CN105839082A - Ce-Ni-B/GO chemical composite deposition layer and ultrasonic-assisted preparation method thereof - Google Patents

Ce-Ni-B/GO chemical composite deposition layer and ultrasonic-assisted preparation method thereof Download PDF

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Publication number
CN105839082A
CN105839082A CN201610420175.7A CN201610420175A CN105839082A CN 105839082 A CN105839082 A CN 105839082A CN 201610420175 A CN201610420175 A CN 201610420175A CN 105839082 A CN105839082 A CN 105839082A
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composite deposition
composite
ultrasonic
preparation
deposition liquid
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蒋继波
钱炜
冯晨萁
韩生
朱丽莹
初胜亚
吕冲
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

The invention provides a Ce-Ni-B/GO chemical composite deposition layer and an ultrasonic-assisted preparation method thereof. The ultrasonic-assisted preparation method is prepared by the following step of carrying out ultrasonic treatment on a low carbon steel workpiece in Ce-Ni-B/GO composite deposition liquid to prepare the Ce-Ni-B/GO chemical composite deposition layer on the surface of low carbon steel, wherein in the composite deposition liquid, the composite deposition liquid per L is prepared from the following components in parts by weight: 0.1-5g of cerium, 20-55g of nickel chloride hexahydrate, 0.5-4g of sodium borohydride, 20-65g of sodium hydroxide, 15-65g of ethylenediamine, 0.1-2g of sodium dodecyl sulfate and 0.1-10g of graphene oxide. According to the ultrasonic-assisted preparation method, the multifunctional nano composite deposition layer on the surface of the low carbon steel based on an ultrasonic wave and chemical plating technology by adopting the composite deposition liquid; and the prepared composite deposition layer is capable of effectively improving the performances including the corrosion resistance, the surface hardness and the wear resistance of the low carbon steel and effectively solving the problem that particles crack.

Description

A kind of Ce-Ni-B/GO Composite electroless deposit layer and ultrasound wave auxiliary preparation method thereof thereof
Technical field
The invention belongs to technical field of inorganic material, particularly relate to a kind of Ce-Ni-B/GO Composite electroless deposit layer and ultrasonic Ripple assistant preparation method.
Background technology
Chemical plating refers to that adding suitable reducing agent in the plating solution makes metal ion at a kind of novel surface of the spontaneous reduction in surface Reason technology.Owing to without additional power source, cost is relatively low, and it is uniform to enable to coating, has preferable decorative effect, Have begun to replace electroplating technology in many fields, can obtain in the industry such as electronics, valve manufacture, machinery and automobile extensively Ground application.
Nineteen forty-four, the discovery of A.Brenner and G.Riddell of NBS, understand the catalysis forming coating Characteristic, it was found that the method depositing non-powder nickel, makes chemical plating nickel technology commercial Application have a probability, but change at that time Learn nickel plating solution extremely unstable, therefore say there is no real value on stricti jurise.Through constantly exploring and research, closely for many years Within several years, development pole is ripe.Chemical nickel plating is suitable for almost the nickel plating of all metal surfaces.As: iron and steel nickel plating, rustless steel plates Nickel, aluminum nickel plating, copper nickel plating etc., it is equally applicable to nonmetallic surface nickel plating.Such as: pottery nickel plating, glass nickel plating, Diamond nickel plating, carbon plate nickel plating, plastics nickel plating, resin nickel plating etc..With the coating of electroless nickel deposition, there are some different Characteristic in deposition layer.Hardness is high, wearability is good.The hardness of electroless nickel layer is only l60~180HV, and chemical nickel plating The hardness of layer is generally 400~700HV, also can further improve the hard of close even more than chrome plating after appropriate heat treatment Degree, therefore wearability is good, it more difficult to obtain is that chemical Ni-plating layer has had both good anti-corrosion and anti-wear performance.Chemical stability height, Binding force of cladding material is good.In an atmosphere and in other media, the chemical stability of chemical Ni-plating layer is higher than the change of electroless nickel layer Learn stability.With being well combined of the matrixes such as common iron and steel, copper, adhesion is not less than the adhesion of electroless nickel layer and matrix.
Rare earth has the laudatory title of " industry vitamin ".There is due to it physical characteristics such as excellent photoelectromagnetic, can form with other materials Different properties, new material various in style, its most significant function is exactly quality and the performance increasing substantially other products. Such as increase substantially for manufacturing tank, aircraft, the steel of guided missile, aluminium alloy, magnesium alloy, the tactical qualities of titanium alloy. And, rare earth is many high-tech lubricants such as electronics, laser, nuclear industry, superconduction equally.
But there is presently no about the ultrasonic correlational study preparing Ce-Ni-B multi-functional composite sedimentary layer liquid.Even if minority relates to And the research to Ni-B alloy, but it does not relate to ultrasonic and doped with rare-earth elements and graphene oxide GO.
Summary of the invention
For above-mentioned technical problem of the prior art, it is an object of the invention to provide a kind of Ce-Ni-B/GO chemically composited Sedimentary and ultrasound wave auxiliary preparation method thereof thereof, this method preparing Ce-Ni-B/GO Composite electroless deposit layer of the present invention Solve that surface of low-carbon steel of the prior art is corrosion-resistant, crocking resistance and the highest technical problem of hardness.
Technical solution of the present invention is specifically described as follows.
The present invention provides the ultrasound wave auxiliary preparation method thereof of a kind of Ce-Ni-B/GO Composite electroless deposit layer, and it is first to low-carbon (LC) The surface of steel workpiece carries out pretreatment, is then put in Ce-Ni-B/GO composite deposition liquid by pretreated mild steel workpiece At a temperature of 80-90 DEG C ultrasonic, finally take out mild steel workpiece and be dried, i.e. prepare Ce-Ni-B/GO chemistry at surface of low-carbon steel multiple Close sedimentary;Wherein: in described Ce-Ni-B/GO composite deposition liquid, every heave hydrops includes following component: cerium 0.1~5g, Nickel dichloride hexahydrate 20~55g, sodium borohydride 0.5~4g, sodium hydroxide 20~65g, ethylenediamine 15~65 grams, dodecyl Sodium sulfate 0.2~2g, graphene oxide GO 0.1~10g.
In the present invention, Ce-Ni-B/GO composite deposition liquid ammonia regulates pH value between 13~14.
In the present invention, pre-treatment step includes sand paper scrubbing successively, acetone defat, chlorohydric acid pickling and hydrochloric acid activation four Step.
In the present invention, ultrasound intensity is between 100~700W, and supersonic frequency is between 20-40KHZ;In ultrasonic procedure, Rotating speed is 200r/min.
In the present invention, baking temperature is 15-25 DEG C.
The present invention also provides for the Ce-Ni-B/GO Composite electroless deposit layer that a kind of above-mentioned preparation method obtains.
In the present invention, the preparation method of a kind of Ce-Ni-B/GO composite deposition liquid, weigh respectively according to rate of charge or measure Cerium, Nickel dichloride hexahydrate, sodium borohydride, sodium hydroxide, ethylenediamine and the sodium lauryl sulphate processed in advance, successively Join in distilled water and dissolve, then the GO of surface modification is joined in above-mentioned deposition liquid, finally regulate with ammonia spirit PH value, to 13~14, i.e. obtains the deposition liquid for preparing the multi-functional composite sedimentary layer of Ce-Ni-B/GO.
In the present invention, by the composite deposition of the Ce-Ni-B that above-mentioned surface based on acoustic-electric chemical technology gained sample is formed Rotating fields is born of the same parents' shape, non-crystal structure.
In preparation method of the present invention, by ultrasonic assistant and chemical plating method, the Composite electroless deposit liquid of the present invention is applied to The surface of carbon steel, is formed on carbon steel work-piece surface containing rare earth (RE) and the multi-functional composite sedimentary layer of nickel boron of GO, ultrasonic The cavitation effect produced when ripple is propagated in liquid medium and mechanical shearing effect, can have in Nano-composite Electrodeposition technique Effect ground dispersing nanoparticles, crystal grain thinning, thus ensure that nano-composite plate has good structure property, improve coating brilliant To, increase coating brightness, improve hardness and corrosion resistance etc..
A kind of Ce-Ni-B/GO Composite electroless deposit liquid of the present invention, owing to adding rare earth in original Ni-B deposition liquid Elements C e and GO, therefore apply this Composite electroless deposit liquid when the plating of carbon steel work-piece surface, be ultimately formed The wearability of Ce-Ni-B/GO composite sedimentary layer strengthens.I.e. by the performance of rare earth RE and GO, significantly improve the external world Wearability to steel surface layer.Utilizing the present invention, the composite sedimentary layer of the Ce-Ni-B/GO of gained is stronger corrosion-resistant Performance, its corrosion resistance shown is better than simple Ni-B alloy-layer, and to the physical property of matrix material without any Impact;Additionally, introduce ultrasound wave in preparation process, refine coating surface crystal grain further and improve oxidation in coating The content of graphite GO and uniformity.Therefore, the Ce-Ni-B/GO composite sedimentary layer being ultimately formed has the corrosion resistant of excellence Erosion performance, rub resistance and high rigidity.
Accompanying drawing explanation
Fig. 1 is the coating that the surface of embodiment 2 gained is coated with the steel and alloy plating piece A of rare earth Graphene nickel boron Composite Coatings coating The scanning electron microscope (SEM) photograph on surface.
Fig. 2 is the coating that the surface of embodiment 4 gained is coated with the steel and alloy plating piece B of rare earth Graphene nickel phosphorus Composite Coatings coating The scanning electron microscope (SEM) photograph on surface.
Fig. 3 is the coating that the surface of embodiment 6 gained is coated with the steel and alloy plating piece C of rare earth Graphene nickel phosphorus Composite Coatings coating The scanning electron microscope (SEM) photograph on surface.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further described, but under the present invention is not limited to State embodiment.
Various raw materials used in various embodiments of the present invention, if no special instructions, are commercially available.
Embodiment 1
A kind of Ce-Ni-B/GO composite deposition liquid, is calculated by every liter of solution, and its composition and content are as follows:
Cerium 0.1g
Nickel dichloride hexahydrate 20g
Sodium borohydride 0.5g
Sodium hydroxide 30g
Ethylenediamine 30g
Sodium lauryl sulphate 0.2g
Graphene oxide GO 0.5g
Surplus is water.
It is added sequentially to steam by cerium, Nickel dichloride hexahydrate, sodium borohydride, sodium hydroxide, ethylenediamine, sodium lauryl sulphate Dissolving in distilled water, the graphene oxide GO being subsequently adding surface modification joins in above-mentioned deposition liquid, finally regulates pH value To 14, i.e. obtain Ce-Ni-B/GO composite deposition liquid.
Embodiment 2
The multifunctional chemical composite deposition liquid of embodiment 1 gained is applied to surface of low-carbon steel to form the many merits of Ce-Ni-B/GO Can Composite electroless deposit layer, specifically include following steps:
(1), the surface of mild steel workpiece is removed by the pretreatment on the surface of carbon steel work-piece successively through 01#, 02# and 03 coated abrasive working Dirt, then with acetone at ultrasonic cleaner defat 60s, uses deionized water rinsing 1min;Use mass percent the most again Concentration is the chlorohydric acid pickling 30s of 20%, uses deionized water rinsing 1min;It is finally 5% with mass percent concentration Hydrochloric acid activation 15s, uses deionized water rinsing 1min;
(2), step (1) carbon steel work-piece after pretreatment is put in Ce-Ni-B/GO Composite electroless deposit liquid, solution temperature Controlling at 85 DEG C, rotating speed is 200r/min, and ultrasound intensity is at 200W, and supersonic frequency is taken out after 20KHZ, 1h, spends After ionized water carries out cleaning, controlling after temperature is dried at 25 DEG C, obtaining surface, to be coated with Ce-Ni-B/GO chemically composited The sample A of layer.Fig. 1 is the steel and alloy plating piece that the surface of embodiment 2 gained is coated with rare earth Graphene nickel boron Composite Coatings coating The scanning electron microscope (SEM) photograph of the coating surface of A.Result display coating is born of the same parents' shape, non-crystal structure.Coating is carried out Vickers hardness Measurement examination, hardness number is 638.3HV, and the corrosion electric current density order of magnitude has reached 10-5
Embodiment 3
A kind of Ce-Ni-B/GO composite deposition liquid, is calculated by every heave hydrops, and its composition and content are as follows:
Cerium 1g,
Nickel dichloride hexahydrate 30g
Sodium borohydride 1g
Sodium hydroxide 30g
Ethylenediamine 30g
Sodium lauryl sulphate 0.2g
Graphene oxide GO 4g
Surplus is distilled water.
Cerium, Nickel dichloride hexahydrate, sodium borohydride, sodium hydroxide, ethylenediamine, sodium lauryl sulphate are added sequentially to Distilled water dissolves, is subsequently adding the graphene oxide GO of surface modification, finally with ammonia regulation pH value to 14, to obtain final product To Ce-Ni-B/GO composite deposition liquid.
Embodiment 4
The composite deposition liquid of embodiment 3 gained is applied to steel surface compound heavy to form Ce-Ni-B/GO multifunctional nano Lamination, specifically includes following steps:
(1), the surface of carbon steel work-piece is removed by the pretreatment on the surface of carbon steel work-piece successively through 01#, 02# and 03 coated abrasive working Dirt, then with acetone at ultrasonic cleaner defat 60s, uses deionized water rinsing 1min;Use mass percent the most again Concentration is the chlorohydric acid pickling 30s of 20%, uses deionized water rinsing 1min;It is finally 5% with mass percent concentration Hydrochloric acid activation 15s, uses deionized water rinsing 1min;
(2), step (1) carbon steel work-piece after pretreatment is put in Ce-Ni-B/GO chemical sinking effusion, solution temperature Controlling at 85 DEG C, rotating speed is 200r/min, and ultrasound intensity is at 150W, and supersonic frequency is taken out after 25KHZ, 1h, uses After deionized water carries out cleaning, after control temperature is dried at 25 DEG C, obtains surface and be coated with Ce-Ni-B/GO chemistry again Close the sample B of sedimentary.Fig. 2 is that the surface of embodiment 4 gained is coated with the iron and steel of rare earth Graphene nickel phosphorus Composite Coatings coating and closes The scanning electron microscope (SEM) photograph of the coating surface of gold plating piece B.Result display coating is born of the same parents' shape, non-crystal structure.Coating is tieed up Family name's durometer is tested, and hardness number has reached 750.9HV, and the corrosion electric current density order of magnitude has reached 10-6
Embodiment 5
A kind of Ce-Ni-B composite deposition liquid, is calculated by every liter of solution, and its composition and content are as follows:
Cerium 1g
Nickel dichloride hexahydrate 30g
Sodium borohydride 1g
Sodium hydroxide 30g
Ethylenediamine 45g
Sodium lauryl sulphate 0.2g
Graphene oxide GO 8g
Surplus is distilled water.
It is added sequentially to cerium, Nickel dichloride hexahydrate, sodium borohydride, sodium hydroxide, ethylenediamine and sodium lauryl sulphate steam Distilled water is dissolved, is then added thereto to the GO of surface modification, and with ammonia regulation pH value to 14, i.e. obtains Ce-Ni-B/GO composite deposition liquid.
Embodiment 6
The composite deposition liquid of embodiment 5 gained is applied to steel surface compound heavy to form Ce-Ni-B/GO multifunctional chemical Lamination, specifically includes following steps:
(1), the surface of carbon steel work-piece is removed by the pretreatment on the surface of carbon steel work-piece successively through 01#, 02# and 03 coated abrasive working Dirt, then with acetone at ultrasonic cleaner defat 60s, uses deionized water rinsing 1min;Use mass percent the most again Concentration is the chlorohydric acid pickling 30s of 20%, uses deionized water rinsing 1min;It is finally 5% with mass percent concentration Hydrochloric acid activation 15s, uses deionized water rinsing 1min;
(2), by step (1) carbon steel work-piece after pretreatment putting in Ce-Ni-B/GO deposition liquid, bath temperature controls At 85 DEG C, rotating speed is 200r/min, and ultrasound intensity is at 200W, and supersonic frequency is taken out after 20KHZ, 1h, uses deionization After water carries out cleaning, after control temperature is dried at 25 DEG C, obtains surface and be coated with Ce-Ni-B/GO Composite electroless deposit The sample C of layer.Fig. 3 is the steel and alloy plating piece that the surface of embodiment 6 gained is coated with rare earth Graphene nickel phosphorus Composite Coatings coating The scanning electron microscope (SEM) photograph of the coating surface of C, result display coating is born of the same parents' shape, non-crystal structure.Coating is carried out Vickers Test, hardness number has reached 684.0HV, and corrosion electric current density has reached 10-6

Claims (6)

1. the ultrasound wave auxiliary preparation method thereof of a Ce-Ni-B/GO Composite electroless deposit layer, it is characterised in that it is first to low-carbon (LC) The surface of steel workpiece carries out pretreatment, is then put in Ce-Ni-B/GO composite deposition liquid by pretreated mild steel workpiece At a temperature of 80-90 DEG C ultrasonic, finally take out mild steel workpiece and be dried, i.e. prepare Ce-Ni-B/GO chemistry at surface of low-carbon steel multiple Close sedimentary;Wherein: in described Ce-Ni-B/GO composite deposition liquid, every heave hydrops includes following component: cerium 0.1~5g, Nickel dichloride hexahydrate 20~55g, sodium borohydride 0.5~4g, sodium hydroxide 20~65g, ethylenediamine 15~65 grams, dodecyl Sodium sulfate 0.1~2g, graphene oxide GO 0.1~10g.
Preparation method the most according to claim 1, it is characterised in that Ce-Ni-B/GO composite deposition liquid ammonia regulates body The pH value of system is between 13~14.
Preparation method the most according to claim 1, it is characterised in that ultrasound intensity between 100~700W, supersonic frequency Between 20~40KHZ, in ultrasonic procedure, rotating speed is 200r/min.
Preparation method the most according to claim 1, it is characterised in that pre-treatment step includes sand paper scrubbing successively, acetone Defat, chlorohydric acid pickling and four steps of hydrochloric acid activation.
Preparation method the most according to claim 1, it is characterised in that baking temperature is 15~25 DEG C.
6. the Ce-Ni-B/GO Composite electroless deposit layer obtained according to the preparation method one of claim 1-6 Suo Shu.
CN201610420175.7A 2016-06-13 2016-06-13 Ce-Ni-B/GO chemical composite deposition layer and ultrasonic-assisted preparation method thereof Pending CN105839082A (en)

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Cited By (5)

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CN106637158A (en) * 2016-12-27 2017-05-10 上海应用技术大学 Nd-Ni-Mo-P/Go chemical composite deposition layer and preparation method thereof
CN106756908A (en) * 2016-12-27 2017-05-31 上海应用技术大学 A kind of high temperature resistant Ni B Ce Composite electroless deposits layer and its ultrasound wave auxiliary preparation method thereof
CN106894006A (en) * 2017-03-22 2017-06-27 上海应用技术大学 A kind of plating solution, preparation method and applications for Electroless Plating Ni Mo B/GO multifunctional nano composite sedimentary layers
CN109252147A (en) * 2018-11-07 2019-01-22 武汉大学深圳研究院 Prepare method, chemical plating fluid and the plating liquid and preparation method thereof of copper-graphite alkene composite deposite
CN114874023A (en) * 2022-06-01 2022-08-09 内蒙古中晶科技研究院有限公司 Method for preparing carbon-carbon crucible bottom from carbon fiber preform

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CN106637158A (en) * 2016-12-27 2017-05-10 上海应用技术大学 Nd-Ni-Mo-P/Go chemical composite deposition layer and preparation method thereof
CN106756908A (en) * 2016-12-27 2017-05-31 上海应用技术大学 A kind of high temperature resistant Ni B Ce Composite electroless deposits layer and its ultrasound wave auxiliary preparation method thereof
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CN106894006A (en) * 2017-03-22 2017-06-27 上海应用技术大学 A kind of plating solution, preparation method and applications for Electroless Plating Ni Mo B/GO multifunctional nano composite sedimentary layers
CN109252147A (en) * 2018-11-07 2019-01-22 武汉大学深圳研究院 Prepare method, chemical plating fluid and the plating liquid and preparation method thereof of copper-graphite alkene composite deposite
CN114874023A (en) * 2022-06-01 2022-08-09 内蒙古中晶科技研究院有限公司 Method for preparing carbon-carbon crucible bottom from carbon fiber preform
CN114874023B (en) * 2022-06-01 2022-12-20 内蒙古中晶科技研究院有限公司 Method for preparing carbon-carbon crucible bottom from carbon fiber preform

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Application publication date: 20160810