CN109440096B - Preparation method of aluminum alloy surface nano composite chemical conversion coating - Google Patents
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- CN109440096B CN109440096B CN201811238930.5A CN201811238930A CN109440096B CN 109440096 B CN109440096 B CN 109440096B CN 201811238930 A CN201811238930 A CN 201811238930A CN 109440096 B CN109440096 B CN 109440096B
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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- C23—COATING 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
- C23C—COATING 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
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
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- C23—COATING 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
- C23C—COATING 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
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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Abstract
The invention discloses a preparation method of a nano composite chemical conversion coating on the surface of an aluminum alloy, which comprises the following steps: b, soaking the aluminum alloy to be treated in a conversion solution to form a chemical conversion film on the surface of the aluminum alloy, wherein the conversion solution contains carbon nanotubes or nickel-coated carbon nanotubes; according to the invention, the novel modified chromium-free chemical nano composite membrane is rapidly prepared by adding CNT/Ni-CNT serving as an accelerant into a conversion solution containing Ti and Zr, and the formation time of a membrane layer is only 1-2 min; the CNT/Ni-CNT is added, so that the film layer is more smooth and compact; no obvious pores are found on the surface of the film layer, complete coverage is achieved in a short time, and the novel film layer shows more excellent corrosion resistance and conductivity on the base material.
Description
Technical Field
The invention relates to the field of metal surface treatment. More specifically, the invention relates to a preparation method of a nano composite chemical conversion coating on the surface of an aluminum alloy.
Background
Various series of aluminum alloys play an important role in advanced manufacturing processes, such as: the 6XXX series aluminum alloy is suitable for lightweight materials of automobile application, and is used for structures of automobile bodies, wheels, oil tanks, engine cover plates, motor shells and the like, the 2XXX series and the 7XXX series are used as novel high-strength aluminum alloys and are suitable for aerospace aircraft fuselages and many parts of instruments, and the 1XXX series and 8XXX series aluminum foils are widely used as current collectors of lithium ion batteries. Under natural conditions, the pure aluminum alloy surface has thin and porous oxide scale, and is easy to generate cavitation erosion, crevice corrosion and denudation. Scientific research and engineers have conducted a series of studies on corrosion protection of some types of aluminum alloys. The chemical conversion technology is widely applied to the surface treatment of aluminum alloy because of the advantages of simple required materials and manufacturing method, no high energy consumption in the process, good film forming effect on large-area or complex-shape workpieces, strong processing matching property and the like. The chromate chemical conversion technology is stable in process, the corrosion resistance of the passive film is excellent, the film layer is uniform and consistent in golden yellow, and the chromate chemical conversion technology is a process product with the largest application amount in the existing market. However, hexavalent chromium is a highly toxic pollutant and has carcinogenicity, and products containing hexavalent chromium are gradually forbidden in the market.
Researchers have conducted research around aluminum alloy titanium/zirconium conversion films, rare earth conversion films, permanganate conversion films, vanadate conversion films, organosilane films, and the like. Among them, the Ti-Zr based Cr-free conversion process was first proposed by U.S. company in the last 80 th century, and then a lot of research work was carried out by technicians of companies such as Henkel, Japanese Parker, etc., and the main salt of the process formula is zirconium fluoride/titanate. The titanium zirconium conversion film has excellent binding force with a paint film, zirconium metal salt is nontoxic, titanium metal salt is low in toxicity and relatively low in cost, and can be used as main salt for replacing hexavalent chromium. The Ti-Zr conversion film has the disadvantages of poor corrosion resistance, thin and colorless self-healing repair functional film layer without hexavalent chromium conversion film, no identification and no outstanding other functions.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a preparation method of a nano composite chemical conversion coating on the surface of an aluminum alloy, which comprises the following steps:
and step B, soaking the aluminum alloy to be treated in a conversion solution to form a chemical conversion film on the surface of the aluminum alloy, wherein the conversion solution contains carbon nano tubes or nickel-coated carbon nano tubes.
Preferably, in the preparation method of the aluminum alloy surface nanocomposite chemical conversion coating, the nickel-coated carbon nanotube is prepared by the following steps:
step A, adding the pretreated carbon nano tube into a chemical nickel plating solution, adjusting the solution to be alkaline, slowly dripping a sodium hypophosphite solution into the solution until no obvious phenomenon exists, stopping dripping, filtering and washing the solution to be neutral, and drying the solution to obtain a nickel-coated carbon nano tube; wherein the chemical nickel plating solution comprises sodium citrate, ammonium chloride and nickel sulfate.
Preferably, in the step B, the nickel-coated carbon nanotubes are activated by concentrated nitric acid before being added.
Preferably, in the preparation method of the aluminum alloy surface nanocomposite chemical conversion coating, in the step a, the carbon nanotubes are treated as follows before use: firstly, oxidizing and grinding, and then sensitizing and activating.
Preferably, in the preparation method of the aluminum alloy surface nano composite chemical conversion coating, the concentration of sodium citrate is 15-25g/L, the concentration of ammonium chloride is 25-35g/L, and the concentration of nickel sulfate is 25-35g/L in the chemical nickel plating solution.
Preferably, in the preparation method of the aluminum alloy surface nanocomposite chemical conversion coating, in the step a, the solution is adjusted to be alkaline, specifically: ammonia was added to the solution until pH 8.5-9.5.
Preferably, in the preparation method of the aluminum alloy surface nano composite chemical conversion coating, in the step A, the concentration of the sodium hypophosphite solution is 25-35 g/L.
Preferably, in the preparation method of the aluminum alloy surface nano composite chemical conversion coating, in the conversion solution, 28-36g/L of hexafluorotitanic acid and 6-10g/L of hexafluorotitanic acid, and 16-36g/L of nickel-coated carbon nano tubes are adopted.
Preferably, in the step a, after the pretreated carbon nanotubes are added to the electroless nickel plating solution, the aluminum alloy surface nanocomposite chemical conversion coating is subjected to ultrasonic treatment for 5 min.
Preferably, in the preparation method of the aluminum alloy surface nano composite chemical conversion coating, before the aluminum alloy is used, alkali washing oil removal and acid washing activation treatment are carried out on the aluminum alloy.
The invention at least comprises the following beneficial effects: the invention quickly prepares a novel modified chemical nano composite film layer by adding CNT/Ni-CNT (CNT-carbon nano tube, Ni-CNT-nickel coated carbon nano tube) as an accelerant into a Ti and Zr conversion solution, and the forming time of the film layer is only 1-2 min. The added CNT/Ni-CNT makes the film layer more flat and dense. Obvious pores are not found on the surface of the film layer, and the film layer is completely covered in a short time, so that the novel film layer shows more excellent corrosion resistance and conductivity on the base material.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an XPS spectrum of Ni-CNT prepared in example 2;
FIG. 2 is a TEM spectrum of Ni-CNT prepared in example 2;
FIG. 3 is an SEM of AA6061 for example 3 at different conversion reaction times: (a) a Ti-Zr conversion film, (b)1min, (c)2min, (d)4min and (e)10 min;
FIG. 4 is an SEM of AA6061 for example 4 at different conversion reaction times: (a)1min, (b)2min, (c)4min, and (d)10 min;
FIG. 5 is Tafel plots of bare, Ti-Zr/CNT, and Ti-Zr/Ni-CNT films of aluminum alloy AA 6061;
FIG. 6 is an AC impedance spectrum of a bare aluminum alloy AA6061, a Ti-Zr conversion film, a Ti-Zr/CNT conversion film, and a Ti-Zr/Ni-CNT conversion film.
Detailed Description
The present invention is described in further detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description.
Firstly, the operation steps
Example 1
The used material is 6061 aluminum alloy, and the sample size is 60mm x 30mm x 3mm by adopting a linear cutting process for processing. The bare material is pretreated by alkali cleaning, oil removal and acid cleaning activation, and a Ti-Zr chemical conversion film is prepared on an AA6061 alloy substrate by conversion solution treatment. The conversion solution is 32g/L hexafluorotitanic acid and 8g/L hexafluorotitanic acid, the reaction time is 2min, the reaction temperature is 25 ℃, and the reaction pH is 4; and (3) washing the treated substrate by deionized water, baking the substrate in an oven at 60 ℃ for 20min, and aging the substrate for 24h for further detection.
Example 2
2.1 preparation of Ni-CNT
The single-walled Carbon Nanotubes (CNTs) used in this study were provided by the institute of china institute, institute of organic chemistry, limited, and Ni-CNTs were prepared by putting sensitized and activated CNTs into a treatment solution of sodium citrate (complexing agent), ammonium chloride (buffer or stabilizer), nickel sulfate, and sodium hypophosphite. The process flow of the nickel coating treatment is divided into three steps. The method comprises the following specific steps: the first step is as follows: oxidizing and grinding; the second step is that: sensitizing and activating; a third part: and (4) nickel plating. The activated CNT is added into electroless nickel plating solution (20g/L sodium citrate, 30g/L ammonium chloride, 30g/L nickel sulfate) and is subjected to ultrasonic treatment for 5 min. Adjusting the pH value to 8.5-9.5 (ammonia water), keeping the temperature to 25 ℃, slowly dripping sodium hypophosphite solution (30g/L sodium hypophosphite), stopping reaction and filtration after no obvious phenomenon is seen, washing to be neutral, drying, and displaying the appearance of the prepared nickel-coated carbon nano tube that Ni metal is uniformly coated on the CNT (as shown in figure 1 and figure 2).
2.2 preparation of nanocomposite conversion films
The 6061 aluminum alloy to be treated is subjected to alkali cleaning oil removal and acid cleaning activation treatment, and then is soaked in a conversion solution to form a chemical conversion film on the surface of the aluminum alloy, wherein the conversion solution contains carbon nano tubes or nickel-coated carbon nano tubes. In the conversion solution, 32g/L of hexafluorotitanic acid and 8g/L of hexafluorotitanic acid, 16-36g/L of carbon nano tube or nickel-coated carbon nano tube, the reaction time is 1min, the reaction temperature is 25 ℃, and the reaction pH is 4.
Example 3
The preparation process is the same as that of example 2, with the following differences: 32g/L hexafluorotitanic acid, 8g/L hexafluorotitanic acid and 16g/L CNT (activated in concentrated nitric acid for 12h) in the conversion solution; the reaction time is 2min respectively;
example 4
The preparation process is the same as that of example 2, with the following differences: 32g/L hexafluorotitanic acid, 8g/L hexafluorotitanic acid and 32g/L Ni-CNT (activated in concentrated nitric acid for 6h) in the conversion solution; the reaction time is 1min respectively;
examples 1, 3 and 4 correspond to a Ti-Zr conversion film, a Ti-Zr/CNT conversion film and a Ti-Zr/Ni-CNT conversion film, respectively.
Second, characterization means
The Ni content of Ni-CNT was analyzed qualitatively by using ESCALB 250Xi (X-ray Photoelectron Spectrometer) XPS from Thermo Fisher Scientific, USA. The microstructure and structure of Ni-CNT were observed by JEM-2100 model Transmission Electron Microscope (TEM) in Japan. The surface morphology of the chemical composite membrane at different reaction times was observed using a Sigma300 Scanning Electron Microscope (SEM) of ZEISS corporation, germany, and its chemical composition was analyzed based on energy spectroscopy (EDS);
and analyzing the comprehensive performance of the Ti-Zr/Ni-CNT chemical composite film layer, and comparing the Ti-Zr/CNT chemical composite film layer with the Ti-Zr/CNT film layer and the Ti-Zr film layer. And detecting the corrosion resistance of the film layer through an acid dropping experiment, and recording the time for changing the dropping liquid from sky blue to light red as the corrosion resistance time. The electrochemical test is carried out by using CHI660D electrochemical workstation of Shanghai Chenghua company, the experimental medium is 3.5% (mass fraction) NaCl solution, and Tafel curve (scanning speed is 0.01 V.s) is carried out after the open circuit potential of the sample is stabilized in the NaCl solution-1) Scanning of alternating current impedance spectroscopy (EIS). When measuring EIS, the frequency testing range is 10-1-105Hz, a sinusoidal alternating voltage with an amplitude of 0.005V, and was measured at its self-etching potential.
Third, result and discussion
3.1SEM
SEM of Ti-Zr/CNT samples treated at different times is shown in FIG. 3, and surface topography of Ti-Zr/CNT samples untreated and treated at different times is shown in FIGS. 3(a) - (d). The bare AA6061 surface is smooth with some cracks and particles (fig. 3(a)), possibly caused by cracking of the brittle si-containing particles or embedding of debris during material processing. FIG. 3(b) shows a surface image of AA6061 treated in a conversion solution for 1min, with a large number of pores of different diameters present on the substrate surface, probably due to the porous structure formed by the hydrogen evolution that occurs during the formation of the film layer. When the treatment time was increased to 2min (FIG. 3(c)), the surface micropores were substantially completely covered with the vanishing film layer, and the corrosion resistance reached a large value. With the increase of the reaction time, the film layer has no obvious change on the appearance.
The surface topography of the Ti-Zr/Ni-CNT samples at different treatment times is shown in FIGS. 4(a) - (d). FIG. 4(a) shows that the surface of the film is relatively flat when the reaction time is 1min, and the change is not obvious along with the increase of the reaction time, which indicates that the film has a certain corrosion resistance when the reaction time is 1 min. Compared with a Ti-Zr/CNT chemical composite film; the microscopic appearance of the Ti-Zr/Ni-CNT chemical composite film layer is obviously smoother, and the film layer is more uniform.
3.2 acid drip experiment
The results of the copper sulfate dropping experiment are shown in table 1, and the dropping time shows the comprehensive corrosion resistance of the continuity and the pitting corrosion resistance of the film layer. The dropping time of AA6061 treated by the untreated and different treatment liquids is respectively as follows: 23s, 71s, 240s and 234 s. The resistance of the Ti-Zr film layer is obviously higher than that of untreated AA6061 (Table 1), and the dropping time of the Ti-Zr film layer is increased to about 4min after the CNT or Ni-CNT is added and is increased by 3 times compared with that of the Ti-Zr film layer. The similar drop-resistant time of the CNT or the Ni-CNT shows that the two additives play the same role in the film growth process, the integrity of the film layer is perfected by filling the gap of the film layer through adsorption, and the shielding effect on foreign corrosive substances is enhanced.
TABLE 1 copper sulfate drop test results
3.3 Corrosion electrochemical Performance analysis
FIG. 5 shows Tafel plots for bare materials before and after three experimental groups formed a film layer after 30 minutes immersion in 3.5 wt% NaCl solution. Corrosion current density (I)corr) Corrosion potential (E)corr) The anode Tafel slope (. beta.a) and cathode Tafel slope (. beta.c) are shown in Table 2, and I can be seencorr5.869 muA cm never formed into a film-2Respectively making the mixture to be 1.057 muA cm-2、 0.6223μA·cm-2And 0.7114. mu.A. cm-2。IcorrIs one of the most important parameters for evaluating the corrosion resistance of the material, IcorrThe smaller the value, the better the corrosion resistance of the material. The Ti-Zr film layer can effectively enhance the resistance performance of the surface of the aluminum alloy. The addition of the CNT/Ni-CNT can effectively improve the structure of the film layer, so that the film layer has more excellent corrosion resistance. As can be seen from the corrosion potentials obtained from the polarization curves, the untreated substrate has a significantly lower E than the other three samplescorr. Parameter EcorrIs the corrosion tendency of the material when polarized, and provides an indication of the susceptibility to corrosionAnd (5) displaying degree. E of Ti-Zr/Ni-CNT treated samples compared to bare AA6061(-0.945V)corrThe positive shift is 0.261V, and the corrosion resistance of the Ti-Zr/Ni-CNT film layer is increased to a certain extent compared with that of the B, C sample, which shows that the corrosion resistance of the Ti-Zr/Ni-CNT film layer is better, wherein the sample A is bare AA6061, the sample B is a Ti-Zr conversion film, the sample C is a Ti-Zr/CNT conversion film, and the sample D is a Ti-Zr/Ni-CNT conversion film.
TABLE 2 electrochemical parameters of Tafel curves
FIG. 6 is the AC impedance spectrum of AA6061 treated with different transformation liquids, and the analysis result of the film layer by ZSimDemo software can obtain the fitting circuit diagram thereof, wherein R isctThe film resistance is shown (table 3). Visible film resistance RctIncreased from 4010 Ω of experimental group A to 44920 Ω of Ti-Zr, but we can find that the film R is increased after the addition of CNTctThe sharp drop in (A) was the lowest at 8328 Ω when Ni-CNT was added. Film resistance RctOn one hand, the corrosion resistance of the film layer can be shown, and the conductivity of the film layer can also be shown. In the previous acidic dropping experiment and tafel curve, the Ti-Zr/Ni-CNT chemical composite film layer has similar corrosion resistance parameters with the Ti-Zr/CNT film layer, but the R of the Ti-Zr/Ni-CNT chemical composite film layer in the AC impedance spectrogramctThe value is only half of that of the Ti-Zr/CNT chemical composite film layer, which shows that the conductivity of the Ti-Zr/CNT chemical composite film layer is obviously higher than that of the Ti-Zr/CNT chemical composite film layer.
Table 3 parameters of AC impedance
Fourth, conclusion
By adding CNT/Ni-CNT as an accelerant into the Ti and Zr chemical conversion treatment solution, a novel modified chemical nano composite film is rapidly prepared, and the forming time of the film is only 1-2 min. The added CNT/Ni-CNT enables the film layer to be more flat and compact.
The film layer mainly consists of Al, O, C and Ti elements, contains a small amount of F, Zr elements, and is adsorbed CNT and oxide of aluminum and titanium. I of the chemically compounded film layer compared to an untreated substrate according to electrochemical testing of the film layercorrAbout one eighth of the original. It shows that the novel film layer shows more excellent corrosion resistance on the base material. Compared with a Ti-Zr/CNT chemical composite film, the Ti-Zr/Ni-CNT chemical composite film is more excellent in conductivity.
While embodiments of the invention have been disclosed above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in a variety of fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (8)
1. The preparation method of the aluminum alloy surface nano composite chemical conversion coating is characterized by comprising the following steps:
b, soaking the aluminum alloy to be treated in a conversion solution to form a chemical conversion film on the surface of the aluminum alloy, wherein the conversion solution contains nickel-coated carbon nanotubes; the conversion solution consists of 28-36g/L of hexafluorotitanic acid, 6-10g/L of hexafluorozirconic acid and 16-36g/L of nickel-coated carbon nano tube;
the nickel-coated carbon nanotube is prepared by the following steps:
step A, adding the pretreated carbon nano tube into a chemical nickel plating solution, adjusting the solution to be alkaline, slowly dripping a sodium hypophosphite solution into the solution until no obvious phenomenon exists, stopping dripping, filtering and washing the solution to be neutral, and drying the solution to obtain a nickel-coated carbon nano tube; wherein the chemical nickel plating solution comprises sodium citrate, ammonium chloride and nickel sulfate.
2. The method for preparing a nanocomposite chemical conversion coating on an aluminum alloy surface according to claim 1, wherein in the step B, the nickel-coated carbon nanotubes are subjected to concentrated nitric acid activation treatment before being added.
3. The method for preparing the aluminum alloy surface nanocomposite chemical conversion coating according to claim 1, wherein in the step A, the carbon nanotubes are treated as follows before use: firstly, oxidizing and grinding, and then sensitizing and activating.
4. The method for preparing the aluminum alloy surface nanocomposite chemical conversion coating according to claim 1, wherein the chemical nickel plating solution has a sodium citrate concentration of 15-25g/L, an ammonium chloride concentration of 25-35g/L, and a nickel sulfate concentration of 25-35 g/L.
5. The method for preparing the aluminum alloy surface nanocomposite chemical conversion coating according to claim 1, wherein in the step a, the solution is adjusted to be alkaline, specifically: ammonia was added to the solution until pH 8.5-9.5.
6. The method for preparing a nanocomposite chemical conversion coating on an aluminum alloy surface according to claim 1, wherein in the step A, the concentration of the sodium hypophosphite solution is 25 to 35 g/L.
7. The method for preparing the nanocomposite chemical conversion coating on the surface of the aluminum alloy according to claim 1, wherein in the step A, after the pretreated carbon nanotubes are added into the electroless nickel plating solution, the ultrasonic treatment is carried out for 5 min.
8. The method for preparing the aluminum alloy surface nanocomposite chemical conversion coating according to claim 1, wherein the aluminum alloy is subjected to alkali cleaning oil removal and acid cleaning activation treatment before use.
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| CN105316665A (en) * | 2015-11-03 | 2016-02-10 | 合肥海源机械有限公司 | Abrasion-resistant and scraping-resistant aluminum alloy chromium-free passivating agent and preparation method thereof |
| CN105316666A (en) * | 2015-11-03 | 2016-02-10 | 合肥海源机械有限公司 | Contamination-resistant aluminum alloy chromium-free passivating agent and preparation method thereof |
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| US4191596A (en) * | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| CA2072592A1 (en) * | 1990-02-21 | 1991-08-22 | Masayuki Yoshida | Conversion treatment method and composition for aluminum and aluminum alloys |
| US6764553B2 (en) * | 2001-09-14 | 2004-07-20 | Henkel Corporation | Conversion coating compositions |
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| CN105316665A (en) * | 2015-11-03 | 2016-02-10 | 合肥海源机械有限公司 | Abrasion-resistant and scraping-resistant aluminum alloy chromium-free passivating agent and preparation method thereof |
| CN105316666A (en) * | 2015-11-03 | 2016-02-10 | 合肥海源机械有限公司 | Contamination-resistant aluminum alloy chromium-free passivating agent and preparation method thereof |
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| "碳纳米管的表面改性与镍的包覆";易国军等;《中国有色金属学报》;20040331;第14卷(第3期);第479页右栏倒数第1-7行、第480页左栏第6行至倒数第1行及第480页右栏倒数第4行至第481页左栏第4行 * |
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