CN115245796A - Method for preparing micro-nano scale full liquid phase fluid channel - Google Patents
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Abstract
The invention relates to a method for preparing a micro-nano-scale all-liquid-phase fluid channel by inhibiting Plateau-Rayleigh instability, belonging to the technical field of structured liquid. The preparation method comprises the following steps: (1) Dissolving the end-group polymer surfactant in an oil phase, and dispersing the nano particles in a water phase; (2) Fixing the water phase between the substrate and the needle head to form a liquid bridge; (3) Adding the oil phase immersion liquid bridge, wherein the nano particles and the end-group polymer surfactant can generate electrostatic interaction at an oil-water interface, so that a nano particle-polymer interface assembly network is formed on a liquid bridge interface; (4) And stretching the liquid bridge in a quasi-static manner to obtain the micro-nano full-liquid-phase fluid channel. The invention breaks through the size limit of the traditional structured liquid full-liquid-phase fluid channel and breaks through the strict limit of the application scene of the traditional full-liquid-phase fluid channel. Has important application prospect in the field of all-liquid-phase fluid mass transfer.
Description
Technical Field
The invention belongs to the field of structured liquid, and particularly relates to a method for preparing a micro-nano-scale all-liquid-phase fluid channel by inhibiting Plateau-Rayleigh instability.
Background
From rivers to capillaries, from nature to industry, the fluid channels ensure normal ecological circulation and life operation through the directional transfer of energy and the orderly transport of substances. The stability of fluid structures is often dependent on solid phase confinement environments such as riverbeds and pipelines. However, more specific environments, such as in an all liquid phase system, i.e., a fluid channel structure with one fluid in another immiscible phase, are modeled. Due to its specificity of not allowing the participation of the solid phase, the spatial order of the flow channels of the whole liquid phase is broken by the instability of Plateau-Rayleigh after leaving the solid phase-constrained environment. Also, due to the influence of the Laplace pressure difference, the smaller the time scale for the full liquid phase fluid channel with the smaller size, the smaller the time scale for the Plateau-Rayleigh unstable fluid rupture to occur, i.e., the
Wherein tau is the time scale of fluid fracture, alpha (P) is the pressure coefficient, r is the radius of the fluid column, eta e Is the viscosity of the external phase, gamma OW The interfacial tension between oil and water. The fluid structure is difficult to be accurately regulated and controlled due to the influence of factors such as loose arrangement of liquid molecules, surface tension and the like. The size of the all-liquid phase fluid channel constructed at present is still on a macroscopic scale, which limits the application potential in the fields of energy transfer and mass transfer.
Here, the nanoparticle-polymer interface assembly system provides a concept for solving this problem. The nano particles and the polymer ligand are cooperatively assembled at a liquid/liquid interface through electrostatic interaction, so that the interfacial tension between two phases can be effectively reduced, and the nano particles provide excellent mechanical properties for the liquid phase interface. The increase of the interfacial shear modulus is enough to resist the interfacial retraction caused by surface tension, and the instability of Plateau-Rayleigh is inhibited. The process is here quantified by the interfacial shear modulus, i.e.
Wherein
In order to be the interfacial shear modulus,
is the bulk density of the interface particle surface,
the critical interface particle surface packing density for fluid column collapse, beta is the correction term.
Here, the time scale of particle packing is given, i.e.
τ α ＝(k a C 0 η) -1
Wherein, tau α Is the time scale of particle migration, k a For a constant rate of ripening, C 0 η is the concentration of bulk particles and is the correction term.
Surface packing density of particles at interface before fracture of fluid structure
Greater than the critical interface particle surface bulk density
When the entire fluid structure is to be stabilized, i.e.
τ＞τ α
Shi et al, by combining a jet model with a nanoparticle-polymer interface assembly system, constructed a full liquid phase flow channel (Angew. Chem. Int. Ed.2017,56,12594) in a low viscosity toluene phase, and a nanoparticle surfactant formed based on a rod-like cellulose nanocrystal, could be rapidly assembled at a liquid/liquid interface. When interface blocking phase change occurs, the nanoparticle surfactant assembly network brings excellent mechanical properties to the interface, the aqueous solution containing the cellulose nanocrystals freely falls and is jetted into the amino-functionalized polystyrene toluene solution, and the Plateau-Rayleigh instability is completely inhibited. Forming a stable all-liquid phase fluid channel structure. However, because the viscosity of the external toluene phase is low, the time scale tau of fluid fracture is small, and the size of the fluid can only be increased by delaying the fracture of the fluid before the assembly of the nanoparticle interface is completed, the size of the all-liquid-phase fluid channel formed by the method is generally in the millimeter level or hundreds of micrometers, and the all-liquid-phase fluid channel with smaller size cannot be prepared.
Xie and the like prepare a stable three-dimensional water/water structure (Chem 2019,5,5688) by combining a 3D printing technology and an elastic polyanion-polycation coacervation membrane, and realize the wide application of an all-liquid-phase fluid channel by regulating and controlling the mechanical property and functionality of the coacervation membrane. Which utilizes polyanion-polycation electrostatic interaction to replace the electrostatic interaction of the nano particles and the polymer ligand to ensure that the interface assembly rate tau α The significance is improved, but the viscosity of the external phase environment is low, the fluid fracture speed is high, and the size of the formed all-liquid-phase fluid channel is generally in the size range of 100 mu m.
Forth et al, by using 3D printing technology in combination with a nanoparticle-polymer interface assembly system, constructed full liquid phase flow channels (adv. Mater.2018,30, e 1707608) of various diameters (10-1000 μm) in high viscosity silicone oil, with channel lengths of several meters. High viscosity silicone oils are a substantial extension of the time scale of fluid breakup, τ. However, the all-liquid-phase fluid channel constructed by the method depends heavily on the external environment with high viscosity, and the size limit of the constructed all-liquid-phase fluid channel only reaches 10 μm.
In summary, the current research on the all-liquid-phase fluid channel is still in the initial stage, the construction mode generally combines the jet model with the nanoparticle-polymer assembly system, the constructed all-liquid-phase fluid channel has a large size, needs to meet complex and harsh dynamic conditions, is limited by the construction method in applicable environment, generally needs complex instruments and equipment (3D printing facilities), and is complex in experimental operation. Therefore, the research on the full liquid phase fluid channel with loose kinetic conditions, simple operation, stable structure and controllable size has important practical significance.
Disclosure of Invention
The invention breaks through the size limit of the existing constructed full-liquid-phase fluid channel, avoids the complex fluid dynamics and chemical interface assembly dynamics regulation and control in the construction process, and realizes the construction of the structurally stable micro-nano-scale full-liquid-phase fluid in a more universal application scene (no matter high-viscosity external phase or low-viscosity external phase) by a simple technical means. The invention aims to provide a simple and effective micro-nano scale all-liquid-phase fluid channel which is stable in structure and controllable in size and is prepared by inhibiting Plateau-Rayleigh from being unstable.
According to a first aspect of the present invention, there is provided a method for preparing a micro-nano scale all-liquid phase fluid channel by suppressing Plateau-Rayleigh instability, comprising the steps of:
(1) Dissolving the end-group polymer surfactant in an oil phase, and dispersing the nano particles in a water phase;
(2) Dripping the water phase dispersed with the nano particles obtained in the step (1) on a hydrophilic substrate, and contacting the water phase droplets dispersed with the nano particles and suspended from the needle head with the droplets on the hydrophilic substrate to ensure that the two droplets are connected to form a liquid bridge;
(3) Adding the oil phase dissolved with the end-group polymer surfactant obtained in the step (1) into a hydrophilic substrate to immerse a liquid bridge, wherein the nano particles and the end-group polymer surfactant can generate electrostatic interaction at an oil-water interface, so that a nano particle-polymer interface assembly network is formed on the liquid bridge interface;
(4) And (3) performing quasi-static stretching on the liquid bridge, and obtaining the micro-nano scale full liquid phase fluid channel when the diameter of the thin neck of the liquid bridge reaches the micro-nano level.
Preferably, in the stretching process of the quasi-static stretching in the step (4), the liquid bridge interface state is always in the blocking phase transition state, and the liquid bridge is in the metastable state.
Preferably, the dimension of the micro-nano full-liquid-phase fluid channel in step (4) is obtained from the resistance of the liquid bridge system, and the relational expression between the resistance of the liquid bridge system and the dimension of the liquid bridge is as follows: lg R = klg R + b, wherein R is the resistance of the liquid bridge system in Ω, R is the radius of the liquid bridge thin neck in μm, k is the slope, and b is the resistance of the liquid bridge system when the radius of the liquid bridge thin neck is 1 μm.
Preferably, the endcapped polymeric surfactant is an aminated polymer or a polyvinylpyridine-based polymer.
Preferably, the aminated polymer is at least one of monoamino polydimethylsiloxane, bisamino polydimethylsiloxane and penta-amino polydimethylsiloxane; the polyvinyl pyridine polymer is polystyrene-poly (2-vinyl pyridine).
Preferably, the nanoparticles are at least one of polyoxometallate nanoparticles, carboxylated silica nanoparticles and sulfonated cellulose nanocrystals.
Preferably, the oil phase is toluene, chloroform or dichloromethane.
Preferably, the hydrophilic substrate is a glass cuvette, a quartz cuvette, or a metal electrode.
Preferably, the concentration of the end-functionalized polymer surfactant in the oil phase is 0.1mg/mL-0.5mg/mL, and the concentration of the nanoparticles in the aqueous phase is 0.1mg/mL-0.5mg/mL.
According to another aspect of the invention, the micro-nano full-liquid-phase fluid channel prepared by any one of the methods is provided.
Generally, compared with the prior art, the technical scheme conceived by the invention mainly has the following technical advantages:
(1) The invention utilizes a liquid bridge quasi-static stretching model to replace the traditional jet model to be combined with a nanoparticle-polymer interface assembly system, nanoparticles and polymer ligands are cooperatively assembled at an oil-water interface through electrostatic interaction, the formed nanoparticle-polymer interface assembly network endows the interface with enough mechanical properties to inhibit Plateau-Rayleigh instability, the quasi-static stretching process does not need to strictly regulate and control the balance between the hydrodynamic speed and the chemical interface assembly rate, the quasi-static stretching process ensures that the interface state of a liquid bridge is always in a metastable state in the construction process, the time scale of fluid fracture approaches infinity, and the time scale of particle interface assembly is far smaller than that of fluid fracture. The method is free from the constraint of dynamic conditions. Therefore, the size limit (D =10 μm) of the existing method for constructing the all-liquid-phase fluid channel is broken through, and a brand-new all-liquid-phase fluid channel (D =800 nm) with a micro-nano scale is constructed.
(2) The invention is more applicable to more common application scenes, ensures the stability of the whole fluid structure in the quasi-static stretching process, does not need the auxiliary support of the high-viscosity external phase environment, and can also realize the construction of the micro-nano scale full-liquid-phase fluid channel in the low-viscosity toluene phase. Meanwhile, compared with the traditional 3D printing jet model for constructing a full-liquid-phase fluid channel, the method does not need complex 3D printing equipment.
(3) The invention determines the size of the full liquid phase fluid channel by measuring the resistance change of the system, under the micro-nano scale, the size is close to the diffraction limit of an optical microscope, the imaging is fuzzy, for the full liquid phase system, the in-situ size characterization of the full liquid phase fluid channel by a scanning electron microscope is difficult to carry out, the invention determines that the good log linear relation exists between the resistance of the system and the size of the fluid channel, and gives the relation of the two, namely: lg R = klg R + b, wherein R is the resistance of the liquid bridge system in Ω, R is the radius of the liquid bridge thin neck in μm, k is the slope, and b is the resistance of the liquid bridge system when the radius of the liquid bridge thin neck is 1 μm. The size of the all-liquid-phase fluid channel can be accurately calculated by measuring the system resistance.
Drawings
FIG. 1 shows { Mo 72 V 30 }(0.1mg mL -1 ) Immersing in a solution containing PDMS-NH 2 (0.01mg mL -1 ) Dynamic interfacial tension profile of aqueous dispersed phase droplets in toluene solution.
Fig. 2 is a graph showing the self-wrinkling behavior observed when a nanoparticle-polymer interfacial assembly system is formed by assembly at an interface.
FIG. 3 is a cross-sectional view of the symmetrical fracture dynamics of an all-liquid phase flow channel when a nanoparticle-polymer interface assembly system is present in the system.
FIG. 4 is a graph of system resistance versus channel size for an all-liquid phase fluid.
Fig. 5 is a graph showing the results when the system is free of a nanoparticle-polymer interface assembly system (water: { Mo 72 V 30 }(0.1mg mL -1 ) Oil: pure toluene) full liquid phase flow channel symmetric fracture kinetics cross-sectional view.
FIG. 6 is a cross-sectional view of the dynamic of a symmetric fracture of an all-liquid phase flow channel when the system is without a nanoparticle-polymer interface assembly system (water: pure water/oil: pure toluene).
FIG. 7 shows the case where the system is free of the nanoparticle-polymer interface assembly system (water: pure water/oil: PDMS-NH) 2 (0.1mg mL -1 ) Toluene solution) full liquid phase flow channel symmetric fracture dynamics cross-sectional view.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The quasi-static stretching of the liquid bridge is combined with the assembly of the nano particle-polymer interface, and the nano particle aqueous solution is fixed between the substrate and the needle head to form the liquid bridge; and then adding an oil phase in which the end group functionalized polymer ligand is dissolved, immersing the water phase, rapidly assembling the nano particles and the end group functionalized polymer ligand at an oil-water interface due to electrostatic interaction, stretching a liquid bridge, and completely depending on the retraction of a needle in the drainage process of the liquid bridge. The substrate and needle are hydrophilic to ensure that the three-phase contact line is fixed to the interface during needle retraction, interfacial forces effectively limit the stability of the liquid bridge structure before Plateau-Rayleigh instability occurs, stretching is halted when the Plateau-Rayleigh instability limit is reached, and sufficient time is allowed for the nanoparticle-polymer interface assembly network to assemble at the interface until maximum surface packing density is reached
The blocking phase change of the interface causes the shear modulus of the interface
Sufficient to inhibit Plateau-Rayleigh instability. Then the needle is retracted for a distance dL, the center of the liquid bridge can leak a new oil-water interface to cause the bulk density of the particle surface to be reduced, and the retraction distance is only required to be controlled to ensure that
Leaving the system in a metastable state. Then waiting for the nano particle-polymer interface assembly network to be completely assembled on the new interface, and the surface packing density of the particles
To maximum surface bulk density
The needle can be retracted again. And (4) circularly reciprocating to obtain the nano-scale all-liquid-phase fluid channel.
According to the purpose of the invention, the method for preparing the micro-nano full-liquid-phase fluid channel with stable structure and controllable size by inhibiting Plateau-Rayleigh instability comprises the following steps:
(1) Dissolving an end-functionalized polymer surfactant in an oil phase, and dispersing nanoparticles with complementary functional groups in an aqueous phase, wherein the nanoparticles with complementary functional groups and the end-functionalized polymer surfactant can perform electrostatic interaction at an oil-water interface;
(2) Fixing the water phase between the substrate and the needle head to form a liquid bridge;
(3) Adding the oil phase immersion liquid bridge, and forming a nano particle-polymer interface assembly network on a liquid bridge interface;
(4) And stretching the liquid bridge in a quasi-static manner to obtain the micro-nano full-liquid-phase fluid channel.
In some embodiments, the end-group functionalized polymer surfactant dissolution in step (1) is achieved using a vortex mixer, and the nanoparticle dissolution with complementary functional groups in step (1) is achieved using a vortex mixer.
In some embodiments, the micro-nano scale all-liquid-phase fluid channel in step (4) realizes controllable size of the fluid channel by regulating the concentration of the polymeric surfactant and the nano particles and the topology of the polymeric surfactant.
Preferably, the end-functionalized polymer surfactant is an aminated polymer or a polyvinylpyridine-based polymer, and preferably, the end-functionalized polymer surfactant is monoaminopolydimethylsiloxane (PDMS-NH) 2 ) Bis-amino polydimethylsiloxane (PDMS-2 NH) 2 ) Pentamidopolydimethylsiloxane (PDMS-5 NH) 2 ) And polystyrene-poly (2-vinylpyridine) (PS-b-PVP).
Preferably, the nanoparticles with complementary functional groups are polyoxometallates { Mo 72 V 30 }, carboxylated Silica (SiO) 2 -COOH), sulfonated cellulose nanocrystals (CNC-OHSO) 3 ) Any one of them.
Preferably, the oil phase is any one of organic solvents immiscible with water, and preferably, the organic solvent is any one of toluene, chloroform and dichloromethane.
Preferably, the selected substrate is any one of a glass cuvette, a quartz cuvette, and a metal electrode.
Preferably, the dissolution of the end-group functionalized polymeric surfactant in step (1) is achieved using a vortex mixer.
Preferably, the nanoparticle having complementary functional groups in step (1) is dissolved by using a vortex mixer.
Preferably, the micro-nano scale full-liquid-phase fluid channel in the step (4) realizes controllable size of the fluid channel by regulating the concentrations of the polymer surfactant and the nano particles and the topological structure of the polymer surfactant.
Preferably, the quasi-static stretching of the liquid bridge in the step (4) ensures that the interface state of the liquid bridge is always in the stretching process,
namely blocking phase transition occurs, the liquid bridge is in a metastable state, wherein Ca is the capillary number eta e Is the viscosity of the oil phase in cSt, v e Is the tensile shear rate in mm s -1 ，ν 0w Is the interfacial tension between oil and water in mN m -1 And tau is the time scale of the liquid bridge breakage and is expressed by s.
Preferably, the size characterization of the micro-nano-scale all-liquid-phase fluid channel in step (4) is obtained by the resistance of a system, and the relational expression between the resistance of the system and the size of the liquid bridge is as follows:
lg R＝k lg r+b，k＝f(α，σ，...)
wherein R is the resistance of the liquid bridge system, the unit is omega, R is the radius of the liquid bridge thin neck, the unit is mu m, k is the slope, b is the resistance value of the liquid bridge system when the radius of the liquid bridge thin neck is 1 mu m, alpha is a morphological factor, and sigma is the conductivity of the water phase. Wherein the morphology alpha of the slope k and the liquid bridge is related to the conductivity alpha of the aqueous phase.
Monoaminopolydimethylsiloxane (PDMS-NH) of the invention 2 ) Bis-amino polydimethylsiloxane (PDMS-2 NH) 2 ) Pentamidopolydimethylsiloxane (PDMS-5 NH) 2 ) Polystyrene-poly (2-vinylpyridine) (PS-b-P2 VP), carboxylated Silica (SiO) 2 -COOH), sulfonated cellulose nanocrystals (CNC-OHSO) 3 ) And rubidium chloride (Rbcl) are purchased from the market. Polyoxometallate { Mo 72 V 30 Prepared experimentally by reacting 35mL of VOSO 4 ·5H 2 O(2.53g,10mmol，H 2 O) aqueous solution to 8mL Na 2 MoO 4 ·2H 2 O(2.42g,10mmol，0.5M H 2 SO 4 ) In an erlenmeyer flask of sulfuric acid solution, the solution was stirred and the resulting dark purple mixture was stirred at room temperature for 30 minutes (the flask was sealed with a rubber stopper) before addition of Kcl (0.65g, 8.72mmol). After stirring for 30 minutes, the solution was stored in a flask closed with a rubber stopper. Standing for 5 days, filtering to collect purple black rhombohedral crystals, washing with cold water, and air drying to obtain polyoxometallate { Mo 72 V 30 }. Wherein the vanadyl sulfate (VOSO) 4 ·5H 2 O), sodium molybdate (Na) 2 MoO 4 ·2H 2 O) and potassium chloride (Kcl) are all purchased from the market.
Example 1
(1) Weighing 2mg of polymetalOxidate { Mo 72 V 30 Stirring and mixing the mixture for 5 minutes in a reagent bottle filled with 20mL of deionized water by using a vortex mixer at the rotating speed of 800 rpm to obtain 0.1mg/mL of { Mo } solution 72 V 30 And (4) water dispersion.
(2) 2mg of monoamino polydimethylsiloxane (PDMS-NH) were weighed out 2 ) Stirring and mixing the mixture in a reagent bottle filled with 20mL of toluene for 5 minutes by using a vortex mixer at the rotating speed of 800 rpm to obtain a solution of 0.1mg/mL of PDMS-NH 2 Toluene solution.
(3) Deionized water is placed in a pure toluene phase, and an interfacial viscoelastic measuring instrument is utilized to test interfacial tension between two phases.
(4) And (2) placing the aqueous phase solution prepared in the step (1) into a pure toluene phase, and testing the interfacial tension between the two phases by using an interfacial viscoelasticity measuring instrument.
(5) Putting deionized water into the PDMS-NH prepared in the step (2) 2 In a toluene solution, an interfacial viscoelastic measuring instrument is used for testing the interfacial tension between two phases.
(6) Placing the aqueous phase solution prepared in the step (1) in the PDMS-NH prepared in the step (2) 2 In a toluene solution, an interfacial viscoelastic measuring instrument is used for testing the interfacial tension between two phases.
Interfacial tension as shown in FIG. 1, { Mo-in contrast to pure water/pure toluene System 72 V 30 Has no interfacial activity, where { Mo } 72 V 30 }(0.1mg mL -1 ) The interfacial tension of the aqueous solution in toluene is the same as that of pure water in toluene, and gamma =34mN m -1 。PDMS-NH 2 In toluene (0.01 mg mL) -1 ) Medium soluble, (. Gamma. =28mN m) -1 Which acts as a surfactant at the toluene/water interface. { Mo 72 V 30 } aqueous solution (0.1 mg ml) -1 ) In PDMS-NH 2 (0.01mg mL -1 ) With gamma =18mN m-1, the interfacial energy rapidly and significantly decreased, indicating the formation and assembly of a nanoparticle-polymer interfacial assembly network at the interface.
Example 2
(1) 0.0386g rubidium chloride (Rbcl) was weighed into a reagent bottle containing 20mL deionized water, and stirred and mixed for 5 minutes by a vortex mixer at 800 rpm to obtain a solution of 1.93mg/mL Rbcl aqueous dispersion.
(2) Taking 0.2mg/mL { Mo in example 1 72 V 30 10mL of the aqueous dispersion was mixed with 10mL of the aqueous dispersion of Rbcl obtained in step (1) of this example in a reagent bottle, and the mixture was stirred and mixed for 5 minutes by means of a vortex mixer at 800 rpm to give a solution of 0.1mg/mL { Mo } 72 V 30 Aqueous dispersion (containing 0.97mg/mL Rbcl).
(3) Taking the { Mo ] prepared in the step (2) 72 V 30 0.1mg/mL PDMS-NH as suspended in example 1 2 And in the toluene solution, observing the appearance of the droplet interface.
As shown in fig. 2, the pendant drop interface formed a self-wrinkled film within 10 seconds, which illustrates the rapid assembly of the nanoparticle-polymer interface assembly network at the liquid-liquid interface under this system. The formation of a self-wrinkled film indicates that the areal packing density of the particles at the interface has approached the maximum areal packing density and a blocking phase transition has occurred.
Example 3
(1) 0.1mg/mL { Mo ] prepared in example 2 was used 72 V 30 Aqueous dispersion (containing 0.97mg/mL Rbcl) was placed in a 100. Mu.L syringe.
(2) 0.1mg/mL { Mo/Mo { prepared in example 2 was added in 1.5. Mu.L of a droplet 72 V 30 And (4) dispersing the water solution in the substrate of a glass cuvette, wherein the size of the covering surface of a liquid drop of the water solution is consistent with that of a needle of a syringe.
(3) Overhang 3.5 μ L { Mo 72 V 30 And (3) contacting the aqueous phase droplets with the droplets on the cuvette substrate in the step (2), connecting the two aqueous phase droplets into a section of liquid bridge, and adjusting the height of the syringe needle to keep the liquid bridge uniform up and down.
(4) To the cuvette in step (2) was added 2mL of PDMS-NH, 0.1mg/mL as prepared in example 1 2 Toluene solution, oil phase completely submerged water phase.
(5) Standing for 20 seconds, and slowly moving the needle up dL when the liquid bridge interface nanoparticle-polymer interface assembly network is completely assembled and the particle surface bulk density reaches the maximum value, wherein the upward movement ensures that the liquid bridge only has a ductility effect and does not have a capillary effect.
(6) Standing for 10 seconds, when the liquid bridge interface nanoparticle-polymer interface assembly network is completely reassembled, the particle surface bulk density reaches the maximum value again, slowly moving the needle head dL upwards, and moving upwards to ensure that the liquid bridge only has a ductility effect and does not have a capillary effect.
(7) And (5) repeating the step (6) until the target size (less than 1 μm) is reached. The diameter of the liquid bridge thin neck is less than 1 μm.
As shown in FIG. 3, in the process of quasi-static stretching of the liquid bridge, the development of the Plateau-Rayleigh instability process is completely inhibited due to the formation of the nanoparticle-polymer interface assembly network, and the stretching process of the whole liquid bridge only has a ductility effect and does not have the influence of a capillary effect. The size of the liquid bridge central thin neck, namely the full liquid phase fluid channel can reach the nanometer scale, and the structure is stable.
Example 4
(1) 0.1mg/mL { Mo ] prepared in example 2 was used 72 V 30 Aqueous dispersion (containing 0.97mg/mL Rbcl) was placed in a 100. Mu.L syringe.
(2) 0.1mg/mL { Mo/Mo { prepared in example 2 was added in 1.5. Mu.L of a droplet 72 V 30 And (4) dispersing the aqueous dispersion on the substrate of the metal electrode, wherein the size of the covering surface of the liquid drop of the aqueous dispersion is consistent with that of the needle of the syringe.
(3) Overhang 3.5 μ L { Mo 72 V 30 And (3) contacting the aqueous phase droplets with the droplets on the cuvette substrate in the step (2), connecting the two aqueous phase droplets to form a section of liquid bridge, and adjusting the height of the needle of the syringe to keep the liquid bridge uniform up and down.
(4) To the cuvette in step (2) was added 2mL of PDMS-NH of 0.1mg/mL as prepared in example 1 2 Toluene solution, oil phase completely submerged water phase.
(5) And (3) connecting the syringe needle with the electrode in the step (2) by using an electrochemical workstation to form a closed path.
(6) The construction method of the nanoscale all-liquid-phase fluid channel in the embodiment 3 is repeated, and the system resistance is detected in situ.
As shown in FIG. 4, there is a significant log-linear relationship between the system resistance and the size of the all-liquid phase fluid channel, which can be expressed by fitting, i.e., the relationship
lg R＝k lg r+b，k＝f(α，σ，...)
Wherein R is the resistance of the liquid bridge system with the unit of omega, R is the radius of the liquid bridge thin neck with the unit of mu m, k is the slope, and b is the resistance of the liquid bridge system when the radius of the liquid bridge thin neck is 1 mu m. The final system resistance was measured to be 11.27 M.OMEGA.and the relationship was substituted to obtain a full liquid phase flow channel with a radius of 400nm.
Comparative example 1
(1) 0.1mg/mL { Mo ] prepared in example 2 was used 72 V 30 Aqueous dispersion (containing 0.97mg/mL Rbcl) was placed in a 100. Mu.L syringe.
(2) 0.1mg/mL { Mo/Mo { prepared in example 2 was added in 1.5. Mu.L of a droplet 72 V 30 And (4) dispersing the water solution in the substrate of a glass cuvette, wherein the size of the covering surface of a liquid drop of the water solution is consistent with that of a needle of a syringe.
(3) Overhang 3.5 μ L { Mo 72 V 30 And (3) contacting the aqueous phase droplets with the droplets on the cuvette substrate in the step (2), connecting the two aqueous phase droplets into a section of liquid bridge, and adjusting the height of the syringe needle so that the liquid bridge keeps uniform up and down.
(4) And (3) adding a pure toluene solution into the cuvette in the step (2), and completely immersing the oil phase into the water phase.
(5) And (3) quasi-statically stretching the liquid bridge, and recording the radius of the broken central thin-neck fluid channel of the liquid bridge.
As shown in fig. 5, when the liquid phase interface cannot form the nanoparticle-polymer interface assembly system, the system cannot inhibit the development of Plateau-Rayleigh instability process, and the liquid bridge is broken under the combined action of ductility effect and capillary effect, the breaking radius is 0.375mm, which is more than 1000 times of that of the nanoparticle-polymer interface assembly system.
Comparative example 2
(1) Ultrapure water was taken in a 100. Mu.L syringe.
(2) 1.5 mu L of ultrapure water is dripped on the substrate of the glass cuvette, and the size of the covering surface of the liquid drop is consistent with that of the needle of the syringe.
(3) And (3.5 mu L of ultra-pure water drops are suspended and contacted with the drops on the substrate of the cuvette in the step (2), the two aqueous phase drops are connected into a section of liquid bridge, and the height of the needle head of the syringe is adjusted to ensure that the liquid bridge keeps uniform up and down.
(4) And (3) adding a pure toluene solution into the cuvette in the step (2), and completely immersing the oil phase into the water phase.
(5) And (3) quasi-statically stretching the liquid bridge, and recording the radius of the broken central thin-neck fluid channel of the liquid bridge.
As shown in fig. 6, when the liquid phase interface cannot form a nanoparticle-polymer interface assembly system, the system cannot inhibit the development of Plateau-Rayleigh instability process, and the liquid bridge is broken under the combined action of ductility effect and capillary effect.
Comparative example 3
(1) Ultrapure water was taken in a 100. Mu.L syringe.
(2) 1.5 microliter of ultrapure water is dripped on the substrate of the glass cuvette, and the size of the droplet coverage surface is consistent with that of the syringe needle.
(3) And (3.5 mu L of ultra-pure water drops are suspended and contacted with the drops on the substrate of the cuvette in the step (2), the two aqueous phase drops are connected into a section of liquid bridge, and the height of the needle head of the syringe is adjusted to ensure that the liquid bridge keeps uniform up and down.
(4) Adding 0.1mg/mL PDMS-NH of example 1 to the cuvette in step (2) 2 Toluene solution, oil phase completely submerged water phase.
(5) And (3) quasi-statically stretching the liquid bridge, and recording the radius of the broken central thin-neck fluid channel of the liquid bridge.
As shown in fig. 7, when the liquid phase interface fails to form a nanoparticle-polymer interface assembly system, the system fails to inhibit the development of Plateau-Rayleigh instability process, and the liquid bridge is broken under the combined action of ductility effect and capillary effect.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a micro-nano-scale all-liquid-phase fluid channel by inhibiting Plateau-Rayleigh instability is characterized by comprising the following steps of:
(1) Dissolving the end-group polymer surfactant in an oil phase, and dispersing the nano particles in a water phase;
(2) Dripping the water phase dispersed with the nano particles obtained in the step (1) on a hydrophilic substrate, and contacting the water phase droplets dispersed with the nano particles and suspended from the needle head with the droplets on the hydrophilic substrate to ensure that the two droplets are connected to form a liquid bridge;
(3) Adding the oil phase dissolved with the end-group polymer surfactant obtained in the step (1) into a hydrophilic substrate to immerse a liquid bridge, wherein the nano particles and the end-group polymer surfactant can generate electrostatic interaction at an oil-water interface, so that a nano particle-polymer interface assembly network is formed on the liquid bridge interface;
(4) And (3) performing quasi-static stretching on the liquid bridge, and obtaining the micro-nano scale full-liquid-phase fluid channel when the diameter of the thin neck of the liquid bridge reaches the micro-nano level.
2. The method for preparing an all-liquid-phase fluid channel with a micro-nano scale by inhibiting Plateau-Rayleigh instability as claimed in claim 1, wherein in the stretching process of the quasi-static stretching in the step (4), the liquid bridge interface state is always in a blocking phase transition state, and the liquid bridge is in a metastable state.
3. The method for preparing the micro-nano-scale all-liquid-phase fluid channel by inhibiting Plateau-Rayleigh instability according to claim 1 or 2, wherein the size of the micro-nano-scale all-liquid-phase fluid channel in the step (4) is obtained by the liquid bridge system resistance, and the relation between the liquid bridge system resistance and the liquid bridge size is as follows: lgR = klgr + b, where R is the resistance of the liquid bridge system in Ω, R is the radius of the liquid bridge neck in μm, k is the slope, and b is the resistance of the liquid bridge system at a radius of the liquid bridge neck of 1 μm.
4. The method for preparing a micro-nano scale all-liquid phase fluid channel by suppressing Plateau-Rayleigh instability as claimed in claim 1, wherein the end-functionalized polymer surfactant is an aminated polymer or a polyvinylpyridine type polymer.
5. The method for preparing a micro-nano scale all-liquid phase fluid channel by suppressing Plateau-Rayleigh instability according to claim 4, wherein the aminated polymer is at least one of monoaminopolydimethylsiloxane, bisaminopolydimethylsiloxane, and pentaaminopolydimethylsiloxane; the polyvinyl pyridine polymer is polystyrene-poly (2-vinyl pyridine).
6. The method for preparing a micro-nano scale all-liquid phase fluid channel by suppressing Plateau-Rayleigh instability according to claim 1, wherein the nanoparticle is at least one of polyoxometallate nanoparticles, carboxylated silica nanoparticles and sulfonated cellulose nanocrystals.
7. The method for preparing a micro-nano scale all-liquid phase fluid channel by inhibiting Plateau-Rayleigh instability according to claim 1, wherein the oil phase is toluene, chloroform or dichloromethane.
8. The method for preparing a micro-nano scale all-liquid phase fluid channel by suppressing Plateau-Rayleigh instability as claimed in claim 1, wherein the hydrophilic substrate is a glass cuvette, a quartz cuvette or a metal electrode.
9. The method for preparing a micro-nano scale all-liquid phase fluid channel by inhibiting Plateau-Rayleigh instability according to claim 1, wherein the concentration of the end-functionalized polymer surfactant in the oil phase is 0.1mg/mL-0.5mg/mL, and the concentration of the nanoparticles in the aqueous phase is 0.1mg/mL-0.5mg/mL.
10. The micro-nano scale all-liquid-phase fluid channel prepared by the method according to any one of claims 1 to 9.
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