CN113582591B - Preparation method of densified titanium carbide composite film - Google Patents
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Abstract
The invention relates to a method for preparing a densified titanium carbide composite film, which comprises the steps of firstly, preparing a sodium carboxymethyl cellulose (CMC) and titanium carbide (Ti) 3 C 2 T x ) Nano-sheet adsorption construction Ti 3 C 2 T x CMC heterogeneous basic element material, assembling the heterogeneous basic element material into a hydrogen bond cross-linked titanium carbide (HBM) composite film through vacuum filtration, and finally soaking the HBM composite film in sodium tetraborate (Na) 2 B 4 O 7 ) In the water solution, the titanium carbide (SBM) composite film with orderly cross-linked hydrogen bonds and covalent bonds is prepared by vacuum calcination. The SBM composite film has the maximum compactness of 94.7 percent, the corresponding tensile strength of 583MPa, the Young modulus of 27.8GPa and the toughness of 15.9MJ/m 3 The conductivity is 6115S/cm, and the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 56.4dB.
Description
Technical Field
The invention relates to a preparation method of a densified titanium carbide composite film, belonging to the field of preparation of nano composite materials.
Background
Titanium carbide (Ti) 3 C 2 T x ) The nanosheet has excellent mechanical (Sci.adv.2018, 4, eaat 0491.) and electrical (appl.Phys.Lett.2016, 108, 033102.) performances, and has wide application prospects in the fields of flexible electronic devices, aerospace and the like (nat.Rev.Mater.2017, 2, 16098.), so that Ti needs to be added 3 C 2 T x Macroscopic high-performance Ti assembled by nanosheets 3 C 2 T x A nanocomposite material.
In recent years, scientists have produced a large number of high-performance layered Ti by using various interfacial crosslinking strategies 3 C 2 T x And (3) compounding the film. For example, gogotsi et al (Proc. Natl. Acad. Sci. USA 2014 111, 16676.) in Ti 3 C 2 T x Polyvinyl alcohol is introduced between layers, and Ti with high strength and conductivity is prepared through hydrogen bond crosslinking 3 C 2 T x Compounding a film; in Ti by Medium vibration et al (J.Mater.chem.C 2020,8, 1673.) 3 C 2 T x Aluminum ions are introduced between layers, and Ti with high strength and high efficiency electromagnetic shielding is prepared through the ionic bond crosslinking effect 3 C 2 T x Compounding a film; king et al (adv. Funct. Mater.2018,28, 1801511.) in Ti 3 C 2 T x Boric acid radical is introduced between layers, and rigid Ti is prepared through covalent bond crosslinking 3 C 2 T x A composite membrane having excellent gas separation performance; taylor et al (Nanoscale 2019,11, 20295.) prepare high-strength conductive Ti by enhancing toughening effect through montmorillonite nanosheets 3 C 2 T x Compounding a film; feng Xinliang et al (nat. Commun.2019,10, 2920.) prepare Ti with strength, toughness and integration and high-efficiency salt difference energy power generation through aramid nano-fiber reinforced toughening effect 3 C 2 T x Compounding a film; chengdu Peak et al (Proc. Natl. Acad. Sci. USA 2020,117, 27154.) in Ti 3 C 2 T x Sodium alginate and calcium ions are orderly introduced between layers, and high-strength conductive Ti is prepared through the cross-linking action of hydrogen bonds and ionic bonds 3 C 2 T x And (3) compounding the film. The above work in designing interfacial crosslinking strategies generally focuses only on Ti 3 C 2 T x The interface strength between the nanosheet layers is improved, and Ti is ignored 3 C 2 T x Structural defects between nanosheet layers. Although these interfacial crosslinking strategies improve Ti to some extent 3 C 2 T x The properties of the composite film, however, due to Ti 3 C 2 T x Larger pores exist among the nano-sheet layers, and the Ti 3 C 2 T x The mechanical and electrical properties of the composite film are still far lower than those of the corresponding single-layer Ti 3 C 2 T x The properties of the nanoplatelets, which greatly limit Ti 3 C 2 T x And (3) practical application of the film.
Therefore, there is a need to develop new interfacial crosslinking strategies that not only effectively enhance Ti 3 C 2 T x Interface strength between nanosheets and greatly eliminates Ti 3 C 2 T x Pores between the nano-sheet layers, thereby greatly improving Ti 3 C 2 T x Mechanical and electrical properties of the film. Up to now, there is no document and patent report on the preparation of densified titanium carbide composite films by utilizing hydrogen bonds and covalent bond ordered crosslinking.
Disclosure of Invention
The technical solution of the present invention is: the defects of the prior art are overcome, and the prepared film has higher compactness, excellent tensile strength, young modulus, toughness, conductivity and electromagnetic shielding efficiency.
The invention is realized by the following technical scheme: a process for preparing the densified titanium carbide composite film includes such steps as stirring at room temp to make sodium carboxymethyl cellulose (CMC) be adsorbed to Ti by hydrogen bond 3 C 2 T x Constructing Ti on the surface of the nano-sheet 3 C 2 T x -CMC heterogeneous elementary material; then Ti is filtered by vacuum filtration 3 C 2 T x -assembling the CMC heterogeneous elementary materials into a hydrogen-bond crosslinked titanium carbide (HBM) composite film; finally, soaking the HBM composite film in sodium tetraborate (Na) 2 B 4 O 7 ) In the water solution, the titanium carbide (SBM) composite film with orderly cross-linked hydrogen bonds and covalent bonds is prepared by vacuum calcination. The concrete implementation steps are as follows:
a preparation method of a densified titanium carbide composite film comprises the following steps:
(1) Mixing and ultrasonic processing Ti 3 C 2 T x Preparing uniform Ti 3 C 2 T x An aqueous solution;
(2) Under continuous stirring, adding Ti 3 C 2 T x Adding CMC aqueous solution into the aqueous solution drop by drop to ensure that the CMC is adsorbed on the Ti through hydrogen bond 3 C 2 T x Nanosheet surface to obtain Ti 3 C 2 T x -a dispersion of CMC heterogeneous cellular material;
(3) Vacuum filtering the Ti 3 C 2 T x Assembling the CMC heterogeneous elementary material dispersion into the HBM composite film;
(4) Soaking the HBM composite film in Na 2 B 4 O 7 And washing and vacuum calcining the mixture in a water solution to obtain the SBM composite film.
In the step (1), the Ti 3 C 2 T x The aqueous solution contains Ti 3 C 2 T x A nanosheet.
In the step (1), ti 3 C 2 T x The concentration of the aqueous solution is 0.5-1 mg/mL, and the solution is continuously stirred and subjected to ultrasonic treatment to Ti 3 C 2 T x Introducing argon into the aqueous solution, stirring for 3-5 min, performing ultrasonic treatment for 1-2 min, and performing ultrasonic treatment in an ice-water bath at a power of 50-70W to prevent Ti from being damaged 3 C 2 T x In the case of the nanosheet structure, ti is uniformly dispersed 3 C 2 T x A nanosheet.
In the step (2), the concentration of the CMC aqueous solution is 0.25-0.5 mg/mL, and the CMC aqueous solution is continuously stirred to Ti 3 C 2 T x Introducing argon into the mixed aqueous solution of CMC to prevent Ti 3 C 2 T x Oxidized; the stirring time is 5-10 min, so that the CMC is fully adsorbed on the Ti 3 C 2 T x The surface of the nanosheet; obtained Ti 3 C 2 T x -Ti in the dispersion of the CMC foreign-cellular material 3 C 2 T x The mass ratio of the titanium dioxide to the CMC is 8.5-9.5, and too little CMC can not completely coat Ti 3 C 2 T x Nanosheets, too much CMC will be at Ti 3 C 2 T x Excessive deposition on the surface of the nano sheet is not beneficial to Ti in the vacuum filtration process in both cases 3 C 2 T x -densified assembly of CMC heterogeneous elementary materials, and subsequent borate ion with CMC and Ti 3 C 2 T x And crosslinking the nanosheets.
In the step (3), a vacuum filtration method is adopted, and the specific implementation process comprises the following steps:
(1) Firstly, evenly stirring Ti 3 C 2 T x -adding the dispersion of the CMC heterogeneous cellular material drop by drop into a vacuum flask;
(2) Starting a vacuum pump, and carrying out vacuum filtration, wherein the vacuum degree is 0.5-1 Pa;
(3) With the progress of suction filtration, ti 3 C 2 T x Assembling the CMC heterogeneous basic material into a laminated structure under the action of water flow, and obtaining the HBM composite film after suction filtration is finished.
Said step (4)) In, na 2 B 4 O 7 The concentration of the aqueous solution is 1-9 mg/mL, and the borate ions with too low concentration cannot react with CMC and Ti 3 C 2 T x The nanosheets are fully crosslinked, and too high a concentration of borate ions will react with CMC and Ti 3 C 2 T x The nano sheets are excessively crosslinked, the compactness and the mechanical property of the SBM composite film are not favorably improved, the preferable concentration range is 4-8 mg/mL, and Na is used for better optimizing the compactness and the performance of the SBM composite film 2 B 4 O 7 The concentration of the aqueous solution is respectively selected to be 1mg/mL, 2mg/mL, 4mg/mL and 8mg/mL, and the corresponding prepared 4 SBM composite films are respectively marked as SBM-I, SBM-II, SBM-III and SBM-IV; in Na 2 B 4 O 7 The soaking time in the water solution is 12-14 h, so that borate ions can fully permeate into the film to be crosslinked.
In the step (4), the washing method comprises the steps of soaking in deionized water for 20-30 min to completely remove the uncrosslinked borate ions; the vacuum calcination procedure is that the vacuum calcination is carried out for 3.5 to 4.5 hours at the temperature of between 85 and 95 ℃, the vacuum degree is 1 to 5Pa, and borate ions, CMC and Ti are added 3 C 2 T x The nanosheets further undergo a dehydration condensation reaction to form a more compact covalently crosslinked network.
In the step (4), the boron element content of the prepared SBM composite film is 0.33-1.5 wt%.
In the step (4), the prepared SBM composite film is circular, the diameter is 2-4 cm, the thickness range is 1-10 mu m, an excessively thin film is not easy to prepare, and an excessively thick film is easy to prepare in Ti during the preparation process 3 C 2 T x Additional pores are formed between the nano-sheet layers, which is not beneficial to improving the compactness and the performance.
The principle of the invention is as follows: through the evolution of hundreds of millions of years, the natural abalone shell has excellent mechanical properties, mainly due to the compact layered structure and rich interface interaction, and is characterized in that a small amount of flexible natural organic matrix can be used for filling the pores among rigid calcium carbonate micron sheets, so that the compactness and the mechanical properties of the shell are greatly improved. Inspired by this, the invention is in Ti 3 C 2 T x A small amount of flexible hydrogen bond crosslinking agent and covalent crosslinking agent with strong adhesive force are orderly introduced between layers to promote Ti 3 C 2 T x Interlayer interface strength and effective elimination of Ti 3 C 2 T x Pores between layers, thereby preparing densified Ti 3 C 2 T x The composite film greatly improves the mechanical and electrical properties. Compared with the prior preparation of Ti 3 C 2 T x Compared with the technology of the composite film, the invention has the characteristics and advantages that:
(1) CMC molecular chain is softer and can be effectively filled in rigid Ti 3 C 2 T x Pores are eliminated among the nanosheet layers; in addition, CMC has great amount of hydroxyl groups in its molecular chain capable of reacting with Ti 3 C 2 T x F, OH and = O functional groups on the surface of the nano sheet are subjected to hydrogen bond crosslinking, so that Ti is promoted 3 C 2 T x Interlayer interface strength;
(2) The borate ions have small size and can permeate Ti 3 C 2 T x In the micro pores of the film, further with CMC and Ti 3 C 2 T x Covalent crosslinking is carried out on the nano sheets to heal the micro pores, so that the compactness and Ti of the film are further improved 3 C 2 T x Interlayer interface strength;
(3) The hydrogen bond and covalent bond ordered crosslinking strategy can greatly improve Ti under the condition of introducing a small amount of CMC and borate ions 3 C 2 T x The mechanical property of the composite film is effectively maintained, and Ti is effectively maintained 3 C 2 T x The intrinsic high conductivity of the conductive material.
Therefore, the SBM composite film prepared by the invention has higher compactness (90.8-94.7%), high tensile strength (432-583 MPa), high Young modulus (14.2-27.8 GPa) and high toughness (12.2-15.9 MJ/m) 3 ) High conductivity (5850-6484S/cm) and excellent electromagnetic shielding effectiveness (55.3-59.1 dB).
Drawings
FIG. 1 shows a process for preparing a densified SBM composite film, comprising: firstly, CMC molecules are adsorbed on Ti by stirring 3 C 2 T x Constructing Ti on the surface of the nanosheet 3 C 2 T x -CMC heterogeneous elementary material; then vacuum filtering is adopted to remove the Ti 3 C 2 T x -assembling the CMC heterogeneous elementary materials into the HBM composite film; finally, soaking the HBM composite film in Na 2 B 4 O 7 In the water solution, washing and vacuum calcining are carried out to obtain a compact SBM composite film;
FIG. 2 shows uncrosslinked Ti 3 C 2 T x (MXene), HBM, covalently crosslinked Ti 3 C 2 T x (CBM), SBM-III film A) Scanning Electron Microscope (SEM) picture of ion beam cut section and B) compactness;
FIG. 3 shows A) X-ray diffraction (XRD) curves and B) infrared spectra (FTIR) of MXene, HBM, CBM, SBM-III films, C) Ti 2p, D) X-ray photoelectron spectroscopy (XPS) of C1 s of SBM-III composite films; compared with the MXene film, the interlayer spacing of the CBM composite film is reduced mainly due to the covalent crosslinking effect of borate ions, and the interlayer spacing of the HBM composite film is increased mainly due to the insertion of larger CMC molecular chains into Ti 3 C 2 T x Interlamination; compared with MXene film, the (-OH peak is positioned at 3432 cm) -1 ) the-OH peak of the HBM composite film was red-shifted to 3418cm -1 With the simultaneous appearance of a new-COO - Peak (1591 cm) -1 ) Mainly due to hydrogen bonding crosslinking of CMC, while the-OH peak (3432 cm) of the CBM composite film -1 ) The intensity is reduced, and a new B-O peak (1125 cm) appears -1 ) Mainly due to the covalent crosslinking of borate ions; ti of SBM-III compared to HBM (455.8 eV and 457.1 eV) 2+ (I,II,IV)2p 3/2 And Ti 3+ (I,II,IV)2p 3/2 The peak was shifted up to 456.4eV and 457.6eV, respectively, while the C-OH peak intensity was decreased and a new C-O-B peak (286.4 eV) appeared, further confirming borate ion together with CMC and Ti 3 C 2 T x Covalent crosslinking of the nanosheets;
FIG. 4 shows the A) tensile stress-strain curve and B) tensile strength, young's modulus, toughness, electrical conductivity, and shielding factor against electromagnetic waves having a frequency of 0.3 to 18GHz of MXene, HBM, CBM, SBM-III thin films;
FIG. 5 shows an SBM-III film and a literature report of Ti 3 C 2 T x Tensile strength, electrical conductivity and toughness of the composite film.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments. The following examples are only for explaining the present invention, the scope of the present invention shall include the full contents of the claims, and the full contents of the claims of the present invention can be fully realized by those skilled in the art through the following examples.
As shown in fig. 1, the method of the present invention is implemented as: firstly stirring at room temperature to make CMC adsorbed on Ti by means of hydrogen bond action 3 C 2 T x Constructing Ti on the surface of the nano-sheet 3 C 2 T x -CMC heterogeneous elementary material; then Ti is filtered by vacuum filtration 3 C 2 T x -assembling CMC heterogeneous base material into HBM composite film; finally, soaking the HBM composite film in Na 2 B 4 O 7 And (3) in the aqueous solution, and then carrying out vacuum calcination to obtain the SBM composite film. By changing Na 2 B 4 O 7 The concentration of the aqueous solution can regulate and control the content of the boron element in the SBM composite film through covalent crosslinking, thereby optimizing the compactness and the performance of the SBM composite film. When the content of boron element is 0.97wt%, the performance of the SBM composite film is optimal and is marked as SBM-III, the compactness of the SBM composite film is as high as 94.7%, the corresponding tensile strength is 583MPa, the Young modulus is 27.8GPa, and the toughness is 15.9MJ/m 3 The conductivity is 6115S/cm, and the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 56.4dB.
The Ti 3 C 2 T x The nano-film is a two-dimensional nano-film, the surface of the nano-film contains functional groups such as-F, -OH, = O and the like, and the nano-film is easy to dissolve in water; the biomacromolecule is CMC, the molecular chain of which contains a large number of hydroxyl groups, and not only can be reacted with Ti 3 C 2 T x The functional groups on the surface of the nanosheet are subjected to hydrogen bond crosslinking and can be subjected to covalent bond crosslinking with borate ions; the covalent cross-linking agent is borate ion and can be added into CMC,CMC and Ti 3 C 2 T x 、Ti 3 C 2 T x With Ti 3 C 2 T x Form stronger covalent bonds.
The titanium carbide composite film with orderly cross-linked hydrogen bonds and covalent bonds is circular, the corresponding diameter is 2-4 cm, and the thickness range is 1-10 mu m.
Example 1
0.5mg/mL of Ti was prepared in advance 3 C 2 T x Aqueous solution: 18mg of Ti were weighed 3 C 2 T x Adding the mixture into 36mL of deionized water, mechanically stirring for 3min under the protection of continuously introducing argon, and then ultrasonically dispersing for 1min in an ice-water bath (60W) to obtain a dark green solution; preparing 0.25mg/mL CMC water solution: weighing 10mg of CMC, adding into 40mL of deionized water, mechanically stirring for 35min, and then ultrasonically dispersing for 15min in an ice-water bath (60W); preparation of 1mg/mL Na 2 B 4 O 7 Aqueous solution: weighing 10mg of Na 2 B 4 O 7 Adding the mixture into 10mL of deionized water, mechanically stirring for 5min, and then ultrasonically dispersing for 1min in an ice-water bath (60W); then Ti prepared by the method is stirred continuously under the protection of argon 3 C 2 T x Dropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained 3 C 2 T x Dropwise adding the CMC heterogeneous elementary material dispersion liquid into a vacuum filtration bottle, then starting a vacuum pump, and carrying out vacuum filtration when the vacuum degree is 0.7Pa to ensure that Ti is subjected to vacuum filtration 3 C 2 T x -assembling the CMC heterogeneous elementary materials into a layered HBM composite film under the action of water flow; finally, the HBM composite film is soaked in the prepared Na 2 B 4 O 7 Soaking and washing the Ti in the aqueous solution for 25min by using deionized water after being taken out, and calcining the Ti in a vacuum oven (the temperature is 90 ℃ and the vacuum degree is 3 Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds 3 C 2 T x (SBM-I) composite film, the diameter of the SBM-I composite film is 4cm, and the thickness of the SBM-I composite film is 3.1 +/-0.2 mu m.
The content of boron element in the SBM-I composite film is 0.33wt%; the density test shows that the compactness of the product is 90.8%; for 3 to 5The mechanical and electrical property test of the sample strip (3 multiplied by 10 mm) shows that the tensile strength is 432 +/-17 MPa, the Young modulus is 14.2 +/-0.8 GPa, and the toughness is 13.1 +/-0.7 MJ/m 3 The conductivity is 6484 +/-59S/cm; the electromagnetic shielding effectiveness test shows that the shielding coefficient of the electromagnetic wave shielding material to the electromagnetic wave with the frequency of 0.3-18 GHz is about 59.1dB.
Example 2
0.5mg/mL of Ti was prepared in advance 3 C 2 T x Aqueous solution: 18mg of Ti were weighed 3 C 2 T x Adding the mixture into 36mL of deionized water, mechanically stirring for 3min under the protection of continuous argon, and then ultrasonically dispersing for 1min in an ice-water bath (60W) to obtain a dark green solution; preparing 0.25mg/mL CMC water solution: weighing 10mg of CMC, adding into 40mL of deionized water, mechanically stirring for 35min, and then ultrasonically dispersing for 15min in an ice-water bath (60W); 2mg/mL of Na is prepared 2 B 4 O 7 Aqueous solution: weighing 20mg of Na 2 B 4 O 7 Adding the mixture into 10mL of deionized water, mechanically stirring for 5min, and then dispersing for 1min by ice-water bath ultrasound (60W); then Ti prepared by the method is stirred continuously under the protection of argon 3 C 2 T x Dropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained 3 C 2 T x Dropwise adding the CMC heterogeneous elementary material dispersion liquid into a vacuum filtration bottle, starting a vacuum pump, and carrying out vacuum filtration when the vacuum degree is 0.7Pa to ensure that Ti is subjected to vacuum filtration 3 C 2 T x Assembling CMC heterogeneous basic materials into a layered HBM composite film under the action of water flow; finally, soaking the HBM composite film in the prepared Na 2 B 4 O 7 Soaking and washing the Ti in the aqueous solution for 25min by using deionized water after being taken out, and calcining the Ti in a vacuum oven (the temperature is 90 ℃ and the vacuum degree is 3 Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds 3 C 2 T x (SBM-II) composite film, the diameter of the SBM-II composite film is 4cm, and the thickness of the SBM-II composite film is 3.1 +/-0.1 mu m.
The content of boron element in the SBM-II composite film is 0.59wt%; the density test shows that the compactness of the product is 93.1 percent; mechanical and electrical properties were carried out on 3 to 5 sample bars (3X 10 mm)The test result shows that the tensile strength is 518 plus or minus 19MPa, the Young modulus is 24.0 plus or minus 2.2GPa, and the toughness is 15.3 plus or minus 1.0MJ/m 3 The conductivity is 6328 +/-71S/cm; the electromagnetic shielding effectiveness test shows that the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 57.9dB.
Example 3
0.5mg/mL of Ti was prepared in advance 3 C 2 T x Aqueous solution: weighing 18mg of Ti 3 C 2 T x Adding the mixture into 36mL of deionized water, mechanically stirring for 3min under the protection of continuous argon, and then ultrasonically dispersing for 1min in an ice-water bath (60W) to obtain a dark green solution; preparing 0.25mg/mL CMC water solution: weighing 10mg of CMC, adding into 40mL of deionized water, mechanically stirring for 35min, and then ultrasonically dispersing for 15min in an ice-water bath (60W); 4mg/mL of Na was prepared 2 B 4 O 7 Aqueous solution: 40mg of Na are weighed 2 B 4 O 7 Adding the mixture into 10mL of deionized water, mechanically stirring for 5min, and then ultrasonically dispersing for 1min in an ice-water bath (60W); then Ti prepared by the method is stirred continuously under the protection of argon 3 C 2 T x Dropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained is 3 C 2 T x Dropwise adding the CMC heterogeneous elementary material dispersion liquid into a vacuum filtration bottle, starting a vacuum pump, and carrying out vacuum filtration when the vacuum degree is 0.7Pa to ensure that Ti is subjected to vacuum filtration 3 C 2 T x Assembling CMC heterogeneous basic materials into a layered HBM composite film under the action of water flow; finally, the HBM composite film is soaked in the prepared Na 2 B 4 O 7 Soaking and washing the Ti in the aqueous solution for 25min by using deionized water after being taken out, and calcining the Ti in a vacuum oven (the temperature is 90 ℃ and the vacuum degree is 3 Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds 3 C 2 T x (SBM-III) composite film, the diameter of the SBM-III composite film is 4cm, and the thickness of the SBM-III composite film is 3.0 +/-0.1 mu m.
The content of boron element in the SBM-III composite film is 0.97wt%; the density test shows that the compactness of the product is 94.7%; mechanical and electrical performance tests are carried out on 3-5 sample strips (3 multiplied by 10 mm), and the results show that the tensile strength of the sample strips is high583 + -16 MPa, young's modulus 27.8 + -2.8 GPa, toughness 15.9 + -1.0 MJ/m 3 The conductivity is 6115 + -62S/cm. As shown in fig. 5, the tensile strength, toughness and electrical conductivity are superior to most titanium carbide composite films reported in the literature (ACS Nano 2018,12,4583.; proc. Natl. Acad. Sci. U.s.a.2014,111,16676.; adv. Mater.2019,31,1902977.; adv. Electron. Mater.2020,6,1901094.; j. Mater.chem.c 2019,7,9820.; adv Funct. Mater.2018,28,1803360.; proc. Natl.acad.sci.u.s.a.2020,117, 27154.). The electromagnetic shielding effectiveness test shows that the shielding coefficient of the film to electromagnetic waves with the frequency of 0.3-18 GHz is about 56.4dB, which is better than most titanium carbide composite films with similar thickness reported in the literature (Nanoscale 2019,11,20295.; J.Mater.chem.C 2020,8,1673.; nanoscale 2019,11, 23382.).
Example 4
0.5mg/mL of Ti was prepared in advance 3 C 2 T x Aqueous solution: 18mg of Ti were weighed 3 C 2 T x Adding the mixture into 36mL of deionized water, mechanically stirring for 3min under the protection of continuous argon, and then ultrasonically dispersing for 1min in an ice-water bath (60W) to obtain a dark green solution; preparing 0.25mg/mL CMC water solution: weighing 10mg of CMC, adding into 40mL of deionized water, mechanically stirring for 35min, and then ultrasonically dispersing for 15min in an ice-water bath (60W); 8mg/mL of Na is prepared 2 B 4 O 7 Aqueous solution: 80mg of Na was weighed 2 B 4 O 7 Adding the mixture into 10mL of deionized water, mechanically stirring for 5min, and then ultrasonically dispersing for 1min in an ice-water bath (60W); then Ti prepared by the method is stirred continuously under the protection of argon 3 C 2 T x Dropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained 3 C 2 T x Dropwise adding the CMC heterogeneous elementary material dispersion liquid into a vacuum filtration bottle, starting a vacuum pump, and carrying out vacuum filtration when the vacuum degree is 0.7Pa to ensure that Ti is subjected to vacuum filtration 3 C 2 T x -assembling the CMC heterogeneous elementary materials into a layered HBM composite film under the action of water flow; finally, soaking the HBM composite film in the prepared Na 2 B 4 O 7 Soaking in water solution for 13h, taking out, soaking and washing with deionized water for 25min,calcining for 4h in a vacuum oven (the temperature is 90 ℃ and the vacuum degree is 3 Pa) to obtain Ti with orderly cross-linked hydrogen bonds and ionic bonds 3 C 2 T x (SBM-IV) composite film, the diameter of the SBM-IV composite film is 4cm, and the thickness of the SBM-IV composite film is 2.9 +/-0.1 mu m.
The content of boron element in the SBM-IV composite film is 1.47wt%; the density test shows that the compactness of the product is 94.2 percent; mechanical and electrical performance tests are carried out on 3-5 sample strips (3 multiplied by 10 mm), and the results show that the tensile strength is 529 +/-18 MPa, the Young modulus is 26.4 +/-2.5 GPa, and the toughness is 12.2 +/-0.5 MJ/m 3 The conductivity is 5850 +/-54S/cm; the electromagnetic shielding effectiveness test shows that the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 55.3dB.
As shown in FIG. 2, the cross-sectional macropores of the HBM composite film were significantly reduced compared to the MXene film, and only a few small-pore defects were present, confirming that the larger-sized CMC molecules can be filled with Ti 3 C 2 T x Larger pores between nanosheet layers; while the small pores on the section of the CBM composite film are obviously reduced, only a few large pore defects are shown, and the fact that the borate ions with smaller size can fill Ti 3 C 2 T x Smaller pores between nanosheet layers; furthermore, the SBM-III composite film has obviously reduced large and small pores in cross section, which is proved to be in Ti 3 C 2 T x CMC molecules and borate ions are orderly introduced among the nanosheet layers and can be cooperatively filled with Ti 3 C 2 T x Large and small pores between nanosheet layers to further densify Ti 3 C 2 T x And (3) compounding the film. The microstructural changes of these films are consistent with their corresponding magnitude of solidity.
As shown in FIG. 3, it was confirmed by XRD that the CMC molecules and borate ions were intercalated into Ti 3 C 2 T x Between layers; the CMC and Ti were confirmed by FTIR spectroscopy 3 C 2 T x Hydrogen bond crosslinking exists between the nano sheets, and borate ions, CMC and Ti 3 C 2 T x The nano sheets can form covalent cross-linking; the covalent bond crosslinking described above can be further confirmed by XPS spectroscopy. Increasing the content of covalently cross-linked boron from 0.33wt%When the weight of the SBM composite film is 0.97 percent, the compactness, the tensile strength, the Young modulus and the toughness of the SBM composite film are gradually increased; further increasing the content of boron element, these properties of the SBM composite film are degraded. Therefore, these properties of the SBM composite film are maximized at a boron element content of 0.97wt%, and the corresponding composite film is labeled as SBM-III. As shown in fig. 4, the SBM-III composite film has better tensile strength, young's modulus and toughness than MXene, HBM and CBM films due to higher compactness and stronger interfacial strength. In addition, since in Ti 3 C 2 T x CMC and borate ion content introduced between the nanosheet layers are low, the microstructure is compact, and the SBM-III composite film has excellent electrical properties. As shown in FIG. 5, the SBM-III composite film has better tensile strength, electrical conductivity and toughness than other Ti reported in the literature 3 C 2 T x And (3) compounding the film.
In conclusion, the titanium carbide composite film with orderly crosslinked hydrogen bonds and covalent bonds, which is obtained by the invention, has higher compactness (94.7%), high tensile strength (583 MPa), high Young modulus (27.8 GPa) and high toughness (15.9 MJ/m) 3 ) High conductivity (6115S/cm) and excellent electromagnetic shielding effectiveness (the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 56.4 dB). The densified high-performance titanium carbide composite film can be widely applied to the fields of flexible electronic devices, aerospace and the like.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and portions of the invention not described in detail are not known in the art.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (5)
1. The preparation method of the densified titanium carbide composite film is characterized by comprising the following steps:
(1) Stirring and ultrasonic processing titanium carbide (Ti) at room temperature 3 C 2 T x ) Preparing uniform Ti 3 C 2 T x Aqueous solution of the Ti 3 C 2 T x The aqueous solution contains Ti 3 C 2 T x Nanosheets;
(2) Adding Ti obtained in the step (1) under continuous stirring 3 C 2 T x Adding sodium carboxymethylcellulose (CMC) aqueous solution dropwise into the aqueous solution, and adding Ti 3 C 2 T x The CMC is adsorbed on the Ti by the hydrogen bond action in the mixed aqueous solution of the CMC and the CMC 3 C 2 T x Nanosheet surface to provide Ti 3 C 2 T x -a dispersion of CMC heterogeneous cellular material;
(3) Adopting a vacuum filtration method to carry out vacuum filtration on the Ti obtained in the step (2) 3 C 2 T x Assembling the CMC heterogeneous basic material dispersion into a hydrogen bond cross-linked titanium carbide (HBM) composite film;
(4) Soaking the HBM composite film obtained in the step (3) in sodium tetraborate (Na) 2 B 4 O 7 ) In water solution, washing and vacuum calcining to obtain a titanium carbide (SBM) composite film with orderly cross-linked hydrogen bonds and covalent bonds;
in the step (1), ti 3 C 2 T x The concentration of the aqueous solution is 0.5-1 mg/mL, and the Ti content is continuously added during stirring and ultrasonic treatment 3 C 2 T x Introducing argon into the aqueous solution, stirring for 3-5 min, carrying out ultrasonic treatment for 1-2 min at the ultrasonic power of 50-70W, and carrying out ultrasonic treatment in an ice-water bath;
in the step (2), the concentration of the CMC aqueous solution is 0.25-0.5 mg/mL, and the CMC aqueous solution is continuously stirred to Ti 3 C 2 T x Introducing argon into the mixed aqueous solution of the Ti and the CMC, and stirring for 5-10 min to obtain the Ti 3 C 2 T x -Ti in the dispersion of the CMC foreign-cellular material 3 C 2 T x The mass ratio of the CMC to the CMC is 8.5 to 9.5;
in the step (4), na 2 B 4 O 7 The concentration of the aqueous solution is1-9 mg/mL, and the soaking time is 12-14 h.
2. The method of claim 1, wherein the method comprises the steps of: in the step (3), the Ti obtained in the step (2) is filtered by vacuum filtration 3 C 2 T x The specific implementation process of assembling the CMC heterogeneous basic material dispersion liquid into the hydrogen bond cross-linked titanium carbide (HBM) composite film comprises the following steps:
(1) Ti to be stirred uniformly 3 C 2 T x -adding the dispersion of the CMC heterogeneous elementary material drop by drop into a vacuum flask;
(2) Starting a vacuum pump, and carrying out vacuum filtration, wherein the vacuum degree is 0.5-1 Pa;
(3) With the progress of suction filtration, ti 3 C 2 T x Assembling the CMC heterogeneous basic material into a layered structure under the action of water flow, and obtaining the hydrogen bond crosslinked titanium carbide (HBM) composite film after suction filtration is finished.
3. The method of claim 1, wherein the method comprises the steps of: in the step (4), the washing is realized by soaking in deionized water for 20-30 min, the vacuum calcination is realized by vacuum calcination for 3.5-4.5 h at 85-95 ℃, and the vacuum degree is 1-5 Pa.
4. The method of claim 1, wherein the method comprises the steps of: in the step (4), the boron element content of the prepared SBM composite film is 0.33-1.5 wt%.
5. The method of claim 1, wherein the method comprises the steps of: in the step (4), the prepared SBM composite film is circular, the diameter is 2-4 cm, and the thickness range is 1-10 mu m.
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