CN113582591A - Preparation method of densified titanium carbide composite film - Google Patents

Preparation method of densified titanium carbide composite film Download PDF

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CN113582591A
CN113582591A CN202110916999.4A CN202110916999A CN113582591A CN 113582591 A CN113582591 A CN 113582591A CN 202110916999 A CN202110916999 A CN 202110916999A CN 113582591 A CN113582591 A CN 113582591A
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composite film
aqueous solution
titanium carbide
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程群峰
万思杰
李响
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Beihang University
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Abstract

The invention relates to a preparation method of a densified titanium carbide composite film, which comprises the steps of firstly, mixing sodium carboxymethylcellulose (CMC) and titanium carbide (Ti)3C2Tx) Adsorption construction of Ti by nanosheet3C2TxCMC heterogeneous element material, assembling the heterogeneous 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)2B4O7) 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/m3The conductivity is 6115S/cm, and the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 56.4 dB.

Description

Preparation method of densified titanium carbide composite film
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)3C2Tx) The nanosheet hasExcellent mechanical (Sci.adv.2018,4, eaat0491.) and electrical (appl.Phys.Lett.2016,108,033102.) performances, and wide application prospect in the fields of flexible electronic devices, aerospace and the like (Nat.Rev.Mater.2017,2,16098.) therefore, Ti is required to be added3C2TxMacroscopic high-performance Ti assembled by nanosheets3C2TxA nanocomposite material.
In recent years, scientists have prepared a large number of high-performance layered Ti by using various interfacial crosslinking strategies3C2TxAnd (3) compounding the film. For example, Gogotsi et al (Proc. Natl. Acad. Sci. USA 2014,111,16676.) in Ti3C2TxPolyvinyl alcohol is introduced between layers, and Ti with high strength and conductivity is prepared through hydrogen bond crosslinking3C2TxCompounding a film; in Ti by Medium vibration et al (J.Mater.chem.C 2020,8,1673.)3C2TxAluminum ions are introduced between layers, and Ti with high strength and high efficiency electromagnetic shielding is prepared through the ionic bond crosslinking effect3C2TxCompounding a film; king et al (adv. Funct. Mater.2018,28,1801511.) in Ti3C2TxBoric acid radical is introduced between layers, and rigid Ti is prepared through covalent bond crosslinking3C2TxA 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 nanosheets3C2TxCompounding a film; von Xinliang et al (nat. Commun.2019,10,2920.) prepare Ti with strength, toughness, integration and high-efficiency salt difference energy power generation through aramid nano-fiber reinforced toughening effect3C2TxCompounding a film; chengdu Peak et al (Proc. Natl. Acad. Sci. USA 2020,117,27154.) in Ti3C2TxSodium 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 bonds3C2TxAnd (3) compounding the film. The above work in designing interfacial crosslinking strategies generally focuses only on Ti3C2TxThe interface strength between the nanosheet layers is improved, and Ti is ignored3C2TxStructural defects between nanosheet layers. Although these interfacial crosslinking strategies improve Ti to some extent3C2TxThe properties of the composite film, however, due to Ti3C2TxLarger pores exist among the nano-sheet layers, and the Ti3C2TxThe mechanical and electrical properties of the composite film are still far lower than those of the corresponding single-layer Ti3C2TxThe properties of the nanoplatelets, which greatly limit Ti3C2TxThe practical application of the film.
Therefore, there is a need to develop a novel interfacial crosslinking strategy that not only effectively enhances Ti3C2TxInterface strength between nanosheets and greatly eliminates Ti3C2TxThe interlayer pores of the nano-sheets, thereby greatly improving Ti3C2TxMechanical 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 problem of the invention is solved: 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 bond3C2TxConstructing Ti on the surface of the nanosheet3C2Tx-CMC heterogeneous elementary material; then Ti is filtered by vacuum filtration3C2Tx-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)2B4O7) 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 method comprises the following concrete steps:
a preparation method of a densified titanium carbide composite film comprises the following steps:
(1) mixing Ti by ultrasonic method3C2TxPreparing uniform Ti3C2TxAn aqueous solution;
(2) under continuous stirring, adding Ti3C2TxAdding CMC aqueous solution into the aqueous solution drop by drop to ensure that the CMC is adsorbed on the Ti through hydrogen bond3C2TxNanosheet surface to provide Ti3C2Tx-a dispersion of CMC heterogeneous cellular material;
(3) vacuum filtering the Ti3C2TxAssembling the CMC heterogeneous elementary material dispersion into the HBM composite film;
(4) soaking the HBM composite film in Na2B4O7And washing and vacuum calcining the mixture in a water solution to obtain the SBM composite film.
In the step (1), the Ti3C2TxThe aqueous solution contains Ti3C2TxNanosheets.
In the step (1), Ti3C2TxThe concentration of the aqueous solution is 0.5-1 mg/mL, and the solution is continuously stirred and subjected to ultrasonic treatment to Ti3C2TxIntroducing 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 so as not to damage Ti3C2TxIn the case of the nanosheet structure, Ti is uniformly dispersed3C2TxNanosheets.
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 towards Ti3C2TxIntroducing argon into the mixed aqueous solution of CMC to prevent Ti3C2TxOxidized; the stirring time is 5-10 min, so that the CMC is fully adsorbed on the Ti3C2TxThe surface of the nanosheet; obtained Ti3C2Tx-Ti in the dispersion of the CMC foreign-cellular material3C2TxThe mass ratio of the titanium powder to the CMC is 8.5-9.5, and too little CMC cannot completely coat Ti3C2TxNanosheets, too much CMC will be at Ti3C2TxExcessive deposition on the surface of the nano sheet is not beneficial to Ti in the vacuum filtration process in both cases3C2Tx-densified assembly of CMC heterogeneous elementary materials, and subsequent borate ion with CMC and Ti3C2TxAnd 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 Ti3C2Tx-adding the dispersion of the CMC heterogeneous cellular material drop by drop into a vacuum flask;
(2) starting a vacuum pump, and performing vacuum filtration, wherein the vacuum degree is 0.5-1 Pa;
(3) with the progress of suction filtration, Ti3C2TxAssembling 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.
In the step (4), Na2B4O7The concentration of the aqueous solution is 1-9 mg/mL, and borate ions with too low concentration cannot react with CMC and Ti3C2TxThe nanoplatelets are fully crosslinked, while too high a concentration of borate ions will react with CMC and Ti3C2TxThe nanosheets 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 in order to better optimize the compactness and the performance of the SBM composite film, Na2B4O7The 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 Na2B4O7The soaking time in the aqueous solution is 12-14 hours, 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; vacuum calcining furnaceCalcining the mixture in vacuum at 85-95 ℃ for 3.5-4.5 h and the vacuum degree of 1-5 Pa to ensure that borate ions, CMC and Ti3C2TxThe 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 at Ti in the preparation process3C2TxAdditional 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 because of the compact layered structure and rich interface interaction, and is characterized in that a small amount of flexible natural organic matrix can be filled in the pores between the 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 Ti3C2TxA small amount of flexible hydrogen bond crosslinking agent and covalent crosslinking agent with strong adhesive force are orderly introduced between layers to promote Ti3C2TxInterlayer interface strength and effective elimination of Ti3C2TxPores between layers, thereby preparing densified Ti3C2TxThe composite film greatly improves the mechanical and electrical properties. Compared with the prior preparation of Ti3C2TxCompared 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 Ti3C2TxPores are eliminated among the nanosheet layers; in addition, CMC contains a large number of hydroxyl groups in its molecular chain, which can react with Ti3C2Txthe-F, -OH and-O functional groups on the surface of the nano sheet are subjected to hydrogen bond crosslinking to promote Ti3C2TxInterlayer interface strength;
(2) the borate ions have small size and can permeate Ti3C2TxIn the micro pores of the film, further with CMC and Ti3C2TxCovalent crosslinking is carried out on the nano sheets to heal the micro pores, so that the compactness and Ti of the film are further improved3C2TxInterlayer 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 ions3C2TxThe mechanical property of the composite film is effectively maintained, and Ti is effectively maintained3C2TxThe 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 stirring3C2TxConstructing Ti on the surface of the nanosheet3C2Tx-CMC heterogeneous elementary material; then vacuum filtering is adopted to obtain the Ti3C2Tx-assembling the CMC heterogeneous elementary materials into the HBM composite film; finally, soaking the HBM composite film in Na2B4O7In the water solution, washing and vacuum calcining are carried out to obtain a compact SBM composite film;
FIG. 2 shows uncrosslinked Ti3C2Tx(MXene), HBM, covalently crosslinked Ti3C2Tx(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; the interlayer spacing of the CBM composite film is reduced compared to the MXene film, mainly due to borate ion covalent cross-linkingThe effect is that the interlayer spacing of the HBM composite film is increased mainly due to the insertion of larger CMC molecular chains into Ti3C2TxInterlamination; compared with MXene film, the (-OH peak is at 3432 cm)-1) the-OH peak of the HBM composite film was red-shifted to 3418cm-1With 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 covalent crosslinking of borate ions; ti of SBM-III compared to HBM (455.8eV and 457.1eV)2+(I,II,IV)2p3/2And Ti3+(I,II,IV)2p3/2The peaks shifted up to 456.4eV and 457.6eV, respectively, with a decrease in the intensity of the C-OH peak and the appearance of a new C-O-B peak (286.4eV), further confirming borate ion with CMC and Ti3C2TxCovalent 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 coefficient against electromagnetic waves with frequency of 0.3 to 18GHz of MXene, HBM, CBM, and SBM-III films;
FIG. 5 shows an SBM-III film and a literature report of Ti3C2TxTensile 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 ensure that CMC is adsorbed on Ti through hydrogen bond3C2TxConstructing Ti on the surface of the nanosheet3C2Tx-CMC heterogeneous elementary material; then Ti is filtered by vacuum filtration3C2Tx-assembling the CMC heterogeneous elementary materials into the HBM composite film; finally, soaking the HBM composite film in Na2B4O7And (3) in the aqueous solution, and then carrying out vacuum calcination to obtain the SBM composite film. By changing Na2B4O7The 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 0.97 wt%, 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/m3The conductivity is 6115S/cm, and the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 56.4 dB.
The Ti3C2TxThe surface of the two-dimensional nano sheet contains functional groups such as-F, -OH and ═ O and the like, and the two-dimensional nano sheet is easy to dissolve in water; the biomacromolecule is CMC, the molecular chain of which contains a large amount of hydroxyl groups, and not only can be reacted with Ti3C2TxThe 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 and CMC, CMC and Ti3C2Tx、Ti3C2TxWith Ti3C2TxForm stronger covalent bond.
The titanium carbide composite film with the orderly crosslinked 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 advance3C2TxAqueous solution: 18mg of Ti were weighed3C2TxAdding 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 Na2B4O7Aqueous solution: weighing 10mg of Na2B4O7Adding into 10mL deionized water, and processingMechanically stirring for 5min, and ultrasonically dispersing for 1min in an ice-water bath (60W); then Ti prepared by the method is stirred continuously under the protection of argon3C2TxDropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained3C2TxDropwise 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 filtration3C2Tx-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 Na2B4O7Soaking 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 3Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds3C2Tx(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 0.33 wt%; the density test shows that the compactness of the product is 90.8%; mechanical and electrical performance tests are carried out on 3-5 sample strips (3 multiplied by 10mm), and the results show 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/m3The 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 59.1 dB.
Example 2
0.5mg/mL of Ti was prepared in advance3C2TxAqueous solution: 18mg of Ti were weighed3C2TxAdding 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); 2mg/mL of Na is prepared2B4O7Aqueous solution: 20mg of Na was weighed2B4O7Adding into 10mL deionized water, mechanically stirring for 5min, and performing ultrasonic treatment in ice water bath (60W)Dispersing for 1 min; then Ti prepared by the method is stirred continuously under the protection of argon3C2TxDropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained3C2TxDropwise 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 filtration3C2Tx-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 Na2B4O7Soaking 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 3Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds3C2Tx(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 0.59 wt%; the density test shows that the compactness of the product is 93.1 percent; mechanical and electrical performance tests are carried out on 3-5 sample strips (3 multiplied by 10mm), and the results show that the tensile strength is 518 +/-19 MPa, the Young modulus is 24.0 +/-2.2 GPa, and the toughness is 15.3 +/-1.0 MJ/m3The conductivity is 6328 +/-71S/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 57.9 dB.
Example 3
0.5mg/mL of Ti was prepared in advance3C2TxAqueous solution: 18mg of Ti were weighed3C2TxAdding 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); 4mg/mL of Na was prepared2B4O7Aqueous solution: 40mg of Na are weighed2B4O7Adding the mixture into 10mL of deionized water, mechanically stirring for 5min, and then ultrasonically dispersing for 1min in an ice-water bath (60W); then under the protection of argon and continuously stirringStirring the Ti powder to the prepared Ti powder3C2TxDropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained3C2TxDropwise 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 filtration3C2Tx-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 Na2B4O7Soaking 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 3Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds3C2Tx(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 0.97 wt%; the density test shows that the compactness of the product is 94.7 percent; mechanical and electrical performance tests are carried out on 3-5 sample strips (3 multiplied by 10mm), and the results show that the tensile strength is 583 +/-16 MPa, the Young modulus is 27.8 +/-2.8 GPa, and the toughness is 15.9 +/-1.0 MJ/m3The 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.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, and the film is superior to most titanium carbide composite films with similar thicknesses reported in literatures (nanoscales 2019,11, 20295.; J.Mater.Chem.C 2020,8, 1673.; nanoscales 2019,11, 23382.).
Example 4
0.5mg/mL of Ti was prepared in advance3C2TxAqueous solution: 18mg of Ti were weighed3C2TxAdding into 36mL deionized water under the protection of continuous argonMechanically stirring for 3min, and ultrasonically dispersing for 1min in ice-water bath (60W) to obtain 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 prepared2B4O7Aqueous solution: 80mg of Na was weighed2B4O7Adding 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 argon3C2TxDropwise adding 8mL of the prepared CMC aqueous solution into the aqueous solution; after stirring for 8min, the homogeneous Ti obtained3C2TxDropwise 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 filtration3C2Tx-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 Na2B4O7Soaking 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 3Pa) for 4h to obtain the Ti with orderly crosslinked hydrogen bonds and ionic bonds3C2Tx(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 1.47 wt%; 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 10mm), 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/m3The conductivity is 5850 +/-54S/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 55.3 dB.
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 Ti3C2TxLarger pores between nanosheet layers; the CBM composite film has small pores on the cross sectionShows little macro-porosity defect and confirms that the borate ions with smaller size can fill Ti3C2TxSmaller 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 Ti3C2TxCMC molecules and borate ions are orderly introduced among the nanosheet layers and can be cooperatively filled with Ti3C2TxLarge and small pores between the nano-sheet layers further densify Ti3C2TxAnd (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 Ti3C2TxInterlamination; the CMC and Ti were confirmed by FTIR spectroscopy3C2TxHydrogen bond crosslinking exists between the nano sheets, and borate ions, CMC and Ti3C2TxThe nanosheets all form covalent crosslinks; the covalent bond crosslinking described above can be further confirmed by XPS spectroscopy. The compactness, tensile strength, Young modulus and toughness of the obtained SBM composite film are gradually increased along with the increase of the content of the covalently crosslinked boron element from 0.33 wt% to 0.97 wt%; 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 0.97 wt%, 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 solidity and stronger interfacial strength. In addition, since in Ti3C2TxCMC and borate ion content introduced between the nanosheet layers is 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 literature3C2TxAnd (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 percent) and high tensile strengthDegree (583MPa), high Young's modulus (27.8GPa) and high toughness (15.9 MJ/m)3) High conductivity (6115S/cm) and excellent electromagnetic shielding performance (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 is 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 the invention has not been described in detail so as not to obscure the present invention.
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 (8)

1. The preparation method of the densified titanium carbide composite film is characterized by comprising the following steps of:
(1) stirring and ultrasonic processing titanium carbide (Ti) at room temperature3C2Tx) Preparing uniform Ti3C2TxAqueous solution of the Ti3C2TxThe aqueous solution contains Ti3C2TxNanosheets;
(2) adding Ti obtained in the step (1) under continuous stirring3C2TxAdding sodium carboxymethylcellulose (CMC) aqueous solution dropwise into the aqueous solution, and adding Ti3C2TxThe CMC is adsorbed on the Ti by the action of hydrogen bonds in the mixed aqueous solution of the CMC and the CMC3C2TxNanosheet surface to provide Ti3C2Tx-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)3C2TxThe CMC heterogeneous basic material dispersion liquid is assembled into a hydrogen bond cross-linked titanium carbide (HBM) composite filmA film;
(4) soaking the HBM composite film obtained in the step (3) in sodium tetraborate (Na)2B4O7) In water solution, washing and vacuum calcining to obtain the titanium carbide (SBM) composite film with orderly cross-linked hydrogen bonds and covalent bonds.
2. The method of claim 1, wherein the method comprises the steps of: in the step (1), Ti3C2TxThe concentration of the aqueous solution is 0.5-1 mg/mL, and the solution is continuously stirred and subjected to ultrasonic treatment to Ti3C2TxIntroducing argon into the aqueous solution, stirring for 3-5 min, carrying out ultrasonic treatment for 1-2 min, and carrying out ultrasonic treatment in an ice-water bath at the ultrasonic power of 50-70W.
3. The method of claim 1, wherein the method comprises the steps of: 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 towards Ti3C2TxIntroducing argon into the mixed aqueous solution of the Ti and the CMC, and stirring for 5-10 min to obtain Ti3C2Tx-Ti in the dispersion of the CMC foreign-cellular material3C2TxAnd the mass ratio of the CMC to the CMC is 8.5-9.5.
4. 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 filtration3C2TxThe 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 uniformly3C2Tx-adding the dispersion of the CMC heterogeneous cellular material drop by drop into a vacuum flask;
(2) starting a vacuum pump, and performing vacuum filtration, wherein the vacuum degree is 0.5-1 Pa;
(3) with the progress of suction filtration, Ti3C2Tx-CMC heterogeneous matrix material inAnd assembling the titanium carbide composite film into a laminated structure under the action of water flow, and obtaining the hydrogen bond crosslinked titanium carbide (HBM) composite film after suction filtration is finished.
5. The method of claim 1, wherein the method comprises the steps of: in the step (4), Na2B4O7The concentration of the aqueous solution is 1-9 mg/mL, wherein the preferable concentration range is 4-8 mg/mL, and the soaking time is 12-14 h.
6. 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.
7. 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%.
8. 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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CN115650235A (en) * 2022-11-16 2023-01-31 北京航空航天大学 Preparation method of flake intercalation densification titanium carbide film
CN115806293A (en) * 2022-12-02 2023-03-17 盐城工学院 Method for preparing titanium carbide hydrogel film by using ultrasonic-suction filtration method
CN115818644A (en) * 2022-11-16 2023-03-21 北京航空航天大学 Preparation method of synergetic densified titanium carbide composite film

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CN111718518A (en) * 2020-07-30 2020-09-29 北京航空航天大学 Preparation method of high-strength high-conductivity titanium carbide composite film
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CN115650235A (en) * 2022-11-16 2023-01-31 北京航空航天大学 Preparation method of flake intercalation densification titanium carbide film
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