CN105506717A - Composite coating with high MWCNTs-nickel-tungsten content and preparation method for composite coating - Google Patents

Composite coating with high MWCNTs-nickel-tungsten content and preparation method for composite coating Download PDF

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Publication number
CN105506717A
CN105506717A CN201511000242.1A CN201511000242A CN105506717A CN 105506717 A CN105506717 A CN 105506717A CN 201511000242 A CN201511000242 A CN 201511000242A CN 105506717 A CN105506717 A CN 105506717A
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China
Prior art keywords
mwcnts
nickel
preparation
deionized water
composite coating
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CN201511000242.1A
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Chinese (zh)
Inventor
何毅
杨强斌
范毅
徐伟
李函
曾广勇
张磊
詹迎青
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Southwest Petroleum University
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Southwest Petroleum University
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Priority to CN201511000242.1A priority Critical patent/CN105506717A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current

Abstract

The invention discloses a composite coating with high MWCNTs-nickel-tungsten content. A preparation method for the composite coating comprises the following steps: (1) adding polyethyleneimine and sodium sulfate into deionized water to uniformly mix, then, adding MWCNTs to stir for one hour at a speed of 200r/min, carrying out suction filtration on the deionized water, and drying at a temperature of 60 DEG C to obtain PEI-modified MWCNTs; (2) weighing and sequentially adding trisodium citrate, NH4Cl, NaBr, Na2WO4.2H2O, NiSO4.6H2O and modified MWCNTs into the deionized water to uniformly mix, thereby obtaining an electroplating solution; (3) putting a grinded and polished steel plate into sulfuric acid with concentration being 1mol/L to activate, and then, electroplating the steel plate in the electroplating solution; and (4) adopting a pulse electro-deposition method in the electroplating process, wherein the deposition parameters are as follows: a temperature of 70 DEG C, current density of 5A/dm<3>, a duty ratio of 0.8 and deposition time of one hour. The composite coating is good in dispersion and is low in cost.

Description

A kind of high composite deposite containing MWCNTs-nickel-tungsten and preparation method thereof
Technical field
The invention belongs to composite deposite and fabricating technology field thereof, be specifically related to a kind of high composite deposite containing MWCNTs-nickel-tungsten and preparation method thereof.
Background technology
Composite plating adopts electrochemical method to make metal (or alloy) and solia particle (or fiber) codeposition, thus obtain composite deposite.Even if but in bath system of the same race, different dispersed particles due to surface tissue different with charge property, their depositions in matrix metal have very big difference, namely some particle is easier to precipitation in certain plating solution, and the deposition of some particle seldom or hardly deposits, thus the finishing of dispersed particle is very crucial for the successful preparation of composite deposite.
The high composite deposite containing MWCNTs (multi-walled carbon nano-tubes)-nickel-tungsten of existing preparation, adopts following several method usually: MWCNTs directly adds in plating solution and carries out codeposition by (1); (2) some tensio-active agents are added in the plating solution to improve MWCNTs dispersiveness in the plating solution, as added the tensio-active agents such as hexadecyl quaternary ammonium salt, sodium lauryl sulphate, triton x-100; (3) to the dispersiveness that MWCNTs carries out modification to improve in the plating solution, as acidifying carbon nanotube.But MWCNTs specific surface area is comparatively large, is easy in the plating solution reunite, after adding tensio-active agent, reduce interfacial tension, but limited to the improvement of MWCNTs dispersiveness effect, and under electroplating temperature, some tensio-active agent loses and improves dispersed effect, shows extremely unstable.Acidified MWCNTs, surface has some polar groups, and the water molecules in these polar groups and plating solution forms hydrogen bond, the dispersiveness of MWCNTs is made moderate progress, but in long electroplating process, the phase still can reunite after plating in this improvement, does not have persistence.
Summary of the invention
The present invention is directed to above-mentioned weak point and a kind of high composite deposite containing MWCNTs-nickel-tungsten of providing and preparation method thereof, adopt suitable processing condition to MWCNTs modification, improve its dispersiveness in the plating solution, and under electroplating temperature, still keep this dispersiveness well, obtain the plating solution of the MWCNTs of good distribution, carry out plating and realize high carbon nanotubes in coating.
For achieving the above object, the technical solution adopted for the present invention to solve the technical problems is:
A preparation method for the high composite deposite containing MWCNTs-nickel-tungsten, comprises the following steps:
(1) modification of MWCNTs
PEI (polymine) and sodium sulfate are added in deionized water and mix, and then add MWCNTs, under the rotating speed of 200r/min, stir 1h, after suction filtration, deionized water wash, 60 DEG C of dryings, obtain the MWCNTs of PEI modification;
(2) preparation of electroplate liquid
Take Na 3cit (trisodium citrate), NH 4cl, NaBr, Na 2wO 42H 2o, NiSO 46H 2o, modified MWCNTs, add in deionized water successively, before often adding a kind of material, should ensure that front a kind of material dissolves completely;
(3) to processing the early stage of plating piece
To polish successively base material 45# carbon steel with 400,800,1200 object sand paper, the sulfuric acid that 1mol/L put into by the steel disc of sanding and polishing is carried out activation 5-15s, puts into electroplate liquid after activation immediately and electroplate;
(4) pulse electrodeposition
Electroplating process adopts pulse electrodeposition method, deposition parameter: temperature 70 C, current density 5A/dm 3, dutycycle 0.8, depositing time 1h.
Further, in step (1), the mass ratio of polymine and MWCNTs is 0.8 ~ 1:1, and the mass ratio of sodium sulfate and MWCNTs is 5 ~ 5.5:1.
Further, trisodium citrate, NH in step (2) 4cl, NaBr, Na 2wO 42H 2o, NiSO 46H 2the concentration of O, modified MWCNTs is respectively 140-155g/L, 25-30g/L, 13-18g/L, 42-52g/L, 14-18g/L, 0.08-0.12g/L.
A kind of high composite deposite containing MWCNTs-nickel-tungsten provided by the invention and preparation method thereof, has following several beneficial effect:
(1) PEI modification is carried out to MWCNTs, its dispersiveness in the plating solution can be improved, and under electroplating temperature, still keep this dispersiveness well.
(2) with the MWCNTs of small amount, the high composite deposite containing MWCNTs-nickel-tungsten can be prepared, can reduce costs.
Embodiment
Embodiment 1
A preparation method for the high composite deposite containing MWCNTs-nickel-tungsten, comprises the following steps:
(1) modification of MWCNTs
0.5gPEI (polymine) and 2.6g sodium sulfate are added in 100mL deionized water and mixes, and then add 0.5gMWCNTs, under the rotating speed of 200r/min, stir 1h, after suction filtration, deionized water wash, 60 DEG C of dryings, obtain the MWCNTs of PEI modification;
(2) preparation of electroplate liquid
Take Na 3cit (trisodium citrate) 14.7g, NH 4cl2.67g, NaBr1.5g, Na 2wO 42H 2o4.6g, NiSO 46H 2o1.6g, modified MWCNTs0.01g, add in 100mL deionized water successively, before often adding a kind of material, should ensure that front a kind of material dissolves completely;
(3) to processing the early stage of plating piece
To polish successively base material 45# carbon steel with 400,800,1200 object sand paper, the sulfuric acid that 1mol/L put into by the steel disc of sanding and polishing is carried out activation 10s, puts into electroplate liquid after activation immediately and electroplate;
(4) pulse electrodeposition
Electroplating process adopts pulse electrodeposition method, deposition parameter: temperature 70 C, current density 5A/dm 3, dutycycle 0.8, depositing time 1h.
EDS sign is carried out to without PEI modification (unmodified) with through the composite deposite of the MWCNTs-nickel-tungsten of PEI modification (modification), C, O, Ni, W content in two kinds of coating is different, the results are shown in Table 1, the microhardness of two kinds of coating is tested simultaneously, the test of microhardness is 300g metallic nickel in applying weight, when loading time is 10-15s, test gets its mean value 5 times, and test result is in table 2.
Constituent content in the different coating of table 1
Content (wt%) C O Ni W
Unmodified 8.18 1.41 48.83 41.59
Modification 16.66 1.49 44.12 37.72
The microhardness of the different coating of table 2
From table 1 and table 2, in the composite deposite of the MWCNTs-nickel-tungsten of PEI modification, the content of MWCNTs is obviously improved, microhardness is compared with the composite deposite of the MWCNTs-nickel-tungsten without PEI modification, also obviously increase, this is because content higher contributing to of MWCNTs enhances the dispersion-strengthened action of nano material to coating, thus improves the microhardness of coating.

Claims (4)

1. a preparation method for the high composite deposite containing MWCNTs-nickel-tungsten, is characterized in that, comprise the following steps:
(1) modification of MWCNTs
Polymine and sodium sulfate are added in deionized water and mix, and then add MWCNTs, 200r/min stirs 1h, and after suction filtration, deionized water wash, 60 DEG C of dryings, obtain the MWCNTs of PEI modification;
(2) preparation of electroplate liquid
Take trisodium citrate, NH 4cl, NaBr, Na 2wO 42H 2o, NiSO 46H 2o, modified MWCNTs, add in deionized water successively, mixing;
(3) to processing the early stage of plating piece
To polish successively base material 45# carbon steel with 400,800,1200 object sand paper, the sulfuric acid that 1mol/L put into by the steel disc of sanding and polishing is carried out activation 5-15s, then put into electroplate liquid and electroplate;
(4) pulse electrodeposition
Electroplating process adopts pulse electrodeposition method, deposition parameter: temperature 70 C, current density 5A/dm 3, dutycycle 0.8, depositing time 1h.
2. the preparation method of a kind of high composite deposite containing MWCNTs-nickel-tungsten according to claim 1, it is characterized in that, in step (1), the mass ratio of polymine and MWCNTs is 0.8 ~ 1:1, and the mass ratio of sodium sulfate and MWCNTs is 5 ~ 5.5:1.
3. the preparation method of a kind of high composite deposite containing MWCNTs-nickel-tungsten according to claim 1, is characterized in that, trisodium citrate, NH in step (2) 4cl, NaBr, Na 2wO 42H 2o, NiSO 46H 2the concentration of O, modified MWCNTs is respectively 140-155g/L, 25-30g/L, 13-18g/L, 42-52g/L, 14-18g/L, 0.08-0.12g/L.
4. the height that the method as described in any one of claim 1-3 is prepared contains the composite deposite of MWCNTs-nickel-tungsten.
CN201511000242.1A 2015-12-25 2015-12-25 Composite coating with high MWCNTs-nickel-tungsten content and preparation method for composite coating Pending CN105506717A (en)

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CN109267121A (en) * 2018-11-20 2019-01-25 大连理工大学 A kind of method that composite electrodeposition prepares PtM/C catalyst

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Application publication date: 20160420