CN114655945A - Carbon nano tube surface coated amorphous or crystalline chromium oxide nano functional coating and preparation method and application thereof - Google Patents
Carbon nano tube surface coated amorphous or crystalline chromium oxide nano functional coating and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention belongs to the technical field of nano composite functional coatings, and particularly discloses a nano functional coating with amorphous or crystalline chromium oxide coated on the surface of a carbon nano tube, and a preparation method and application thereof. The method can prepare a nano-structure composite functional body, and the CNTs are coated with amorphous continuous Cr2O3A nano-coating; the amorphous chromium oxide nano coating in the composite functional body can be efficiently converted into crystalline Cr through heat treatment2O3Nano coatings or nano particles, CNTs and Cr2O3Nano coating or Cr2O3Passing Cr between nano particlesxCyThe nanometer transition layer is connected, and the microstructure of the nanometer coating can be accurately regulated and controlled by regulating the coating process and the heat treatment temperature. The method can reduce the length-diameter ratio of the CNTs, improve the interface adaptability of the CNTs and substrates such as metal, ceramic, polymer and the like, and can greatly expand the application field of the CNTs as a reinforcement or functional additive.
Description
Technical Field
The invention belongs to the technical field of nano composite functional coatings. Provides a carbon nano tube surface coating amorphous or crystalline chromium oxide nano functional coating and a preparation method and application thereof.
Background
Under the promotion of new technical revolution and industrial upgrading, the requirements of new generation information technology, high-end equipment manufacturing, new energy vehicles and other strategic emerging industries on the comprehensive properties (mechanical, optical, electrical, thermal and the like) of materials for key parts are higher and higher, such as the development of super integration and miniaturization of integrated circuits, the development of electrified railways, pulsed magnetic fields and the like are often limited by the material properties, and the compositing of materials becomes an important approach and development trend for meeting the multifunctional requirements. This is because the composite material can fully utilize the performance and structural advantages of each component material (matrix and reinforcement) to complement each other, and generate a synergistic effect, thereby not only retaining the important characteristics of the matrix material, but also coupling the unique performance of the original matrix material but also the reinforcement material.
The Carbon Nanotubes (CNTs) have good mechanical properties, conductivity, heat transfer performance, optics and other good properties, and the excellent comprehensive properties of the carbon nanotubes enable the carbon nanotubes to have great application potential in the field of composite material reinforcement and toughening and in the field of functionalization of electronic components and the like. However, the CNTs reinforcement prepared in the existing research still has a large difference between the composite effect of the composite material and the expected ideal value, and the main reasons can be summarized as the following two points: 1) CNTs have great length-diameter ratio and specific surface area, the CNTs are easy to be tangled and seriously agglomerated, when the CNTs are applied as a reinforcement, the CNTs often exist in an agglomerate form in a matrix material, and the matrix performance can be greatly deteriorated by the CNTs agglomerate and pores existing in the CNTs agglomerate under the condition of poor dispersion effect; 2) CNTs and base materials such as metal, ceramic, polymer and the like have the problem of weak interface bonding, and the potential huge composite effect of the CNTs is difficult to exert due to the weak interface bonding. Based on the existing needs and problems, in order to fully develop the potential composite effect of CNTs and prepare a high-performance CNTs reinforced composite material, two key problems of difficult dispersion of CNTs and weak bonding with a matrix interface need to be solved.
In addition, it should be noted that CNTs have a wide application prospect in the field of functionalized coatings, special functional structural members, and special functional materials, but are limited to the intrinsic properties of CNTs and cannot meet the requirements of specific functionalization in the related fields. Obviously, the CNTs coated with the functionalized coating can break through the limitation of the intrinsic characteristics of the CNTs, and the functionalized coating can reduce the agglomeration of the CNTs and improve the wettability problem of the CNTs and a matrix interface, so that the CNTs are endowed with specific functionalized characteristics while the technical problem is solved. Cr (chromium) component2O3Has the physical and functional characteristics of wear resistance, corrosion resistance, heat resistance, high hardness, high refractive index, antiferromagnetic property under 307K (TN) and the like, obviously represented by Cr2O3After the nano coating is modified, the composite effect of the CNTs as a reinforcement body of materials such as metal/ceramic/polymer and the like can be improved, and the application of the CNTs in other structural functional materials can be expanded, such as the fields of high-temperature-resistant inorganic pigments, super-hydrophobic functional film layers, wear-resistant, corrosion-resistant and heat-resistant functional coatings, high-temperature wear-resistant lubricating materials, organic catalysis/photocatalysis materials, photoelectromagnetic special functional materials and the like, so that the complex functional application is realized.
Disclosure of Invention
The invention aims to solve the application limit of a carbon nano tube as an enhancer or a functional material additive, and provides a carbon nano tube surface-coated amorphous or crystalline chromium oxide nano functional coating, and a preparation method and application thereof. The specific microstructure is that the surfaces of CNTs are coated with amorphous or crystalline Cr2O3Nano-coating, CNTs and Cr2O3Presence of chromium carbide (Cr)xCy) Nano transition layer, thereby enabling Cr2O3The nano-coating tightly encapsulates the CNTs. The method can greatly reduce the length-diameter ratio of the CNTs, solve the problem of wettability of the CNTs and various matrix interfaces and provide a solution for multifunctional application of the CNTs. The specific technical implementation route of the invention is as follows: purification of CNTs and their surfaceChemical functional groups are introduced, and the step can effectively improve the dispersity of the CNTs and provide Cr2O3Nucleation sites, then fully dispersing the nucleation sites, putting the solution into an inorganic Cr salt solution, and generating uniform amorphous Cr on the surface of the solution by a preferred chemical process2O3Nano coating, CNTs are coated with amorphous Cr2O3After coating, amorphous Cr can be treated by heat treatment2O3Transformation of nanocoatings into crystalline Cr2O3Nano-coating or crystalline Cr2O3And (3) granules.
CNTs and Cr2O3With Cr between nano-coatingsxCyThe nanometer transition layer is connected, and the further advantage is that Cr can be realized by adjusting the coating process and the heat treatment parameters2O3The crystallization behavior of the nano coating and the controllable optimization of the microstructure of the nano coating.
A method for preparing a carbon nano tube surface coated amorphous or crystalline chromium oxide nano functional coating comprises the following specific steps:
The mixed acid solution in the step (1) comprises concentrated nitric acid (98%) and concentrated sulfuric acid (67%), the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1:2.5-3.5, the mass volume ratio of CNTs to the mixed acid solution is 1:300-1000g/mL, the temperature of constant-temperature modification treatment is 30-90 ℃, preferably 50 ℃, and the time of constant-temperature modification treatment is 2-8 hours, preferably 5 hours.
And (2) after the modification treatment in the step (1) is finished, diluting the obtained product by 4-10 times of volume, carrying out suction filtration on the diluted CNTs, and washing to be neutral to obtain the purified CNTs for later use.
The main salt solution in the step (2) is Cr2(SO4)3、CrSO4、KCr(SO4)2、Cr2(CO3)3、Cr(NO3)3、CrCl3、CrBr3、Cr(CH3COO)3And CrPO4At least one of the solutions is prepared in a mass concentration of 0.002 to 0.5g/mL, preferably 0.01 to 0.25g/mL, and more preferably 0.01 to 0.1 g/mL. The mass-volume ratio of the CNTs to the main salt solution is 1:350-1500g/mL, and the ultrasonic treatment time for the dispersion treatment is 10-120 minutes.
The constant temperature in the step (3) is 30-60 ℃, preferably 50 ℃, the pH alkaline regulating solution is at least one of NaOH solution, KOH solution and the like, the mass concentration of the pH alkaline regulating solution is 0.005-0.1g/mL, preferably 0.025-0.1g/mL, the mass-to-volume ratio of the CNTs to the pH alkaline regulating solution is 1:100-650g/mL, the titration speed is 1.0-5 mL/min, preferably 3.5mL/min, and the reaction time is 10-60 minutes, preferably 30 minutes.
Preferably, after the reaction in step (3) is completed, the obtained reaction solution is dried and fully ground to obtain a self-assembly precursor CNTs-Cr (OH)3。
And (4) the inert atmosphere in the step (4) is Ar atmosphere and/or rare gas (more than or equal to 99.99%), the heating rate of the heat treatment is 5-20 ℃/min, the heat treatment temperature is 400-1200 ℃, and the heat treatment time is 10-60 minutes.
The carbon nanotube surface is coated with the amorphous or crystalline chromium oxide nano functional coating, and the coating is prepared by the method.
The carbon nano tube is a multi-wall carbon nano tube (the purity is more than or equal to 98%) produced by a chemical vapor deposition method.
The carbon nanotube surface is coated with an amorphous or crystalline chromium oxide nano functional coating and is applied to the preparation of structural functional materials or functional composite materials. The structural functional material is high-temperature resistant inorganic pigment, a super-hydrophobic functional film layer, a wear-resistant, corrosion-resistant and heat-resistant functional coating, a high-temperature wear-resistant lubricating material, an organic catalysis/photocatalysis material, a photoelectromagnetic special functional material and the like.
According to the step (1) of modification treatment, the surface oxygen-containing functional groups can be formed on the outer carbon wall of the multi-walled carbon nano tube under the action of the mixed acid solution, so that a good foundation is provided for the subsequent formation of a continuous nano coating precursor.
The nano-structure composite functional body obtained in the step (4) of the invention can be used for adjusting the Cr on the surface of the CNTs through adjusting the steps (1) to (3)2O3Content of Cr2O3The thickness of the nano-coating, etc.; cr can be effectively regulated and controlled by controlling different heat treatment temperatures in the step (4)2O3The crystallization behavior of the nanocoating and the nanocoating microstructure, which properties are further explained in the figures and examples.
The invention has the advantages that the uniform amorphous chromium oxide nano-coating can be grown on the carbon nano-tube, and the crystallization degree of the chromium oxide nano-coating and the nano Cr can be efficiently regulated and controlled by regulating the heat treatment temperature in the step (4)2O3The growth behavior of (c), etc.
The method provided by the invention is simple to operate, controllable in process, stable and efficient, is very suitable for industrial production, and is expected to realize engineering application in a plurality of the subdivision fields.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is an X-ray diffraction analysis pattern of the nanocomposite functional body in example 1 at different target reaction temperatures.
FIG. 2 is a graph of the results of X-ray photoelectron spectroscopy characterization of the nanostructured composite functional body in example 1 with a heat treatment temperature of 880 ℃.
FIG. 3 is a graph of the results of scanning transmission electron microscopy characterization of the nanostructured composite functional bodies in example 2 with a heat treatment temperature of 500 ℃.
FIG. 4 is a graph of the TEM characterization results of the nanostructured composite functional bodies with a heat treatment temperature of 500 ℃ in example 2.
FIG. 5 is a scanning transmission electron microscope characterization of the nanostructured composite functional bodies with a heat treatment temperature of 880 ℃ in example 3.
FIG. 6 is a graph of TEM characterization results of nanostructured composite functional bodies with a heat treatment temperature of 880 ℃ in example 3.
FIG. 7 shows TEM (left) and SAED (right) results of the nanostructured composite functional bodies obtained in example 4.
FIG. 8 shows the results of HRTEM characterization of CNTs obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The room temperature and the unspecified temperature are both 20-30 ℃.
Example 1:
And 4, putting the precursor product obtained in the step 3 into a tube furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the protection of Ar (99.99%) atmosphere, preserving heat for 10 minutes, cooling along with the furnace, and taking out to obtain the nano-structure composite functional body CNTs- (Cr)xCy,Cr2O3)。
In this example, the heat treatment temperature in step 4 was tested in a gradient manner at 60 deg.C, 500 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 880 deg.C, and 1100 deg.C to obtain nanostructured composite functional bodies CNTs- (Cr) with different annealing temperaturesxCy,Cr2O3). The X-ray diffraction (XRD) analysis pattern of the freshly prepared nanocomposite functionality is shown in figure 1.
As can be seen from FIG. 1, the plating precursors obtained in step 3 were treated at different temperatures in the presence of Cr2O3Obvious difference is shown on the crystallization behavior of the plating layer, the annealing product of the plating layer precursor which reacts at the temperature of 600 ℃ and below is an amorphous plating layer after the plating layer precursor is dried at the temperature of 60 ℃, the amorphous plating layer begins to crystallize at the temperature of about 650 ℃, and the amorphous plating layer is shown as crystallized Cr with higher purity2O3Coating of Cr with increasing temperature2O3The significant increase in peak intensity means that the coating is more abundantly oriented in the crystal planes, a phenomenon that will be further explained in the results of the microscopic characterization of the examples described below. Overall, this demonstrates that the nanostructured composite functional bodies can effectively control Cr by setting different heat treatment temperatures in step (4) during the implementation process2O3Crystallization behavior of the nanocoating.
Made newlyThe results of X-ray photoelectron spectroscopy (XPS) characterization of the nanostructured composite functional bodies with a heat treatment temperature of 880 ℃ are shown in FIG. 2. The left full spectrum characterization part in the graph shows that the chemical elements mainly comprise O, Cr and C, and the right full spectrum characterization part performs peak fitting on a Cr2p fine spectrum to show that the chemical components mainly comprise Cr2O3In the presence of chromium carbide compounds, chromium carbide (Cr)xCy) With Cr3C2、Cr7C3As the main component, this shows that the nano-structured composite functional body is made of CrxCyConnecting CNTs and Cr2O3Nanocoating, as further confirmed in the results of the microscopic characterization of the examples described below.
Example 2:
And 4, putting the precursor product obtained in the step 3 into a tube furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the protection of Ar (99.99%) atmosphere, preserving heat for 30 minutes, cooling along with the furnace, and taking out to obtain the composite work of the nano structureEnergy CNTs- (Cr)xCy,Cr2O3)。
Scanning Transmission Electron Microscopy (STEM) characterization of the freshly prepared nanostructured composite functional bodies is shown in figure 3. In FIG. 3, a is a part of a new CNTs- (Cr)xCy,Cr2O3) From which it can be seen that there is a reduction of at least one order of magnitude in the aspect ratio of CNTs with a diameter generally less than 50nm, indicating moderate nanocoating thickness. Further, the high resolution surface scanning element analysis result of the white rectangular frame selected area in the part a of fig. 3 is shown in the part b of fig. 3, and from the part b, the coating elements of the CNTs are Cr, O and C, and the nano coating is proved to be mainly chromium oxide, and the nano structure is formed into CNTs/CrxCy/Cr2O3。
The Transmission Electron Microscopy (TEM) characterization of the freshly prepared nanostructured composite functional bodies is shown in fig. 4. In FIG. 4, part a is a new CNTs- (Cr)xCy,Cr2O3) The microscopic morphology of (a); section c of fig. 4 is a High Resolution Transmission Electron Microscope (HRTEM) characterization map of the white oval boxed area labeled c in section a of fig. 4; part d of fig. 4 is an HRTEM image of the boxed area of the white rectangle marked d in part a of fig. 4; part b of fig. 4 is a plot of the Selected Area Electron Diffraction (SAED) results for the white rectangular box select area in part d of fig. 4.
From FIG. 4, it can be seen that the novel CNTs- (Cr)xCy,Cr2O3) The CNTs surface is evenly coated with nano coating with the thickness of 3-5nm, and the CNTs coated with the coating still keep higher crystallinity, the wall thickness is about 0.37nm, and the part b in figure 4 can determine that the coating of the embodiment mainly contains amorphous Cr2O3This is consistent with the 500 ℃ characterization results in fig. 1 of example 1. Overall, this fully confirms the nano-Cr2O33 the feasibility and partial superiority of coating CNTs, further explained in the microscopic characterization results of the examples described below.
Example 3:
And 4, putting the precursor product obtained in the step 3 into a tube furnace, heating to 880 ℃ at a heating rate of 10 ℃/min under the protection of Ar (99.99%) atmosphere, preserving heat for 30 minutes, cooling along with the furnace, and taking out to obtain the nano-structure composite functional body CNTs- (Cr)xCy,Cr2O3)。
STEM characterization results of the freshly prepared nanostructured complex functional bodies are shown in fig. 5. Part a in FIG. 5 is a new CNTs- (Cr)xCy,Cr2O3) The part b in FIG. 5 shows the result of further performing high-resolution elemental analysis on the white rectangular frame selected area in the part a in FIG. 5, and the part c in FIG. 5 shows the partially enlarged new CNTs- (Cr. sub.xCy,Cr2O3) The part d in fig. 5 is a STEM point scan result diagram of the white frame part c in fig. 5.
FIG. 5A shows that Cr is coated2O3CNTs (carbon nanotubes) in the form of short rods and irregular particlesThe particles are transformed, dispersed uniformly and increased in size significantly. From part a, it is statistically determined that the average size of irregular particles is about 60nm, the short rod-like particles are about 25nm thick, about 115nm long, and the aspect ratio is about 4.6, which is attributed to the increase of the reaction temperature in step 4 causing Cr to grow2O3The nano coating generates migration and local growth and growth phenomena appear. In FIG. 5, part a can see the degradation of part of the CNTs coating, but can still be found in the image. Referring to fig. 5 c, the main component of the particles is Cr2O3And CNTs/CrxCy. Overall, this demonstrates that different target reaction temperatures in step 4 can regulate the Cr coating on CNTs2O3Microstructure of nano-coating comprising Cr2O3Nanometer coating thickness, crystallized Cr2O3Nanoparticle size, as further explained in the microscopic characterization results described below.
TEM and HRTEM characterization of the freshly prepared nanostructured composite functional bodies are shown in fig. 6. In FIG. 6, part a is new CNTs- (Cr)xCy,Cr2O3) The microscopic morphology of (a); part b in fig. 6 is an HRTEM representation result map of the white rectangular frame selection area marked as part b in part a in fig. 6, and two small insets at the upper right corner and the left and right corners of part b in fig. 6 are respectively presented graphs of the inverse fourier transform (IFFT) performed on the two rectangular frame selection areas marked as parts 1 and 2 in part b in fig. 6; part c in fig. 6 is an HRTEM of the white rectangular frame selection area marked as c in part a in fig. 6, and the left and right small inset diagrams in the lower right corner of part c in fig. 6 are respectively presented by performing IFFT on the two rectangular frame selection areas marked as 3 and 4 in part c in fig. 6; in FIG. 6, the d part is a new CNTs- (Cr)xCy,Cr2O3) Local HRTEM micro-topography.
As can be seen from FIG. 6, as the reaction annealing temperature is increased in step 4, CNTs- (Cr) is newly preparedxCy,Cr2O3) Nano coating Cr coated on CNTs2O3Crystallization occurred, which is consistent with the XRD pattern of example 1. As is apparent from the portions b and c in FIG. 6, Cr is observedxCyThe existence of transition layer presents a uniform transitionTransitional state, after local corrosion of outer carbon wall of CNTs and Cr2O3Partially reacted, however, its crystallinity is relatively poor due to the possible presence of Cr in the examples, the reaction conditions failing to satisfy the thermodynamic conditions for promoting the complete reaction thereof3C2-xWhen the intermediate reactant is equal, C with better crystallinity can still be found in local area3C2Present as shown in fig. 6 at the c part 4 mark. From the local amplification result, Cr can be obviously found2O3The nano coating migrates and grows, the nano coating on the CNTs migrates to local part to grow irregular large particles, as shown in part d in figure 6, the particles are 6-10nm, the nano coating is obviously thinned, the thickness is about 1.1-1.6nm, and the thickness is far less than that of amorphous Cr shown in figure 4 in the embodiment 2 of low-temperature annealing (the reaction heat treatment temperature in the step 4 is less than 600 ℃)2O3And (4) nano coating.
Example 4:
TEM (left) and SAED (right) results for the new nanostructured composite functions are shown in FIG. 7, which differ from the new nanostructured composite functions in example 2 by better coating of CNTs and amorphous Cr coating on CNTs2O3The nano coating begins to transform into crystallized Cr2O3The nano coating shows amorphous and crystalline Cr by diffraction pattern results2O3The nanocoating coexisted, consistent with the XRD characterization of fig. 1.
Comparative example 1
And 3, performing magnetic stirring on the suspension obtained in the step 2 at room temperature, adding a magnetic rotor for stirring, weighing 1.15g of NaOH (95%) and 50mL of deionized water to prepare pH alkaline regulating solution, adding the pH alkaline regulating solution into the suspension for reacting for 30 minutes, drying the obtained reaction solution at the temperature of 60 ℃ for 24 hours, taking out the reaction solution, and fully grinding the reaction solution to obtain a newly prepared powder sample.
And 4, putting the powder sample obtained in the step 3 into a tube furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the protection of Ar (99.99%) atmosphere, preserving heat for 30 minutes, cooling along with the furnace, and taking out to obtain a new prepared comparison sample.
This comparative example differs from example 2 in that step 3 employs a different process.
The HRTEM characterization of CNTs obtained by this process is shown in FIG. 8, which indicates that the product CNTs have no Cr2O3Coating with the effect of uncoated Cr after the treatment of step 12O3As are the coated CNTs.
In summary, the nanostructure composite functional body described in the controllable method for coating the surface of the carbon nanotube with the amorphous or crystalline chromium oxide nano-functional coating can efficiently convert the amorphous chromium oxide nano-functional coating in the composite functional body into the crystalline Cr through different heat treatment processes2O3Nano coating or nano particles, and the microstructure (including Cr) of the nano coating can be precisely regulated and controlled by regulating the coating process and the heat treatment temperature2O3Content of Cr2O3Thickness of nano-coating, Cr2O3Nanoparticle size, etc.), which are explained in the above examples and drawings and which partly represent the advantages of the invention.
The above embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (10)
1. A method for preparing a carbon nano tube surface coated with an amorphous or crystalline chromium oxide nano functional coating is characterized by comprising the following specific steps:
step 1, adding CNTs into a mixed acid solution, and carrying out constant-temperature modification treatment to obtain standby CNTs;
step 2, preparing an inorganic main salt solution, and dispersing the standby CNTs obtained in the step 1 in the inorganic main salt solution to obtain a standby CNTs chemical suspension;
step 3, heating the suspension obtained in the step 2 and keeping the temperature constant, then adding pH alkaline regulating solution, reacting, and finally obtaining the productDrying to obtain a self-assembly precursor CNTs-Cr (OH)3；
Step 4, carrying out heat treatment on the precursor obtained in the step 3 under the protection of inert atmosphere to obtain the composite functional body CNTs- (Cr) containing the nano structurexCy,Cr2O3) The surface of the carbon nano tube is coated with an amorphous or crystalline chromium oxide nano functional coating.
2. The method of claim 1, wherein:
the main salt solution in the step (2) is Cr2(SO4)3、CrSO4、KCr(SO4)2、Cr2(CO3)3、Cr(NO3)3、CrCl3、CrBr3、Cr(CH3COO)3And CrPO4At least one of the solutions has a mass concentration of 0.002-0.5 g/mL.
3. The method of claim 1, wherein:
the mass-to-volume ratio of the CNTs to the main salt solution in the step (2) is 1:350-1500 g/mL.
4. The production method according to claim 1, characterized in that:
the mixed acid solution in the step (1) comprises concentrated nitric acid and concentrated sulfuric acid.
5. The method of claim 1, wherein:
the mass-volume ratio of the CNTs to the mixed acid solution in the step (1) is 1:300-1000 g/mL;
the temperature of the constant-temperature modification treatment is 30-90 ℃; the time of constant temperature modification treatment is 2-8 hours.
6. The method of claim 1, wherein:
the constant temperature in the step (3) is 30-60 ℃; the pH alkaline regulating solution is at least one of NaOH solution and KOH solution, the mass concentration of the pH alkaline regulating solution is 0.005-0.1g/mL, the mass-to-volume ratio of the CNTs to the pH alkaline regulating solution is 1:100-650g/mL, the titration speed is 1.0-5 mL/min, and the reaction time is 10-60 minutes.
7. The method of claim 1, wherein:
the heat treatment temperature is 400-1200 ℃, and the heat treatment time is 10-60 minutes.
8. The method of claim 1, wherein:
after the modification treatment in the step (1) is finished, diluting the obtained product by 4-10 times of volume, carrying out suction filtration on the diluted CNTs, and washing to be neutral to obtain purified CNTs for later use;
the dispersion treatment in the step (2) is ultrasonic treatment for 10-120 minutes;
and (4) the heating rate of the heat treatment in the step (4) is 5-20 ℃/min.
9. A carbon nano tube surface coated with an amorphous or crystalline chromium oxide nano functional coating, which is prepared by the method of any one of claims 1 to 8.
10. The use of the carbon nanotube surface-coated amorphous or crystalline chromium oxide nano-functional coating according to claim 9 in the preparation of a structural functional material or a functional composite material.
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