阅读说明：本技术 用于智能操纵液滴的跨物种生物激发原位可逆三重可切换润湿性表面结构及应用 (Cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligently manipulating liquid drops and application ) 是由 宋岳干 李国强 曾春兰 杨益 陈羿宇 于 2021-08-19 设计创作，主要内容包括：本发明公开了一种用于智能操纵液滴的跨物种生物激发原位可逆三重可切换润湿性表面结构,其加工方法为：采用飞秒激光直写技术在聚四氟乙烯上制作微孔阵列作为模板；将双面胶带粘在聚四氟乙烯模板的底部,将聚二甲基硅氧烷、固化剂和羰基铁粉的混合物浇注在聚四氟乙烯模板中,形成微米柱阵列；将硅胶浇铸在聚四氟乙烯模板上,旋涂,固化,将聚四氟乙烯模板剥离,得到超疏水高粘附表面结构；飞秒激光对得到的超疏水高粘附表面结构进行修饰,得到用于智能操纵液滴的跨物种生物激发原位可逆三重可切换润湿性表面结构。该润湿性表面结构具有以原位可逆方式在莲花状效应、稻叶状各向异性和玫瑰花瓣状效应之间切换的优越能力。(The invention discloses a cross-species biological excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops, which comprises the following processing methods: manufacturing a micropore array on polytetrafluoroethylene as a template by adopting a femtosecond laser direct writing technology; adhering a double-sided adhesive tape to the bottom of a polytetrafluoroethylene template, and pouring a mixture of polydimethylsiloxane, a curing agent and carbonyl iron powder into the polytetrafluoroethylene template to form a micron column array; casting silica gel on a polytetrafluoroethylene template, spin-coating, curing, and stripping the polytetrafluoroethylene template to obtain a super-hydrophobic high-adhesion surface structure; modifying the obtained super-hydrophobic high-adhesion surface structure by femtosecond laser to obtain a cross-species biological excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops. The wetting surface structure has superior ability to switch between lotus-like effect, rice leaf-like anisotropy, and rose petal-like effect in an in-situ reversible manner.)

1. A cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets, the method of processing the wetting surface structure comprising the steps of:

step one, manufacturing a micropore array with the diameter of 100-200 mu m on polytetrafluoroethylene as a template by adopting a femtosecond laser direct writing technology;

tightly adhering a double-sided adhesive tape to the bottom of a polytetrafluoroethylene template, pouring a mixture of polydimethylsiloxane, a curing agent and carbonyl iron powder into the polytetrafluoroethylene template, degassing in a vacuum cavity for 8-15 min, and removing excessive mixture by using a knife to form a micron column array;

step three, casting silica gel on a polytetrafluoroethylene template, degassing in a vacuum cavity for 3-8 min, spin-coating a silica gel coating by using a spin coater, then curing in an oven at 120-135 ℃ for 25-45 min to integrate the silica gel and the micron column array, and stripping off the polytetrafluoroethylene template to obtain a super-hydrophobic high-adhesion surface structure;

and step four, modifying the super-hydrophobic high-adhesion surface structure obtained in the step three by femtosecond laser in a cross grid line mode to obtain a cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops.

2. The in-situ reversible triple switchable wetting surface structure for cross-species bio-excitation of smart manipulation droplets according to claim 1, wherein in the first step, the power of the femtosecond laser direct writing technology is 200-400 mW, the scanning speed is 15-25 mm/s, and the scanning times are 350.

3. The cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets of claim 1, wherein the polytetrafluoroethylene has a thickness of 600-1000 μ ι η.

4. The cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligent manipulation of liquid drops according to claim 1, wherein in the second step, the mass ratio of polydimethylsiloxane, the curing agent and the carbonyl iron powder is 10:1: 3-6.

5. The cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligent manipulation of liquid droplets according to claim 1, wherein the carbonyl iron powder has a particle size of 3-5 μm and a purity of 99.9% or more.

6. The cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligent manipulation of liquid droplets according to claim 1, wherein in the third step, a spin coater is used to spin-coat the silica gel coating at a speed of 400-600 r/min; the spin coating time is 45-90 s.

7. The in-situ reversible triple switchable wetting surface structure for cross-species bio-excitation for intelligent manipulation of droplets of claim 1, wherein in the fourth step, the power of the femtosecond laser is 180-250 mW, and the scanning speed is 25-35 mm/s.

8. Use of a cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets according to any of claims 1 to 7, wherein the cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets is stretched to reversibly switch its wetting surface in-situ between lotus-like effect, rice leaf-like anisotropy and rose petal-like effect triple wetting states.

9. Use of a cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets according to any of claims 1 to 7, wherein the cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets is used for capture, vertical transport and release of droplets.

Technical Field

The invention relates to the technical field of wettability surface structures, in particular to a cross-species biological excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops and application thereof.

Background

The prior art realizes specific functions by simulating the surface wettability of specific organisms, and makes great contribution to human life. Such as a single bionic lotus leaf surface self-cleaning function surface, a single rice leaf anisotropic function surface and a single rose petal pinning effect simulated function surface. From the viewpoint of scientific research and practical application, the development of the bionic functional surface is greatly limited by a single structure. Therefore, the research on cross-species biomimetic surfaces with switchable multi-wettability has been the direction of effort of researchers.

It is well known that the wettability of a surface is a result of the synergy of the surface microstructure with its chemical composition. Therefore, in order to obtain functional surfaces with dynamically switchable wettability, some research has been devoted to the modulation of surface chemistry by external stimulation. However, the conditioning process tends to be time consuming, costly, poorly biocompatible, and the like. On the other hand, since Shape Memory Polymers (SMPs) have good shape memory effects, some efforts have been made on Shape Memory Polymers (SMPs) in an attempt to achieve this target dynamic wettability switch. However, almost all previous work has focused on the microstructural changes in shape memory polymers caused by thermal stimuli. Recently, elastic substrates have been widely used to dynamically adjust the surface microstructure through mechanical strain. The prior art reports anisotropic structured surfaces with dual-scale roughness on which droplets roll more easily in a direction parallel to the wrinkles. The surface of the ethylene-vinyl acetate (EVA) film with adjustable adhesion is manufactured by further stretching, and the pick-up and transfer of the liquid drop are shown on the basis of the surface. In addition, the liquid drop picking and placing are realized through mechanical stretching, and a composite surface with switchable wettability and adhesiveness is prepared, wherein the composite surface is in a lotus state or a rose petal state.

As can be seen from the above discussion, while prior art studies have provided successful experience with switchable wetting surfaces, there are still some deficiencies to be improved upon. First, the tunable wettability on superhydrophobic surfaces is always tuned by ex situ means, which greatly limits their application in certain fields, such as intelligent manipulation of droplets. Furthermore, to our knowledge, some tunable wettability surfaces have been demonstrated, but exhibit dual switchable wettability, whether by tuning surface chemistry or microstructure. It is emphasized that none of them can achieve triple dynamic switching. Broadening the multiple wettability of switchable surfaces is of great importance.

The invention herein provides a novel cross-species biomimetic surface that can be reversibly switched in situ between triple wetting states of lotus-like effect, rice leaf-like anisotropy, and rose petal-like effect. The surface consists of a stretchable substrate and an array of micro-columns. With good tensile properties, the surface morphology can be adjusted in a very rapid, reversible manner to achieve different wetting properties. Due to the triple wetting transition on the same surface, it can be used for the application of intelligent in-situ control of droplets, including the capture, vertical transport and release of droplets, and directional transport as droplets. The invention provides a novel method for a functional surface with reversible switchable multiple wettability.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.

To achieve these objects and other advantages in accordance with the purpose of the invention, there is provided a cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of liquid droplets, the processing method of the wetting surface structure comprising the steps of:

step one, manufacturing a micropore array with the diameter of 100-200 mu m on polytetrafluoroethylene as a template by adopting a femtosecond laser direct writing technology;

tightly adhering a double-sided adhesive tape to the bottom of a polytetrafluoroethylene template, pouring a mixture of polydimethylsiloxane, a curing agent and carbonyl iron powder into the polytetrafluoroethylene template, degassing in a vacuum cavity for 8-15 min, and removing excessive mixture by using a knife to form a micron column array;

step three, casting silica gel on a polytetrafluoroethylene template, degassing in a vacuum cavity for 3-8 min, spin-coating a silica gel coating by using a spin coater, then curing in an oven at 120-135 ℃ for 25-45 min to integrate the silica gel and the micron column array, and stripping and taking down the polytetrafluoroethylene template to obtain a super-hydrophobic high-adhesion surface structure;

and step four, modifying the super-hydrophobic high-adhesion surface structure obtained in the step three by femtosecond laser in a cross grid line mode to obtain a cross-species biological excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops.

Preferably, in the first step, the power of the femtosecond laser direct writing technology is 200-400 mW, the scanning speed is 15-25 mm/s, and the scanning times are 350 times.

Preferably, the polytetrafluoroethylene has a thickness of 600 to 1000 μm.

Preferably, in the second step, the mass ratio of the polydimethylsiloxane, the curing agent and the carbonyl iron powder is 10:1: 3-6.

Preferably, the particle size of the carbonyl iron powder is 3-5 μm, and the purity is more than or equal to 99.9%.

Preferably, in the third step, a spin coater is used for spin-coating the silica gel coating at a speed of 400-600 r/min; the spin coating time is 45-90 s.

Preferably, in the fourth step, the power of the femtosecond laser is 180-250 mW, and the scanning speed is 25-35 mm/s.

The invention also provides application of the cross-species biological excitation in-situ reversible triple switchable wettability surface structure for intelligently manipulating the liquid drop, which is characterized in that the cross-species biological excitation in-situ reversible triple switchable wettability surface structure for intelligently manipulating the liquid drop is stretched to enable the wettability surface of the cross-species biological excitation in-situ reversible triple switchable wettability surface structure to be reversibly switched among triple wettability states of lotus-shaped effect, rice leaf-shaped anisotropy and rose petal-shaped effect.

The invention also provides application of the cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligently manipulating liquid droplets, which is characterized in that the cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligently manipulating liquid droplets is used for capturing, vertically conveying and releasing the liquid droplets.

The laser beam of the femtosecond laser of the invention comes from a regenerative amplifier: sapphire femtosecond laser system (Coherent) with repetition frequency of 1kHz, pulse width of 104fs and center wavelength of 800 nm.

The invention at least comprises the following beneficial effects: the invention prepares a cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops, and the wettability surface structure has the excellent capability of switching among lotus-shaped effect, rice leaf-shaped anisotropy and rose petal-shaped effect in an in-situ reversible mode. On this basis, triple controllable wettability is achieved by microstructural changes induced by simple methods of applying or removing tension.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Description of the drawings:

FIG. 1 is a concept and a process for the preparation of a cross-species biomimetic in situ reversible triple-switch wetting surface of the present invention, wherein (a-b) is a concept and schematic diagram inspired by three typical wetting surface prototypes; (c-h) schematic preparation process of in-situ reversible triple switchable wettable surface structure;

FIG. 2 is a micro-morphological and wettability characterization of an in situ reversible triple switchable wettable surface structure of the present invention, wherein (a-f) scanning electron microscope images (SEM) of the structure before and after laser modification; the contact angle and the rolling angle (i) of the silica gel substrate before laser modification (g) and after laser modification (i); contact angles and rolling angles (h) (j) at the tops of the micro-meter columns before and after laser modification; (k) stretching the optical images of the front and rear structures; (l) SEM image of the structure after stretching.

FIG. 3 is an in-situ reversible three switches of the in-situ reversible triple switchable wetting surface structure of the present invention; wherein (a) three-dimensional (3D) models of the structure before and after stretching; (b) tensile and recovery performance testing of the samples under 20 cycles of stretch-relaxation; (c) lambda and p_x、p_yA quantitative relationship between; (d) draw ratios λ and RA_x(e) λ and RA_yA quantitative relationship between; (f-m) an optical image of surface in-situ reversible switches;

FIG. 4 is a schematic representation of an in situ reversible triple switchable wetting surface structure of the present invention for droplet diversification operation, wherein (a) is the surface self-cleaning result; (b) directional transport of 2 μ Ι _ droplets and (c) parallel transport of a plurality of 3 μ Ι _ droplets; (d-e) schematic and optical images of capture, vertical transport and release of 2 μ L droplets.

The specific implementation mode is as follows:

the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description.

It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.

Example 1:

a cross-species bio-excitation in-situ reversible triple switchable wetting surface structure for intelligent manipulation of droplets, the processing method of the wetting surface structure comprising the steps of:

step one, adopting a femtosecond laser direct writing technology (the power is 300mW, the scanning speed is 20mm/s, and the scanning times is 350 times), and manufacturing a micropore array with the diameter of 140 micrometers on polytetrafluoroethylene (the thickness is 800 micrometers) as a template, as shown in FIG. 1 c;

step two, tightly adhering a double-sided adhesive tape to the bottom of a polytetrafluoroethylene template, pouring a mixture of polydimethylsiloxane, a curing agent and carbonyl iron powder (the particle size is 3-5 mu m, the purity is more than or equal to 99.9%) into the polytetrafluoroethylene template, degassing for 10min in a vacuum cavity, and removing excessive mixture by using a knife to form a micron column array (shown in figure 1d and figure 1 e); wherein the polydimethylsiloxane and the curing agent are Dow Corning 184 silicone rubber, and are a kit product consisting of liquid components, and comprise basic components and a curing agent (Sylgard 184, Dow Corning); the mass ratio of the polydimethylsiloxane to the curing agent to the carbonyl iron powder is 10:1: 4;

step three, pouring silica gel (Dragon Skin 10Slow, USA, A: B is 1:1, weight ratio) on a polytetrafluoroethylene template, degassing for 5min in a vacuum cavity, spin-coating the silica gel coating by using a spin coater (the spin-coating speed is 500 r/min; the spin-coating time is 60s), then curing for 30min in an oven at 130 ℃ to integrate the silica gel and the micron column array (as shown in figure 1 f), and peeling off the polytetrafluoroethylene template to obtain a super-hydrophobic high-adhesion surface structure (as shown in figure 1 g);

step four, modifying the super-hydrophobic high-adhesion surface structure obtained in the step three by femtosecond laser (the laser power is 200mW, and the scanning speed is 30mm/s) in a cross grid line mode to obtain a cross-species bio-excitation in-situ reversible triple switchable wettability surface structure (as shown in figure 1 h) for intelligently manipulating the liquid drop; the obtained in-situ reversible triple switchable wettability surface structure can skillfully integrate three typical wetting surface prototypes in nature together to generate an in-situ reversible triple switchable wettability surface (shown in figures 1 a-b);

in order to better understand the prepared in-situ reversible triple switchable wettability surface structure and the change thereof, a scanning electron microscope is adopted to represent and analyze the change of the surface micro-morphology; before the femtosecond laser modification of step four, the top of both the original silica gel substrate and the micropillars were relatively smooth (fig. 2 a-c). The droplets showed a Contact Angle (CA) ≈ 106.4 ° hydrophobicity on the silicone substrate (fig. 2g), while super-hydrophobicity (CA ≈ 152.5 °) was exhibited on the top of the micropillars (fig. 2h), due to the wenzel model formed by the top of the micropillar array. When the sample is rotated by 180 degrees, the liquid drops on the silica gel substrate and the micron column array can not fall off, and high adhesion is shown (fig. 2 g-h).

After the laser modification in step four, it can be found that the silica gel substrate and the top of the micro-pillars are uniformly covered with cauliflower-like micro-nano structured particles (fig. 2d-f), which are generated by deposition during laser ablation and ablation, so the hydrophobicity of the silica gel substrate varies from 106.4 ° to 135.1 ° (fig. 2i), while the CA of the droplets at the top of the micro-pillars (about 153.2 °) hardly varies (fig. 2j), because the CA of the surface of the micro-pillars is mainly determined by the micro-pillar array itself, not the micro-morphology at the top thereof. Furthermore, due to its material properties, the droplets remain firmly fixed on the silica gel substrate after laser modification, as shown in fig. 2 i. In sharp contrast, the Rolling Angle (RA) of the droplets on the microarray was reduced to 5.3 (FIG. 2 j). And the surface of the microcolumn showed ultra-hydrophobic low adhesion to the droplet, but the silica gel substrate showed high adhesion. In addition, after the silicon substrate is gradually applied with tensile force, the micron columns on the silicon substrate are arranged regularly, and uncontrollable deformation and distortion cannot occur (fig. 2 k-l).

The structure can be switched between the lotus-like effect, rice leaf-like anisotropy and rose petal-like effect triple wetting states in an in situ reversible manner by a simple method of gradually applying or removing tension.

For this purpose, the tensile properties of the structure were first tested. As shown in FIG. 3a, the length of the structure (L) when stretched₀) Gradually increases to λ L₀Where λ represents the draw ratio of the structure. p is a radical of_xAnd p_yRespectively, the pitch (p) of the micron columns along the x and y axes. The structure can be stretched to λ ═ 3 and recover its original shape after 20 cycles without any breakage or observable deformation (fig. 3b), indicating that it has excellent tensile properties. Meanwhile, it can be found that when p is 400, 500 and 600 μm, p_xIncreasing with increasing λ. However, p is_yDecrease (fig. 3 c). Switchable due to the dynamics of the surfaceWettability, stretch ratio (λ) and drop length x (RA)_x) And y-axis (RA)_y) The roll angle of (a) is shown in fig. 3 d-e. RA_xAnd RA_yAre gradually increased with the stretch ratio (λ). It is particularly noted that when p is 400 μm, RA is_xAnd RA_yIncreases with increasing lambda, but the roll angle is small in both directions, resulting in no rose petal effect. When p is 500 μm and λ ≧ 2.5, the droplet will be immobilized on the surface. By comparison, the rosette pinning phenomenon has occurred when p is 600 μm and λ is 2. The results of the above analysis confirm the experimental intermediate distance selection of p 500 μm, which contributes to the feasibility of a triple wetting surface design, including lotus-like isotropy with λ 1, rice-like anisotropy with 1 < λ < 2.5, and rose petal-like effects with λ ≧ 2.5.

In the original state without external force, the silicone substrate can be seen to be covered by equally spaced micro-pillars along the x and y axes (fig. 3 f). Notably, the structured surface exhibited a pronounced scalloped surface effect. By way of verification, the droplets were clearly seen to be spherical by placing the droplets (droplet diameter d greater than the micron-column pitch p) on the surface of the micron-column with a syringe. At the same time, RA in both directions is almost the same, since the energy barriers along the x and y axes are the same (fig. 3 f).

With good tensile properties, not only does the draw ratio (λ) increase with increasing external tensile force, but also the anisotropic character of the surface tends to be apparent after application of external tensile force. It is emphasized that the RA of the drop in the x-direction is always larger than its RA in the y-direction, resulting in easier movement of the drop in the y-direction (fig. 3 g). According to the above results, the microstructure was adjusted by the stretching action to give anisotropy similar to rice leaf.

The spacing of the micron columns along the x-axis increases with increasing tension. When the diameter of the droplet is less than the micron post spacing (p) along the x-axis_x) At this time, as shown in fig. 3h, the droplet rolls into the groove between the micropillars and comes into full contact with the silica gel substrate, where it is firmly held. Even if the sample was rotated 90 °, the droplets did not roll off, indicating that the structure had successfully switched to the rosette state (fig. 3 i).

As described above, under the action of tensile force, the surface can be changed from lotus leaf-shaped effect to rice leaf-shaped anisotropy and then to rose petal-shaped effect in situ. It was subsequently found that after a slow reduction of the pulling force, the wetting state was exactly reversed. As shown in FIG. 3j, the pitch (p) of the micron columns along the x-axis_x) Decreases with increasing tension. When p is_x<d, the droplet is squeezed out of the groove back to the top of the micron column (fig. 3 k). The structure switches back to the anisotropic mode (fig. 3 l). Further reduction in tension until complete release, it was found that the droplets immediately drop off the surface when tilted under the influence of gravity, confirming the in situ change of wetting mode to a scalloped surface (fig. 3 m).

In order to verify the self-cleaning effect of the cross-species bio-excitation in-situ reversible triple switchable wettability surface structure for intelligently operating liquid drops, a contrast experiment is designed and the antifouling performance of the surfaces of the micro-pillars before and after femtosecond laser modification is tested. Two samples before and after femtosecond laser modification were completely immersed in rhodamine solution for 5 minutes. As shown in fig. 4a, it can be seen that, contrary to the surface before the femtosecond laser modification, no rhodamine residue is found on the modified surface, and excellent antifouling and self-cleaning performances are shown in the original lotus leaf effect state.

To further evaluate the anisotropic wetting effect under stretch control, the sample was first stretched to λ ═ 1.5, and then droplets were added. Due to the presence of carbonyl iron powder within the micron column, it can be seen that the droplets are transported by orientation (fig. 4 b). After further stretching to λ 2.0, parallel transport of multiple droplets is achieved, as shown in fig. 4 c. As mentioned above, the application of the rice leaf-shaped anisotropic surface with dynamic control in the directional transmission of liquid drops opens up a new way for the control of microfluid.

On this basis, cross-species bio-excitation in-situ reversible triple switchable wetting surface structures for intelligent manipulation of droplets are used for droplet capture, vertical transport and release, resembling a freely retractable "robot" (fig. 4 d-e). The wetting surface structure was inverted and two droplets were placed on the underlying PDMS superhydrophobic film. When the further stretching is carried out to a lambda of 2.5, it is noted that d is now present<p_xThe device is moved downwards until a position is reached where the droplets can contact the silicon substrate with high adhesion. The capture of the droplets is achieved in turn. The wetting surface structure is then moved up to the target predetermined position, completing the vertical transport of the droplet. Finally, as the tension is reduced, the droplet is squeezed out to complete the droplet release. From the above, based on the wettability surface structure, diverse manipulation of the liquid droplet can be achieved by the triple wettability switch of its in-situ reversible mode, including but not limited to surface self-cleaning, directional transport of the liquid droplet, capture of the liquid droplet, vertical transport and release.

While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor with which the invention may be practiced, and further modifications may readily be effected therein by those skilled in the art, without departing from the general concept as defined by the claims and their equivalents, which are not limited to the details given herein and the examples shown and described herein.