CN115613354A - Preparation method of nano-silica in-situ deposition natural fiber multi-scale reinforcement - Google Patents
Preparation method of nano-silica in-situ deposition natural fiber multi-scale reinforcement Download PDFInfo
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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- D06M2101/02—Natural fibres, other than mineral fibres
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- D06M2101/06—Vegetal fibres cellulosic
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Abstract
The invention discloses a nano SiO 2 A method for preparing in-situ deposited natural fiber multi-scale reinforcement, the method comprising: pretreating the surface of the natural fiber by adopting a carboxymethyl method; preparing nano SiO with different microstructures and shapes on the surface of natural fiber by in-situ deposition process 2 Deposited layer, i.e. nano-SiO 2 Gel, nano SiO 2 Array and nano SiO 2 Clustering to obtain nano SiO 2 And depositing the natural fiber multi-scale reinforcement in situ. By utilizing the invention, the nano SiO is realized 2 The controllable preparation of in-situ deposited natural fiber multi-scale reinforcement solves the problems that the natural fiber is difficult to be effectively combined with a polymer matrix andthe problem of poor mechanical property of the composite material is solved, so that the requirement of high performance of the green environment-friendly fiber reinforced material in the design and application process of the composite material is met.
Description
Technical Field
The invention relates to the technical field of preparation of green environment-friendly materials, in particular to nano SiO 2 A method for preparing in-situ deposited natural fiber multi-scale reinforcement.
Background
With the increasing severity of the problems of environmental pollution and energy shortage, the natural fiber is taken as a renewable, degradable and excellent mechanical property biological resource, is very suitable to be used as a reinforcement of a polymer matrix, is widely applied to the preparation of polymer composite materials, and is expected to become a powerful competitor for partially replacing chemical fibers such as glass fibers and the like.
However, natural fibers suffer from the following disadvantages: (1) The surface of the natural fiber contains a large amount of hydroxyl, so that the natural fiber has stronger polarity and hydrophilicity, and is difficult to realize good interface combination with a non-polar polymer matrix, so that the reinforcing effect of the natural fiber cannot be effectively exerted; (2) The unique gully structure on the surface of the natural fiber not only affects the surface evenness of the natural fiber and reduces the mechanical property of the natural fiber, but also is difficult to fill by a nonpolar polymer matrix, and is one of the main reasons for forming the interface defects of the natural fiber reinforced polymer composite material. The above disadvantages of natural fibers, compared to chemical fibers, limit their further applications and developments in the field of composite materials.
Therefore, in order to fully utilize the abundant resources of natural fibers, it is critical to further expand the applications and development of natural fibers to realize high performance of natural fibers. Meanwhile, natural fibers are used for replacing part of chemical fibers, so that the problems of large energy consumption, difficult recovery and other resources and environments caused by the current large amount of chemical fibers can be solved, and the method has great significance for promoting environmental protection and economic development.
Disclosure of Invention
In view of the above, the present invention is directed to provide a nano SiO 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement solves the problems that natural fibers are difficult to effectively combine with a polymer matrix and the mechanical property of the natural fibers is poor, so that the high-performance requirement on the green environment-friendly fiber reinforcement material in the design and application process of the composite material is realized.
In order to achieve the purpose, the invention provides nano SiO 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement comprises the following steps:
pretreating the surface of the natural fiber by adopting a carboxymethyl method; and
preparing different microstructures and shapes on the surface of natural fiber by in-situ deposition processNano SiO of appearance 2 Depositing a layer to obtain nano SiO 2 Natural fiber multi-scale reinforcement is deposited in situ.
In the above scheme, the pretreatment of the natural fiber surface by the carboxymethyl method includes: and (3) carrying out alkali treatment and etherification treatment on the surface of the natural fiber by adopting a carboxymethyl method so as to optimize the micro appearance and chemical structure of the surface of the natural fiber.
In the above scheme, the alkali treatment of the natural fiber surface by the carboxymethyl method specifically comprises: preparing an alkaline solution of 20wt.% of isopropanol/10 wt.% of NaOH, and ultrasonically oscillating for 10min at 25 ℃; soaking jute fiber in the alkaline solution at 40 deg.C for 90min.
In the above scheme, the etherification treatment of the natural fiber surface by the carboxymethyl method specifically comprises: preparing a mixed solution of 2.5mol/L sodium chloroacetate, 8.0wt.% of isopropanol and 0.04 mol/L4-dimethylaminopyridine, wherein 0.04 mol/L4-dimethylaminopyridine is used as a catalyst, adding the mixed solution into an alkaline solution soaked with jute fibers, and magnetically stirring for 4 hours at the temperature of 60 ℃; transferring jute fiber to dilute H of 0.05mol/L 2 SO 4 Soaking in the solution at 25 deg.C for 2h; taking out the jute fiber, cleaning, and drying for later use.
In the above scheme, after the natural fiber surface is pretreated by the carboxymethyl method, the method further comprises: and (3) cleaning and drying the natural fiber subjected to carboxymethylation pretreatment.
In the scheme, the natural fiber subjected to carboxymethylation pretreatment is cleaned by alternately cleaning the natural fiber by using distilled water and an ethanol solution; the drying treatment of the natural fiber after the carboxymethylation pretreatment is to dry the natural fiber in a drying oven with the temperature of 60-70 ℃.
In the scheme, the nano SiO with different microstructures and appearances is prepared on the surface of the natural fiber by adopting an in-situ deposition process 2 In the step of depositing the layer, the in-situ deposition process adopts a sol-gel method.
In the scheme, the sol-gel method is adopted to prepare the nano SiO with different microstructures and shapes on the surface of the natural fiber 2 Depositing a layer, wherein the specific process parameters are as follows: the concentration of tetraethyl orthosilicate (TEOS) is 0.08mol/L; the reaction time is 6h; the reaction temperature is 60 ℃; the concentration of ammonia water is 0.15-0.75 mol/L.
In the scheme, the in-situ deposition process is adopted to prepare the nano SiO with different microstructures and appearances on the surface of the natural fiber 2 In the step of depositing the layer, the nano SiO with different microstructures and shapes 2 The deposited layer comprises nano SiO 2 Gel, nano SiO 2 Array and nano SiO 2 And (4) clustering.
In the above scheme, the nano SiO 2 The deposition layer is in-situ deposited in a gully structure on the surface of the natural fiber through the action of a C-O-Si chemical bond, so that the surface microstructure and the appearance of the natural fiber are effectively regulated and controlled, and the natural fiber is endowed with excellent surface wetting performance and mechanical property.
According to the technical scheme, the invention has the following beneficial effects:
1. the invention provides nano SiO 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement optimizes the micro-morphology and chemical structure of the natural fiber surface by adopting a carboxymethyl method to pretreat the natural fiber surface, and prepares nano SiO with different micro-structures and morphologies on the natural fiber surface by combining the regulation and control of an in-situ deposition process 2 Depositing a layer to obtain nano SiO 2 The in-situ deposition of the natural fiber multi-scale reinforcement solves the problems that the natural fiber is difficult to be effectively combined with the polymer matrix and the mechanical property of the natural fiber is poor, and realizes the nano SiO 2 The controllable preparation of the in-situ deposited natural fiber multi-scale reinforcement meets the high performance requirement on the green environment-friendly fiber reinforcement material in the design and preparation process of the composite material.
2. The invention provides nano SiO 2 Preparation method of in-situ deposition natural fiber multi-scale reinforcement and prepared nano SiO 2 The in-situ deposited natural fiber multi-scale reinforcement has excellent surface impregnationLubricating property and mechanical property. Wherein, compared with common natural fiber, the fiber is processed by nano SiO 2 By the in-situ deposition treatment of the array, the spreading coefficient of the interface between the natural fiber and the polymer matrix and the tensile strength of the natural fiber and the polymer matrix are respectively improved by 35.8 percent and 22.7 percent, and the in-situ deposition treatment is expected to further replace chemical fibers such as glass fibers.
3. The invention provides nano SiO 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement has the characteristics of abundant, harmless and renewable raw materials, simple and easily-controlled preparation process, low energy consumption and CO released by natural fibers in the waste treatment process 2 The amount of CO absorbed during its growth 2 The amounts are equal. The development and application of the novel green environment-friendly fiber reinforced material accord with the development trend of low-carbon economy and lightweight products, and the novel green environment-friendly fiber reinforced material has great economic potential and social and ecological benefits.
Drawings
The invention is further illustrated by the following examples in conjunction with the drawings.
FIG. 1 is a diagram of the preparation of nano SiO 2 A flow chart of a method for in situ deposition of natural fiber multi-scale reinforcement.
FIG. 2 shows an embodiment of a nano SiO 2 Schematic diagram of controllable preparation process of in-situ deposition natural fiber multi-scale reinforcement.
FIG. 3 is a surface micro-topography of a comparative example, examples 1-3, provided by the present invention, wherein (a) is the surface micro-topography of the comparative example; (b) is the surface microtopography of example 1; (c) is the surface microtopography of example 2; (d) is the surface microtopography of example 3.
FIG. 4 shows comparative example, example 2 and nano SiO 2 An infrared spectrum of (1).
FIG. 5 is a graph showing the interfacial spreading factor between a polymer matrix and comparative examples, examples 1 to 3, provided by the present invention.
FIG. 6 is an interfacial microtopography between a comparative example, examples 1-3 and a polymer matrix provided by the present invention, wherein (a) is the interfacial microtopography between the comparative example and the polymer matrix; (b) Is the interfacial microtopography between example 1 and the polymer matrix; (c) Is the interfacial microtopography between example 2 and the polymer matrix; (d) Is the interfacial microtopography between example 3 and the polymer matrix.
FIG. 7 is a graph showing the mechanical properties of comparative examples, examples 1 to 3, provided by the present invention, wherein (a) is a tensile stress-strain curve; (b) is tensile strength and Young's modulus; and (c) is the Weibull distribution curve for tensile strength.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Aiming at the problem that the reinforcing effect can not be effectively exerted because the interface with strong combination is difficult to form between the natural fiber and the nonpolar polymer matrix and the mechanical property of the natural fiber is poor, researches find that the nano SiO 2 The in-situ deposition treatment can effectively improve the surface wetting property of the natural fiber and the mechanical property thereof, and solve the problem that the modification effect of the traditional physical or chemical modification method on the natural fiber is very limited. Nano SiO 2 The effect of in-situ deposition treatment depends on the microstructure and the morphology of the nano particles, how to utilize the specific microstructure and chemical structure of the natural fiber surface and combine an effective in-situ deposition process to prepare the nano particle deposition layer with the controllable microstructure and morphology on the natural fiber surface so as to improve the surface wettability of the natural fiber and the mechanical property of the natural fiber, so that the natural fiber fully exerts the inherent enhancement advantages, and the method is a key technical problem to be solved urgently for the green and environment-friendly fiber reinforced material.
In view of this, the present invention provides a nano SiO 2 The method for preparing the in-situ deposited natural fiber multi-scale reinforcement optimizes the micro-morphology and chemical structure of the surface of the natural fiber by adopting a carboxymethyl method to pretreat the surface of the natural fiber; and preparing nano SiO with different microstructures and appearances on the surface of the natural fiber by adopting an in-situ deposition process 2 Depositing a layer to obtain nano SiO 2 Natural fiber multi-scale reinforcement is deposited in situ. AAspect, nano SiO 2 The deposition layer fills a gully structure on the surface of the natural fiber, which is not easy to be infiltrated by the polymer matrix, so that the contact area between the natural fiber and the polymer matrix is increased, and the spreading capability of the polymer matrix on the surface of the natural fiber is effectively improved; on the other hand, nano SiO 2 The deposit layer reduces the stress concentration area on the surface of the natural fiber and obviously improves the tensile property of the natural fiber. Effectively regulating and controlling nano SiO by combining carboxymethylation pretreatment and in-situ deposition process 2 The microstructure and the appearance of the deposited layer are adopted to prepare the natural fiber reinforcement with high performance.
As shown in FIG. 1, FIG. 1 is a diagram of the method for preparing nano SiO according to the present invention 2 A flow diagram of a method for in situ deposition of natural fiber multi-scale reinforcement, the method comprising the steps of:
step S1: pretreating the surface of the natural fiber by adopting a carboxymethyl method;
step S2: preparing nano SiO with different microstructures and shapes on the surface of natural fiber by in-situ deposition process 2 Depositing a layer to obtain nano SiO 2 Natural fiber multi-scale reinforcement is deposited in situ.
According to the embodiment of the invention, the step S1 of pretreating the surface of the natural fiber by using a carboxymethyl method comprises the following steps: and (3) carrying out alkali treatment and etherification treatment on the surface of the natural fiber by adopting a carboxymethyl method so as to optimize the micro appearance and chemical structure of the surface of the natural fiber. On one hand, the carboxymethylation pretreatment can effectively remove the colloid on the surface of the natural fiber, so that the gully structure on the surface of the natural fiber is exposed, and the nano SiO is reduced 2 Heterogeneous nucleation free energy of the deposited layer promotes the nano SiO 2 Heterogeneous nucleation and growth of the deposited layer; on the other hand, carboxymethylation pretreatment can introduce carboxyl on the surface of natural fiber to enhance natural fiber and nano SiO 2 Interaction between the deposited layers.
In step S1, the carboxymethylation pretreatment is divided into two parts: alkali treatment and etherification treatment. Wherein the alkali treatment specifically comprises: preparing an alkaline solution of 20wt.% of isopropanol/10 wt.% of NaOH, and ultrasonically oscillating for 10min at 25 ℃; placing jute fiber in the alkaliSoaking in the neutral solution at 40 deg.C for 90min; the etherification treatment specifically comprises: preparing a mixed solution of 2.5mol/L sodium chloroacetate, 8.0wt.% of isopropanol and 0.04 mol/L4-dimethylaminopyridine, wherein 0.04 mol/L4-dimethylaminopyridine is used as a catalyst, adding the mixed solution into an alkaline solution soaked with jute fibers, and magnetically stirring for 4 hours at the temperature of 60 ℃; transferring jute fiber to dilute H of 0.05mol/L 2 SO 4 Soaking in the solution at 25 deg.C for 2h; taking out the jute fiber, cleaning, and drying for later use.
In step S1, after the natural fiber surface is pretreated by the carboxymethyl method, the method further comprises: and (3) carrying out cleaning treatment and drying treatment on the natural fiber subjected to carboxymethylation pretreatment. The natural fiber subjected to carboxymethylation pretreatment is cleaned by alternately cleaning the natural fiber by using distilled water and an ethanol solution; the drying treatment of the natural fiber after the carboxymethylation pretreatment is to dry the natural fiber in a drying oven at the temperature of 60-70 ℃.
According to the embodiment of the invention, the step S2 of preparing the nano SiO with different microstructures and morphologies on the surface of the natural fiber by adopting the in-situ deposition process 2 In the step of depositing the layer, the in-situ deposition process adopts a sol-gel method. The sol-gel method is adopted to prepare nano SiO with different microstructures and shapes on the surface of natural fiber 2 Depositing a layer, wherein the specific process parameters are as follows: the concentration of tetraethyl orthosilicate (TEOS) is 0.08mol/L; the reaction time is 6h; the reaction temperature is 60 ℃; the concentration of ammonia water is 0.15-0.75 mol/L. Alternatively, the ammonia concentration may be 0.15mol/L, 0.60mol/L, 0.75mol/L.
In step S2, the nano SiO with different microstructures and shapes is prepared on the surface of the natural fiber by adopting an in-situ deposition process 2 In the step of depositing the layer, the nano SiO with different microstructures and shapes 2 The deposited layer comprises nano SiO 2 Gel, nano SiO 2 Array and nano SiO 2 And (4) clustering. The nano SiO 2 The deposition layer is in-situ deposited in the gully structure on the surface of the natural fiber through the action of C-O-Si chemical bondThe surface microstructure and the morphology of the natural fiber are effectively regulated and controlled, and the natural fiber is endowed with excellent surface wettability and mechanical properties. Wherein, compared with common natural fiber, the fiber is processed by nano SiO 2 By the in-situ deposition treatment of the array, the interfacial spreading coefficient between the natural fiber and the polymer matrix and the tensile strength of the natural fiber and the polymer matrix are respectively improved by 35.8 percent and 22.7 percent.
Therefore, the nano SiO provided by the invention 2 The preparation method of in-situ deposited natural fiber multi-scale reinforcement firstly proposes to prepare nano SiO with different microstructures and appearances on the surface of the natural fiber 2 The deposition layer effectively regulates and controls the surface infiltration performance and the mechanical property of the natural fiber, so as to solve the problems that the natural fiber is difficult to effectively combine with a polymer matrix and the mechanical property is poor, prepare the high-performance natural fiber reinforcement and effectively improve the surface infiltration performance and the self mechanical property of the natural fiber reinforcement.
The following further describes specific embodiments of the present invention in conjunction with examples, and therefore does not limit the invention to the scope of the examples described.
Examples 1 to 3: nano SiO 2 The preparation method of the in-situ deposition jute fiber multi-scale reinforcement comprises the following steps:
(1) Soaking 1g of jute fiber in alkaline solution of isopropanol (20 wt.%)/NaOH (10 wt.%), and soaking at 40 deg.C for 90min to obtain alkali-treated jute fiber; preparing 100ml of etherification solution, wherein the concentration of sodium chloroacetate is 2.60mol/L, the concentration of isopropanol is 1.70mol/L, the concentration of catalyst 4-dimethylaminopyridine is 0.04mol/L, transferring the alkali-treated jute fiber into the etherification solution, and magnetically stirring for 4 hours at the temperature of 60 ℃ to obtain the etherified jute fiber; subjecting etherified jute fiber to dilute H with concentration of 0.05mol/L 2 SO 4 Soaking in the solution for 2h; and then, selecting distilled water and ethanol solution to alternately clean the jute fiber, and placing the jute fiber in an oven with the temperature of 60-70 ℃ for drying to obtain the jute fiber subjected to carboxymethylation treatment.
(2) Weighing 0.1g of the jute fiber obtained in the step (1), and mixing the jute fiberSoaking in mixed solution of TEOS (0.08 mol/L)/anhydrous ethanol (30 ml); then, distilled water (1.4 ml)/absolute ethyl alcohol (10 ml) solution and ammonia water/absolute ethyl alcohol (5 ml) solution are sequentially and slowly dripped into the TEOS solution, and ultrasonic oscillation is carried out for 1h under the condition of 25 ℃, wherein the concentrations of the ammonia water are 0.15mol/L (example 1), 0.60mol/L (example 2) and 0.75mol/L (example 3) respectively; the solution was then transferred to a water bath; magnetically stirring at 40 deg.C for 5 hr, taking out jute fiber, washing with distilled water and ethanol solution alternately, and drying. By regulating and controlling the concentration of ammonia water, the nano SiO is obtained 2 Gel in-situ deposition jute fiber multi-scale reinforcement and nano SiO 2 Array in-situ deposition jute fiber multi-scale reinforcement and nano SiO 2 And (3) cluster in-situ deposition of a jute fiber multi-scale reinforcement.
(3) The nano SiO obtained in the step (2) 2 Gel in-situ deposition jute fiber multi-scale reinforcement and nano SiO 2 Array in-situ deposition jute fiber multi-scale reinforcement and nano SiO 2 Cluster in-situ deposition jute fiber multi-scale reinforcement corresponding to the nano SiO prepared in examples 1, 2 and 3 2 And depositing the jute fiber multi-scale reinforcement in situ.
Comparative example: the method for processing jute fiber by carboxymethylation specifically comprises the following steps:
(1) Soaking 1g of jute fiber in alkaline solution of isopropanol (20 wt.%)/NaOH (10 wt.%), and soaking at 40 deg.C for 90min to obtain alkali-treated jute fiber; preparing 100ml of etherification solution, wherein the concentration of sodium chloroacetate is 2.60mol/L, the concentration of isopropanol is 1.70mol/L, the concentration of catalyst 4-dimethylaminopyridine is 0.04mol/L, transferring the alkali-treated jute fiber into the etherification solution, and magnetically stirring for 4 hours at the temperature of 60 ℃ to obtain the etherified jute fiber; subjecting etherified jute fiber to dilute H with concentration of 0.05mol/L 2 SO 4 Soaking in the solution for 2h; and then, selecting distilled water and ethanol solution to alternately clean the jute fiber, and placing the jute fiber in an oven with the temperature of 60-70 ℃ for drying to obtain the jute fiber subjected to carboxymethylation treatment.
(2) The carboxymethylated jute fiber obtained in the step (1) is the comparative example.
FIG. 2 shows an embodiment of a nano SiO 2 A schematic diagram of a controllable preparation process of in-situ deposition natural fiber multi-scale reinforcement, showing examples 1-3 of high-performance nano SiO 2 The controllable preparation process of the in-situ deposited natural fiber multi-scale reinforcement can be seen, and the preparation process is simple and easy to control, low in energy consumption and free of pollution.
And (3) micro-morphology characterization:
the surface microtopography of examples 1 to 3 and comparative example was performed using a scanning electron microscope (SEM, fei Quanta 200 type). Before characterization, the metal spraying treatment was performed on the examples 1 to 3 and the comparative example.
FIG. 3 shows the surface micro-topography of comparative examples and examples 1 to 3 provided by the present invention. For the comparative example, the surface had a structure of ravines distributed along the axial direction of the fiber, and the surface was rough (fig. 3 a). Through nano SiO 2 In-situ deposition treatment, when the concentration of ammonia water is lower (0.15 mol/L), the nano SiO 2 The nucleation and growth of particles are difficult, and the nano SiO 2 Coated on the surface of the example 1 in the form of gel. n-SiO 2 The thickness of the gel is thin (80-90 nm), which is not enough to completely fill the ravine structure on the surface of jute fiber (fig. 3 b). When the concentration of ammonia water is 0.60mol/L, the nano SiO is 2 The surface of the sample 2 is coated with the gel firstly. With the reaction time extended (6 h), TEOS had enough reaction time to complete the hydrolysis and condensation process, and spherical particles with uniform size were obtained on the surface of example 2, and the average particle size was 60-70 nm. The spherical particles formed ordered nano-SiO in the ravine structure on the surface of example 2 2 The array effectively fills the surface gully structure of example 2 (fig. 3 c). When the concentration of ammonia water is 0.75mol/L, a layer of nano SiO is still obtained on the surface of the first layer in the example 3 2 And (4) gelling. With the extension of the reaction time (6 h), the nano SiO 2 Particles (average particle diameter 95-105 nm) are distributed on the surface of example 3 in a cluster mode, and nano SiO is 2 The structure of the cluster is not as good as that of nano SiO 2 Array warping (FIG. 3 d).
And (3) characterizing a chemical structure:
comparison example, example 2 and nano-SiO by Nicolet Nexus 670 infrared spectrometer 2 Infrared spectrum analysis is carried out on the particles, and the scanning wave number range is 4000-400 cm -1 。
FIG. 4 shows comparative example, example 2 and nano SiO 2 Infrared spectrum of (2). Comparison example at 1611cm after carboxymethylation pretreatment -1 、1419cm -1 And 1330cm -1 The characteristic peak of carboxyl appears, which indicates that hydroxyl on the molecular chain of the cellulose of the comparative example is replaced by carboxyl, and the carboxyl is successfully introduced into the surface of the comparative example. At the same time, at 1737cm -1 And 1245cm -1 The characteristic peaks of pectin, lignin, hemicellulose and other colloids do not appear, and the carboxymethylation treatment removes the colloids on the surface of the comparative example. Nano SiO 2 2 The characteristic peaks of the particles are respectively bending vibration peaks (460 cm) of Si-O-Si -1 ) Symmetric oscillation peak of Si-O-Si (800 cm) -1 ) Si-OH stretching vibration peak (954) c m-1) and the asymmetric stretching vibration peak (1097 cm) of Si-O-Si -1 ). Through nano SiO 2 In situ deposition treatment, example 2 at 1080cm -1 And 456cm -1 Respectively show C-O-Si chemical bond and nano SiO 2 Characteristic peak of the particle, indicating nano SiO 2 The deposited layer is coated on the surface of the embodiment 2 through the chemical bonding of C-O-Si, and a firmly combined interface exists between the deposited layer and the embodiment 2. Further, example 2 absorption vibration peak of cellulose β -D glucosidic bond (898 cm) -1 ) Almost has no change, which indicates that the carboxymethylation pretreatment and the nano SiO 2 The in-situ deposition process had less effect on the framework structure of example 2.
Surface wetting property characterization:
contact angle tests were performed on the surfaces of examples 1 to 3 and comparative example using a JC2000D7M type contact angle measuring instrument. The test liquids were distilled water and ethylene glycol, and each set of samples was tested 5 times, and the contact angle (θ) thereof was averaged. The polar component and the nonpolar component and the surface energy of examples 1 to 3 and comparative example were calculated from the expressions (1) to (3). The interfacial spreading coefficient (S) between examples 1 to 3 and comparative example and the PP matrix was calculated according to the formulas (4) to (5).
S＝γ f -(γ m +γ f / m ) (5)
In the formula, gamma f ，γ m (30.9mN·m -1 )，
(72.8mN·m -1 ) And
(48.0mN·m -1 ) Respectively the surface energy of jute fiber, a PP matrix, distilled water and ethylene glycol;
(1.0mN·m -1 )，
(51.0mN·m -1 ) And
(19.0mN·m -1 ) Respectively the polar components of jute fiber, a PP matrix, distilled water and glycol;
(29.9mN·m -1 )，
(21.8mN·m -1 ) And
(29.0mN·m -1 ) Respectively, the nonpolar components of jute fiber, PP matrix, distilled water and ethylene glycol.
FIG. 5 is a graph showing the interfacial spreading factor between comparative examples, examples 1 to 3 and a polymer matrix, which are provided by the present invention. As can be seen from the graph, the interfacial spreading coefficients between the comparative example, examples 1 to 3 and the PP matrix are all negative, indicating that none of the PP matrices can spontaneously spread on the surfaces of the comparative example, examples 1 to 3. By the pair of nano SiO 2 The microstructure and the morphology of the deposition layer are regulated, and the spreading coefficients of the interfaces between the embodiments 1 to 3 and the PP matrix are improved to different degrees. Compared with the comparative example, the spreading coefficients of the interfaces between the examples 1-3 and the PP matrix are respectively improved by 13.5 percent, 35.8 percent and 19.0 percent. By comparison, the interfacial spreading factor between example 2 and the PP matrix is improved most significantly.
And (3) characterization of microscopic morphology of an interface:
the microscopic morphology of the comparative examples, examples 1-3 and the interface between the polymer matrix was characterized using a scanning electron microscope (SEM, fei Quanta 200). First, PP composites reinforced in comparative examples, examples 1 to 3 were prepared, and then treated with liquid nitrogen freezing and brittle-broken to prepare fracture surfaces of the sample composites. And carrying out gold spraying treatment on the fracture surface of the sample composite material before characterization. FIG. 6 is a microscopic view of the interface between the comparative example, examples 1-3 and the polymer matrix provided by the present invention. For the comparative example, there was a significant interfacial defect between the jute and PP, indicating poor interfacial bonding performance (fig. 6 a). The interfacial bonding performance of example 1 was improved compared to the comparative example, and although there was a significant interfacial slip phenomenon, the interfacial defects were significantly reduced (fig. 6 b). Compared with the comparative example and the example 1, the fracture surfaces of the examples 2 to 3 are smoother, the jute fibers and the PP matrix are fractured almost simultaneously, and the obvious interface slippage phenomenon does not occurThe brittle fracture characteristics are shown (fig. 6c and 6 d). The bonding of the jute fibers to the PP matrix was much tighter in example 2 than in example 3. The nano SiO can be demonstrated through the calculation of the interface spreading coefficient and the analysis of the interface micro-topography 2 The influence of the array in-situ deposition treatment on the interface wetting performance between the jute fiber and the PP matrix is most obvious.
And (3) testing mechanical properties:
according to GB/T5886-1986, YG001A type fiber electronic strength tester is selected to test the tensile properties of the samples of examples 1 to 3 and the comparative example, the distance between the upper and lower clamps is 30mm, the tensile speed is 20mm/min, the pre-tension is 0.20cN, and the number of the test samples is not less than 40. The diameters of different parts of each sample were measured by an optical microscope three times, and the average value of the diameters was obtained. The tensile strength of examples 1 to 3 and comparative example was calculated by the formula (6).
In the formula, σ t 、F s And d is the tensile strength, tensile strength and diameter of the sample, respectively.
Examples 1-3 and comparative examples were analyzed for tensile strength using two-parameter Weibull statistical theory, i.e.
In the formula, σ 0 Is a scale parameter; m is a shape parameter.
Two logarithms are taken on both sides of formula (7), and the results are shown below:
ln[-ln(1-F)]＝mlnσ t -mlnσ 0 (8)
the probability (F) of tensile failure of the specimen was calculated from equation (8).
In the formula, N is the total number of the samples; n is a tensile strength lower than sigma t The number of samples.
Mixing ln [ -ln (1-F)]For ln sigma t The Weibull distribution curves of the tensile strengths of examples 1 to 3 and comparative examples were plotted by a linear fitting method.
FIG. 7 is a schematic diagram of mechanical properties of examples 1 to 3 and comparative example provided by the present invention. The natural fiber belongs to a brittle material, the included angle between a macromolecular chain and the axial direction of the fiber is small, no obvious turning point exists in the stretching and breaking process, and the natural fiber follows Hooke's law and is typical elastic deformation. Due to the nano SiO 2 The in-situ deposition treatment mainly occurs on the surface of the natural fiber without changing the composition and structure of the natural fiber, and thus, the tensile stress-strain curves of examples 1 to 3 are substantially straight lines similar to those of the comparative example (fig. 7 a). By comparison, examples 1-3 all show superior tensile strength, tensile modulus and Weibull shape parameters over the comparative examples. Compared with the comparative example, the tensile strength of examples 1 to 3 was improved by 6.3%, 22.7% and 15.0%, respectively (fig. 7 b), the tensile modulus of examples 1 to 3 was improved by 8.1%, 15.3% and 8.9%, respectively (fig. 7 b), and the Weibull shape parameter of examples 1 to 3 was improved by 12.5%, 62.5% and 50.0%, respectively (fig. 7 c). Mechanical Properties and Nano SiO of examples 1 to 3 2 The microstructure of the deposited layer is related to the shape, wherein the nano SiO is 2 The array in-situ deposition treatment has the most remarkable influence on the mechanical properties of the jute fiber.
Therefore, the invention provides the nano SiO 2 A process for preparing the multi-scale reinforcing body of in-situ deposited natural fibre features that the carboxymethylation pretreatment is used to optimize and design the microscopic shape and chemical structure of natural fibre surface, and the in-situ deposition process is used to prepare nano SiO particles with different microscopic structures and shapes on the surface of natural fibre 2 Deposition layer (i.e. nano SiO) 2 Gel, nano SiO 2 Array and nano SiO 2 Cluster), thereby effectively regulating and controlling the interface infiltration performance between the natural fiber and the polymer matrix and the mechanical property thereof, and fully exerting the unique reinforcing advantage of the natural fiber. Wherein, the nano SiO 2 Array in situ depositionThe product treatment effectively fills the gully structure of the natural fiber surface which is not easy to be infiltrated by the polymer matrix, not only increases the contact area between the natural fiber and the polymer matrix, but also reduces the stress concentration area on the natural fiber surface, and obviously improves the interfacial spreading coefficient between the natural fiber and the polymer matrix and the tensile strength of the natural fiber and the polymer matrix. Compared with common natural fiber, the fiber is processed by nano SiO 2 By the in-situ deposition treatment of the array, the interface wetting performance between the natural fibers and the polymer matrix is improved by 35.8%, and the tensile strength, the tensile film quantity and the Weibull shape parameter of the natural fibers are respectively improved by 22.7%, 15.3% and 62.5%. The invention provides nano SiO 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement opens up new possibility for the wide application of high-performance green environment-friendly fiber reinforced materials, and helps the preparation of new-generation environment-friendly natural fiber reinforced composite materials.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Nano SiO 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement is characterized by comprising the following steps:
pretreating the surface of the natural fiber by adopting a carboxymethyl method; and
preparing nano SiO with different microstructures and shapes on the surface of natural fiber by in-situ deposition process 2 Depositing a layer to obtain nano SiO 2 And depositing the natural fiber multi-scale reinforcement in situ.
2. Nano-SiO of claim 1 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement is characterized in that the surface of the natural fiber is pretreated by adopting a carboxymethyl methodThe method comprises the following steps:
and (3) carrying out alkali treatment and etherification treatment on the surface of the natural fiber by adopting a carboxymethyl method so as to optimize the micro appearance and chemical structure of the surface of the natural fiber.
3. Nano-SiO according to claim 2 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement is characterized in that the carboxymethyl method is adopted to carry out alkali treatment on the surface of the natural fiber, and specifically comprises the following steps:
preparing an alkaline solution of 20wt.% of isopropanol/10 wt.% of NaOH, and ultrasonically oscillating for 10min at 25 ℃; soaking jute fiber in the alkaline solution at 40 deg.C for 90min.
4. Nano-SiO of claim 3 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement is characterized in that the natural fiber surface is etherified by a carboxymethyl method, and the method specifically comprises the following steps:
preparing a mixed solution of 2.5mol/L sodium chloroacetate, 8.0wt.% of isopropanol and 0.04 mol/L4-dimethylaminopyridine, wherein 0.04 mol/L4-dimethylaminopyridine is used as a catalyst, adding the mixed solution into an alkaline solution soaked with jute fibers, and magnetically stirring for 4 hours at the temperature of 60 ℃; transferring jute fiber to dilute H of 0.05mol/L 2 SO 4 Soaking in the solution at 25 deg.C for 2h; taking out the jute fiber, cleaning and drying for later use.
5. Nano-SiO according to claim 1 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement is characterized in that after the natural fiber surface is pretreated by adopting a carboxymethyl method, the preparation method further comprises the following steps:
and (3) carrying out cleaning treatment and drying treatment on the natural fiber subjected to carboxymethylation pretreatment.
6. Nano-SiO according to claim 1 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement is characterized in that，
The natural fiber subjected to carboxymethylation pretreatment is cleaned by alternately cleaning the natural fiber by using distilled water and an ethanol solution;
the drying treatment of the natural fiber after the carboxymethylation pretreatment is to dry the natural fiber in a drying oven with the temperature of 60-70 ℃.
7. Nano-SiO according to claim 1 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement is characterized in that the in-situ deposition process is adopted to prepare nano SiO with different microstructures and appearances on the surface of the natural fiber 2 In the step of depositing the layer, the in-situ deposition process adopts a sol-gel method.
8. Nano-SiO of claim 7 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement is characterized in that the sol-gel method is adopted to prepare nano SiO with different microstructures and appearances on the surface of the natural fiber 2 Depositing a layer, wherein the specific process parameters are as follows:
the concentration of tetraethyl orthosilicate (TEOS) is 0.08mol/L; the reaction time is 6h; the reaction temperature is 60 ℃; the concentration of ammonia water is 0.15-0.75 mol/L.
9. Nano-SiO according to claim 1 2 The preparation method of the in-situ deposition natural fiber multi-scale reinforcement is characterized in that the in-situ deposition process is adopted to prepare nano SiO with different microstructures and appearances on the surface of the natural fiber 2 In the step of depositing the layer, the nano SiO with different microstructures and appearances 2 The deposited layer comprises nano SiO 2 Gel, nano SiO 2 Array and nano SiO 2 And (4) clustering.
10. Nano SiO according to claim 9 2 The preparation method of the in-situ deposited natural fiber multi-scale reinforcement is characterized in that the nano SiO 2 The deposited layer is made by C-O-Si chemical bondThe natural fiber is used and deposited in situ in a gully structure on the surface of the natural fiber, so that the surface microstructure and the appearance of the natural fiber are effectively regulated and controlled, and the natural fiber is endowed with excellent surface wettability and mechanical properties.
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