CN110668398A - Preparation method and application of extremely progressive rigid-flexible gradient micro-column structure of bionic gecko - Google Patents
Preparation method and application of extremely progressive rigid-flexible gradient micro-column structure of bionic gecko Download PDFInfo
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Abstract
The invention belongs to the technical field of bionic materials, and particularly relates to a preparation method and application of an extreme progressive rigid-flexible gradient micro-column structure of a bionic gecko. The invention utilizes the self-floating photoinitiator technology and the gradient distribution of magnetic field driven magnetic enhanced particles, and can realize the preparation of a micro-column structure with extreme mechanical gradient (local elastic modulus changes by more than 3 magnitude levels: 10 MPa-10 GPa); meanwhile, one end of the micro-column array is a pure matrix, the other end of the micro-column array is highly mixed and filled with particles with different sizes, and the middle of the micro-column array is gradually distributed according to the particle size and concentration levels.
Description
Technical Field
The invention belongs to the technical field of bionic materials, and particularly relates to a preparation method and application of an extreme progressive rigid-flexible gradient micro-column structure of a bionic gecko.
Background
In the early century, the development of gecko adhesion mechanism and gecko-like adhesion material has been developed as a research hotspot crossing multiple disciplines in academia. The gecko adhesion is derived from a special multi-level micro-nano seta array structure on the sole of a foot, and the structure can promote the gecko sole and a complex surface in the nature to form good shape fusion, so that the actual contact area and the molecular acting force between contact surfaces are maximized. Based on the adhesion mechanism dominated by the structure, the artificial material (such as polymer) is processed into a micro-nano columnar array structure, so that the general strategy for developing the bionic adhesion material is realized.
The bionic adhesion micro-column structure is widely concerned once being put forward, but the flexibility and the stability of the bionic adhesion micro-column structure are in intrinsic contradiction, so that the existing adhesion material is difficult to combine high adhesion strength and high durability. In the aspect of material selection, the microcolumns made of softer materials can be effectively deformed when being in contact with the substrate, so that the increase of the adhesive strength is facilitated, however, the side collapse and the clustering of the soft microcolumns are easily caused by high surface force under a small scale, and the buckling or large deformation failure of the microcolumns is easily caused by the action of contact external force, so that the structural stability and the adhesive durability of the soft microcolumn array are poor. The hard material can effectively improve the stability of the structure, but the rigidity of the microcolumn prevents the microcolumn from being subjected to surface compliance when the microcolumn is contacted with a substrate, and the improvement of the adhesive strength is not facilitated.
The Chinese patent with application number CN201811485889.1 discloses a preparation method of a bionic functional gradient coating, which is an invention patent applied by an applicant to the national knowledge agency in 2018, and the technical scheme of the application document is mainly that a mixed solution containing magnetic nanoparticles is coated on a resin substrate, then a magnetic field is applied in the vertical direction, so that the magnetic nanoparticles are redistributed in the product, and finally, the product is solidified, and the bionic functional gradient coating is obtained. However, the technology is only limited to the preparation of a coating structure, and the gradient degree which can be generated when the micro-column structure is prepared cannot meet the actual requirement.
Chinese patent application No. CN201310592837.5 discloses preparation method of bionic gecko composite microarray by mixing prepared TiO2Nano meterAnd dipping the pipe microarray in a trichloromethane solution of polydimethylsiloxane, taking out the pipe microarray, and curing to obtain the TiO2/PDMS composite microarray.
The existing composite micro-column structure based on geometric and material design as described above has achieved a success in coordinating contact flexibility and structural stability, but still has certain disadvantages.
1) The preparation process of the geometric composite multi-level structure is complex, the cost is high, interfaces among levels are not easy to control, and the synergistic modification effect is poor;
2) the metal reinforced polymer composite micro-column has over-high structural cost and poor interface compatibility between the metal coating and the polymer micro-column;
3) the soft/hard polymer composite micro-column structure faces the contradiction of material selection, if the material with the small rigidity difference is selected, the composite effect cannot be achieved, and if the rigidity difference is too large, high mismatch stress at a combination interface under the action of external load can be caused, so that the cyclic bearing and durable adhesion capability of the structure are negatively influenced;
4) the gradient degree of the composite microcolumn prepared by simply regulating and controlling the spatial distribution of the magnetic nano reinforced particles in the polymer matrix through an external magnetic field is far from the required value, and meanwhile, the length-diameter ratio of the structurally stable composite microcolumn is limited by the gradient.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method and application of an extreme progressive rigid-flexible gradient micro-column structure of a bionic gecko.
The invention is realized in this way, a preparation method of a bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which comprises the following steps:
step 1: preparing a self-floating photo-initiated cross-linking agent;
step 2: adding magnetic nano reinforced particles with different sizes and a self-floating photo-initiated cross-linking agent into a polymer monomer to obtain a mixed solution;
and step 3: preparing templates with holes of different sizes and length-diameter ratios, transferring the mixed liquid prepared in the step 2 to the templates, and infiltrating the holes;
and 4, step 4: standing to redistribute the photoinitiated crosslinking agent in the product;
and 5: placing the template in a magnetic field to redistribute the magnetic nano-reinforcing particles inside the product;
step 6: carrying out ultraviolet irradiation on the product III to enable the polymerization monomer to be crosslinked and cured;
and 7: and stripping to remove the template to obtain the rigid-flexible gradient micro-column array structure.
Further, in step 1, a self-floating polysiloxane-based photo-initiated crosslinker is prepared by introducing polysiloxane groups onto the photoinitiator.
Further, in the step 2, the polymer monomer is ultraviolet curing polyurethane acrylate.
Further, the magnetic nano reinforced particle Fe in the step 23O4@SiO2And (3) granules.
Further, the concentration of the self-floating photo-initiated cross-linking agent in the mixed solution in the step 2 is 4.0 multiplied by 10-3mol/L。
Further, the sizes and the dosages of the magnetic nano reinforced particles in the mixed solution in the step 2 are respectively 15 vol% at a ratio of 20:50:100 nm: 15 vol%: 15 vol%.
Further, the standing time in step 4 was 60 min.
The preparation method of the bionic gecko extreme progressive rigid-flexible gradient micro-column structure is applied to preparation of the rigid-flexible gradient micro-column structure.
In summary, the advantages and positive effects of the invention are:
the invention utilizes the self-floating photoinitiator technology and the gradient distribution of magnetic field driven magnetic enhanced particles, and can realize the preparation of a micro-column structure with extreme mechanical gradient (local elastic modulus changes by more than 3 magnitude levels: 10 MPa-10 GPa); meanwhile, one end of the micro-column array is a pure matrix, the other end of the micro-column array is highly mixed and filled with particles with different sizes, and the middle of the micro-column array is gradually distributed according to the particle size and concentration levels.
The extremely progressive gradient structure can minimize side collapse and clustering of the bristles while maximizing the adhesive strength, can effectively avoid the interface problem of rigid-flexible material combination, and endows the microcolumn with excellent rough surface compliance and durable adhesive performance. The extreme gradient micro-column structure not only realizes the initial application in the bionic adhesion field, namely important engineering fields of crawling robots, pollution-free transportation, medical skin patches, transfer printing, micro-nano sensing, space grabbing and the like, but also can be applied to a plurality of complex mechanical working environments related to the combination of rigid and flexible materials, and the development of the micro-column array with stable structure and high length-diameter ratio has important reference and guidance significance in the heat door fields of energy collection, biosensing, extreme hydrophobicity/wetting, self-cleaning surfaces and the like.
Drawings
In FIG. 1, a-g are flow charts of the preparation method of a rigid-flexible gradient micro-column structure according to the present invention; in the figure, h is a schematic diagram of the configuration of matrix polymer chains and the distribution of reinforcing particles in different areas of a single extreme gradient microcolumn;
FIG. 2 is a schematic diagram of the preparation of gradient polymers by molecular self-assembly;
FIG. 3 is a schematic diagram of magnetic field driven preparation of gradient nanocomposites;
FIG. 4 shows the results of polymer molecular weight distribution measurements;
FIG. 5 is a scanning electron microscope and nanoindentation load-depth curves, elastic moduli, and profile plots of elastic modulus distributions of various microcolumns;
fig. 6 is a microcolumn shear adhesion measurement result and an SEM image.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the equipment and reagents used in the examples and test examples are commercially available without specific reference. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Examples controllable preparation of matrix, reinforcing phase dual gradient polymer-based nanocomposites
The invention discloses a preparation method and application of a bionic gecko extreme progressive rigid-flexible gradient micro-column structure, wherein the preparation process is shown in figure 1.
Step 1: preparation of self-floating polysiloxane-based photo-initiated cross-linking agents.
First, HHMP (26.9g,0.12mol), TsCl (19.0g,0.10mol), KOH (22.4g,0.40mol) were dissolved in 300mLCH2Cl2In a 500mL three-necked round bottom flask equipped with a mechanical stirrer and a condenser. Stirred at room temperature (25 ℃) for 2h and rinsed three times with deionized water. Organic layer in Na2SO4Drying, filtering and vacuum distilling. The crude product was purified by silica gel (200-300mesh) column chromatography using ethyl acetate and dichloromethane (volume ratio 1:20) as eluents, with a yield of 62.5%. The synthetic scheme is as follows:
thereafter, HHMP-S (13.7g,0.04mol), A-Si (9.0g,0.02mol) and K were added2CO3(19.9g,0.14mol) was dissolved in 300mL of DMF and placed in a 500mL four necked round bottom flask equipped with mechanical stirrer, thermometer and condenser. The solution was stirred at 110 ℃ for 24 h. Washed three times with 10% aqueous sodium hydroxide and deionized water, respectively. The solvent was removed by vacuum distillation. Then, the crude product is purified by silica gel (200-300mesh) column chromatography with ethyl acetate and n-hexane (volume ratio of 1:4) as eluents. The yield was 58.7%. The molecular weight was about 897 by GPC. The synthetic scheme is as follows:
then, NH2-HHMP (0.62g,0.68mmol), 3-bromopropene (0.33g,2.72mmol), and K were added2CO3(1.88g,13.60mmol) was dissolved in 20mL of acetone and placed in a 100mL three-necked round bottom flask equipped with a mechanical stirrer, thermometer and condenser. The solution was refluxed at 70 ℃ for 12h and washed three times with deionized water. Organic layer in Na2SO4Drying, filtering and vacuum distilling. And (3) purifying the crude product by using ethyl acetate and n-hexane (1:4v/v) as an eluent and adopting a silica gel (200-300mesh) column chromatography to obtain the initiated crosslinking agent, namely the self-floating polysiloxane-based photoinitiated crosslinking agent modified by polysiloxane, wherein the yield is 47.3%. The molecular weight was about 1073 by GPC. The synthetic scheme is as follows:
the following table gives the data relating to the preparation of photoinitiators in different ratios of the amounts of the materials used in the other examples:
as shown in a in FIG. 2, by introducing polysiloxane groups on the photoinitiator, the very low surface tension characteristic of the latter is utilized to drive the initiator to perform self-floating movement, i.e., the initiator spontaneously floats to the surface of the polymerization system, so as to form a concentration gradient distribution of the initiator. As shown in b of fig. 2, the purpose is that under the subsequent irradiation of light, the high-concentration initiator can generate more free radicals in unit volume, so as to initiate more monomers to undergo polymerization reaction, and form a short-distance, dense and highly crosslinked rigid polymer chain network; the low concentration of initiator forms a long-range, relatively loose, and low cross-linked flexible polymer chain network; the polymerization system with initiator concentration gradient distribution can form a polymerization product with gradient of rigidity and flexibility through a curing reaction. And the gradient degree can be controlled by controlling the concentration of the initiator so as to adapt to the actual requirements of different occasions or situations. The partial technology can prepare the gradient PUA matrix with the local elastic modulus different by more than 1 magnitude (<10 MPa-100 MPa).
Step 2: controllable preparation of gradient nanometer composite material driven by external field.
Mixing magnetic nano reinforced particles with different sizes and self-floating polysiloxane-based photo-initiated cross-linking agent into polymer monomer, in this embodiment, the polymer monomer isUltraviolet curing urethane acrylate (PUA), the initiator crosslinking agent and the magnetic particles are used in the following amounts: initiator: 4.0X 10-3mol/L; magnetic particles: 20:50:100nm are respectively 15 vol%: 15 vol%: 15 vol%. As shown in fig. 3, the aim is to apply a gradient magnetic field in a subsequent processing step
When the method is used, the gradient distribution of the particles in the matrix can be controlled, so that the gradient degree of the composite material is greatly improved.
The magnetic reinforcing particles are Fe3O4@SiO2Including particles of different sizes, mainly 20nm, 50nm, 100nm, etc. Fe of different sizes3O4Coating of particles with SiO by ligand exchange and modified Stober process2A housing. Wherein the magnetic particles of 20nm, 50nm and 100nm are respectively 10nm, 25nm and 50nm of Fe3O4The particles are used as magnetic cores, and SiO is controlled by changing the amount of TEOS precursor2The thickness of the coating, in turn, controls the overall diameter of the nanomagnetic reinforcing particles. The proportion of the three size particles is 15 vol%: 15 vol%: 15 vol%.
The preparation method of the magnetic reinforced particles comprises the following steps: fe to be preserved in cyclohexane3O4(0.2ml) was transferred to a 15ml flask, and diluted with 5ml of a mixed solution of dimethylformamide and dichloromethane (volume ratio 1:1), followed by addition of 60mg of PVP and reflux at 100 ℃ for 12h or overnight. The mixed solution was dropped into 10mL of diethyl ether to precipitate particles. The precipitate was washed with ether and centrifuged at 4500rpm for 5 min. The sediment was transferred to 6.5mL of ethanol to obtain a stably dispersed PVP-stabilized Fe3O4. The 6.5mL of the product was transferred to a 15mL bottle, 0.28mL of 30% ammonia was added, and 0.065mL of Tetraethylorthosilicate (TEOS) -ethanol solution (10% by volume) was added and stirred at room temperature for 15 hours. The pellets were separated by centrifugation at 9000rpm for 1h and washed with ethanol. The collected particles were dispersed in distilled water, and 4mL of a TEOS-ethanol solution (volume fraction 3%) was injected at a rate of 0.4mL/h using a syringe. Stirring at room temperature for one day, separating at 8500rpm for 5 daysmin, the final Fe can be obtained3O4@SiO2Granules, and dispersed in an ethanol solution.
Wherein 10nm of Fe3O4 produced 20nm of reinforcing particles: fe3O4 was 0.2ml, TEOS-ethanol solution (volume fraction 3%) was 1ml, and injection rate was 0.1 ml/h. 25nm Fe3O4 enhanced particles of 50 nm: fe3O4 (0.2ml), TEOS-ethanol solution (3% by volume) 4ml, and injection rate 0.4 ml/h. 50nm Fe3O4 enhanced particles of 100 nm: 0.2ml of Fe3O4, 15ml of TEOS-ethanol solution (volume fraction of 3 percent) and 0.8ml/h of injection speed
The small-sized particles can enable the formed gradient to be more gentle, the large-sized particles have higher magnetic inductivity and are easier to generate magnetic migration, meanwhile, the large-sized particles are lower in specific surface area and can greatly improve the maximum filling content of the large-sized particles in a matrix, and then the gradient degree of the composite material can be greatly improved through an improved external magnetic field device, so that the change of the local elastic modulus is expanded to 2 orders of magnitude.
And step 3: the templates with holes of different sizes and length-diameter ratios are prepared by an electrochemical corrosion method. Then, the polymer monomer mixed with the initiation cross-linking agent and the magnetic nano reinforced particles is transferred to the holes of the regular template, and the mixture liquid deeply infiltrates the holes of the template by using the capillary action assisted by the hollow environment to form a product I.
And 4, step 4: the immersed mix was allowed to stand for about 60min to redistribute the initiator/crosslinker within the product to form product II.
And 5: and applying a magnetic field in the vertical direction of the product II to enable the magnetic enhancement particles to form a large-scale gradient distribution of an enhancement phase in the product II so as to form a product III. Magnetic field strength in this example: NdFeB magnet having a diameter of 60mm, a thickness of 5mm and a full magnetization of 1.3T. The two magnets are arranged at a distance of 10mm according to the mutual exclusion directions of the magnetic poles, the sample is arranged on the magnet at the bottom, the action of the magnetic field is 2h, and the magnetic field intensity is 150 mT.
Step 6: ultraviolet irradiation is carried out on the product III, so that the self-floating polysiloxane-based photoinitiator is further promoted while the polymerization monomer is crosslinked and curedIs distributed. The strength required for complete curing of the coating is 50mw/cm2Is irradiated for 2 min.
And 7: stripping off the template to obtain the rigid-flexible gradient micro-column array. H in FIG. 1 is a schematic diagram of the configuration of the matrix polymer chains and the distribution of the reinforcing particles in different regions of a single extreme gradient microcolumn; wherein T, M, B is a schematic of the polymer chain configuration and the distribution of reinforcing particles at the apex (top), middle (middle), base (base), respectively.
And (3) detecting data:
1. for the compound with HHMP-Si-CC (1.0X 10)-3mol L-1) The molecular weight distribution of the polymer obtained for the photoinitiator was examined and the results are shown in FIG. 4. As can be seen from FIG. 4, the gradient distribution of HHMP-Si-CC as the photoinitiator can obtain the gradient distribution of the molecular weight of the polymer, i.e. a flexible polymer chain network with long-range, large molecular weight, relative looseness and low degree of crosslinking is formed at the top; and a rigid polymer chain network with short range, small molecular weight, compactness and high crosslinking is formed at the bottom, so that a polymerization product with gradient of rigidity and flexibility can be obtained.
2. As shown in fig. 5, (a) - (f) are scanning electron microscope images of a vertical soft column, a vertical rigid column, a vertical gradient functional micro column, an inclined soft column, an inclined rigid column and an inclined gradient functional micro column in sequence, wherein the column properties are formed by the prepared template in a limiting way; graph (g) is a nanoindentation load-depth curve at different locations along a single microcolumn. Panel (h) is the elastic modulus measured along the nanoindentation test of a single microcolumn. The dashed line connecting the data points is used to aid in the observation. The shaded areas in graphs (g) and (h) represent the standard deviation of the measured values. Fig. (i) is a profile view of the elastic modulus distribution of various microcolumns corresponding to fig. (a) to (f).
The soft column in the figure is a pure polymer micro-column without adding magnetic nano reinforced particles; the rigid column is a polymer microcolumn which is added with magnetic nano reinforced particles and is not driven by a magnetic field and uniformly distributed with the reinforced particles; the gradient functional micro-column is a polymer micro-column (the concentration of particles is 15 vol%) added with magnetic nano enhanced particles and subjected to magnetic field driven enhanced particle gradient distribution.
It can be seen from the graphs (a) and (d) that the top ends of the soft columns have good surface compliance, can be in good contact with the substrate, and is beneficial to increasing the adhesive strength, but the insufficient rigidity easily causes the side collapse and clustering of the soft columns, so that the structural stability and the adhesive durability of the soft column array are poor.
It can be seen from the graphs (b) and (e) that the rigid pillars have excellent stability, but at the tips of the microcolumns, the rigidity of the microcolumns hinders surface conformability when they are in contact with the substrate, which is disadvantageous for improvement of adhesive strength.
It can be seen from the graphs (c) and (f) that the gradient functional microcolumn has a relatively flexible top portion while giving consideration to rigidity.
It can be seen from the graphs (g) and (h) that the rigidity of the soft and rigid pillars is not changed basically, while the rigidity of the gradient functional micro-pillars is increased uniformly from the top to the bottom, which is beneficial to simultaneously improving the adhesive strength and the structural stability of the micro-pillar array.
3. As shown in fig. 6, (a) a photograph of a tilted gradient functional microcolumn placed on a PET support layer and a schematic view of a suspension device for shear adhesion measurement, with a scale bar of 1 cm; graph (b) shear adhesion performance of different microcolumns in 200 replicates, fitting data points to obtain a dashed line to aid in observation; the graphs (c) - (h) are SEM images of different microcolumns after 200 repeated shear adhesion tests, and the insert in the upper right corner is the stress distribution under the same shear load obtained by finite element analysis. The stress is scaled to the same magnitude as in figure (c) with a scale bar of 10 um.
The shear adhesion ability of the soft and rigid columns rapidly deteriorates with the evolution period of attachment/detachment, and the critical cycle number of the soft column is about 10 times and the critical cycle number of the rigid column is about 60 times. While the gradient functional microcolumn showed excellent durability, it still maintained almost the same shear adhesion ability after 200 attachment/detachment cycles, which could be increased to about 2000 cycles. From graphs (c) (d) it can be seen that the soft column completely collapsed after cyclic loading; from the graphs (e) (f), it can be seen that the pillars are broken and lose the adhesion; in contrast, the gradient functional microcolumn maintained a perfect array structure, and thus, after cycling experiments, still maintained almost constant adhesion properties.
On the other hand, at present, the maximum length-to-diameter ratio of the micro-column structure prepared by using a pure flexible polymer material is about 8, and the durability is poor. After the gradient microcolumn structure is made, the length-diameter ratio can be 12, and the structure is stable. And the length-diameter ratio of the extreme gradient structure manufactured according to the technology in the application reaches about 40.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A preparation method of a bionic gecko extreme progressive rigid-flexible gradient micro-column structure is characterized by comprising the following steps:
step 1: preparing a self-floating photo-initiated cross-linking agent;
step 2: adding magnetic nano reinforced particles with different sizes and a self-floating photo-initiated cross-linking agent into a polymer monomer to obtain a mixed solution;
and step 3: preparing templates with holes of different sizes and length-diameter ratios, transferring the mixed liquid prepared in the step 2 to the templates, and infiltrating the holes;
and 4, step 4: standing to redistribute the photoinitiated crosslinking agent in the product;
and 5: placing the template in a magnetic field to redistribute the magnetic nano-reinforcing particles inside the product;
step 6: carrying out ultraviolet irradiation on the product III to enable the polymerization monomer to be crosslinked and cured;
and 7: and stripping to remove the template to obtain the rigid-flexible gradient micro-column array structure.
2. The method for preparing the bionic gecko extremely-progressive rigid-flexible gradient micro-column structure according to claim 1, wherein the method comprises the following steps: in step 1, a self-floating polysiloxane-based photo-initiated crosslinker is prepared by introducing polysiloxane groups onto a photoinitiator.
3. The method for preparing the bionic gecko extremely-progressive rigid-flexible gradient micro-column structure according to claim 1, wherein the method comprises the following steps: and 2, the polymer monomer is ultraviolet curing polyurethane acrylate.
4. The method for preparing the bionic gecko extremely-progressive rigid-flexible gradient micro-column structure according to claim 1, wherein the method comprises the following steps: step 2, the magnetic nano reinforced particles Fe3O4@SiO2And (3) granules.
5. The method for preparing the bionic gecko extremely-progressive rigid-flexible gradient micro-column structure according to claim 4, wherein the method comprises the following steps: the concentration of the self-floating photoinitiation crosslinking agent in the mixed solution in the step 2 is 4.0 multiplied by 10-3mol/L。
6. The method for preparing the bionic gecko extremely-progressive rigid-flexible gradient micro-column structure according to claim 4, wherein the method comprises the following steps: the sizes and the dosages of the magnetic nano reinforced particles in the mixed solution in the step 2 are respectively 15 vol% at a ratio of 20:50:100 nm: 15 vol%: 15 vol%.
7. The method for preparing the bionic gecko extremely-progressive rigid-flexible gradient micro-column structure according to claim 1, wherein the method comprises the following steps: the standing time in step 4 is 60 min.
8. The use of the method of any one of claims 1 to 7 for the preparation of a bionic gecko extremely progressive rigid-flexible gradient microcolumn structure in the preparation of a rigid-flexible gradient microcolumn structure.
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