CN103333495B - Adhesive material used for imitating gecko sole adhesive arrays and preparation method thereof - Google Patents
Adhesive material used for imitating gecko sole adhesive arrays and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an adhesive material used for imitating gecko sole adhesive arrays and a preparation method thereof. The adhesive material comprises A component which is a silicone elastomer main reagent, B component which is a cross-linking agent, and carbon nanotube. Carbon nanotube is added according to a certain proportion, and the composite material is prepared by solidification at an appropriate temperature (70 to 100 DEG C). Wherein the silicone elastomer main reagent A component is the A component of Dow Corning 184, and the cross-linking agent B component is a mixture of the B component of Dow Corning 184 and the B component of Dow Corning 186. Tangential adhesion force can reach 4 N/cm<2>, and normal adhesion force can reach 1 N/cm<2>. The adhesive material of the invention has preferable adhesion performance, relatively high elastic modulus, and reusability, so that the adhesive material can be applied in the development of gecko-imitating robot sole adhesive arrays. The invention discloses the preparation method of the adhesive material.
Description
Technical field
The present invention relates to a kind of adhesion material for imitative gecko sole adhesion Array and preparation method thereof, belong to imitative gecko and adhere to sole adhesion material technical field.
Background technology
Millions of superfine bristles are had in the bottom of the every leg of gecko, and every root bristle end is had an appointment 400 to 1000 thinner branches.1 mm
2upper about have 5000 length to be the bristle of 30 ~ 130 μm, every leg just there are nearly 500,000 bristles, every root bristle has again 400 ~ 1000 length about 0.5 μm, width about 0.2 μm, the fine hair of thickness about 5 nm, nano level fine hair contacts with surface in contact and produces " Van der Waals force ", complete attachment (the Autumn K of sole, Sitti M, Liang Y A, et al. Evidence for van der Waals adhesion in gecko setae. PNAS, 2002, (99): 12252-12256.).Do a lot of work in the development of biomimetic gecko adhesion array both at home and abroad, and obtain very large progress.The size that array adheres to pole has grade, micron order and nano level.Preparation method has micro-mould injection moulding, reactive plasma etching method, electrostatic induction etching method, self-organizing structures casement plate casting etc., and wherein micro-mould injection moulding is used more.Mould material generally selects the viscosity such as urethane (PU), polyethylene siloxanes (PVS), polypropylene (PP) better, the organic polymer that Young's modulus is higher.
The people such as the Gorb of Germany Ma Pu metal institute, have developed pole end is mushroom micro-adhesion Array.Making method adopts mold injection method, mould material be polyethylene siloxanes (PVS, Coltene Whaledent AG, Altstatten, Switzerland,
e=3 MPa), obtain long 100 μm after the demoulding, micro-adhesion Array of diameter 40 μm, maximum normal direction adhesion strength can reach 6 N/cm
2(Gorb S, Varenberg M, Peressadko A, Tuma J. Biomimetic mushroom-shaped fibrillar adhesive microstructure. J. R. Soc. Interface, 2007,4,271-275.).The people such as Stanford Univ USA Mark Cutkosky adhere to pole pattern from optimization, have developed the inclination grade array that end is sharp-pointed.Adopt the preparation of micro-mould casting, mould material be urethane (Innovative polymers, IE-20 AH Polyurethane,
e=0.3 MPa), the adhesion Array adhesion strength that pouring experiment obtains is about 0.24 N/cm
2and there is obvious anisotropy, slip stick similar in gecko crawling process can be realized, Preliminary Applications is on imitative gecko climbing robot, achieve good effect (Santos D, Kim S, Spenko M, Parness A, Cutkosky M. Directional adhesive structures for controlled climbing on smooth vertical surfaces. 2007 IEEE International Conference on Robotics and Automation, Roma, Italy, 10-14 April 2007.).The people such as Carnegie Mellon University Metin Sitti have developed end and expand the micro-adhesion Array structure of bionic structure bristle, mould material be polyurethane material (ST-1060 A/B, BJB Enterprises, USA,
e=3 MPa) to expand micro-adhesion Array pole long 100 μm for end, and diameter 35 μm, pole angle of inclination is about 34 °, and array substrate thickness is about 1 mm.Adhesion property test finds: end expands micro-adhesion Array and stretches along bristle direction, and maximum tangential adhesion strength can reach 10 N/cm
2, the maximum tangential adhesion strength of inverse bristle direction stretching is about 2 N/cm
2, normal direction maximum adhesion intensity can reach 1.6N/cm
2(Murphy M P, Aksak B, Sitti M. Gecko-inspired directional and controllable adhesion. Small, 2009,5 (2), 170-175.).California university Lee etc., utilize polypropylene (polypropylene, TF-225-4, Premier Lab Supply, Inc.,
e=1.5 Gpa) as preparing material, prepare the highdensity micron order bionical bristle adhesion Array structure of inclination bristle pole, bristle pole angle of inclination is 45 °, diameter 0.6 μm, length 18 μm, spacing 1.5 μm, array substrate material is polyimide, and thickness is 25 μm.Adhesion property test finds, the bristle array of preparation has obvious anisotropic, and wherein forward slippage adhesion strength is 4.5 N/cm
2, reverse slippage adhesion strength is 0.1 N/cm
2(Lee J, Majidi C, Schubert B, Fearing R S. Sliding inducedadhesion of stiff polymer microfiber arrays:
. Macroscale behaviour. Journal of the Royal Society, Interface, 2008,5,835-844.).At home, the Mei Tao seminar of Hefei Institute Of Intelligent Machines Chinese Academy Of Sciences utilizes ICP deep etching method to prepare template, and cast silicon rubber and polyimide, curing and demolding obtains micro-adhesion Array of multiple length-to-diameter ratio.Array vertical distribution and substrate, it is cylindric for adhering to bar, and bar is long is respectively 1 μm, 5 μm, 15 μm, and diameter is 2 μm.Wherein long 5 μm, the normal direction adhesion strength measured by the array that diameter is 2 μm is maximum, can reach 1.94 N/cm
2(Chen Shirong, Mei Tao, Ni Lin, etc. the technique preparation of the imitative micro-nano adhesion Array of gecko. MEMS and technology, 2006,9,434-437).
In sum in order to obtain biomimetic gecko adhesion array, each research institution have employed different materials and structures to imitate the adhesion property of gecko bristle, but compares with biological gecko bristle, need to improve in adhesion property and the strength of materials.
Summary of the invention
The invention provides a kind of adhesion material for imitative gecko sole adhesion Array, be intended to the adhesion property and the strength of materials that improve material, better adapt to the application in gecko-emulated robot sole adheres to.
For an adhesion material for imitative gecko sole adhesion Array, it is characterized in that: by silicone elastomer host component A, crosslinking agent B component, carbon nanotube forms; Wherein component A and B component mass ratio are 10:1 ~ 15:1, and the massfraction of carbon nanotube controls 0.1% ~ 1%, above-mentioned carbon nanotube caliber 8 ~ 20 nm, length 2 ~ 20 μm.
The described adhesion material for imitative gecko sole adhesion Array, is characterized in that: silicone elastomer host component A is the component A of DOW CORNING 184, and crosslinking agent B component is mixed by the B component of DOW CORNING 184 and the B component of DOW CORNING 186 and forms; Wherein the B component of DOW CORNING 184 and the B component mass ratio of DOW CORNING 186 are 1:9 ~ 5:5.
The described adhesion material for imitative gecko sole adhesion Array, it is characterized in that: the component A of above-mentioned DOW CORNING 184, the B component of DOW CORNING 184, the B component of DOW CORNING 186, carbon nanotube mass ratio is: 10:0.3:0.7:0.03.
The preparation method of the described adhesion material for imitative gecko sole adhesion Array, is characterized in that comprising following process:
Step 1. adds the B component of DOW CORNING 184 successively in the component A of DOW CORNING 184, the B component of DOW CORNING 186, and carbon nanotube, stirs;
Step 2. is evacuated to bubble and eliminates completely, and be heating and curing at 70 ~ 100 DEG C 2 ~ 4 h film forming in vacuum oven.
The described adhesion material for imitative gecko sole adhesion Array prepares the method for gecko sole adhesion Array, it is characterized in that comprising following process:
Step 1. adds the B component of DOW CORNING 184 successively in the component A of DOW CORNING 184, the B component of DOW CORNING 186, and carbon nanotube, stirs, and is evacuated to bubble and eliminates completely;
Above-mentioned mixed polymer solution is poured into the mould of designed processing by step 2., and be heating and curing at 70 ~ 100 DEG C 2 ~ 4 h in vacuum oven, obtains the bionical inclination adhesion Array based on this adhesion material after the demoulding;
Step 3. is expanded structure preparation technology by end and is prepared end and expand structural adhesive array.
The B component of DOW CORNING 184 that the present invention is mixed by employing, the B component of DOW CORNING 186 improve its adhesion property as linking agent, improve its Young's modulus and the strength of materials by adding carbon nanotube.Tangential adhesion can reach ~ 4 N/cm
2, normal direction adheres to can reach ~ 1 N/cm
2.Adopt the B component of the B component of the DOW CORNING 184 of mixing, DOW CORNING 186 as linking agent, because the B component of DOW CORNING 186 has larger relative molecular mass compared with the B component of DOW CORNING 184, molecular chain is longer, easily tangle with intermolecular chain in molecule, its degree of crosslinking can be reduced, increase surface energy, thus improve its adhesion property.Add the Young's modulus that carbon nanotube adds adhesion material, for ensureing effective contact area, adhere to heavier object and provide mechanics and ensure, in order to prepare, imitative gecko tilts, end expands conveniently stripped the providing safeguard of structure and pole end mushroom adhesion Array, also can prevent the adhesion Array prepared to collapse adhesion phenomenon.
Accompanying drawing explanation
Fig. 1 novel polydimethylsiloxaneoxygen-enrichment-carbon nanotube adhesion material SEM section;
The Young's modulus that Fig. 2 does not add the novel polydimethylsiloxaneoxygen-enrichment adhesion material of carbon nanotube (NPWOC) and interpolation carbon nanotube (NPWC) compares;
Fig. 3 adhesion material is tangential, normal direction adheres to and the relation of load;
Tangential force when Fig. 4 load is 50 mN;
Normal force during Fig. 5 load 50 mN;
Fig. 6 revision test is tangential on adhesion material, the impact of normal adhesion force;
Tangential and (b) normal direction of Fig. 7 (a) adheres to schematic diagram. (a) 4.975 Kg; (b) 1.975 Kg; In figure 1: Novel sticky enclosure material, 2: wrought aluminium ring (0.975 Kg), 3: rope yarn, 4: counterweight (4Kg), 5: wrought aluminium ring, 6: Novel sticky enclosure material (4 pieces), 7: wrought aluminium ring, 8: rope yarn, 9: counterweight (1 Kg);
Fig. 8 imitates gecko inclination adhesion Array pouring technology;
Fig. 9 end expands structural adhesive array and prepares schematic diagram. in figure 11: inclination adhesion Array, 12: Novel sticky enclosure material glue, 13: silicon chip, 14: the inclination adhesion Array being soaked with Novel sticky enclosure material glue, 15: the inclination adhesion Array being soaked with Novel sticky enclosure material glue after precompressed, 16: end expands structural adhesive array;
The bionical inclination of Figure 10 (a) and (b) end expand the SEM face of structural adhesive array.
Embodiment
Embodiment 1.
1. the preparation of the novel polydimethylsiloxaneoxygen-enrichment matrix material of carbon nanotube enhancing
Adopt LOAD CELLS (plum Teller-Tuo benefit, AL204, Switzerland) in mass ratio routine 10:0.3:0.7:0.03 weigh the component A of DOW CORNING 184 respectively, the B component of DOW CORNING 184, the B component of DOW CORNING 186, carbon nanotube (caliber 20 nm, length 2 μm), mixing and stirring, vacuum suction bubble, until eliminate completely, solidifies 2 h at vacuum oven 70 DEG C, obtains the novel polydimethylsiloxaneoxygen-enrichment matrix material that carbon nanotube strengthens, as shown in Figure 1, the interpolation of carbon nanotube can increase its Young's modulus to its profile scanning electron microscopic picture.Adjustment carbon nanotube mass, can prepare the novel polydimethylsiloxaneoxygen-enrichment matrix material of different carbon nanotube mass mark.
The preparation of carbon nanotube novel polydimethylsiloxaneoxygen-enrichment adhesion material is not added in contrast: adopt LOAD CELLS (plum Teller-Tuo benefit, AL204, Switzerland) in mass ratio routine 10:0.3:0.7 weigh the component A of DOW CORNING 184 respectively, the B component of DOW CORNING 184, the B component of DOW CORNING 186, mixing and stirring, vacuum suction bubble is until eliminate completely, solidify 2 h at vacuum oven 70 DEG C, obtain novel polydimethylsiloxaneoxygen-enrichment adhesion material.The B component of DOW CORNING 184, the B component mass ratio of DOW CORNING 186 can be changed as required, preparation novel polydimethylsiloxaneoxygen-enrichment adhesion material.
2. Young's modulus test
The Young's modulus of embodiment 1 and 2 sample is measured with microcomputer controlled electronic universal tester (WDW-100, Changchun section is new, China).Do not add Young's modulus 0.0279 MPa of the adhesion material of carbon nanotube, add Young's modulus 0.22 MPa of the adhesion material of carbon nanotube, as shown in Figure 2.If Young's modulus is lower, adhesion Array prepared by adhesion material can collapse adhesion phenomenon, and can reduce with the effective contact area adhering to object, causes adhesiving effect not good, and therefore the present invention improves its Young's modulus by adding carbon nanotube.The above results shows that the interpolation of carbon nanotube adds the Young's modulus of adhesion material, for ensureing effective contact area, adhere to heavier object and provide mechanics and ensure, can prevent the adhesion Array prepared to collapse adhesion phenomenon, be also the imitative gecko of preparation tilts, end expands structure and pole end mushroom adhesion Array conveniently stripped providing safeguard simultaneously.
3. adhesive power test
Adopt the normal direction of dimension sensor system testing adhesion material to adhere to and tangential adhesion, upper sample is that (contact area is 0.5 cm to aluminium block
2), lower sample is adhesion material.As shown in Figure 3, result shows its adhesive power data, preload be between 0 ~ 50 mN in, adhesive power increases with the increase of load, and when 50 ~ 500 mN, load does not have much affect to adhesive power.Illustrate at lower load (50 mN, 0.1 N/ cm
2) when, namely this adhesion material has higher adhesion property, and tangential adhesion reaches 0.72 N/ cm
2, normal direction adheres to and reaches 0.25 N/ cm
2.Be under the condition of 50 mN at preload, the tangential force of adhesion material and normal force change are respectively as shown in Figure 4,5.Done 10 replica tests to this adhesion material on this basis, as shown in Figure 6, test shows that it tangentially adheres to and normal direction adhesion property is stablized, and remains on 0.72,0.25 N/cm substantially respectively
2left and right, has good reusability, can keep its adhesion property in addition after the test of hundreds of times by soap cleaning.The people such as Stanford Univ USA Mark Cutkosky adhere to pole pattern from optimization, have developed the inclination grade array that end is sharp-pointed.Adopt the preparation of micro-mould casting, mould material be urethane (Innovative polymers, IE-20 AH Polyurethane,
e=0.3 MPa), the tangential adhesion strength of the adhesion Array that pouring experiment obtains is about 0.24 N/cm
2(Santos D, Kim S, Spenko M, Parness A, Cutkosky M. Directional adhesive structures for controlled climbing on smooth vertical surfaces. 2007 IEEE International Conference on Robotics and Automation, Roma, Italy, 10-14 April 2007.), under the condition that Young's modulus is more or less the same, namely the tangential adhesion property of the adhesion material in the present invention improves 3 times.This be DOW CORNING 184 owing to present invention employs mixing, DOW CORNING 186 B component as linking agent, because the B component of DOW CORNING 186 has larger relative molecular mass compared with the B component of DOW CORNING 184, molecular chain is longer, hydrogen richness reduces relatively, tensile strength can be improved, improve elongation, simultaneously sterically hindered compared with the Si-H in long-chain Silicon Containing Hydrogen molecular chain relatively little, crosslinking reaction is more complete, but owing to easily tangling with intermolecular long-chain in molecule, excessively crosslinked, cause surface energy to increase, thus improve its adhesion property.According to bibliographical information (the Gorb S of Gorb etc., Varenberg M, Peressadko A, Tuma J. Biomimetic mushroom-shaped fibrillar adhesive microstructure. Journal of the Royal Society Interface, 2007
4, 271-275. Varenberg M, Peressadko A, Gorb S, Arzt E. Effect of real contact geometry on adhesion. Applied Physics Letters, 2006,
89, 1219051-3.), actual contact girth determines adhesion property, so has the adhesion property of the adhesion Array of a fixed structure (as tilted, mushroom) by higher than the adhesion material not having structure.Therefore have the adhesion Array of a fixed structure according to the adhesion material preparation in the present invention, its adhesion property must have larger raising.
4. the adhesive power demonstration of adhesion material
Adsorption test subject material is wrought aluminium ring, and weight is 0.975 Kg, and surface impurity, through phosphoric acid process, need be removed with ethanol in surface, improves the bonding force with polymkeric substance.For testing the maximum adhesion power of adhesion material, adopt 4 standard weightss, weight is 1 Kg, tests the tangential of material and normal adhesion force respectively.In tangential adhesion property test, hand-held adhesion material one end, the other end adheres to wrought aluminium ring surface by adhesion itself performance, and effective contact area of adhesion material is about 12 cm
2(long × wide × high, 5 cm × 1, cm × 3 cm), gain in weight gradually on this basis to 4.975 Kg, adhesion material adsorbs with wrought aluminium annulus all the time, and it adheres to schematic diagram as shown in Fig. 7 (a).
In normal direction adhesion property, it is 4 cm that wrought aluminium annulus has been uniformly distributed four pieces of areas
2(long × wide × high, 2 cm × 0.3, cm × 2 cm) adhesion material, adhesion material adheres between two aluminium rings by adhesion itself performance, aluminium ring above hand-held, add loads to 1.975 Kg, adhesion material adsorbs with wrought aluminium annulus all the time, and it adheres to schematic diagram as shown in Fig. 7 (b).Can find out that the tangential adhesion of material is by 0.72 N/ cm
2be increased to 4 N/ cm
2, normal direction adhere to by 0.25 N/ cm
2be increased to 1 N/ cm
2, illustrate that this adhesion material has better adsorptive power to aluminium after phosphoric acid process.
Embodiment 2.
1. bionical inclination and end expand the preparation of bristle adhesion Array
Step 1. adds the B component of DOW CORNING 184 successively in the component A of DOW CORNING 184, the B component of DOW CORNING 186, and carbon nanotube, stirs, and is evacuated to bubble and eliminates completely;
Step 2. Design and Machining mould comprises sleeve, bed die, middle mould, backform, pour above-mentioned mixed polymer solution into assemble mould, be heating and curing at 70 ~ 100 DEG C 2 h in vacuum oven, take out hot setting rear mold in baking box, be cooled to the room temperature demoulding, because the Young's modulus that adhesion material is higher makes to be convenient in demoulding, can obtain the bionical inclination adhesion Array based on this adhesion material, Fig. 8 is shown in its technical process;
Step 3. selects above-mentioned preparation inclination adhesion Array, cover in one deck embodiment 1 at its pole end and join adhesion material solution, array substrate applies certain load, form one layer of polymeric at pole end and expand thin film layer, be heating and curing 2 h, obtain end after the demoulding and expand structural adhesive array, end expands structure preparation technology and sees Fig. 9.
The imitative gecko inclination adhesion Array that Figure 10 obtains after giving the demoulding and end expand adhesion Array.
2. the preparation of the mushroom adhesion Array of pole end
If report mould (Cheung E in processing document, Sitti M. Adhesion of biologically inspired polymer microfibers on soft surfaces. Langmuir, 2009, 25 (12), 6613-6616. Gorb S, Varenberg M, Peressadko A, Tuma J. Biomimetic mushroom-shaped fibrillar adhesive microstructure. J. R. Soc. Interface, 2007, 4, 271-275.), adopt the adhesion material that in the present invention, imitative gecko adheres to sole can produce the mushroom adhesion Array of pole end.
Claims (4)
1. for an adhesion material for imitative gecko sole adhesion Array, it is characterized in that: by silicone elastomer host component A, crosslinking agent B component, carbon nanotube forms; Wherein component A and B component mass ratio are 10:1 ~ 15:1, and the quality of carbon nanotube accounts for 0.1% ~ 1% of adhesion material total mass, above-mentioned carbon nanotube caliber 8 ~ 20 nm, length 2 ~ 20 μm;
Above-mentioned silicone elastomer host component A is the component A of DOW CORNING 184;
Above-mentioned crosslinking agent B component is mixed by the B component of DOW CORNING 184 and the B component of DOW CORNING 186 and forms, and wherein the B component of DOW CORNING 184 and the B component mass ratio of 186 are 1:9 ~ 5:5.
2. the adhesion material for imitative gecko sole adhesion Array according to claim 1, it is characterized in that: the component A of above-mentioned DOW CORNING 184, the B component of DOW CORNING 184, the B component of DOW CORNING 186, carbon nanotube mass ratio is: 10:0.3:0.7:0.03.
3. the preparation method of the adhesion material for imitative gecko sole adhesion Array according to claim 1, is characterized in that comprising following process:
Step 1. adds the B component of DOW CORNING 184 successively in the component A of DOW CORNING 184, the B component of DOW CORNING 186, and carbon nanotube, stirs;
Step 2. is evacuated to bubble and eliminates completely, and be heating and curing at 70 ~ 100 DEG C 2 ~ 4 h film forming in vacuum oven.
4. utilize the adhesion material for imitative gecko sole adhesion Array described in claim 1 to prepare the method for gecko sole adhesion Array, it is characterized in that comprising following process:
Step 1. adds the B component of DOW CORNING 184 successively in the component A of DOW CORNING 184, the B component of DOW CORNING 186, and carbon nanotube, stirs, and is evacuated to bubble and eliminates completely;
Above-mentioned mixed polymer solution is poured into the mould of designed processing by step 2., and be heating and curing at 70 ~ 100 DEG C 2 ~ 4 h in vacuum oven, obtains the bionical inclination adhesion Array based on this adhesion material after the demoulding;
Step 3. is expanded structure preparation technology by end and is prepared end and expand structural adhesive array.
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| CN107796789B (en) * | 2017-08-29 | 2021-05-07 | 南京航空航天大学 | Preparation method of gecko-like end charged oriented carbon nanotube dry adhesion array |
| CN108192559B (en) * | 2017-11-24 | 2020-01-21 | 南京航空航天大学 | Bionic fiber dry adhesion material used in extreme environment and preparation method and application thereof |
| CN108638403B (en) * | 2018-05-28 | 2020-01-07 | 北京航空航天大学 | Dry adhesion pad based on van der waals force effect and manufacturing method thereof |
| CN111493732A (en) * | 2020-04-26 | 2020-08-07 | 陕西科技大学 | Gecko-like glass wiping robot and glass wiping method |
| CN112919129B (en) * | 2021-01-28 | 2022-06-17 | 南京航空航天大学 | Bionic adhesion and desorption device, bionic dry adhesion material and preparation process |
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