CN104862676B - A kind of graphene oxide nickel phosphorus composite plating bath and its preparation method and application - Google Patents
A kind of graphene oxide nickel phosphorus composite plating bath and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of graphene oxide nickel phosphorus composite plating bath and preparation method and application, the graphene oxide nickel phosphorus composite plating bath is by every liter of calculating, it is made up of the distilled water of graphene oxides of 0.5 1g after reduction treatment, 25 40g nickel sulfates, 15 20g sodium hypophosphites, 15g sodium acetates, 8 10g citric acids, 4ml lactic acid, 41mg compound stabilizers and surplus, its preparation method includes preparation and 2 steps of preparation of graphene oxide nickel phosphorus composite plating bath of the graphene oxide after reduction treatment.The graphene oxide nickel phosphorus composite plating bath of gained can be to carry out plating at 50 70 DEG C to steel in relatively low temperature, and gained graphene oxide nickel-phosphorus composite deposit thickness is uniform, and any surface finish is smooth, tight.And preparation method is simple, can be continuously produced.
Description
Technical field
The present invention relates to a kind of graphene oxide nickel phosphorus composite plating bath and preparation method thereof and using it in steel and alloy
Surface carries out chemical plating formation graphene oxide nickel-phosphorus composite deposit.
Technical background
Chemical plating is metal ion is carried out under the autocatalysis of metal surface by reducing agent appropriate in solution
The metal deposition process of reduction.Chemical deposit can be the one kind for extending the materials'use life-span with reinforcement material anti-corrosive properties, wearability
The most economic technological means.With the development of science and technology, the chemical nickel plating of unification can not increasingly meet wanting for industrial development
Ask.Therefore the Ni-P with superperformance just grows up.Composite Coatings are on the basis of original single chemical plating
A kind of process of surface treatment developed, and have the combination property of matrix metal and the class material of composite particles two concurrently.Study table
Bright, the composite particles of addition are conducive to changing the institutional framework and performance of coating, and different particle types have different to coating
Effect.Current people are to various elemental metals or nonmetallic, oxide, carbide, nitride, sulfide, diamond or graphite
There is certain research etc. the composite electroless-plating and its coating performance of various particles.Newest composite deposite research mainly has stone
Ink, diamond, Al2O 3, graphene etc..But the cladding wearability obtained before this is not universal high, its polishing scratch sectional area is in 35-
50um2In the range of.
Graphene oxide is product of the powdered graphite after chemical oxidation and stripping, and graphene oxide has single atomic layer
Structure, can expand to some tens of pm on lateral dimension at any time, therefore, the general chemistry of its construct trans and material science
Typical size.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, the characteristic with amphipathic molecule.Cause
This, graphene oxide can generally there are interface such as interfacial agent, and reduce the energy between interface so that metal ion can be
It is uniform under relatively mild reaction temperature, rapidly deposit sub- matrix surface.The addition of graphene oxide can improve the wear-resisting of coating
Performance, industrial energy consumption is reduced with gentle reaction temperature.
However, being not yet related to the research containing graphene oxide nickel phosphorus Composite Coatings at present.
Graphene is added to the report that composite deposite is made in chemical plating fluid, such as Hu Qinghua uses chemical nickel plating method,
Using graphene platelet as matrix, Ni- graphenes are prepared in nickel sulfate solution, find to be deposited on graphite after characterizing it
Alkene piece surface Ni mass fraction is very high, and the dispersiveness with height, but this method and does not extend into Ni graphenes
It is co-deposited on matrix material；The method that Wu Huihui uses chemical nickel plating, it is co-deposited on steel substrate surface, prepare stone
Black alkene nickel-phosphorus composite deposit, the coating is compared has better performance with nickel-phosphorus coating.But graphene nickel-phosphorus composite deposit is not
It is enough smooth, uniform, and reaction temperature is higher in plating process, generally 80 DEG C -90 DEG C, therefore energy consumption is more.
The content of the invention
An object of the present invention is to solve the graphene nickel phosphorus used in above-mentioned graphene nickel-phosphorus composite deposit
Composite plating bath carries out that required reaction temperature during chemical plating is high, the technical problem such as energy consumption is big and a kind of graphene oxide nickel phosphorus is provided
Composite plating bath, the graphene oxide nickel phosphorus composite plating bath, which has been selected, to be easier with the graphene oxide of metal co-deposition to be compound grain
Son, therefore reaction temperature required during using its progress chemical plating is low, only 50-70 DEG C, because the energy consumption of plating process is low, from
And reduce chemical plating cost.
The second object of the present invention is the preparation method for providing a kind of above-mentioned graphene oxide nickel phosphorus composite plating bath.
The third object of the present invention is to provide a kind of to be made using a kind of above-mentioned graphene oxide nickel phosphorus composite plating bath
Graphene oxide nickel-phosphorus composite deposit obtained by the method for standby graphene oxide nickel-phosphorus composite deposit, this method solves above-mentioned
Graphene nickel-phosphorus composite deposit it is not uniform and smooth enough the problem of, that is, used hydrophilic graphene oxide, and it is carried out
Pretreatment, makes it easier to, is uniformly deposited on the surface of metallic matrix to be formed with excellent anti-wear performance, outer sightseeing
The graphene oxide nickel-phosphorus composite deposit of sliding attractive in appearance the features such as.
Technical scheme
A kind of graphene oxide nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 0.5-1g after reduction treatment
Nickel sulfate 25-40g
Sodium hypophosphite 15-20g
Sodium acetate 15g
Citric acid 8-10g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
A kind of preparation method of above-mentioned graphene oxide nickel phosphorus composite plating bath, specifically includes following steps：
（1）, graphene oxide after reduction treatment preparation, step is as follows:
1., graphene oxide is cleaned
Add graphene oxide into cleaning fluid, ultrasonic disperse 5-30min at 40 DEG C, then suction filtration, gained filter cake is used
Deionized water is washed at least three times, obtains the graphene oxide after cleaned processing；
The cleaning fluid is that the NaOH aqueous solution or mass percent concentration that mass percent concentration is 10-40% are 10-
The 40% KOH aqueous solution；
2., graphene oxide is sensitized
Graphene oxide after cleaned processing is transferred in sensitizing solution, at room temperature ultrasonic disperse 15-30min, then
Suction filtration, gained filter cake is washed with deionized at least three times, obtains the graphene oxide after sensitized treatment；
The sensitizing solution is to contain HCl and SnCl2The aqueous solution, wherein HCl concentration are 10-30mL/L, SnCl2Concentration is 10-
40g/L；
3., graphene oxide is activated
At room temperature, the graphene oxide after sensitized treatment is placed in activating solution, then ultrasonic disperse 10-60min takes out
Filter, gained filter cake is washed with deionized at least three times, obtains the graphene oxide after activated processing；
The activating solution is to contain HCl and PdCl2The aqueous solution, wherein HCl concentration be 10-30mL/L, PdCl2Concentration is
0.1-0.5g/L；
4., graphene oxide is reduced
At room temperature, the graphene oxide after activated processing is added to the reducing agent aqueous solution that concentration is 20-50g/L
In, ultrasonically treated 20-40min, then suction filtration, gained filter cake is washed with deionized to neutrality, controls temperature to enter for 20-60 DEG C
Row vacuum drying, obtains the graphene oxide after reduction treatment；
The reducing agent is the mixed of one or both of sodium hypophosphite, sodium borohydride, diethylamine borane composition described above
Compound；
（2）, graphene oxide nickel phosphorus composite plating bath prepare
By every liter of calculating, by 20-40g nickel sulfates, 15-20g sodium hypophosphites, 15g sodium acetates, 8-10g citric acids, 4ml
After the distilled water of lactic acid, 41ml compound stabilizers and surplus is mixed and dissolved, with the hydrogen-oxygen that mass percent concentration is 10%
Change sodium water solution and adjust pH value to 4-6, then control temperature at 50-70 DEG C, by 0.5-1g steps（1）The warp of gained also original place
Graphene oxide after reason is added thereto, ultrasonic disperse processing 10min, produces graphene oxide nickel phosphorus composite plating bath.
Application of the above-mentioned graphene oxide nickel phosphorus composite plating bath in graphene oxide nickel-phosphorus composite deposit is prepared, specifically
Comprise the following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
By the surface of steel and alloy workpiece successively after 320# and 280# coated abrasive workings, first with temperature be 80-100 DEG C,
Mass percent concentration washes 15-20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then mass percent is used
Concentration is 10% aqueous hydrochloric acid solution pickling 30s, uses distilled water flushing 1min；Finally with the hydrochloric acid that mass percent concentration is 5%
Activated in water solution 30s, uses distilled water flushing 1min, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into graphene oxide nickel phosphorus composite plating bath after pretreatment
In, it is 50-70 DEG C that temperature is controlled under stirring condition, is incubated 30-90 min, then takes out, body is pressed with by deionized water and ethanol
Product is than being 1：The mixed liquor of 3 compositions is washed, until washing efflux is in neutrality, then 105 DEG C of dryings, i.e., in iron and steel parts
Surface obtain one layer of graphene oxide nickel-phosphorus composite deposit.
The surface of above-mentioned gained is coated with the graphite oxide that graphene oxide nickel phosphorus is combined on the steel and alloy workpiece of coated coating
Alkene nickel phosphorus is combined coated coating, i.e., in the way of chemical nickel plating, and graphene oxide particulate is arrived into coating with nickel-phosphorus alloy co-deposition
Middle formation graphene oxide nickel-phosphorus composite deposit, the graphene oxide nickel phosphorus formed is combined the structure of coated coating in born of the same parents' shape, non-
Crystal structure.
Beneficial effects of the present invention
A kind of graphene oxide nickel phosphorus composite plating bath of the present invention and its preparation method of coating, due to graphene oxide
Pre-processed with steel substrate, then prepare composite plating bath with pretreated amphipathic graphene oxide, reaction is more held
Easily carry out.Can be in relatively mild reaction temperature（50-70℃）It is lower to realize the preparation of graphene oxide nickel-phosphorus composite deposit, so as to drop
Low energy consumption.
A kind of graphene oxide nickel phosphorus composite plating bath of the present invention, due to adding pre- place in original ni-p electroless plating
Graphene oxide after reason, prepares graphene oxide nickel phosphorus composite plating bath, then coprecipitated on steel substrate after the pre-treatment
Product forms graphene oxide nickel phosphorus and is combined coated coating.The composite deposite is due to the presence of abrasion-proof particle graphene oxide, wearability
Enhancing, polishing scratch sectional area is after testing up to 20-25um2, solve the problem of nickel-phosphorus chemical plating wears no resistance in the prior art.
Further, using a kind of preparation method of graphene oxide nickel-phosphorus composite deposit of the invention, using to oxidation stone
Black alkene and steel substrate are pre-processed, then plating.In steel and alloy workpiece surface plating, the composite deposite more light of formation
It is sliding uniform, solved on the basis of retaining the good wearability of coating graphene coating it is not smooth enough, it is uniform the problem of.
Brief description of the drawings
Fig. 1 a, the surface of the gained of Application Example 1 are coated with the steel and alloy plating piece A's of graphene oxide nickel-phosphorus composite deposit
The scanning electron microscope (SEM) photograph of coating surface；
Fig. 1 b, the steel and alloy plating piece B for being coated with using the surface of the gained of comparative examples 1 graphene nickel-phosphorus composite deposit
The scanning electron microscope (SEM) photograph of coating surface；
Fig. 2 a, the surface of the gained of Application Example 2 are coated with the steel and alloy plating piece A's of graphene oxide nickel-phosphorus composite deposit
The scanning electron microscope (SEM) photograph of coating surface；
Fig. 2 b, the steel and alloy plating piece B for being coated with using the surface of the gained of comparative examples 2 graphene nickel-phosphorus composite deposit
The scanning electron microscope (SEM) photograph of coating surface.
Fig. 3 a, the surface of the gained of Application Example 3 are coated with the steel and alloy plating piece A's of graphene oxide nickel-phosphorus composite deposit
The scanning electron microscope (SEM) photograph of coating surface；
Fig. 3 b, the steel and alloy plating piece B for being coated with using the surface of the gained of comparative examples 3 graphene nickel-phosphorus composite deposit
The scanning electron microscope (SEM) photograph of coating surface.
Embodiment
Technical scheme is further described with reference to specific embodiment, but the present invention is not limited to
Following embodiments.
Various raw materials used, are commercially available unless otherwise specified in various embodiments of the present invention.
Embodiment 1
A kind of graphene oxide nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 0.5g after reduction treatment
Nickel sulfate 25g
Sodium hypophosphite 15g
Sodium acetate 15g
Citric acid 8g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
A kind of preparation method of above-mentioned graphene oxide nickel phosphorus composite plating bath, specifically includes following steps：
（1）, graphene oxide after reduction treatment preparation, step is as follows:
1., graphene oxide is cleaned
Add graphene oxide into cleaning fluid, ultrasonic disperse 20min at 40 DEG C, then suction filtration, gained filter cake is spent
Ion water washing at least three times, obtains the graphene oxide after cleaned processing；
The cleaning fluid is the NaOH aqueous solution that mass percent concentration is 20%；
2., graphene oxide is sensitized
Graphene oxide after cleaned processing is transferred in sensitizing solution, at room temperature ultrasonic disperse 20min, then taken out
Filter, gained filter cake is washed with deionized at least three times, obtains the graphene oxide after sensitized treatment；
The sensitizing solution is to contain HCl and SnCl2The aqueous solution, wherein HCl concentration be 10mL/L, SnCl2Concentration is 10g/
L；
3., graphene oxide is activated
At room temperature, the graphene oxide after sensitized treatment is placed in activating solution, ultrasonic disperse 30min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after activated processing；
The activating solution is to contain HCl and PdCl2The aqueous solution, wherein HCl concentration be 10mL/L, PdCl2Concentration is
0.1g/L；
4., graphene oxide is reduced
At room temperature, the graphene oxide after activated processing is added in the reducing agent aqueous solution that concentration is 20 g/L,
Ultrasonically treated 30min, then suction filtration, gained filter cake is washed with deionized to neutrality, is controlled temperature to carry out vacuum for 50 DEG C and is done
It is dry, obtain the graphene oxide after reduction treatment；
The reducing agent is sodium hypophosphite.
(2), graphene oxide nickel phosphorus composite plating bath is prepared
By every liter of calculating, by 25g nickel sulfates, 15g sodium hypophosphites, 15g sodium acetates, 8g citric acids, 4ml lactic acid, 41ml
It is water-soluble for 10% sodium hydroxide with mass percent concentration after compound stabilizer and the distilled water of surplus are mixed and dissolved
Liquid adjusts pH value to 4.8, and it is 70 DEG C then to control temperature, by 0.5g steps（1）The graphite oxide after reduction treatment of gained
Alkene is added thereto, ultrasonic disperse processing 10min, produces graphene oxide nickel phosphorus composite plating bath.
Application Example 1
The graphene oxide nickel phosphorus composite plating bath of the gained of embodiment 1, in graphene oxide nickel-phosphorus composite deposit is prepared
Using specifically including following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
Temperature is used to be 80 DEG C, quality after 320# and 280# coated abrasive workings, first successively on the surface of steel and alloy workpiece
Percent concentration washes 20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then it is with mass percent concentration
10% aqueous hydrochloric acid solution pickling 30s, uses distilled water flushing 1min；Finally with the aqueous hydrochloric acid solution that mass percent concentration is 5%
30s is activated, distilled water flushing 1min is used, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into the graphene oxide of the gained of embodiment 1 after pretreatment
In nickel phosphorus composite plating bath, it is 70 DEG C that temperature is controlled under stirring condition, is incubated 60min, then takes out, with by deionized water and ethanol
It is 1 by volume：The mixed liquor of 3 compositions is washed, until washing efflux is in neutrality, then 105 DEG C of dryings, i.e., in steel
The surface of workpiece obtains one layer of graphene oxide nickel-phosphorus composite deposit A1.
Using SEM instrument（Hitachi SEM S-3400N）By the above-mentioned table in iron and steel parts
Face obtains one layer of graphene oxide nickel-phosphorus composite deposit A1 and is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in 1a, from Fig. 1 a
It can be seen that the black alkene nickel-phosphorus composite deposit surface of oxidation is born of the same parents' shape, non-crystal structure.
Using comparative examples 1
A kind of graphene nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene 0.5g
Nickel sulfate 25g
Sodium hypophosphite 15g
Sodium acetate 15g
Citric acid 8g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
Using the graphene nickel phosphorus composite plating bath of above-mentioned gained, its application in graphene nickel-phosphorus composite deposit is prepared,
Specifically include following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
The surface of steel and alloy workpiece is removed through 320# and 280# coated abrasive workings successively, is first 80 DEG C, quality hundred with temperature
Specific concentration is divided to wash 20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then it is with mass percent concentration again
10% chlorohydric acid pickling 30s, uses distilled water flushing 1min；Finally, with the hydrochloric acid activation 30s that mass percent concentration is 5%, with steaming
Distilled water rinses 1min, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into graphene nickel phosphorus composite plating bath after pretreatment, is stirred
It is 90 DEG C that temperature is controlled under the conditions of mixing, and is incubated 60min, then takes out, and is 1 by volume with by deionized water and ethanol：3 compositions
Mixed liquor washed, until washing efflux is in neutrality, then 105 DEG C of dryings obtain one on the surface of iron and steel parts
Layer graphene nickel-phosphorus composite deposit B1.
Using SEM instrument（Hitachi SEM S-3400N）By the above-mentioned table in iron and steel parts
Face obtains a layer graphene nickel-phosphorus composite deposit B1 and is scanned, and the scanning electron microscope (SEM) photograph of gained, can be with from Fig. 1 b as shown in 1b
It is graininess, concavo-convex non-crystal structure to find out graphene nickel-phosphorus composite deposit surface.
Comparison diagram 1a and Fig. 1 b, it can be seen that using the graphene oxide nickel phosphorus composite plating bath of the gained of embodiment 1
The graphene oxide nickel-phosphorus composite deposit A1 for learning gained after plating is more uniform, smooth.
The above-mentioned surface in iron and steel parts is obtained into one layer of graphene oxide nickel-phosphorus composite deposit A1 and graphene nickel phosphorus is answered
Close the method that contrast polishing scratch sectional area is respectively adopted in coating B1（Shao Jianbing, Zhu Yongwei etc., Ni-P- diamond chemical composite platings
Study on Wear-resistance, diamond and grinding materials and grinding tool engineering, 2008）, in MMD-1 multifunction friction wear testing machines（Jinan benefit China
Tribology tester Technology Co., Ltd.）Detected, its polishing scratch sectional area is respectively in 20-25um2And 35-40um2, it is indicated above that
The above-mentioned one layer of graphene oxide nickel-phosphorus composite deposit A1 obtained in surface of steel workpiece has preferable wearability.
Contrasted by the plating process to Application Example 1 and application comparative examples 1, it can be seen that application implementation
Graphene oxide composite plating bath can form the uniform and good composite deposite of anti-wear performance 70 DEG C at gentle temperature in example 1,
And apply the graphene composite plating bath in comparative examples 1 to need to carry out plating at 90 DEG C, uniform and wearability could be formed
The good composite deposite of energy.It is indicated above that can be in reduction energy consumption using a kind of graphene oxide nickel phosphorus composite plating bath of the present invention
Under conditions of prepare uniform, the more preferable graphene oxide nickel-phosphorus composite deposit of anti-wear performance.
Embodiment 2
A kind of graphene oxide nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 1g after reduction treatment
Nickel sulfate 40g
Sodium hypophosphite 20g
Sodium acetate 15g
Citric acid 10g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
A kind of preparation method of above-mentioned graphene oxide nickel phosphorus composite plating bath, specifically includes following steps：
（1）, graphene oxide after reduction treatment preparation, step is as follows:
1., graphene oxide is cleaned
Add graphene oxide into cleaning fluid, ultrasonic disperse 20min at 40 DEG C, then suction filtration, gained filter cake is spent
Ion water washing at least three times, obtains the graphene oxide after cleaned processing；
The cleaning fluid is the NaOH aqueous solution that mass percent concentration is 40%；
2., graphene oxide is sensitized
Graphene oxide after cleaned processing is transferred in sensitizing solution, at room temperature ultrasonic disperse 20min, then taken out
Filter, gained filter cake is washed with deionized at least three times, obtains the graphene oxide after sensitized treatment；
The sensitizing solution is to contain HCl and SnCl2The aqueous solution, wherein HCl concentration be 30mL/L, SnCl2Concentration is 40g/
L；
3., graphene oxide is activated
At room temperature, the graphene oxide after sensitized treatment is placed in activating solution, ultrasonic disperse 30min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after activated processing；
The activating solution is to contain HCl and PdCl2The aqueous solution, wherein HCl concentration be 30mL/L, PdCl2Concentration is
0.5g/L；
4., graphene oxide is reduced
At room temperature, the graphene oxide after activated processing is added in the reducing agent aqueous solution that concentration is 40g/L, surpassed
Sonication 30min, then suction filtration, gained filter cake is washed with deionized to neutrality, controls temperature to be dried in vacuo for 50 DEG C,
Graphene oxide that must be after reduction treatment；
The reducing agent is sodium hypophosphite；
(2), graphene oxide nickel phosphorus composite plating bath is prepared
By every liter of calculating, by 40g nickel sulfates, 20g sodium hypophosphites, 15g sodium acetates, 10g citric acids, 4ml lactic acid, 41ml
It is water-soluble for 10% sodium hydroxide with mass percent concentration after compound stabilizer and the distilled water of surplus are mixed and dissolved
Liquid adjusts pH value to 4.8, then control temperature at 50 DEG C, by 1g steps（1）The graphite oxide after reduction treatment of gained
Alkene is added thereto, ultrasonic disperse processing 10min, produces graphene oxide nickel phosphorus composite plating bath.
Application Example 2
The graphene oxide nickel phosphorus composite plating bath of the gained of embodiment 2, in graphene oxide nickel-phosphorus composite deposit is prepared
Using specifically including following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
The surface of steel and alloy workpiece is removed through 320# and 280# coated abrasive workings successively, is first 80 DEG C, quality hundred with temperature
Specific concentration is divided to wash 20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then it is with mass percent concentration again
10% chlorohydric acid pickling 30s, uses distilled water flushing 1min；Finally, with the hydrochloric acid activation 30s that mass percent concentration is 5%, with steaming
Distilled water rinses 1min, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into graphene oxide nickel phosphorus composite plating bath after pretreatment
In, it is 50 DEG C that temperature is controlled under stirring condition, is incubated 60min, then takes out, and is 1 by volume with by deionized water and ethanol：
The mixed liquor of 3 compositions is washed, until washing efflux is in neutrality, then 105 DEG C of dryings obtain on the surface of iron and steel parts
To one layer of graphene oxide nickel-phosphorus composite deposit A2.
Using SEM instrument（Hitachi SEM S-3400N）By the above-mentioned table in iron and steel parts
Face obtains one layer of graphene oxide nickel-phosphorus composite deposit A2 and is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in 2a, from Fig. 2 a
It can be seen that the black alkene nickel-phosphorus composite deposit surface of oxidation is born of the same parents' shape, non-crystal structure.
Using comparative examples 2
A kind of graphene nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene 1g
Nickel sulfate 40g
Sodium hypophosphite 20g
Sodium acetate 15g
Citric acid 10g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
The graphene nickel phosphorus composite plating bath of above-mentioned gained, the application in graphene nickel-phosphorus composite deposit is prepared, specific bag
Include following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
Temperature is used to be 80 DEG C, quality after 320# and 280# coated abrasive workings, first successively on the surface of steel and alloy workpiece
Percent concentration washes 20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then it is with mass percent concentration
10% aqueous hydrochloric acid solution pickling 30s, uses distilled water flushing 1min；Finally with the aqueous hydrochloric acid solution that mass percent concentration is 5%
30s is activated, distilled water flushing 1min is used, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into graphene nickel phosphorus composite plating bath after pretreatment, is stirred
It is 70 DEG C that temperature is controlled under the conditions of mixing, and is incubated 60min, then takes out, and is 1 by volume with by deionized water and ethanol：3 compositions
Mixed liquor washed, until washing efflux is in neutrality, then 105 DEG C of dryings obtain one on the surface of iron and steel parts
Layer graphene nickel-phosphorus composite deposit B2.
Using SEM instrument（Hitachi SEM S-3400N）By the above-mentioned table in iron and steel parts
Face obtains a layer graphene nickel-phosphorus composite deposit B2 and is scanned, and the scanning electron microscope (SEM) photograph of gained, can be with from Fig. 2 b as shown in 2b
Graphene nickel-phosphorus composite deposit surface is found out for graininess, concavo-convex non-crystal structure and has obvious gully shape.
Comparison diagram 2a and Fig. 2 b, it can be seen that using the graphene oxide nickel phosphorus composite plating bath of the gained of embodiment 2
The graphene oxide nickel-phosphorus composite deposit A2 for learning gained after plating is more uniform, smooth.
The above-mentioned surface in iron and steel parts is obtained into one layer of graphene oxide nickel-phosphorus composite deposit A2 and graphene nickel phosphorus is answered
Close the method that contrast polishing scratch sectional area is respectively adopted in coating B2（Shao Jianbing, Zhu Yongwei etc., Ni-P- diamond chemical composite platings
Study on Wear-resistance, diamond and grinding materials and grinding tool engineering, 2008）, in MMD-1 multifunction friction wear testing machines（Jinan benefit China
Tribology tester Technology Co., Ltd.）Detected, its polishing scratch sectional area is respectively in 20-25um2And 35-40um2, it is indicated above that
The above-mentioned surface in iron and steel parts, which obtains one layer of graphene oxide nickel-phosphorus composite deposit A2, has preferable wearability.
By being contrasted to Application Example 2 and using comparative examples 2, it can be seen that aoxidized in Application Example 2
Graphene composite plating bath can form the uniform and good composite deposite of anti-wear performance 50 DEG C at gentle temperature, and apply pair
According in embodiment 2 graphene composite plating bath need plating is carried out at 70 DEG C, could be formed uniformly and anti-wear performance well
Composite deposite.It is indicated above that can be under conditions of reduction energy consumption using a kind of graphene oxide nickel phosphorus composite plating bath of the present invention
Prepare uniform, the more preferable graphene oxide nickel-phosphorus composite deposit of anti-wear performance.
Embodiment 3
A kind of graphene oxide nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 0.75g after reduction treatment
Nickel sulfate 30g
Sodium hypophosphite 17g
Sodium acetate 15g
Citric acid 9g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
A kind of preparation method of above-mentioned graphene oxide nickel phosphorus composite plating bath, specifically includes following steps：
（1）, graphene oxide after reduction treatment preparation, step is as follows:
1., graphene oxide is cleaned
Add graphene oxide into cleaning fluid, ultrasonic disperse 20min at 40 DEG C, then suction filtration, gained filter cake is spent
Ion water washing at least three times, obtains the graphene oxide after cleaned processing；
The cleaning fluid is the NaOH aqueous solution that mass percent concentration is 30%；
2., graphene oxide is sensitized
Graphene oxide after cleaned processing is transferred in sensitizing solution, at room temperature ultrasonic disperse 20min, then taken out
Filter, gained filter cake is washed with deionized at least three times, obtains the graphene oxide after sensitized treatment；
The sensitizing solution is to contain HCl and SnCl2The aqueous solution, wherein HCl concentration be 20mL/L, SnCl2Concentration is 25g/
L；
3., graphene oxide is activated
At room temperature, the graphene oxide after sensitized treatment is placed in activating solution, ultrasonic disperse 30min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after activated processing；
The activating solution is to contain HCl and PdCl2The aqueous solution, wherein HCl concentration be 20mL/L, PdCl2Concentration is
0.3g/L；
4., graphene oxide is reduced
At room temperature, the graphene oxide after activated processing is added in the reducing agent aqueous solution that concentration is 30 g/L,
Ultrasonically treated 30min, then suction filtration, gained filter cake is washed with deionized to neutrality, is controlled temperature to carry out vacuum for 50 DEG C and is done
It is dry, obtain the graphene oxide after reduction treatment；
The reducing agent is sodium hypophosphite；
(2), graphene oxide nickel phosphorus composite plating bath is prepared
By every liter of calculating, by 30g nickel sulfates, 17g sodium hypophosphites, 15g sodium acetates, 9g citric acids, 4ml lactic acid, 41ml
It is water-soluble for 10% sodium hydroxide with mass percent concentration after compound stabilizer and the distilled water of surplus are mixed and dissolved
Liquid adjusts pH value to 4.8, and it is 60 DEG C then to control temperature, by 0.5g steps（1）The graphite oxide after reduction treatment of gained
Alkene is added thereto, ultrasonic disperse processing 10min, produces graphene oxide nickel phosphorus composite plating bath.
Application Example 3
The graphene oxide nickel phosphorus composite plating bath of the gained of embodiment 3, in graphene oxide nickel-phosphorus composite deposit is prepared
Using specifically including following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
Temperature is used to be 80 DEG C, quality after 320# and 280# coated abrasive workings, first successively on the surface of steel and alloy workpiece
Percent concentration washes 20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then it is with mass percent concentration
10% aqueous hydrochloric acid solution pickling 30s, uses distilled water flushing 1min；Finally with the aqueous hydrochloric acid solution that mass percent concentration is 5%
30s is activated, distilled water flushing 1min is used, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into the graphene oxide of the gained of embodiment 3 after pretreatment
In nickel phosphorus composite plating bath, it is 70 DEG C that temperature is controlled under stirring condition, is incubated 60min, then takes out, with by deionized water and ethanol
It is 1 by volume：The mixed liquor of 3 compositions is washed, until washing efflux is in neutrality, then 105 DEG C of dryings, i.e., in steel
The surface of workpiece obtains one layer of graphene oxide nickel-phosphorus composite deposit A3.
Using SEM instrument（Hitachi SEM S-3400N）By the above-mentioned table in iron and steel parts
Face obtains one layer of graphene oxide nickel-phosphorus composite deposit A3 and is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in 3a, from Fig. 3 a
It can be seen that the black alkene nickel-phosphorus composite deposit surface of oxidation is born of the same parents' shape, non-crystal structure.
Using comparative examples 3
A kind of graphene nickel phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene 0.75g
Nickel sulfate 30g
Sodium hypophosphite 17g
Sodium acetate 15g
Citric acid 9g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：Iodate
Potassium is 1:20:20 ratio is composited.
Using the graphene nickel phosphorus composite plating bath of above-mentioned gained, its application in graphene nickel-phosphorus composite deposit is prepared,
Specifically include following steps：
（1）, steel and alloy workpiece surface to be plated pretreatment
The surface of steel and alloy workpiece is removed through 320# and 280# coated abrasive workings successively, is first 80 DEG C, quality hundred with temperature
Specific concentration is divided to wash 20min, distilled water flushing 1min for 20% sodium hydrate aqueous solution；Then it is with mass percent concentration again
10% chlorohydric acid pickling 30s, uses distilled water flushing 1min；Finally, with the hydrochloric acid activation 30s that mass percent concentration is 5%, with steaming
Distilled water rinses 1min, that is, completes the pretreatment of steel and alloy workpiece surface to be plated；
（2）, by step（1）Steel and alloy workpiece to be plated is put into graphene nickel phosphorus composite plating bath after pretreatment, is stirred
It is 80 DEG C that temperature is controlled under the conditions of mixing, and is incubated 60min, then takes out, and is 1 by volume with by deionized water and ethanol：3 compositions
Mixed liquor washed, until washing efflux is in neutrality, then 105 DEG C of dryings obtain one on the surface of iron and steel parts
Layer graphene nickel-phosphorus composite deposit B3.
Using SEM instrument（Hitachi SEM S-3400N）By the above-mentioned table in iron and steel parts
Face obtains a layer graphene nickel-phosphorus composite deposit B3 and is scanned, and the scanning electron microscope (SEM) photograph of gained, can be with from Fig. 3 b as shown in 3b
It is graininess, concavo-convex non-crystal structure to find out graphene nickel-phosphorus composite deposit surface.
Comparison diagram 3a and Fig. 3 b, it can be seen that using the graphene oxide nickel phosphorus composite plating bath of the gained of embodiment 3
The graphene oxide nickel-phosphorus composite deposit A3 for learning gained after plating is more uniform, smooth.
The above-mentioned surface in iron and steel parts is obtained into one layer of graphene oxide nickel-phosphorus composite deposit A3 and graphene nickel phosphorus is answered
Close the method that contrast polishing scratch sectional area is respectively adopted in coating B3（Shao Jianbing, Zhu Yongwei etc., Ni-P- diamond chemical composite platings
Study on Wear-resistance, diamond and grinding materials and grinding tool engineering, 2008）, in MMD-1 multifunction friction wear testing machines（Jinan benefit China
Tribology tester Technology Co., Ltd.）Detected, its polishing scratch sectional area is respectively in 20-25um2And 35-40um2, it is indicated above that
The above-mentioned surface in iron and steel parts, which obtains one layer of graphene oxide nickel-phosphorus composite deposit A3, has preferable wearability.
Contrasted by the plating process to Application Example 3 and application comparative examples 3, it can be seen that application implementation
Graphene oxide composite plating bath can form the uniform and good composite deposite of anti-wear performance 60 DEG C at gentle temperature in example 3,
And apply the graphene composite plating bath in comparative examples 3 to need to carry out plating at 80 DEG C, uniform and wearability could be formed
The good composite deposite of energy.It is indicated above that can be in reduction energy consumption using a kind of graphene oxide nickel phosphorus composite plating bath of the present invention
Under conditions of prepare uniform, the more preferable graphene oxide nickel-phosphorus composite deposit of anti-wear performance.
Above-mentioned Application Example 1-3 illustrates that graphene oxide nickel phosphorus composite plating bath can be gentleer（50-70℃）Condition
It is lower to form uniform, wear-resisting graphene oxide nickel-phosphorus composite deposit.And apply and used under the same conditions in comparative examples 1-3
Graphene replaces graphene oxide, and temperature is improved 20 DEG C of progress platings, graphene nickel-phosphorus composite deposit is prepared；Contrast respectively
The coating of gained finds, graphene oxide nickel-phosphorus composite deposit not only, surface light more uniform than graphene nickel-phosphorus composite deposit thickness
Sliding, tight, and with higher anti-wear performance.
In summary, a kind of graphene oxide nickel phosphorus composite plating bath of the invention, can be 50-70 DEG C in relatively low temperature
Under plating is carried out to steel, the graphene oxide nickel phosphorus Composite Coatings thickness of gained is uniform, surface is smooth, tight, and has
Higher anti-wear performance.And preparation method is simple, can be continuously produced.
Described above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, without departing from the technical principles of the invention, some improvement and modification can also be made, these improve and become
Type also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of graphene oxide nickel phosphorus composite plating bath, it is characterised in that the graphene oxide nickel phosphorus composite plating bath, by every liter
Calculate, its raw material composition and content are as follows：
Graphene oxide 0.5-1g after reduction treatment
Nickel sulfate 25-40g
Sodium hypophosphite 15-20g
Sodium acetate 15g
Citric acid 8-10g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water；
The compound stabilizer, by thiocarbamide, Potassiumiodate and KI, is calculated, i.e. thiocarbamide in mass ratio：Potassiumiodate：KI is
1:20:20 ratio is composited；
The described graphene oxide after reduction treatment, which is made by the steps, to be formed：
1., graphene oxide is cleaned
Add graphene oxide into cleaning fluid, ultrasonic disperse 5-30min at 40 DEG C, then suction filtration, gained filter cake spend from
Sub- water washing at least three times, obtains the graphene oxide after cleaned processing；
The cleaning fluid is that the NaOH aqueous solution or mass percent concentration that mass percent concentration is 10-40% are 10-40%'s
The KOH aqueous solution；
2., graphene oxide is sensitized
Graphene oxide after cleaned processing is transferred in sensitizing solution, at room temperature ultrasonic disperse 15-30min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after sensitized treatment；
The sensitizing solution is to contain HCl and SnCl2The aqueous solution, wherein HCl concentration be 10-30mL/L, SnCl2Concentration is 10-
40g/L；
3., graphene oxide is activated
At room temperature, the graphene oxide after sensitized treatment is placed in activating solution, ultrasonic disperse 10-60min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after activated processing；
The activating solution is to contain HCl and PdCl2The aqueous solution, wherein HCl concentration be 10-30mL/L, PdCl2Concentration is 0.1-
0.5g/L；
4., graphene oxide is reduced
At room temperature, the graphene oxide after activated processing is added in the reducing agent aqueous solution that concentration is 20-50g/L, surpassed
Sonication 20-40min, suction filtration, gained filter cake are washed with deionized to neutrality, are controlled temperature to carry out vacuum for 20-60 DEG C and are done
It is dry, obtain the graphene oxide after reduction treatment；
The reducing agent is the mixture of one or both of sodium hypophosphite, sodium borohydride, diethylamine borane composition described above.
2. a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, it is characterised in that the graphene oxide nickel
Phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 0.5g after reduction treatment
Nickel sulfate 25g
Sodium hypophosphite 15g
Sodium acetate 15g
Citric acid 8g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water.
3. a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, it is characterised in that the graphene oxide nickel
Phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 1g after reduction treatment
Nickel sulfate 40g
Sodium hypophosphite 20g
Sodium acetate 15g
Citric acid 10g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water.
4. a kind of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, it is characterised in that the graphene oxide nickel
Phosphorus composite plating bath, by every liter of calculating, its raw material composition and content are as follows：
Graphene oxide 0.75g after reduction treatment
Nickel sulfate 30g
Sodium hypophosphite 17g
Sodium acetate 15g
Citric acid 9g
Lactic acid 4ml
Compound stabilizer 41mg
Surplus is distilled water.
5. a kind of preparation method of graphene oxide nickel phosphorus composite plating bath as claimed in claim 1, it is characterised in that specific bag
Include following steps：
（1）, graphene oxide after reduction treatment preparation, step is as follows:
1., graphene oxide is cleaned
Add graphene oxide into cleaning fluid, ultrasonic disperse 5-30min at 40 DEG C, then suction filtration, gained filter cake spend from
Sub- water washing at least three times, obtains the graphene oxide after cleaned processing；
The cleaning fluid is that the NaOH aqueous solution or mass percent concentration that mass percent concentration is 10-40% are 10-40%'s
The KOH aqueous solution；
2., graphene oxide is sensitized
Graphene oxide after cleaned processing is transferred in sensitizing solution, at room temperature ultrasonic disperse 15-30min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after sensitized treatment；
The sensitizing solution is to contain HCl and SnCl2The aqueous solution, wherein HCl concentration be 10-30mL/L, SnCl2Concentration is 10-
40g/L；
3., graphene oxide is activated
At room temperature, the graphene oxide after sensitized treatment is placed in activating solution, ultrasonic disperse 10-60min, then suction filtration,
Gained filter cake is washed with deionized at least three times, obtains the graphene oxide after activated processing；
The activating solution is to contain HCl and PdCl2The aqueous solution, wherein HCl concentration be 10-30mL/L, PdCl2Concentration is 0.1-
0.5g/L；
4., graphene oxide is reduced
At room temperature, the graphene oxide after activated processing is added in the reducing agent aqueous solution that concentration is 20-50g/L, surpassed
Sonication 20-40min, then suction filtration, gained filter cake is washed with deionized to neutrality, controls temperature to be carried out for 20-60 DEG C true
Sky is dried, and obtains the graphene oxide after reduction treatment；
The reducing agent is the mixture of one or both of sodium hypophosphite, sodium borohydride, diethylamine borane composition described above；
（2）, graphene oxide nickel phosphorus composite plating bath prepare
Nickel sulfate, sodium hypophosphite, sodium acetate, citric acid, lactic acid, compound stabilizer and distilled water are mixed and dissolved
Afterwards, adjust pH value to 4-6 with mass percent concentration for 10% sodium hydrate aqueous solution, then control temperature 50-70 DEG C it
Between, by step（1）The graphene oxide after reduction treatment of gained is added thereto, ultrasonic disperse processing 10min, produces oxidation
Graphene nickel phosphorus composite plating bath.
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| JP6489979B2 (en) * | 2015-09-07 | 2019-03-27 | 新光電気工業株式会社 | Heat dissipation component and manufacturing 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 |
| 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 |
| CN107916415B (en) * | 2017-11-21 | 2019-07-16 | 北京理工大学 | Graphene-phosphatization nickel composite deposite preparation method 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 |
| CN114523104B (en) * | 2021-01-05 | 2023-05-23 | 南京工业大学 | Surface nickel-phosphorus-plated graphene reinforced titanium-based composite material 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 |
| 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 |
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| 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 |
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