CN1544707A - Process for preparing nickel-based nano-tube composite material by composite electrodeposition - Google Patents
Process for preparing nickel-based nano-tube composite material by composite electrodeposition Download PDFInfo
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Abstract
The invention is a method of preparing nickel-based nano carbon tube composite by compound electric deposition method, using any one of the common plating solution systems able to deposit nickel or nickel alloy as basic plating solutions, adding in nano carbon tube processed by routine purification as additive, thus composing a novel compound plating solution, then according to the general plating/chemical plating operating method, with the help of electrifying or spontaneous chemical reacting course, impelling deposition of nickel or nickel alloy on a certain substrate and making the condeposition of nano carbon tube and metal at the same time, and preparing the finished products. The nano carbon tube can be single-wall nano carbon tube and also multi-wall carbon tube. It has simple technique and prepares high-performance composite with the help of excellent properties of nano carbon tube.
Description
Technical field:
The present invention relates to the method that a kind of composite electrodeposition prepares nickel base nanometer carbon pipe matrix material, pass through electro-deposition method, it is effectively compound with metallic nickel that CNT (carbon nano-tube) is strengthened body as structure, constructs high performance nano composite material, belongs to the Composite Preparation technical field.
Background technology:
Composite electrodeposition be exactly by with the method for metal coelectrodeposition, with insoluble solid particulate, be mingled with the technology that forms matrix material in the metal plating equably.It comprises composite plating film and composite electroformed two classes, wherein, composite plating can prepare composite film material, be used for the surface modification and the film composite material preparation of material, the composite electroformed preparation that is used for thick-film composite material and general matrix material and member thereof, many times, composite electrodeposition generally is called composite plating technology.Through high speed development for many years, the composite electrodeposition material has become the important member of field of compound material, has obtained to use widely in engineering.
CNT (carbon nano-tube) is just found a kind of novel carbon structure in 1991, and it is seamless, the hollow tube body that is rolled into by the Graphene lamella that carbon atom forms.Generally can be divided into Single Walled Carbon Nanotube and multiple-wall carbon nanotube, Single Walled Carbon Nanotube is thinner; Multiple-wall carbon nanotube by which floor concentric tube intussusception to tens layers is formed, and it is much thick that the relative single-wall carbon tube of diameter is wanted.Because the diameter of CNT (carbon nano-tube) is very little, length-to-diameter ratio is big, so can be considered quasi-one-dimensional nanometer material.Comprehensive many-sided result of study, the expert thinks that CNT (carbon nano-tube) has excellent microcosmic mechanical characteristics, its intensity approximately is 100 times of steel, and density has only 1/6 of steel, and have good flexible, and therefore be referred to as super fiber, be suitable as very much enhancing body (CNT (carbon nano-tube) preparation, structure, rerum natura and the application of advanced composite materials, Chemical Industry Press, first version in 2002: 1-40).
In order to prepare metal-based nano carbon pipe matrix material, the researchist attempts to start with from the CNT (carbon nano-tube) surface modification, improves itself and metal matrix compound ability.It at first is the metallization of carbon tube-surface, be mixed with matrix material by alloying then, but, not only the surface modification of CNT (carbon nano-tube) is relatively more difficult, even the CNT (carbon nano-tube) of modification also is difficult to and the metal_based material uniform alloyization, chief reason is that the proportion between high-temperature operation and the two-phase differs too big.Also there is the investigator to prepare metal-based nano carbon pipe matrix material with the way of powder metallurgy, satisfactory but effect is difficult to equally, to trace it to its cause, powder extruding and follow-up high-temperature technology are difficult to guarantee that the stability of carbon pipe and biphase are effectively compound.
Analyze from the yardstick and the structural form of carbon pipe, they are particularly suitable for the modified materials as composite deposite, and electrodeposition technology has the outstanding advantage of normal temperature work, can not cause matching problem basic and wild phase because of preparation process temperature acute variation; Do not have intensive mechanical presses operation yet, can not cause the destruction of elongated carbon tubular construction; In addition also might be by the homodisperse ability of CNT (carbon nano-tube) in the solution phase, realize that it has a control uniform distribution in metallographic phase.However, Shang Weijian has the research report of CNT (carbon nano-tube) composite electrodeposition technology success, has only W.X.Chen (Carbon, 2003, Vol.41:215-222) attempt the research of composite chemical plating Ni-P alloy layer on CNT (carbon nano-tube), with this project that the directly compound technological approaches that enters among the metal matrix of CNT (carbon nano-tube) is different fully.
Summary of the invention:
The object of the present invention is to provide a kind of composite electrodeposition to prepare the method for nickel base nanometer carbon pipe matrix material,, improve the functional performance of nickel or nickel-bass alloy material with excellent specific property by CNT (carbon nano-tube).
For realizing such purpose, the present invention with can nickel deposited or the bath system various commonly used of nickelalloy as basic plating bath, CNT (carbon nano-tube) is added wherein as additive, formation can depositing nano carbon pipe matrix material the NEW TYPE OF COMPOSITE plating bath, then according to the working method of general plating/electroless plating, impel nickel or the nickelalloy sedimentary while on certain matrix by energising or spontaneous chemical reaction process, make CNT (carbon nano-tube) and metal codeposition, preparation metal-based nano carbon pipe matrix material.
The basic plating bath that can add CNT (carbon nano-tube) that the present invention adopts comprises the bath system of watt bath system of type nickel plating, the nickel plating of sulfamate type, the bath system of chloride type nickel plating, the bath system of sulfate type ferro-nickel alloy electroplating etc., also has the bath system of plating, chemical nickel phosphorus plating etc.CNT (carbon nano-tube) as additive both can be a Single Walled Carbon Nanotube, also can be multiple-wall carbon nanotube, handled but all need carry out conventional purifying removal of impurities earlier, and addition is preferably between the 0.05-2 grams per liter in the scope of 0.05-5 grams per liter.
The main body of composite plating bath is basic plating bath, and the proper operation condition and the basic plating bath of composite plating bath are approaching, and its institute can sedimentary composite material film, and is also similar at the nickel or the nickel alloy coating of simulated condition deposit to basic plating bath on apparent.
Composite plating bath also can be used as composite electroformed electrolytic solution and uses, and is used for prepared by electrodeposition thick film and block nanometer carbon pipe matrix material.
The character of basis plating bath has certain influence to the codeposition ability of CNT (carbon nano-tube) in the composite plating bath, generally speaking, the composite depositing process that the deposit surface luminance brightness is high, the codeposition amount of CNT (carbon nano-tube) is on the low side, otherwise also sets up.The CNT (carbon nano-tube) content of half light and coarse coating codeposition is higher.
The CNT (carbon nano-tube) of codeposition can be goed deep into coating inside, and is compound fully with metal matrix, and do not have tangible interfacial gap, meets the desirable way of realization of matrix material.
Adding the galvanic deposit electrolyte system of CNT (carbon nano-tube) need work under well-beaten condition, all can as magnetic force rotation stirring, liquid-flow stirring etc., the effect that stirs can influence the apparent pattern of coating, and is simultaneously also influential to the CNT (carbon nano-tube) content in the coating.
Plating bath circulating filtration purification system does not influence its work because of the existence of a large amount of CNT (carbon nano-tube) in the electrolytic solution, selects the aperture obviously greater than the millipore filter of CNT (carbon nano-tube) size, can't significantly hinder CNT (carbon nano-tube) and pass through.
The effect of CNT (carbon nano-tube) in the plating bath and all kinds of electroplating additives of not obvious change still has influence to a certain degree sometimes, can be remedied by adjusting modes such as content.
CNT (carbon nano-tube) is the core composition of composite plating bath of the present invention, and Single Walled Carbon Nanotube and multiple-wall carbon nanotube all can adopt, but all will pass through the purifying pre-treatment.Pretreated purpose mainly is to remove the charcoal of non-carbon pipe charcoal composition wherein and catalyzer etc., and in addition, it can also appropriateness increase the dispersiveness of carbon pipe in plating bath.
The length-to-diameter ratio of carbon pipe is can be with reference to one of factor of selecting, consider that from the intensity that improves matrix material length-to-diameter ratio is big more, helps bringing into play fiber strengthened effect more, but on the competition trend of disperseing and reuniting, suitable length-to-diameter ratio helps the homodisperse of CNT (carbon nano-tube).Test shows that the excessive Single Walled Carbon Nanotube of length-to-diameter ratio might cause reuniting again, also may be difficult to separately because of twining mutually, and many walls carbon nanotube that length-to-diameter ratio can not be too big is usually than being easier to form finely dispersed system.
The concentration of CNT (carbon nano-tube) has remarkably influenced to the content of CNT (carbon nano-tube) in the settling in the composite plating bath, consider from bath stability and operability, the concentration of CNT (carbon nano-tube) should be below 5g/L in the plating bath, too high concentration can make the flowability of solution be affected, and also may produce phenomenons such as coating is coarse, loose.If the content of CNT (carbon nano-tube) can satisfy basic demand in the coating, just should adopt the lower plating bath of CNT (carbon nano-tube) concentration as far as possible, such as the concentration range of 0.05-2g/L, most of bath systems all there is reasonable suitability.
Above-mentioned composite plating bath system of having added CNT (carbon nano-tube), to the deposition matrix do not have particular requirement, to basic bath system require similar.
The above-mentioned galvanic deposit electrolyte system that has added CNT (carbon nano-tube) can be adopted by mask plating or little electroforming system, with preparation high-performance microtexture or structural part, satisfies the demand of MEMS (micro electro mechanical system) to the high performance structures functional materials.
The above-mentioned prepared composite deposition thing of galvanic deposit electrolyte system that has added CNT (carbon nano-tube) can carry out following process according to the aftertreatment technology of conventional coating, with the sedimental surface property of further improvement.
The technology of preparation metal-based nano carbon pipe matrix material proposed by the invention is compared with other methods such as extrusion, melting mixing, and it is simple to have technology, low temperature moulding and compound more high-efficiency reliable remarkable advantage.According to matrix material constitute and characteristic between the universal relation rule, by the superior mechanical properties of CNT (carbon nano-tube), sedimentary nano composite material will have outstanding performance advantage in many-sides such as physical strengths.
Embodiment:
Further specify the implementation detail of technical scheme of the present invention below by a series of application examples, and the excellent properties that embodies of coating of the present invention.
Embodiment 1: the dark nickel base nanometer carbon of galvanic deposit pipe laminated film
Bath system: single nickel salt 200g/L, sodium-chlor 20g/L, boric acid 30g/L, Single Walled Carbon Nanotube 0.3g/L, sodium sulfate 20g/L, sal epsom 20g/L, adjusting the pH value with 2% dilute sulphuric acid or 1% diluted sodium hydroxide solution is 5.3.
Coating bath volume: 2 liters
Negative electrode: sheet copper, area 6cm * 2cm is through alkali cleaning, cleanup acid treatment.
The nickel plate of anode: 10cm * 10cm
The plating bath working temperature is at 30 ℃
The magnetic force rotation is stirred
Current density 0.8A/dm
2, 30 minutes time
Plating is after distilled water flushing, and seasoning
The basic plating bath of the composite plating bath of present embodiment except that CNT (carbon nano-tube) is a concrete example of common nickel plating bath, and it can deposit dark nickel coating, adds the 0.6-1.5g/L asccharin and just can electroplate semi-bright nickel.
Compound plating effect: the coating outward appearance presents darker metalluster, and is careful smooth, observes the microscopic appearance of coating under the emission Electronic Speculum on the scene, can see the distortion linear structure that distributes in the coating, is that the CNT (carbon nano-tube) metal covers the profile that forms.Certain amount of nano carbon pipe codeposition is arranged in coating through the small angle X-ray diffraction analysis.
Embodiment 2: galvanic deposit semi-bright nickel base CNT (carbon nano-tube) matrix material
Bath system: single nickel salt 320g/L, sodium-chlor 25g/L, boric acid 30g/L, Single Walled Carbon Nanotube 1g/L, sodium laurylsulfonate 0.08g/L, asccharin 1g/L, adjusting the pH value with 2% dilute sulphuric acid or 1% diluted sodium hydroxide solution is 5.
The plating bath working temperature is at 50 ℃.
Aqueduct volume: 2 liters
Negative electrode: steel sheet, area 6cm * 2cm is through alkali cleaning, cleanup acid treatment.
The nickel plate of anode: 10cm * 10cm
The magnetic force rotation is stirred
Cathode current density 1.5A/dm
2
30 minutes time
Plating is after distilled water flushing, and seasoning.
The basic plating bath of present embodiment is a concrete example of typical watt nickel electrolyte system, and it both can galvanic deposit semi-bright nickel coating, also can be used for electroforming processing nickel structural part, does not add asccharin wherein, just can the dark nickel coating of galvanic deposit.
Compound plating effect: adopt above-mentioned plating bath and corresponding work condition, the coating outward appearance that galvanic deposit obtains presents silvery white metalluster, careful smooth, observe under the emission Electronic Speculum on the scene, the apparent wire lines that presents many distortions of coating, pattern for CNT (carbon nano-tube) stays after metal covers has certain amount of nano carbon pipe codeposition in coating through the small angle X-ray diffraction analysis.This plating bath can be used for electroforming machining composite material member equally.
Embodiment 3: the Ni-based CNT (carbon nano-tube) matrix material of galvanic deposit light
Plating bath: single nickel salt 320g/L, nickelous chloride 40g/L, boric acid 35g/L, asccharin 1.5g/L, 1,4 butynediol 0.4g/L, Single Walled Carbon Nanotube 5g/L, the about 0.01g/L of sodium laurylsulfonate, adjusting the pH value with 2% dilute sulphuric acid or 1% diluted sodium hydroxide solution is 4.2.
Plating bath working temperature: 55 ℃.
Aqueduct volume: 2 liters
Negative electrode: the high carbon steel steel sheet, area 6cm * 2cm is through alkali cleaning, cleanup acid treatment.
The nickel plate of anode: 10cm * 10cm
The magnetic force rotation is stirred
Cathode current density 3A/dm
2, 30 minutes time.
Plating is after distilled water flushing, and seasoning.
The basic plating bath of composite plating bath is typical bright nickel bath system, is mainly used in galvanic deposit bright nickel coating.Add after the CNT (carbon nano-tube), just can the compound Ni-based film of galvanic deposit CNT (carbon nano-tube), the basic operating conditions of the remarkable plating bath of nano-sized carbon pipeline interpolation the change.
Compound plating effect: the coating outward appearance that galvanic deposit obtains is more smooth, and luminance brightness is slightly less than basic plating bath settling.Observe under the emission Electronic Speculum on the scene, the apparent wire lines that presents distortion of coating, the pattern for CNT (carbon nano-tube) stays after metal covers has certain amount of nano carbon pipe codeposition in coating through the small angle X-ray diffraction analysis.
Embodiment 4: the Ni-based CNT (carbon nano-tube) laminated film of barrel plating
Plating bath: single nickel salt 150g/L, nickelous chloride 60g/L, boric acid 30g/L, asccharin 1.5g/L, brightening agent is an amount of, multiple-wall carbon nanotube 1g/L, sodium laurylsulfonate 0.01g/L, adjusting the pH value with 2% dilute sulphuric acid or 1% diluted sodium hydroxide solution is 4.2.
The plating bath working temperature is at 60 ℃.
Aqueduct volume: 2 liters
Negative electrode: diameter 5mm, the soft steel cylinder of high 3mm, 40, through alkali cleaning, cleanup acid treatment.
The nickel plate of anode: 10cm * 10cm
The birdcage structure negative electrode carrier of simulation drum
Cathodic current 0.5A/dm
2, 30 minutes time.
Plating is after distilled water flushing, and seasoning.
The basic plating bath of present embodiment composite plating bath is the example of typical barrel plating bright nickel plating bath, is mainly used in finding surfacecti proteon and modification.Add after the CNT (carbon nano-tube), just can the compound Ni-based film of galvanic deposit CNT (carbon nano-tube), the interpolation of CNT (carbon nano-tube) does not change the basic operating conditions of plating bath.This plating bath needs continuous filtration when vat is worked, the adding of carbon pipe does not influence the operation of circulation filter.
Compound plating effect: the coating outward appearance that barrel plating obtains presents the metalluster of light, observe under the emission Electronic Speculum on the scene, the apparent wire lines that a small amount of distortion is arranged of coating, pattern for CNT (carbon nano-tube) stays after metal covers has a small amount of CNT (carbon nano-tube) codeposition in coating through the small angle X-ray diffraction analysis.
Embodiment 5: the Ni-based CNT (carbon nano-tube) matrix material of galvanic deposit low-stress
Plating bath: nickel sulfamic acid 400g/L, nickelous chloride 15g/L, boric acid 45g/L, Single Walled Carbon Nanotube 1.5g/L, adjusting the pH value with the nickel hydroxide solution of 2% dilute phosphoric acid or new preparation is 3.3.
The plating bath working temperature is at 60 ℃.
Aqueduct volume: 2 liters
Negative electrode: red copper sheet, area 6cm * 2cm is through alkali cleaning, cleanup acid treatment.
The pure nickel plate of anode: 10cm * 10cm
The magnetic force rotation is stirred
Cathode current density 6A/dm
2
30 minutes time
Plating is after distilled water flushing, and seasoning.
The basic plating bath of present embodiment composite plating bath is an example of typical nickel aminosulfonic bath, both can the dark nickel coating of galvanic deposit, also can be used for electroforming processing nickel structural part.Add after the CNT (carbon nano-tube), just can compound Ni-based film of galvanic deposit CNT (carbon nano-tube) or nickel-base composite material structural part.
Compound plating effect: the coating outward appearance that galvanic deposit obtains presents lead metalluster, smooth, observe under the emission Electronic Speculum on the scene, the apparent wire lines that presents many distortions of coating, pattern for CNT (carbon nano-tube) stays after metal covers has certain amount of nano carbon pipe codeposition in coating through the small angle X-ray diffraction analysis.This plating bath can be used for electroforming machining composite material member equally, and electroforming part surface is dross easily.
Embodiment 6: chemical plating nickel-phosphorus alloy base CNT (carbon nano-tube) composite deposite
Plating bath: single nickel salt 25g/L, inferior sodium phosphate 30g/L, lactic acid (80%) 30g/L, thiocarbamide 1mg/L, Single Walled Carbon Nanotube 0.3g/L, adjusting the pH value with 2% dilute sulphuric acid or 1% diluted sodium hydroxide solution is 4.4.
The plating bath working temperature is at 90 ℃.
Aqueduct volume: 2 liters
Unplated piece: mild-carbon steel strip, area 6cm * 2cm is through alkali cleaning, cleanup acid treatment.
The magnetic force rotation is stirred
30 minutes time
Plating is after distilled water flushing, and seasoning.
The basic plating bath of present embodiment composite plating bath is an example of typical acid chemical plating nickel solution, is used to deposit the nickel-phosphorus alloy of medium phosphorus content, adds after the CNT (carbon nano-tube), just can prepare CNT (carbon nano-tube) composite nickel-phosphorus thin-film material.
Compound plating effect: the coating outward appearance that deposition obtains presents silvery white metalluster, careful smooth, observe under the emission Electronic Speculum on the scene, the apparent wire lines that presents many distortions of coating, pattern for CNT (carbon nano-tube) stays after metal covers has the CNT (carbon nano-tube) codeposition of significant quantity in coating through the small angle X-ray diffraction analysis.
Embodiment 7: electric deposition nickel iron alloy base CNT (carbon nano-tube) matrix material
Plating bath: single nickel salt 100g/L, nickelous chloride 20g/L, boric acid 30g/L, ferrous sulfate 2g/L, asccharin 2g/L, xitix 3g/L, Single Walled Carbon Nanotube 1.5g/L, the about 0.08g/L of sodium laurylsulfonate, brightening agent is an amount of, and adjusting the pH value with 2% dilute sulphuric acid or 1% diluted sodium hydroxide solution is 3.2.
The plating bath working temperature is at 25 ℃.
Aqueduct volume: 2 liters
Negative electrode: steel sheet, area 6cm * 2cm is through alkali cleaning, cleanup acid treatment.
The nickel plate of anode: 10cm * 10cm
The magnetic force rotation is stirred
Cathode current density 1.0A/dm
2
30 minutes time
Plating is after distilled water flushing, and seasoning.
The basic plating bath of present embodiment composite plating bath is an example of typical soft magnetism Rhometal galvanic deposit plating bath, also can be used for electroforming processing Rhometal structural part, add after the CNT (carbon nano-tube), just can compound ferronickel base film of galvanic deposit CNT (carbon nano-tube) or ferronickel based composite material structure spare.
Compound plating effect: the coating outward appearance that galvanic deposit obtains presents the bright metal color and luster, smooth smooth, observe under the emission Electronic Speculum on the scene, the apparent wire lines that presents many distortions of coating, pattern for CNT (carbon nano-tube) stays after metal covers has certain amount of nano carbon pipe codeposition in coating through the small angle X-ray diffraction analysis.This composite plating bath can be used for electroforming machining composite material member equally.
Claims (3)
1, a kind of composite electrodeposition prepares the method for nickel base nanometer carbon pipe matrix material, it is characterized in that with can nickel deposited or the bath system various commonly used of nickelalloy as basic plating bath, to add wherein as additive through the CNT (carbon nano-tube) that conventional purifying removal of impurities is handled, addition is in the scope of 0.05-5 grams per liter, be preferably between the 0.05-2 grams per liter, formation can metal refining base CNT (carbon nano-tube) matrix material the NEW TYPE OF COMPOSITE plating bath, then according to the working method of general plating/electroless plating, with the approaching working conditions of basic plating bath under, impel nickel or the nickelalloy sedimentary while on certain matrix by energising or spontaneous chemical reaction process, make CNT (carbon nano-tube) and metal codeposition, deposition process is carried out under agitation condition, prepares Ni-based or nickel alloy base CNT (carbon nano-tube) matrix material.
2, composite electrodeposition as claimed in claim 1 prepares the method for nickel base nanometer carbon pipe matrix material, it is characterized in that the bath system of described basic plating bath for the bath system of the bath system of the bath system of the bath system of watt type nickel plating, the nickel plating of sulfamate type, chloride type nickel plating, sulfate type ferro-nickel alloy electroplating or plating, chemical nickel phosphorus plating.
3, composite electrodeposition as claimed in claim 1 prepares the method for nickel base nanometer carbon pipe matrix material, it is characterized in that described additive CNT (carbon nano-tube) is Single Walled Carbon Nanotube or multiple-wall carbon nanotube.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396825C (en) * | 2005-11-03 | 2008-06-25 | 武汉化工学院 | Process for producing metal-base nano-composite cladding material |
| CN102650072A (en) * | 2011-02-24 | 2012-08-29 | 新光电气工业株式会社 | Composite plating liquid |
| CN102703936A (en) * | 2012-06-28 | 2012-10-03 | 华南理工大学 | Carbon nano tube/cobalt composite coating and preparation method thereof |
| CN103556132A (en) * | 2013-11-08 | 2014-02-05 | 余姚市易通制动系配件厂 | Nickel-phosphor base composite plating solution containing SiC and graphene for aluminium alloy |
| 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 |
| CN103938255A (en) * | 2014-05-09 | 2014-07-23 | 浙江大学 | Preparation method of nickel-graphene complex phase |
| CN104862676A (en) * | 2015-03-25 | 2015-08-26 | 上海应用技术学院 | Graphene oxide nickel-phosphorus composite plating solution, preparation method and applications thereof |
| CN105220205A (en) * | 2015-11-03 | 2016-01-06 | 哈尔滨工业大学 | A kind of composite electrodeposition prepares the method for CNTs/Ni matrix material |
| CN112701306A (en) * | 2021-01-30 | 2021-04-23 | 江西理工大学 | Nickel iron/carbon film-nickel integrated composite electrode and preparation method thereof |
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2003
- 2003-11-13 CN CNA200310108548XA patent/CN1544707A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396825C (en) * | 2005-11-03 | 2008-06-25 | 武汉化工学院 | Process for producing metal-base nano-composite cladding material |
| CN102650072A (en) * | 2011-02-24 | 2012-08-29 | 新光电气工业株式会社 | Composite plating liquid |
| CN102650072B (en) * | 2011-02-24 | 2016-05-25 | 新光电气工业株式会社 | Composite plating solution |
| CN102703936A (en) * | 2012-06-28 | 2012-10-03 | 华南理工大学 | Carbon nano tube/cobalt composite coating and preparation method thereof |
| CN102703936B (en) * | 2012-06-28 | 2015-06-03 | 华南理工大学 | Carbon nano tube/cobalt composite coating and preparation method thereof |
| 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 |
| CN103556136B (en) * | 2013-08-26 | 2015-10-28 | 上海应用技术学院 | A kind of Graphene nickel-phosphorus electroless plating solution and its preparation method and application |
| CN103556132B (en) * | 2013-11-08 | 2015-09-30 | 余姚市易通制动系配件厂 | The nickel phosphorus base composite plating bath of a kind of aluminium alloy containing SiC and Graphene |
| CN103556132A (en) * | 2013-11-08 | 2014-02-05 | 余姚市易通制动系配件厂 | Nickel-phosphor base composite plating solution containing SiC and graphene for aluminium alloy |
| CN103938255A (en) * | 2014-05-09 | 2014-07-23 | 浙江大学 | Preparation method of nickel-graphene complex phase |
| CN104862676A (en) * | 2015-03-25 | 2015-08-26 | 上海应用技术学院 | Graphene oxide nickel-phosphorus composite plating solution, preparation method and applications thereof |
| CN104862676B (en) * | 2015-03-25 | 2017-08-25 | 上海应用技术学院 | A kind of graphene oxide nickel phosphorus composite plating bath and its preparation method and application |
| CN105220205A (en) * | 2015-11-03 | 2016-01-06 | 哈尔滨工业大学 | A kind of composite electrodeposition prepares the method for CNTs/Ni matrix material |
| CN105220205B (en) * | 2015-11-03 | 2018-02-02 | 哈尔滨工业大学 | A kind of method that composite electrodeposition prepares CNTs/Ni composites |
| CN112701306A (en) * | 2021-01-30 | 2021-04-23 | 江西理工大学 | Nickel iron/carbon film-nickel integrated composite electrode and preparation method thereof |
| CN112701306B (en) * | 2021-01-30 | 2022-03-22 | 江西理工大学 | Nickel iron/carbon film-nickel integrated composite electrode and preparation method thereof |
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