CN110668398B - Preparation method and application of bionic gecko extreme progressive rigid-flexible gradient microcolumn structure - Google Patents
Preparation method and application of bionic gecko extreme progressive rigid-flexible gradient microcolumn structure 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 a bionic gecko extreme progressive rigid-flexible gradient microcolumn structure. The invention utilizes self-floating photoinitiator technology and magnetic field to drive gradient distribution of magnetic reinforced particles, and can realize preparation of microcolumn structure with extreme mechanical gradient (local elastic modulus change is more than 3 orders of magnitude: 10MPa-10 GPa); meanwhile, one end of the micro-column array is a pure matrix, the other end of the micro-column array is filled by high mixing of particles with different sizes, the middle of the micro-column array is distributed gradually according to particle sizes and concentration levels, the problem of interface compatibility and matching of rigid-flexible materials in combination is solved through the gradual gradient structure, and the maximum length-diameter ratio of the structurally stable composite micro-column is greatly improved.
Description
Technical Field
The invention belongs to the technical field of bionic materials, and particularly relates to a preparation method and application of a bionic gecko extreme progressive rigid-flexible gradient microcolumn structure.
Background
At the beginning of the century, the development of gecko adhesion mechanisms and gecko-like adhesion materials has been developed as a research hotspot for interdisciplinary in academia. The adhesion of the gecko is derived from a special multi-level micro-nano bristle array structure on the sole, and the structure can promote the gecko sole to form good shape fusion with the complex surface in nature, so that the actual contact area and the molecular acting force between contact surfaces are maximized. Based on the adhesion mechanism of the structure dominance, processing artificial materials (such as polymers) into micro-nano columnar array structures becomes a common strategy for developing bionic adhesion materials.
Once the bionic adhesion micro-column structure is proposed, attention is paid, but intrinsic contradiction exists between flexibility and stability, so that the existing adhesion material is difficult to achieve both high adhesion strength and high durability. On the material selection, the microcolumn formed by softer materials can be effectively deformed when contacting with a substrate, so that the increase of the adhesive strength is facilitated, but the high surface force under a small scale can easily cause the side collapse and clusters of the soft microcolumn, and the effect of external contact force can easily cause buckling or large deformation failure of the microcolumn, 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 surface compliance when the microcolumn is contacted with a substrate, which is unfavorable for improving the adhesive strength.
The Chinese patent application No. CN201811485889.1 discloses a preparation method of a bionic functional gradient coating, which is an invention patent applied by the applicant to the national institute of knowledge in 2018, and the technical scheme of the application document is mainly that a mixed solution containing magnetic nano particles is coated on a resin substrate, then a magnetic field is applied in the vertical direction, so that the magnetic nano particles are redistributed in the product, and finally solidification is carried out, so that the bionic functional gradient coating is obtained. However, the technology is limited to preparing a coating structure, and the gradient degree generated during the preparation of a micro-column structure cannot meet the actual requirement.
The Chinese patent application No. CN201310592837.5 discloses a method for preparing a bionic gecko composite microarray by preparing TiO 2 The nanotube microarray is immersed in chloroform solution of polydimethylsiloxane, taken out and cured to obtain the TiO2/PDMS composite microarray.
The composite micro-column structure based on the geometric and material design achieves the effect of coordinating the contact flexibility and the structural stability, but still has certain disadvantages.
1) The preparation process of the geometric composite multi-level structure is complex, the cost is high, the interface between the levels is not easy to control, and the synergistic modification effect is poor;
2) The cost of the metal reinforced polymer composite micro-column structure is too high, and the interface compatibility between the metal coating and the polymer micro-column is poor;
3) The soft/hard polymer composite microcolumn structure faces the contradiction of material selection, if materials with small rigidity difference are not enough to achieve the composite effect, high mismatch stress at a bonding interface under the action of external load can be caused when the rigidity difference is too large, and the cyclic bearing capacity and the durable adhesive capacity of the structure are further negatively affected;
4) The gradient degree of the composite microcolumn prepared by regulating the spatial distribution of the magnetic nano reinforced particles in the polymer matrix by the external magnetic field is far different from a required value, and the gradient also limits the length-diameter ratio of the composite microcolumn with stable structure.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method and application of a bionic gecko extreme progressive rigid-flexible gradient micro-column structure.
The invention discloses a preparation method of a bionic gecko extreme progressive rigid-flexible gradient microcolumn structure, which comprises the following steps:
step 1: preparing a self-floating photoinitiating crosslinking agent;
step 2: adding magnetic nano reinforced particles with different sizes and self-floating photoinitiation crosslinking agents into polymer monomers to obtain mixed solution;
step 3: preparing templates with holes with different sizes and length-diameter ratios, transferring the mixed liquid prepared in the step 2 to the templates, and infiltrating the holes;
step 4: standing to redistribute the photoinitiating crosslinking agent inside the product;
step 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 crosslink and solidify the polymerized monomer;
step 7: and stripping and removing the template to obtain the rigid-flexible gradient micro-column array structure.
Further, a self-floating polysiloxane-based photoinitiating crosslinker is prepared in step 1 by introducing polysiloxane groups onto the photoinitiator.
Further, the polymer monomer in the step 2 is ultraviolet curing polyurethane acrylate.
Further, the magnetic nano-reinforced particles Fe in the step 2 3 O 4 @SiO 2 And (3) particles.
Further, the concentration of the self-floating photoinitiating crosslinking agent in the mixed solution in the step 2 is 4.0X10 -3 mol/L。
Further, the size and the dosage of the magnetic nano-reinforced particles in the mixed solution in the step 2 are respectively 15vol percent in a ratio of 20:50:100 nm: 15vol%:15vol%.
Further, the standing time in step 4 was 60 minutes.
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 invention has the advantages and positive effects that:
the invention utilizes self-floating photoinitiator technology and magnetic field to drive gradient distribution of magnetic reinforced particles, and can realize preparation of microcolumn structure with extreme mechanical gradient (local elastic modulus change is more than 3 orders of magnitude: 10MPa-10 GPa); meanwhile, one end of the micro-column array is a pure matrix, the other end of the micro-column array is filled by high mixing of particles with different sizes, the middle of the micro-column array is distributed gradually according to particle sizes and concentration levels, the problem of interface compatibility and matching of rigid-flexible materials in combination is solved through the gradual gradient structure, and the maximum length-diameter ratio of the structurally stable composite micro-column is greatly improved.
The extremely progressive gradient structure can minimize side collapse and clusters of bristles while maximizing adhesion strength, and can effectively avoid interface problems of rigid-flexible material bonding, giving the microcolumn excellent rough surface compliance and durable adhesion properties. The extremely gradient microcolumn structure not only realizes preliminary application in the bionic adhesion field, namely important engineering fields such as crawling robots, pollution-free transportation, medical skin adhesion, 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 rigid-flexible material combination, and the development of the microcolumn array with stable structure and high length-diameter ratio has important reference and guiding significance for the hot fields such as energy collection, biosensing, extremely hydrophobic/wetting, self-cleaning surfaces and the like.
Drawings
FIGS. 1 a-g are flow charts of the preparation method of a rigid-flexible gradient micro-column structure according to the present invention; h is a matrix polymer chain configuration and reinforced particle distribution schematic diagram of different areas of a single extreme gradient microcolumn;
FIG. 2 is a schematic diagram of the preparation of a gradient polymer by molecular self-assembly;
FIG. 3 is a schematic diagram of a magnetic field driven preparation of a gradient nanocomposite;
FIG. 4 shows the results of polymer molecular weight distribution measurements;
FIG. 5 is a profile of the scanning electron microscope and nanoindentation load-depth curves, elastic modulus of various micropillars, and the elastic modulus distribution of various micropillars;
fig. 6 is a micropillar shear adhesion measurement and SEM image.
Description of the embodiments
The present invention will be described in further detail with reference to the following examples, in which the apparatus and reagents used in the respective examples and test examples are commercially available unless otherwise specified. The specific embodiments described herein are to be considered in an illustrative sense only and are not intended to limit the invention.
The invention discloses a preparation method and application of a bionic gecko extreme progressive rigid-flexible gradient micro-column structure, and a preparation flow is shown in figure 1.
Step 1: preparation of self-floating polysiloxane-based photoinitiating crosslinking agents.
First, HHMP (26.9 g,0.12 mol), tsCl (19.0 g,0.10 mol), KOH (22.4 g, 0.40 mol) was dissolved in 300mLCH 2 Cl 2 Is placed in a 500mL three-necked round bottom flask equipped with a mechanical stirrer and condenser. Stirred for 2h at room temperature (25 ℃) and rinsed three times with deionized water. Organic layer on Na 2 SO 4 Drying, filtering and vacuum distilling. The crude product is purified by column chromatography of silica gel (200-300 mesh) with ethyl acetate and dichloromethane (volume ratio of 1:20) as eluent, and the yield is 62.5%. The synthesis scheme is as follows:
thereafter, HHMP-S (13.7 g,0.04 mol), A-Si (9.0 g,0.02 mol) and K 2 CO 3 (19.9 g, 0.14 mol) was dissolved in 300mL of LDMF and placed in a 500mL four-necked round bottom flask equipped with a mechanical stirrer, thermometer and condenser. The solution was stirred at 110℃for 24h. The washing was performed three times with 10% aqueous sodium hydroxide and deionized water, respectively. The solvent was removed by vacuum distillation. Then, ethyl acetate and normal hexane (volume ratio is 1:4) are used as eluent, and silica gel (200-300 mesh) column chromatography is adopted to purify the crude product. The yield was 58.7%. The molecular weight of the GPC was about 897. The synthesis scheme is as follows:
then NH2-HHMP (0.62 g, 0.68 mmol), 3-bromopropene (0.33 g,2.72 mmol), K 2 CO 3 (1.88 g,13.60 mmol) 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 rinsed three times with deionized water. Organic layer on Na 2 SO 4 Drying, filtering and vacuum distilling. The crude product is purified by adopting a silica gel (200-300 mesh) column chromatography with ethyl acetate and n-hexane (1:4v/v) as eluent, and the obtained initiating cross-linking agent is polysiloxane-modified self-floating polysiloxane-based photoinitiating cross-linking agent, and the yield is 47.3%. The molecular weight as determined by GPC was about 1073. The synthesis scheme is as follows:
the following table gives the data relating to the preparation of photoinitiators according to the different ratios of the materials used in the other examples:
as shown in a of fig. 2, by introducing polysiloxane groups on the photoinitiator, the extremely low surface tension characteristic of the latter is utilized to drive the initiator to self-float movement, i.e. the initiator spontaneously floats to the surface of the polymerization system, forming a concentration gradient distribution of the initiator. As shown in b of fig. 2, the aim is that under the subsequent irradiation with light, a high concentration of initiator can generate more free radicals per unit volume, thereby initiating more monomers to polymerize and form a rigid polymer chain network with short-range, compact and high crosslinking; the low concentration of initiator forms a long-range, relatively loose, and low-crosslinking flexible polymer chain network; the polymerization system with the initiator concentration gradient distribution can form a polymerization product with a rigid-flexible gradient through curing reaction. And the gradient degree can be controlled by controlling the initiator concentration so as to adapt to the actual demands of different occasions or circumstances. The partial technology can prepare a gradient PUA matrix with local elastic modulus difference of more than 1 magnitude (< 10MPa- >100 MPa).
Step 2: controllable preparation of the gradient nanocomposite driven by the external field.
The magnetic nano-reinforced particles with different sizes and the self-floating polysiloxane-based photoinitiation crosslinking agent are mixed into a polymer monomer, wherein the polymer monomer in the embodiment is ultraviolet curing polyurethane acrylate (PUA), and the dosages of the initiator crosslinking agent and the magnetic particles are as follows: and (3) an initiator: 4.0X10 -3 mol/L; magnetic particles: 20:50:100nm are 15vol%:15vol%:15vol%. As shown in fig. 3, the aim is to apply a gradient magnetic field ∇ in a subsequent processing stepHaIn this case, the gradient distribution of the particles in the matrix can be controlled to greatly increase the gradient of the composite material.
The magnetism enhancing particles are Fe 3 O 4 @SiO 2 Including particles of different sizes, mainly 20nm, 50nm, 100nm, etc. Fe of different sizes 3 O 4 Coating of particles with SiO by ligand exchange and improved Stober method 2 A housing. Wherein, fe of 10nm, 25nm and 50nm is used as the magnetic particles of 20nm, 50nm and 100nm 3 O 4 Particles as magnetic core, and SiO is controlled by changing the quantity of TEOS precursor 2 The thickness of the coating, in turn, controls the overall diameter of the nanomagnetic reinforcing particles. The proportion of three scale particles is 15vol%:15vol%:15vol%。
The preparation method of the magnetic reinforced particles comprises the following steps: fe to be preserved in cyclohexane 3 O 4 (0.2 ml) was transferred to a 15ml bottle and diluted by adding 5ml of a mixed solution of dimethylformamide and methylene chloride (volume ratio 1:1), and then 60mg of PVP was added thereto and refluxed at 100℃for 12 hours or overnight. The mixed solution was dropped into 10mL of diethyl ether, and the particles were precipitated. The precipitate was washed with diethyl ether and centrifuged at 4500rpm for 5min. Transferring the sediment into 6.5mL of ethanol to obtain PVP-steady Fe with stable dispersion 3 O 4 . The above 6.5mL of the product was transferred to a 15mL bottle, 0.28mL of 30% mass fraction aqueous ammonia was added, and 0.065mL of Tetraethylorthosilicate (TEOS) -ethanol solution (volume fraction 10%) was added, followed by stirring at room temperature for 15 hours. The particles were then separated by centrifugation at 9000rpm for 1h and washed with ethanol. The collected particles were dispersed in distilled water, and 4mL of TEOS-ethanol solution (volume fraction 3%) was injected at a rate of 0.4mL/h using an injection pump. Stirring at room temperature for one day, and separating at 8500rpm for 5min to obtain final Fe 3 O 4 @SiO 2 Particles, and dispersed in an ethanol solution.
Wherein, 10nm of Fe3O4 prepares 20nm of reinforced particles: fe3O4 was 0.2ml, TEOS-ethanol solution (volume fraction 3%) was 1ml, and the injection rate was 0.1ml/h. Fe3O4 at 25nm prepared 50nm reinforcing particles: fe3O4 was 0.2ml, TEOS-ethanol solution (volume fraction 3%) was 4ml, and the injection rate was 0.4ml/h.50nm Fe3O4 preparation of 100nm reinforcing particles: fe3O4 was 0.2ml, TEOS-ethanol solution (volume fraction 3%) was 15ml, and injection rate was 0.8ml/h
The gradient formed by the particles with smaller size is more gentle, the particles with larger size have higher magnetic induction and are easier to generate magnetic migration, meanwhile, the specific surface area of the particles with larger size is lower, the maximum filling content of the particles in a matrix can be greatly improved, and the gradient degree of the composite material can be greatly improved through an improved externally-applied magnetic field device, so that the change of local elastic modulus is enlarged to 2 orders of magnitude.
Step 3: templates with holes of different sizes and length-diameter ratios are prepared by an electrochemical corrosion method. And then, transferring the polymer monomer mixed with the initiating cross-linking agent and the magnetic nano reinforced particles to the holes of the regular template, and deeply infiltrating the mixture liquid into the holes of the template by utilizing the capillary action assisted by the hollow environment to form a product I.
Step 4: the immersed mixture was left to stand for about 60min to redistribute the initiator/crosslinker inside the product to form product ii.
Step 5: a magnetic field is applied in the vertical direction of product ii to cause the magnetically enhanced particles to form a large hierarchical gradient distribution of the enhanced phase within product ii to form product iii. Magnetic field strength in this embodiment: ndFeB magnet with diameter of 60mm, thickness of 5mm and complete magnetization of 1.3T. The two magnets are placed at a distance of 10mm according to the mutual exclusion direction of the magnetic poles, a sample is placed on the bottom magnet, the magnetic field acts for 2 hours, and the magnetic field strength is 150mT.
Step 6: and (3) carrying out ultraviolet light irradiation on the product III to crosslink and solidify the polymerized monomer and further promote the redistribution of the self-floating polysiloxane-based photoinitiator. The strength required for the coating to cure completely is 50mw/cm 2 Is irradiated with blue LED light for 2min.
Step 7: and stripping and removing the template to obtain the rigid-flexible gradient micro-column array. H in fig. 1 is a schematic diagram of matrix polymer chain configuration and reinforced particle distribution of different regions of a single extreme gradient microcolumn; wherein T, M, B is respectively the polymer chain configuration at the top (top), middle (middle), base (base) and the distribution of the reinforcing particles.
Detection data:
1. for HHMP-Si-CC (1.0X10) -3 mol 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 photoinitiator gives a gradient distribution of polymer molecular weight, i.e. a network of long-range, large molecular weight, relatively loose, and low cross-linked flexible high molecular chains 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 and gradual rigidity and softness can be obtained.
2. As shown in fig. 5, (a) - (f) are scanning electron microscope images of vertical soft columns, vertical rigid columns, vertical gradient functional microcolumns, inclined soft columns, inclined rigid columns, inclined gradient functional microcolumns in order, and the column properties are limited by prepared templates; and (g) is a nanoindentation load-depth curve at different locations along a single microcolumn. Graph (h) is the modulus of elasticity measured along the nanoindentation test of individual micropillars. The dashed line connecting the data points is used to aid in viewing. The hatched areas in figures (g) and (h) represent the standard deviation of the measured values. Graph (i) corresponds to a profile of the elastic modulus distribution of the various micropillars of graphs (a) - (f).
The soft columns in the figure are pure polymer micropillars without adding magnetic nano reinforced particles; the rigid columns are polymer microcolumns added with magnetic nano reinforced particles, but the reinforced particles which are not driven by a magnetic field are uniformly distributed; the gradient functional microcolumn is a polymer microcolumn (particle concentration is 15 vol%) to which magnetic nano-reinforcing particles are added and which is subjected to magnetic field-driven gradient distribution of reinforcing particles.
Figures (a) and (d) show that the tips of the soft pillars have good surface compliance and can be well contacted with the substrate, which is beneficial to the increase of the adhesive strength, but the insufficient rigidity easily causes the self side collapse and clusters, so that the structural stability and the adhesive durability of the soft pillar array are poor.
Figures (b) and (e) show that the rigid columns have good stability, but at the tops of the micropillars, the rigidity of the micropillars prevents the surface compliance when the micropillars are in contact with a substrate, which is disadvantageous for improving the adhesive strength.
The figures (c) and (f) can show that the gradient functional microcolumn has equivalent flexibility at the top while taking rigidity into account.
From figures (g) and (h), it can be seen that the stiffness of the soft and rigid columns is substantially unchanged, while the stiffness of the gradient functional micropillars increases uniformly from top to bottom, which is beneficial to simultaneously improving the adhesive strength and structural stability of the micropillar array.
3. As shown in fig. 6, (a) a schematic view of a slant gradient functional micropillar photograph and a suspension device for shear adhesion measurement placed on a PET support layer, scale 1cm; panel (b) the shear adhesion capacity exhibited by the different micropillars in 200 replicates, the data points were fitted to a dashed line to aid in observation; graphs (c) - (h) are SEM images of different microcolumns after 200 repeated shear adhesion tests, and the upper right inset shows 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), to a scale of 10um.
The shear adhesion capability of the soft and rigid columns rapidly deteriorates with the evolution cycle of attachment/detachment, with the critical number of cycles of the soft column being about 10 and the critical number of cycles of the rigid column being about 60. While gradient functional micropillars exhibit excellent durability, remain nearly identical in shear adhesion after 200 attachment/detachment cycles, and can be lifted to about 2000 cycles. From fig. (c) (d), it can be obtained that the soft column completely collapses after cyclic loading; from the figures (e) and (f), the rigid column is broken to lose the adhesion effect; in contrast, gradient functional micropillars maintain a perfect array structure, thus maintaining almost unchanged adhesion performance after cycling experiments.
On the other hand, the maximum ratio of the diameter of the microcolumn structure prepared from the pure flexible polymer material is about 8 at present, and the durability is poor. After the gradient micro-column structure is made, the length-diameter ratio can be 12, and the structure is stable. And the extreme gradient structure is made according to the technology in the application, and the length-diameter ratio reaches about 40.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The preparation method of the bionic gecko extreme progressive rigid-flexible gradient micro-column structure is characterized by comprising the following steps of: step 1: preparing a self-floating photoinitiating crosslinking agent; step 2: adding magnetic nano reinforced particles with different sizes and self-floating photoinitiation crosslinking agents into polymer monomers to obtain mixed solution;
step 3: preparing templates with holes with different sizes and length-diameter ratios, transferring the mixed liquid prepared in the step 2 to the templates, and infiltrating the holes;
step 4: standing to redistribute the photoinitiating crosslinking agent inside the product;
step 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 crosslink and solidify the polymerized monomer;
step 7: stripping and removing the template to obtain a rigid-flexible gradient micro-column array structure;
the preparation of the microcolumn structure with the extreme mechanical gradient can be realized by the method, namely, the local elastic modulus is changed by more than 3 orders of magnitude: and (3) preparing the microcolumn structure with the pressure of 10MPa to 10 GPa.
2. The method for preparing the bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which is disclosed in claim 1, is characterized in that: in step 1, a self-floating polysiloxane-based photoinitiating crosslinker is prepared by introducing polysiloxane groups onto a photoinitiator.
3. The method for preparing the bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which is disclosed in claim 1, is characterized in that: the polymer monomer in the step 2 is ultraviolet curing polyurethane acrylate.
4. The method for preparing the bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which is disclosed in claim 1, is characterized in that: step 2 the magnetic nano-reinforced particle Fe 3 O 4 @SiO 2 And (3) particles.
5. The method for preparing the bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which is disclosed in claim 4, is characterized in that: the concentration of the self-floating photoinitiating cross-linking agent in the mixed solution in the step 2 is 4.0 multiplied by 10 -3 mol/L。
6. The method for preparing the bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which is disclosed in claim 4, is characterized in that: the sizes and the amounts of the magnetic nano-reinforced particles in the mixed solution in the step 2 are respectively 15vol percent in the mode of 20:50:100 nm: 15vol%:15vol%.
7. The method for preparing the bionic gecko extreme progressive rigid-flexible gradient micro-column structure, which is disclosed in claim 1, is characterized in that: and (4) standing for 60min.
8. The use of a method for the preparation of a biomimetic gecko extreme progressive rigid-flexible gradient micro-column structure according to any one of claims 1-7 for the preparation of rigid-flexible gradient micro-column structures.
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