graphene oxide reduction
Under room temperature, the graphene oxide after activated process being joined concentration is in the reductive agent aqueous solution of 40g/L, supersound process 30min, then suction filtration, gained filter cake is with deionized water wash to neutral, and control temperature is 50 DEG C and carries out vacuum-drying, obtains the graphene oxide after reduction treatment;
Described reductive agent is sodium hypophosphite;
(2), graphene oxide nickel phosphorus composite plating bath preparation
By often liter of calculating, the distilled water of 40g single nickel salt, 20g inferior sodium phosphate, 15g sodium acetate, 10g citric acid, 4ml lactic acid, 41ml one package stabilizer and surplus is carried out mixing and after dissolving, by the aqueous sodium hydroxide solution adjust ph to 4.8 that mass percent concentration is 10%, then control temperature is at 50 DEG C, the graphene oxide after reduction treatment of 1g step (1) gained is added wherein, ultrasonic disperse process 10min, obtains graphene oxide nickel phosphorus composite plating bath.
application Example 2
The graphene oxide nickel phosphorus composite plating bath of embodiment 2 gained, preparing the application in graphene oxide nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
The surface of steel and alloy workpiece is removed through 320# and 280# coated abrasive working successively, first with temperature be 80 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 20min, distilled water flushing 1min; And then be the chlorohydric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Finally, be the hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in graphene oxide nickel phosphorus composite plating bath, under agitation condition, control temperature is 50 DEG C, insulation 60min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain one deck graphene oxide nickel-phosphorus composite deposit A2 on the surface of iron and steel parts.
Adopt scanning electronic microscope instrument (Hitachi scanning electronic microscope S-3400N) the above-mentioned surface at iron and steel parts to be obtained one deck graphene oxide nickel-phosphorus composite deposit A2 to scan, the scanning electron microscope (SEM) photograph of gained, as shown in 2a, can find out that from Fig. 2 a the black alkene nickel-phosphorus composite deposit surface of oxidation is born of the same parents' shape, non-crystal structure.
application comparative examples 2
A kind of Graphene nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene 1g
Single nickel salt 40g
Inferior sodium phosphate 20g
Sodium acetate 15g
Citric acid 10g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
The Graphene nickel phosphorus composite plating bath of above-mentioned gained, preparing the application in Graphene nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
By the surface of steel and alloy workpiece successively after 320# and 280# coated abrasive working, first with temperature be 80 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 20min, distilled water flushing 1min; Then be the aqueous hydrochloric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Be finally the aqueous hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in Graphene nickel phosphorus composite plating bath, under agitation condition, control temperature is 70 DEG C, insulation 60min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain a layer graphene nickel-phosphorus composite deposit B2 on the surface of iron and steel parts.
Adopt scanning electronic microscope instrument (Hitachi scanning electronic microscope S-3400N) the above-mentioned surface at iron and steel parts to be obtained a layer graphene nickel-phosphorus composite deposit B2 to scan, the scanning electron microscope (SEM) photograph of gained, as shown in 2b, can find out that from Fig. 2 b Graphene nickel-phosphorus composite deposit surface is particulate state, concavo-convex non-crystal structure and have obvious gully shape.
Comparison diagram 2a and Fig. 2 b, can find out, adopts the graphene oxide nickel phosphorus composite plating bath of embodiment 2 gained to carry out the graphene oxide nickel-phosphorus composite deposit A2 of gained after electroless plating more even, smooth.
The above-mentioned surface at iron and steel parts is obtained the method (Shao Jianbing that one deck graphene oxide nickel-phosphorus composite deposit A2 and Graphene nickel-phosphorus composite deposit B2 adopts contrast polishing scratch sectional area respectively, Zhu Yongwei etc., Ni-P-diamond chemical composite plating Study on Wear-resistance, diamond and grinding materials and grinding tool engineering, 2008), detect at MMD-1 multifunction friction wear trier (Jinan Yihua Tribology Testing Technology Co., Ltd.), its polishing scratch sectional area is respectively at 20-25um
2and 35-40um
2, show thus, the above-mentioned surface at iron and steel parts obtains one deck graphene oxide nickel-phosphorus composite deposit A2 and has good wear resistance.
By contrasting Application Example 2 and application comparative examples 2, can find out, in Application Example 2, graphene oxide composite plating bath can at the temperature of gentleness 50 DEG C, form even and that wear resisting property is good composite deposite, and the Graphene composite plating bath applied in comparative examples 2 needs to carry out plating at 70 DEG C, even and that wear resisting property is good composite deposite could be formed.Show thus, utilize a kind of graphene oxide nickel phosphorus composite plating bath of the present invention can prepare even, the better graphene oxide nickel-phosphorus composite deposit of wear resisting property under the condition reducing energy consumption.
embodiment 3
A kind of graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 0.75g after reduction treatment
Single nickel salt 30g
Inferior sodium phosphate 17g
Sodium acetate 15g
Citric acid 9g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
The preparation method of above-mentioned a kind of graphene oxide nickel phosphorus composite plating bath, specifically comprises the steps:
(1) preparation of the graphene oxide, after reduction treatment, step is as follows:
1., graphene oxide cleaning
Joined by graphene oxide in scavenging solution, ultrasonic disperse 20min, then suction filtration at 40 DEG C, gained filter cake deionized water wash at least three times, obtains through cleaned graphene oxide;
Described scavenging solution to be mass percent concentration be 30% the NaOH aqueous solution;
2., graphene oxide sensitization
To transfer in sensitizing solution through cleaned graphene oxide, ultrasonic disperse 20min, then suction filtration under room temperature, gained filter cake deionized water wash at least three times, obtains the graphene oxide after sensitized treatment;
Described sensitizing solution is for containing HCl and SnCl
2the aqueous solution, wherein HCl concentration is 20mL/L, SnCl
2concentration is 25g/L;
3., graphene oxide activation
Under room temperature, the graphene oxide after sensitized treatment is placed in activation solution, ultrasonic disperse 30min, then suction filtration, gained filter cake deionized water wash at least three times, obtains the graphene oxide after activated process;
Described activation solution is for containing HCl and PdCl
2the aqueous solution, wherein HCl concentration is 20mL/L, PdCl
2concentration is 0.3g/L;
4., graphene oxide reduction
Under room temperature, the graphene oxide after activated process being joined concentration is in the reductive agent aqueous solution of 30 g/L, supersound process 30min, then suction filtration, gained filter cake is with deionized water wash to neutral, and control temperature is 50 DEG C and carries out vacuum-drying, obtains the graphene oxide after reduction treatment;
Described reductive agent is sodium hypophosphite;
(2), graphene oxide nickel phosphorus composite plating bath preparation
By often liter of calculating, the distilled water of 30g single nickel salt, 17g inferior sodium phosphate, 15g sodium acetate, 9g citric acid, 4ml lactic acid, 41ml one package stabilizer and surplus is carried out mixing and after dissolving, by the aqueous sodium hydroxide solution adjust ph to 4.8 that mass percent concentration is 10%, then control temperature is 60 DEG C, the graphene oxide after reduction treatment of 0.5g step (1) gained is added wherein, ultrasonic disperse process 10min, obtains graphene oxide nickel phosphorus composite plating bath.
application Example 3
The graphene oxide nickel phosphorus composite plating bath of embodiment 3 gained, preparing the application in graphene oxide nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
By the surface of steel and alloy workpiece successively after 320# and 280# coated abrasive working, first with temperature be 80 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 20min, distilled water flushing 1min; Then be the aqueous hydrochloric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Be finally the aqueous hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in the graphene oxide nickel phosphorus composite plating bath of embodiment 3 gained, under agitation condition, control temperature is 70 DEG C, insulation 60min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain one deck graphene oxide nickel-phosphorus composite deposit A3 on the surface of iron and steel parts.
Adopt scanning electronic microscope instrument (Hitachi scanning electronic microscope S-3400N) the above-mentioned surface at iron and steel parts to be obtained one deck graphene oxide nickel-phosphorus composite deposit A3 to scan, the scanning electron microscope (SEM) photograph of gained, as shown in 3a, can find out that from Fig. 3 a the black alkene nickel-phosphorus composite deposit surface of oxidation is born of the same parents' shape, non-crystal structure.
application comparative examples 3
A kind of Graphene nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene 0.75g
Single nickel salt 30g
Inferior sodium phosphate 17g
Sodium acetate 15g
Citric acid 9g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited.
Adopt the Graphene nickel phosphorus composite plating bath of above-mentioned gained, it, preparing the application in Graphene nickel-phosphorus composite deposit, specifically comprises the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
The surface of steel and alloy workpiece is removed through 320# and 280# coated abrasive working successively, first with temperature be 80 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 20min, distilled water flushing 1min; And then be the chlorohydric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Finally, be the hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in Graphene nickel phosphorus composite plating bath, under agitation condition, control temperature is 80 DEG C, insulation 60min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain a layer graphene nickel-phosphorus composite deposit B3 on the surface of iron and steel parts.
Adopt scanning electronic microscope instrument (Hitachi scanning electronic microscope S-3400N) the above-mentioned surface at iron and steel parts to be obtained a layer graphene nickel-phosphorus composite deposit B3 to scan, the scanning electron microscope (SEM) photograph of gained, as shown in 3b, can find out that from Fig. 3 b Graphene nickel-phosphorus composite deposit surface is for particulate state, concavo-convex non-crystal structure.
Comparison diagram 3a and Fig. 3 b, can find out, adopts the graphene oxide nickel phosphorus composite plating bath of embodiment 3 gained to carry out the graphene oxide nickel-phosphorus composite deposit A3 of gained after electroless plating more even, smooth.
The above-mentioned surface at iron and steel parts is obtained the method (Shao Jianbing that one deck graphene oxide nickel-phosphorus composite deposit A3 and Graphene nickel-phosphorus composite deposit B3 adopts contrast polishing scratch sectional area respectively, Zhu Yongwei etc., Ni-P-diamond chemical composite plating Study on Wear-resistance, diamond and grinding materials and grinding tool engineering, 2008), detect at MMD-1 multifunction friction wear trier (Jinan Yihua Tribology Testing Technology Co., Ltd.), its polishing scratch sectional area is respectively at 20-25um
2and 35-40um
2, show thus, the above-mentioned surface at iron and steel parts obtains one deck graphene oxide nickel-phosphorus composite deposit A3 and has good wear resistance.
By contrasting the plating process of Application Example 3 and application comparative examples 3, can to find out in Application Example 3 that graphene oxide composite plating bath can at the temperature of gentleness 60 DEG C, form even and that wear resisting property is good composite deposite, and the Graphene composite plating bath applied in comparative examples 3 needs to carry out plating at 80 DEG C, even and that wear resisting property is good composite deposite could be formed.Show thus, utilize a kind of graphene oxide nickel phosphorus composite plating bath of the present invention can prepare even, the better graphene oxide nickel-phosphorus composite deposit of wear resisting property under the condition reducing energy consumption.
Above-mentioned Application Example 1-3 illustrates that graphene oxide nickel phosphorus composite plating bath can form even, wear-resisting graphene oxide nickel-phosphorus composite deposit under the condition of gentleer (50-70 DEG C).And apply in comparative examples 1-3 and replace graphene oxide with Graphene at identical conditions, temperature is improved 20 DEG C and carries out plating, prepare Graphene nickel-phosphorus composite deposit; The coating contrasting gained respectively finds, graphene oxide nickel-phosphorus composite deposit is, smooth surface, tight more even than Graphene nickel-phosphorus composite deposit thickness not only, and has higher wear resisting property.
In sum, a kind of graphene oxide nickel phosphorus composite plating bath of the present invention, at lower temperature and 50-70 DEG C, plating can be carried out to iron and steel, the graphene oxide nickel phosphorus Composite Coatings thickness of gained evenly, smooth surface, tight, and there is higher wear resisting property.And preparation method is simple, can be continuously produced.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (6)
1. a graphene oxide nickel phosphorus composite plating bath, is characterized in that described graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 0.5-1g after reduction treatment
Single nickel salt 25-40g
Inferior sodium phosphate 15-20g
Sodium acetate 15g
Citric acid 8-10g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water;
Described one package stabilizer, by thiocarbamide, Potassium Iodate and potassiumiodide, calculates, i.e. thiocarbamide: Potassium Iodate in mass ratio: potassiumiodide is that the ratio of 1:20:20 is composited;
The described graphene oxide after reduction treatment is prepared from as follows:
Graphene oxide cleans
Joined by graphene oxide in scavenging solution, ultrasonic disperse 5-30min, then suction filtration at 40 DEG C, gained filter cake deionized water wash at least three times, obtains through cleaned graphene oxide;
The NaOH aqueous solution of described scavenging solution to be mass percent concentration be 10-40% or mass percent concentration are the KOH aqueous solution of 10-40%;
2., graphene oxide sensitization
To transfer in sensitizing solution through cleaned graphene oxide, ultrasonic disperse 15-30min, then suction filtration under room temperature, gained filter cake deionized water wash at least three times, obtains the graphene oxide after sensitized treatment;
Described sensitizing solution is for containing HCl and SnCl
2the aqueous solution, wherein HCl concentration is 10-30mL/L, SnCl
2concentration is 10-40g/L;
3., graphene oxide activation
Under room temperature, the graphene oxide after sensitized treatment is placed in activation solution, ultrasonic disperse 10-60min, then suction filtration, gained filter cake deionized water wash at least three times, obtains the graphene oxide after activated process;
Described activation solution is for containing HCl and PdCl
2the aqueous solution, wherein HCl concentration is 10-30mL/L, PdCl
2concentration is 0.1-0.5g/L;
4., graphene oxide reduction
Under room temperature, graphene oxide after activated process being joined concentration is in the reductive agent aqueous solution of 20-50g/L, supersound process 20-40min, suction filtration, gained filter cake are extremely neutral with deionized water wash, control temperature is 20-60 DEG C and carries out vacuum-drying, obtains the graphene oxide after reduction treatment;
Described reductive agent is the mixture of one or more compositions in sodium hypophosphite, sodium borohydride, diethylamine borane.
2. a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, is characterized in that described graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 0.5g after reduction treatment
Single nickel salt 25g
Inferior sodium phosphate 15g
Sodium acetate 15g
Citric acid 8g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water.
3. a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, is characterized in that described graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 1g after reduction treatment
Single nickel salt 40g
Inferior sodium phosphate 20g
Sodium acetate 15g
Citric acid 10g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water.
4. a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, is characterized in that described graphene oxide nickel phosphorus composite plating bath, by often liter of calculatings, its raw material form and content as follows:
Graphene oxide 0.75g after reduction treatment
Single nickel salt 30g
Inferior sodium phosphate 17g
Sodium acetate 15g
Citric acid 9g
Lactic acid 4ml
One package stabilizer 41mg
Surplus is distilled water.
5. the preparation method of a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, is characterized in that specifically comprising the steps:
(1) preparation of the graphene oxide, after reduction treatment, step is as follows:
1., graphene oxide cleaning
Joined by graphene oxide in scavenging solution, ultrasonic disperse 5-30min, then suction filtration at 40 DEG C, gained filter cake deionized water wash at least three times, obtains through cleaned graphene oxide;
The NaOH aqueous solution of described scavenging solution to be mass percent concentration be 10-40% or mass percent concentration are the KOH aqueous solution of 10-40%;
2., graphene oxide sensitization
To transfer in sensitizing solution through cleaned graphene oxide, ultrasonic disperse 15-30min, then suction filtration under room temperature, gained filter cake deionized water wash at least three times, obtains the graphene oxide after sensitized treatment;
Described sensitizing solution is for containing HCl and SnCl
2the aqueous solution, wherein HCl concentration is 10-30mL/L, SnCl
2concentration is 10-40g/L;
3., graphene oxide activation
Under room temperature, the graphene oxide after sensitized treatment is placed in activation solution, ultrasonic disperse 10-60min, then suction filtration, gained filter cake deionized water wash at least three times, obtains the graphene oxide after activated process;
Described activation solution is for containing HCl and PdCl
2the aqueous solution, wherein HCl concentration is 10-30mL/L, PdCl
2concentration is 0.1-0.5g/L;
4., graphene oxide reduction
Under room temperature, graphene oxide after activated process being joined concentration is in the reductive agent aqueous solution of 20-50g/L, supersound process 20-40min, then suction filtration, gained filter cake is extremely neutral with deionized water wash, control temperature is 20-60 DEG C and carries out vacuum-drying, obtains the graphene oxide after reduction treatment;
Described reductive agent is the mixture of one or more compositions in sodium hypophosphite, sodium borohydride, diethylamine borane;
(2), graphene oxide nickel phosphorus composite plating bath preparation
Single nickel salt, inferior sodium phosphate, sodium acetate, citric acid, lactic acid, one package stabilizer and distilled water are carried out mixing and after dissolving, be that the aqueous sodium hydroxide solution adjust ph of 10% is to 4-6 with mass percent concentration, then control temperature is between 50-70 DEG C, the graphene oxide after reduction treatment of step (1) gained is added wherein, ultrasonic disperse process 10min, obtains graphene oxide nickel phosphorus composite plating bath.
6. graphene oxide nickel phosphorus composite plating bath as claimed in claim 1 is preparing the application in graphene oxide nickel-phosphorus composite deposit, it is characterized in that specifically comprising the steps:
(1) pre-treatment of steel and alloy workpiece surface, to be plated
By the surface of steel and alloy workpiece successively after 320# and 280# coated abrasive working, first with temperature be 80-100 DEG C, mass percent concentration be 20% aqueous sodium hydroxide solution wash 15-20min, distilled water flushing 1min; Then be the aqueous hydrochloric acid pickling 30s of 10% with mass percent concentration, use distilled water flushing 1min; Be finally the aqueous hydrochloric acid activation 30s of 5% with mass percent concentration, use distilled water flushing 1min, namely complete the pre-treatment of steel and alloy workpiece surface to be plated;
(2), steel and alloy workpiece to be plated after step (1) pre-treatment is put in graphene oxide nickel phosphorus composite plating bath, under agitation condition, control temperature is at 50-70 DEG C, insulation 30-90 min, then take out, wash with the mixed solution be made up of for 1:3 by volume deionized water and ethanol, until scrub stream fluid is in neutral, then 105 DEG C of dryings, namely obtain one deck graphene oxide nickel-phosphorus composite deposit on the surface of iron and steel parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510133589.7A CN104862676B (en) | 2015-03-25 | 2015-03-25 | A kind of graphene oxide nickel phosphorus composite plating bath and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510133589.7A CN104862676B (en) | 2015-03-25 | 2015-03-25 | A kind of graphene oxide nickel phosphorus composite plating bath and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104862676A true CN104862676A (en) | 2015-08-26 |
| CN104862676B CN104862676B (en) | 2017-08-25 |
Family
ID=53908830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510133589.7A Active CN104862676B (en) | 2015-03-25 | 2015-03-25 | A kind of graphene oxide nickel phosphorus composite plating bath and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104862676B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441911A (en) * | 2015-11-19 | 2016-03-30 | 上海应用技术学院 | Chemical plating solution used for chemically plating Ni-B/GO composite coating on surface of SiCp/Al material and application thereof |
| CN105797756A (en) * | 2016-04-20 | 2016-07-27 | 燕山大学 | Preparation method of molybdenum disulfide-graphite-nickel phosphorus hydrogen evolution composite |
| CN105839082A (en) * | 2016-06-13 | 2016-08-10 | 上海应用技术学院 | Ce-Ni-B/GO chemical composite deposition layer and ultrasonic-assisted preparation method thereof |
| JP2017052978A (en) * | 2015-09-07 | 2017-03-16 | 新光電気工業株式会社 | Heat radiation part and production method thereof |
| CN107916415A (en) * | 2017-11-21 | 2018-04-17 | 北京理工大学 | The preparation method of graphene phosphatization nickel composite deposite and the coating being prepared |
| CN108503921A (en) * | 2018-05-23 | 2018-09-07 | 江南大学 | A kind of preparation method of thiocarbamide functionalized nano Graphene antibiosis material |
| CN108823553A (en) * | 2018-07-25 | 2018-11-16 | 芜湖昌菱金刚石工具有限公司 | A kind of preparation method of diamond surface Electroless Ni-P Plating |
| CN108930031A (en) * | 2018-07-25 | 2018-12-04 | 芜湖昌菱金刚石工具有限公司 | A kind of preparation method of diamond surface Electroless Ni-W-P coating |
| CN110565081A (en) * | 2019-09-11 | 2019-12-13 | 贵州航天电器股份有限公司 | chemical composite nickel-phosphorus-graphene plating solution and preparation method and application thereof |
| CN111424266A (en) * | 2020-03-19 | 2020-07-17 | 西安工程大学 | Preparation method of nickel-coated graphite composite particles |
| CN112210771A (en) * | 2020-10-26 | 2021-01-12 | 长沙岱勒新材料科技股份有限公司 | Method for chemically plating nickel on surface of diamond |
| CN112973459A (en) * | 2021-03-09 | 2021-06-18 | 万华化学集团股份有限公司 | Fluoropolymer hollow fiber porous membrane and preparation method thereof |
| CN114523104A (en) * | 2021-01-05 | 2022-05-24 | 南京工业大学 | Surface nickel-phosphorus-plated graphene reinforced titanium-based composite material and preparation method thereof |
| CN115058746A (en) * | 2022-07-07 | 2022-09-16 | 中国人民解放军陆军装甲兵学院 | Metal coating, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544707A (en) * | 2003-11-13 | 2004-11-10 | 上海交通大学 | Process for preparing nickel-based nano-tube composite material by composite electrodeposition |
| CN103556136A (en) * | 2013-08-26 | 2014-02-05 | 上海应用技术学院 | Graphene-nickel-phosphorus chemical plating liquid, and preparation method and application thereof |
-
2015
- 2015-03-25 CN CN201510133589.7A patent/CN104862676B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544707A (en) * | 2003-11-13 | 2004-11-10 | 上海交通大学 | Process for preparing nickel-based nano-tube composite material by composite electrodeposition |
| CN103556136A (en) * | 2013-08-26 | 2014-02-05 | 上海应用技术学院 | Graphene-nickel-phosphorus chemical plating liquid, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| （美）格迪斯（GHODSSI，R.）等: "《MEMS材料与工艺手册》", 31 March 2014, 东南大学出版社 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017052978A (en) * | 2015-09-07 | 2017-03-16 | 新光電気工業株式会社 | Heat radiation part and production method thereof |
| CN105441911A (en) * | 2015-11-19 | 2016-03-30 | 上海应用技术学院 | Chemical plating solution used for chemically plating Ni-B/GO composite coating on surface of SiCp/Al material and application thereof |
| CN105797756A (en) * | 2016-04-20 | 2016-07-27 | 燕山大学 | Preparation method of molybdenum disulfide-graphite-nickel phosphorus hydrogen evolution composite |
| CN105797756B (en) * | 2016-04-20 | 2018-05-01 | 燕山大学 | The preparation method of molybdenum disulfide-graphite-nickel phosphorus liberation of hydrogen composite material |
| CN105839082A (en) * | 2016-06-13 | 2016-08-10 | 上海应用技术学院 | Ce-Ni-B/GO chemical composite deposition layer and ultrasonic-assisted preparation method thereof |
| CN107916415A (en) * | 2017-11-21 | 2018-04-17 | 北京理工大学 | The preparation method of graphene phosphatization nickel composite deposite and the coating being prepared |
| CN108503921A (en) * | 2018-05-23 | 2018-09-07 | 江南大学 | A kind of preparation method of thiocarbamide functionalized nano Graphene antibiosis material |
| CN108930031A (en) * | 2018-07-25 | 2018-12-04 | 芜湖昌菱金刚石工具有限公司 | A kind of preparation method of diamond surface Electroless Ni-W-P coating |
| CN108823553A (en) * | 2018-07-25 | 2018-11-16 | 芜湖昌菱金刚石工具有限公司 | A kind of preparation method of diamond surface Electroless Ni-P Plating |
| CN110565081A (en) * | 2019-09-11 | 2019-12-13 | 贵州航天电器股份有限公司 | chemical composite nickel-phosphorus-graphene plating solution and preparation method and application thereof |
| CN111424266A (en) * | 2020-03-19 | 2020-07-17 | 西安工程大学 | Preparation method of nickel-coated graphite composite particles |
| CN112210771A (en) * | 2020-10-26 | 2021-01-12 | 长沙岱勒新材料科技股份有限公司 | Method for chemically plating nickel on surface of diamond |
| CN114523104A (en) * | 2021-01-05 | 2022-05-24 | 南京工业大学 | Surface nickel-phosphorus-plated graphene reinforced titanium-based composite material and preparation method thereof |
| CN112973459A (en) * | 2021-03-09 | 2021-06-18 | 万华化学集团股份有限公司 | Fluoropolymer hollow fiber porous membrane and preparation method thereof |
| CN112973459B (en) * | 2021-03-09 | 2022-08-05 | 万华化学集团股份有限公司 | Fluoropolymer hollow fiber porous membrane and preparation method thereof |
| CN115058746A (en) * | 2022-07-07 | 2022-09-16 | 中国人民解放军陆军装甲兵学院 | Metal coating, preparation method and application thereof |
| CN115058746B (en) * | 2022-07-07 | 2024-04-12 | 中国人民解放军陆军装甲兵学院 | Metal coating, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104862676B (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104862676A (en) | Graphene oxide nickel-phosphorus composite plating solution, preparation method and applications thereof | |
| CN103556136B (en) | A kind of Graphene nickel-phosphorus electroless plating solution and its preparation method and application | |
| Zhu et al. | Preparation of copper-coated β-SiC nanoparticles by electroless plating | |
| Sudagar et al. | Electroless nickel, alloy, composite and nano coatings–A critical review | |
| CN105297085B (en) | A kind of method that nickel-plating liquid prepares nickel-base plating coat | |
| CN101113527B (en) | Electroplating product and method for preparing same | |
| CN1329554C (en) | Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof | |
| CN100500935C (en) | Environment-protection brightening type chemical nickel-plating additive | |
| CN102906306B (en) | For the method for the direct metallized of non-conductive substrate | |
| CN103433485B (en) | A kind of Al contained Ni and preparation method | |
| CN102296286B (en) | Long-acting nano-micron composite layer synthetic solution and preparation method thereof | |
| CN104451789A (en) | Plating solution for electroplating nickel on aluminum-based carbon nanotube | |
| JP2004537647A (en) | Paint containing nickel, boron and particles | |
| CN109097812A (en) | The preparation method of deposit N i-Co/SiC nano-composite plate under a kind of three-electrode system | |
| US20140076798A1 (en) | Tribologically Loadable Mixed Noble Metal/Metal Layers | |
| CN110117783A (en) | A kind of method of Electroless Nickel Plating of Aluminum Alloy mixed metal activation | |
| CN100476029C (en) | Direct chemical nickeling process for pressed-cast aluminum alloy | |
| CN103643266A (en) | Nano metal ceramic electrodeposited composite coating at inner hole wall of oil drill pipe and preparation method thereof | |
| CN101161841A (en) | Ultra-fine hard alloy composite powder and method for manufacturing same | |
| JP2014502675A (en) | Electroless plating bath composition and method for plating particulate matter | |
| CN111607817A (en) | Alloy of iron group element and tungsten and silicon carbide composite coating as well as preparation method and application thereof | |
| Nguyen et al. | Nickel composite plating with fly ash as inert particle | |
| Wang et al. | Preparation and characterization of nanodiamond cores coated with a thin Ni–Zn–P alloy film | |
| CN103871540B (en) | A kind of nickel bag glass conductive powder body and preparation method thereof for conductive rubber | |
| CN105039943A (en) | Plating solution for electroless plating of Ni-W-Zn-P alloy coating and coating process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Han Sheng Inventor after: Hang Zhijun Inventor after: Chen Yongyue Inventor after: Jiang Shu Inventor after: Dong Huihuan Inventor after: Gong Wenbo Inventor after: Dong Bo Inventor after: Wu Huihui Inventor after: Liu Fan Inventor after: Chu Lei Inventor after: Ma Peng Inventor after: Huang Qi Inventor before: Han Sheng Inventor before: Gong Wenbo Inventor before: Wu Huihui Inventor before: Liu Fan Inventor before: Dong Huihuan Inventor before: Dong Bo |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |