阅读说明：本技术 一种多功能的智能纤维或织物 (A kind of multi-functional intelligent fiber or fabric ) 是由 陈�峰 曹文涛 马明国 于 2019-09-12 设计创作，主要内容包括：本发明涉及一种多功能的智能纤维或织物,所述多功能的智能纤维或织物是将含有氧化纳米纤维素和MXene材料的混合浆料直接向溶剂中挤出成型得到；所述混合浆料中氧化纳米纤维素和MXene材料的重量比为9:1～3:7,优选为7:3～1:2,更优选为1:1。(The present invention relates to a kind of multi-functional intelligent fiber or fabric, the multi-functional intelligent fiber or fabric are that extrusion molding obtains directly into solvent by the mixed slurry containing oxidation nanometer cellulose and MXene material；The weight ratio of oxidation nanometer cellulose and MXene material is 9:1~3:7, preferably 7:3~1:2, more preferably 1:1 in the mixed slurry.)

1. a kind of multi-functional intelligent fiber or fabric, which is characterized in that the multi-functional intelligent fiber or fabric are will to contain Having the mixed slurry of oxidation nano-cellulose and MXene material, extrusion molding obtains directly into solvent；In the mixed slurry The weight ratio of oxidation nanometer cellulose and MXene material is 9:1~3:7, preferably 7:3~1:2, more preferably 1:1.

2. multi-functional intelligent fiber according to claim 1 or fabric, which is characterized in that the oxidation nanometer cellulose For the nano-cellulose of 2,2,6,6- tetramethyl piperidine -1- oxygroup diketone (TEMPO) oxidation；The ingredient of the MXene material is Ti₃C₂、Ta₄C₃、Nb₂C and Ti₂At least one of C.

3. multi-functional intelligent fiber according to claim 1 or 2 or fabric, which is characterized in that the MXene material Lateral dimension is 0.3~1.2 μm, and average-size is 0.4~0.6 μm, with a thickness of 0.8~1.5 nm.

4. multi-functional intelligent fiber according to any one of claim 1-3 or fabric, which is characterized in that the oxidation The diameter of nano-cellulose is 10~50nm, draw ratio > 10.

5. multi-functional intelligent fiber or fabric described in any one of -4 according to claim 1, which is characterized in that the extrusion Molding is carried out according to the figure being pre-designed by 3D printing technique.

6. multi-functional intelligent fiber according to any one of claims 1-5 or fabric, which is characterized in that the mixing The concentration of slurry is 6~18mg/mL.

7. multi-functional intelligent fiber according to claim 1 to 6 or fabric, which is characterized in that the extrusion It is shaped to directly be directly injected into the mixed slurry in the solvent by syringe needle, the diameter of syringe needle is 0.10~1mm；It is excellent Selection of land, the injection rate of the mixed slurry are 0.1~1ml/ minutes, and the movement speed of syringe needle is 0.5~10mm/ seconds.

8. multi-functional intelligent fiber or fabric described in any one of -7 according to claim 1, which is characterized in that the solvent For at least one of ethyl alcohol, isopropanol, ethylene glycol, acetone.

Technical field

The present invention relates to a kind of multi-functional intelligent fibers that oxidation nanometer cellulose/MXene is compound, fabric.And gained Intelligent fiber, fabric not only mechanical property and electric conductivity with higher, but also photo-thermal, electric heating and mechanics sensitivities may be implemented Can, there is very big application potential in wearable product scope, belong to Material Field.

Background technique

Fibrous material has other excellent performances such as good mechanical property, anisotropy, increasingly by people's Concern, is with a wide range of applications.In recent years, more and more researchers be dedicated to studying fiber with high performance or Fabric.Such as nano-cellulose can be carried out the macroscopic fibres that one-dimensional assembling preparation has strong mechanical property by microfluid spin processes, And with polymorphic, hierarchical structure regenerated silk fiber etc..But current natural fiber or synthetic fibers only have mostly Single function, and be all much electrical isolation or thermal insulation, limit their application range.Therefore, it designs and prepares It, will be with important scientific meaning and practical application value with multi-functional intelligent fiber and textile material.

MXenes is that one kind by the Yury Gogotsi professor of Univ Drexel, the U.S. et al. discovery in 2011 is novel Two dimension (2D) transition metal carbide or carbonitride.Its chemical general formula can use M_n+1X_nT_xIt indicates, wherein M refers to transition group gold Belong to, X refers to that C or/and N, n are generally 1-3, T_xRefer to surface group (such as-F ,=O ,-OH etc.).Currently, MXenes is due to having big It the features such as specific surface area, excellent electricity/thermal conductivity, has been shown in fields such as conductive filler, absorption, sensor, energy storage huge Big potentiality.However, the interaction force between 2D type MXenes nanometer sheet is small, it is difficult to independently form macroscopical 1D structure, limits Its application value.

Nano-cellulose (CNF) is usually prepared by the widest native cellulose in source in global range, is shown Length in micron range and only several nanometers of diameter.These nano-celluloses have excellent comprehensive performance, such as high machinery Performance (fracture tensile strength being up to about within the scope of 100GPa elasticity modulus and GPa), density are low, and (density is about 1.5g cm^-3).In addition, different from other high molecular polymers, nano-cellulose has typical one dimensional nanofibrous structures, receives with conduction It can produce less insulated contact when rice material mixing.In view of these interesting characteristics, nano-cellulose is widely used In the reinforcing agent of composite material, and further apply the various fields such as biomedical, energy stores and electromagnetic interference shield.This Outside, due to nano-cellulose small size in water and polymolecularity, nano-cellulose aqueous dispersion has relatively high viscosity With non-flocculated uniformity.Typical colloid property makes nano-cellulose dispersion may be used as preparing fiber and fabric material Material has huge potentiality for economic and extensive manufacture.But what traditional fibre material and its fabric presence had a single function Problem.

Summary of the invention

In view of the above-mentioned problems, the object of the present invention is to provide a kind of multi-functional intelligent fiber or fabric, it is described more The intelligent fiber or fabric of function are to squeeze the mixed slurry containing oxidation nanometer cellulose and MXene material directly into solvent Molding obtains out；In the mixed slurry weight ratio of oxidation nanometer cellulose and MXene material be 9:1~3:7, preferably 7: 3~1:2, more preferably 1:1.

In the disclosure, acted on by sovent diffusion and organic solvent, one-dimensional oxidation nanometer cellulose and two-dimensional MXene Material is (for example, Ti₃C₂Nanometer sheet etc.) self assembly is carried out, and control and squeeze out direction and speed fiber or fabric (example can be obtained Such as by the prior layout of 3D printing technique, trend and injection speed of injection needle etc. are controlled).As shown in fig. 1, it aoxidizes Nano-cellulose does not dissolve in polar solvent (for example, ethyl alcohol, isopropanol, ethylene glycol, acetone etc.), so by oxidation nanometer fiber When element/MXene mixed slurry is expressed into polar solvent (for example, ethyl alcohol, isopropanol, ethylene glycol, acetone etc.), oxidation nanometer is fine Dimension element, which is wrapped in MXene nanometer sheet, to be separated to form fibre structure from solvent；And since MXene material surface contains Largely-OH ,-F, the functional groups such as-OH can form Hydrogenbond with the-OH on nano-cellulose surface, so that being assembled into has centainly The composite fibre and fabric of intensity.Gained composite fibre or fabric have excellent comprehensive performance, and (excellent mechanics, is led conduction Hot property), there will be good prospect in fiber, the dry goods device of flexible wearable are applied.

Preferably, the oxidation nanometer cellulose is the oxidation of 2,2,6,6- tetramethyl piperidine -1- oxygroup diketone (TEMPO) Nano-cellulose (TOCNFs)；The ingredient of the MXene material is Ti₃C₂、Ta₄C₃、Nb₂C and Ti₂At least one of C.

Preferably, the lateral dimension of the MXene material can be 0.3~1.2 μm, average-size is 0.4~0.6 μm, thick Degree is 0.8~1.5nm.

Preferably, the diameter of the oxidation nanometer cellulose can be 10~50nm, draw ratio > 10.

Preferably, the extrusion molding is carried out according to the figure being pre-designed by 3D printing technique.

Preferably, the concentration of the mixed slurry can be 6~18mg/ml.Concrete meaning contains in every 1ml mixed slurry The gross mass of oxidation nanometer cellulose and MXene material is 6~18mg.

Preferably, the extrusion molding is directly to be directly injected into the mixed slurry in the solvent by syringe needle, The diameter of syringe needle can be 0.10~1mm；Preferably, the injection rate of the mixed slurry can be 0.1~1ml/ minutes, syringe needle Movement speed can be 0.5~10mm/ seconds.

Preferably, the solvent is at least one of ethyl alcohol, isopropanol, ethylene glycol, acetone.

In the disclosure, by the mixed solution of the nano-cellulose (TOCNFs) of TEMPO oxidation and MXene material nano piece It injects in ethyl alcohol, it is multi-functional to prepare TOCNFs/MXene by the diffusion of ethyl alcohol and the self assembly of TOCNFs/MXene compound Intelligent fiber.TOCNFs does not dissolve in ethyl alcohol isopolarity solvent, so being expressed into ethyl alcohol by TOCNFs/MXene mixed slurry When, TOCNFs is wrapped in MXene nanometer sheet and separates to form fibre structure from ethyl alcohol；And since MXene material surface is big Amount-OH ,-F ,-OH functional group can form hydrogen bond with the-OH on the surface TOCNFs, to be assembled into the compound fibre with some strength Peacekeeping fabric.Moreover, the structure and form of the intelligent fiber fabric formed are by using extrusion molding (for example, 3D printing skill Art) it controls in above-mentioned fiber forming process and moves towards regulation.

Beneficial effect

(1) the TOCNFs/MXene fiber of offer according to the present invention has multifunctionality, overcomes traditional fibre material function Single problem, and easy, applied widely, process safety is prepared, products therefrom homogeneity is good；

(2) TOCNFs/MXene intelligent fiber according to the present invention has adjustable mechanical property and electric conductivity: real stretching The tensile stress of 136.5MPa can be born by testing middle highest, and the high conductivity of 211.0S/m has been shown in conductive test；

(3) intelligent fiber according to the present invention has photo-thermal and electro-thermal response ability；

(4) intelligent fiber fabric according to the present invention has mechanics sensing capabilities.

Detailed description of the invention

Fig. 1 is the preparation flow schematic diagram of the multi-functional intelligent fiber of TOCNFs/MXene according to the present invention；

Fig. 2 is scattered according to TOCNFs/MXene composite fibre material object photo, light micrograph and its energy is printed in embodiment 1 Penetrate analysis spectrogram；

Fig. 3 is the tension test figure according to the intelligent fiber prepared under difference TOCNFs and MXene ratio in embodiment 1-3；

Fig. 4 is the electric conductivity test chart according to the intelligent fiber prepared under difference TOCNFs and MXene ratio in embodiment 1-3；

Fig. 5 is the rheology testing figure according to mixed slurry under difference TOCNFs and MXene ratio in embodiment 1-3；

Fig. 6 is the photo that different shape fabric is printed as according to TOCNFs and MXene composite mortar in embodiment 3；

Fig. 7 is the photo-thermal test chart according to the intelligent fiber prepared under difference TOCNFs and MXene ratio in embodiment 1-3；

Fig. 8 is the electric heating test chart according to the intelligent fiber prepared under difference TOCNFs and MXene ratio in embodiment 1-3；

Fig. 9 is according to the TOCNFs/MXene intelligent fiber fabric sensor and its sensing testing figure prepared in embodiment 3；

Figure 10 is to be tried according to monitoring of the TOCNFs/MXene intelligent fiber fabric sensor prepared in embodiment 3 to human motion Test figure.

Specific embodiment

The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this Invention, is not intended to limit the present invention.

In the disclosure, multi-functional intelligent fiber or fabric are by oxidation nanometer cellulose TOCNFs and MXene material (single layer MXene) self assembly is prepared.Wherein, pass through both regulation oxidation nanometer cellulose TOCNFs and MXene material The mechanics and electric property of the adjustable fiber of amount ratio or fabric, such as the weight ratio of TOCNFs and MXene material can be 9:1 To 3:7, preferably 7:3 to 1:1.

In alternative embodiments, nano-cellulose 2,2,6,6- tetramethyl piperidine -1- oxygroup diketone (TEMPO) oxygen The nano-cellulose of change, diameter can be 10~50nm, and draw ratio is preferably greater than 10.The ingredient of MXene material can be Ti₃C₂、 Ta₄C₃、Nb₂C and Ti₂C etc..The lateral dimension of MXene material can be 0.3~1.2 μm, and average-size is 0.4~0.6 μm, thickness For 0.8~1.5nm.

It in the disclosure, can be Ti by ingredient₃C₂MXene material (it should be understood that can show such as the prior art doped with doping Element and/or have surface group) and TEMPO aoxidize cellulose (TOCNFs) be mixed evenly to obtain according to a certain percentage Mixed slurry, then directly by the mixed slurry, into solvent, extrusion molding obtains multifunctional fibre or fabric.Injection can be used Molding.It is generally understood that the direction that squeezes out of control, speed, time control the fiber of formation or the form of fabric and pattern.It is molten Ethyl alcohol, isopropanol, ethylene glycol, acetone etc. can be used in agent.In a preferred example, predetermined pattern, by 3D printing technique, The mixed slurry is printed in ethyl alcohol and is formed, dry macroscopical composite fibre or fabric are taken out.It should be understood that control can be passed through It makes the directly printing such as trend and predetermined pattern of printing and obtains multifunctional fabric, first can also print or be injection moulded the more function of acquisition Energy fiber, is then woven again by the multifunctional fibre and obtains multifunctional fabric.

Preparation method of the invention is easy, and applied widely, process safety, products therefrom homogeneity is good, is a kind of efficient The quick environmental-friendly method for preparing intelligent fiber and fabric.Moreover, in the multi-functional intelligent fiber of gained and fabric TOCNFs/MXene fiber not only mechanical property and electric conductivity with higher, but also possess photo-thermal, electric heating and mechanics sensitivities Can, there is good application potential in wearable textiles product, such as wearable health monitoring fabric field.Following exemplary Illustrate the preparation method of intelligent fiber and intelligent fiber fabric, as shown in Figure 1.

Material quality ratio is set as required, by MXene material aqueous dispersions and TOCNFs aqueous dispersions by different (9:1 to 3:7) is stirred (for example, stirring at room temperature for 24 hours) to the weight ratio of TOCNFs and MXene, obtains uniform TOCNFs/MXene mixed solution (or mixed slurry or composite mortar etc.).Alternatively, by different TOCNFs and MXene (9:1 to 3:7), MXene material is directly added in TOCNFs aqueous dispersions weight ratio and is stirred (for example, room temperature Lower stirring is for 24 hours), obtain uniform TOCNFs/MXene mixed solution.The concentration of the mixed solution can be 6-18mg/ml.

By mixed slurry by way of extrusion molding (for example, needle injection), it is injected into solvent, such as ethyl alcohol, isopropyl In alcohol, ethylene glycol, acetone etc., the compound fiber of TOCNFs/MXene, i.e., multi-functional intelligent fiber are formed.

In the present invention, the tensile stress of intelligent fiber and its fabric of composition can be by regulating and controlling TOCNFs and MXene The ratio of two kinds of components is regulated and controled, and with the increase of TOCNFs content, tensile stress is first increased and reduced afterwards.Intelligent fiber Electric conductivity can be regulated and controled by regulating and controlling the ratio of two kinds of components of TOCNFs and MXene, with the increase of MXene content, Electric conductivity gradually rises.Alternatively, trend and the injection speed for controlling syringe needle used are available by general 3D printing strategy The fabric being made of TOCNFs/MXene composite fibre, the pattern and structure of fabric can be by the 3D printing figures that are pre-designed It is controlled.It prepares intelligent fiber above-mentioned or prepares intelligent fiber fabric process, select the diameter of extrusion molding syringe needle can For 0.10~1mm.The injection rate of mixed slurry can be 0.1~1ml/ minutes.The movement speed of syringe needle can be 0.5~10mm/ Second.

Take out the TOCNFs/MXene in solvent compound fiber or fabric can be obtained by conventional drying process Intelligent fiber and fabric.In general, the diameter of fiber can be by injection needle diameter control in gained intelligent fiber or fabric 0.01~0.5mm.

In the present invention, 180s can be quick under near-infrared (NIR) laser irradiation for intelligent fiber and its fabric of composition Photothermal conversion is realized, so that fiber and fabric are rapidly heated.Specifically, which swashs at near-infrared (NIR, 808nm) Light, which irradiates lower 180s, can be warming up to 28.1 DEG C to 31.2 DEG C, and further preferably 29.4 DEG C to 31.2 DEG C, still more preferably It is 31.2 DEG C.

In the present invention, intelligent fiber and its fabric of composition can be rapidly heated in the case where DC power supply is powered. Specifically, intelligent fiber 180s in the case where DC power supply is powered (5V-20V) can be warming up to 32.8 DEG C to 108.6 DEG C, further preferably 70.0 DEG C to 108.6 DEG C, be still more preferably 108.6 DEG C.

In the present invention, intelligent fiber and its fabric of composition can be used for changing sensor.For example, what intelligent fiber was constituted Fabric may be implemented to monitor in real time for human motion.

Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper In the range of select, and do not really want to be defined in hereafter exemplary specific value.Unless stated otherwise, used in the following embodiment Reagent and instrument are commercially available product.