CN115245796B - Method for preparing micro-nano scale all-liquid-phase fluid channel - Google Patents
Method for preparing micro-nano scale all-liquid-phase fluid channel Download PDFInfo
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Abstract
The invention relates to a method for preparing a micro-nano scale full liquid phase fluid channel by inhibiting Plateau-Rayleigh instability, belonging to the technical field of structured liquid. The preparation method of the invention comprises the following steps: (1) Dissolving an end-capped polymeric surfactant in the oil phase, and dispersing the nanoparticles in the water phase; (2) Fixing the aqueous phase between a substrate and a needle to form a liquid bridge; (3) Adding the oil phase immersed liquid bridge, wherein the nano particles and the end-group polymer surfactant can generate electrostatic interaction on an oil-water interface, so that a nano particle-polymer interface assembly network is formed on the liquid bridge interface; (4) And stretching the liquid bridge in a quasi-static state to obtain the micro-nano scale full liquid phase fluid channel. The invention breaks through the size limit of the existing structured liquid all-liquid-phase fluid channel and breaks through the severe limit of the application scene of the traditional all-liquid-phase fluid channel. Has important application prospect in the field of full 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 full liquid phase fluid channel by inhibiting Plateau-Rayleigh instability.
Background
From river to capillary, from natural to industrial, the fluid channel ensures normal ecological cycle and life operation through directional transfer of energy and ordered delivery of substances. The stability of the fluid structure is generally dependent on the solid phase confined environment, such as the river bed and pipes. However, more specific environments, such as in all-liquid phase systems, are fashioned as a fluid channel structure with one fluid in another immiscible phase. Because of the specificity of not allowing participation of the solid phase, the spatial order of the all-liquid phase fluid channels is disrupted by Plateau-Rayleigh instability after leaving the solid phase limited environment. And, due to the effect of Laplace differential pressure, for a smaller size all-liquid phase fluid channel, the smaller the time scale in which Plateau-Rayleigh unstable fluid rupture occurs, i.e
Where τ is the time scale of the fluid rupture, α (P) is the pressure coefficient, r is the fluid column radius, η e Is of external phase viscosity, gamma OW Is interfacial tension between oil and water. The fluid structure is due to loose arrangement of liquid molecules and surface tensionInfluence and are difficult to accurately regulate. The size of all-liquid-phase fluid channels constructed at present is still on a macroscopic scale, which limits their potential for use in the energy transfer and mass transfer fields.
Here, nanoparticle-polymer interface assembly systems provide a solution to this problem. The nano particles and the polymer ligand are cooperatively assembled on a liquid/liquid interface through electrostatic interaction, so that on one hand, the interfacial tension between two phases can be effectively reduced, and on the other hand, the nano particles provide excellent mechanical properties for a liquid phase interface. The interfacial shear modulus is raised sufficiently to resist interfacial retraction by surface tension and inhibit Plateau-Rayleigh instability. Here the interfacial shear modulus is used to quantify the process, i.e
Wherein the method comprises the steps of
For interfacial shear modulus, < >>
For interface particle areal bulk density, < >>
The critical interface particle surface packing density for fluid column rupture, β is the correction term.
Here the time scale of particle packing is given, i.e
τ α ＝(k a C 0 η) -1
Wherein τ α K is the time scale of particle migration a For constant rate, C 0 Is the concentration of the bulk particles, η is the correction term.
Surface packing density of particles at interface before fluid structure rupture
Greater than critical interfacial particlesSub-surface bulk density
When the whole fluid structure is stabilized, i.e
τ＞τ α
Shi et al utilized a fluidic model in combination with a nanoparticle-polymer interface assembly system to construct a fluid channel of all liquid phases in a low viscosity toluene phase (angel. Chem. Int. Ed.2017,56,12594), nanoparticle surfactants formed based on rod-like cellulose nanocrystals, which can be rapidly assembled at the liquid/liquid interface. When interfacial blocking phase transition occurs, the nanoparticle surfactant assembly network brings excellent mechanical properties to the interface, the free falling jet of aqueous solution containing cellulose nanocrystals enters 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 lower, the time scale tau of fluid rupture is very small, and the fluid rupture is only required to be delayed until the assembly of the nanoparticle interface is completed, the size of the all-liquid-phase fluid channel formed by the method is generally millimeter or hundreds of micrometers, and the all-liquid-phase fluid channel with smaller size cannot be prepared.
Xie et al utilize 3D printing technology to combine with elastic polyanion-polycation to condense membrane and prepare stable three-dimensional water/water structure (Chem 2019,5,5688), realize the wide application of all liquid phase fluid channel through regulating and controlling mechanical properties and functionality of condensing membrane. Which uses polyanion-polycation electrostatic interactions to replace electrostatic interactions of nanoparticles with polymer ligands to cause an interface assembly rate τ α The significance is improved, but the fluid breaks faster due to the smaller viscosity of the external phase environment, and the size of the formed full liquid phase fluid channel is generally in the scale range of 100 mu m.
Forth et al, combined with nanoparticle-polymer interface assembly systems using 3D printing techniques, constructed various diameter (10-1000 μm) all-liquid fluid channels (adv. Mater.2018,30, e 1707608) in high viscosity silicone oils, with channel lengths up to several meters. High viscosity silicone oils are a substantial prolongation of the time scale of fluid rupture τ. However, the full liquid phase fluid channel constructed by the method is seriously dependent on the external environment with high viscosity, and the size limit of the constructed full liquid phase fluid channel only reaches 10 mu m.
In summary, the research on the full liquid phase fluid channel is still in a starting stage at present, the construction mode generally combines a jet model with a nanoparticle-polymer assembly system, the constructed full liquid phase fluid channel has larger size, needs to meet complex and harsh dynamic conditions, is limited by a construction method, generally needs complex instruments and equipment (3D printing facilities), and has complex experimental operation. Therefore, the research on the full liquid phase fluid channel with loose dynamic conditions, simple operation, stable structure and controllable size has important practical significance.
Disclosure of Invention
The invention breaks through the size limit of the current 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 micro-nano scale full liquid phase fluid with stable structure by a simple technical means in more universal application scenes (whether high-viscosity external phase or low-viscosity external phase). The invention aims to provide a micro-nano scale all-liquid-phase fluid channel which is stable in structure and controllable in size, and is prepared simply and effectively by inhibiting Plateau-Rayleigh instability.
According to a first aspect of the present invention there is provided a method of preparing micro-nano scale all liquid phase fluid channels by inhibiting Plateau-Rayleigh instability comprising the steps of:
(1) Dissolving an end-capped polymeric surfactant in the oil phase, and dispersing the nanoparticles in the water phase;
(2) Dropping the water phase dispersed with the nano particles obtained in the step (1) on a hydrophilic substrate, and enabling the water phase liquid drop suspended by a needle head and dispersed with the nano particles to contact with the liquid drop on the hydrophilic substrate so as to enable the two liquid drops to be connected into a section of liquid bridge;
(3) Adding the oil phase of the polymer surfactant dissolved with the end groups obtained in the step (1) into a hydrophilic substrate to immerse a liquid bridge, wherein the nano particles and the polymer surfactant with the end groups can perform electrostatic interaction on an oil-water interface, so that a nano particle-polymer interface assembly network is formed on the liquid bridge interface;
(4) And (3) carrying out quasi-static stretching on the liquid bridge, and obtaining the micro-nano-scale all-liquid-phase fluid channel when the diameter of the liquid bridge neck reaches the micro-nano level.
Preferably, in the stretching process of the quasi-static stretching in the step (4), the interface state of the liquid bridge is always in a blocking phase change state, and the liquid bridge is in a metastable state.
Preferably, in the step (4), the size of the micro-nano-scale all-liquid-phase fluid channel is obtained by a liquid bridge system resistance, and a relationship between the liquid bridge system resistance and the liquid bridge size is: lg r=klgr+b, where R is the liquid bridge system resistance, in Ω, R is the liquid bridge neck radius, in μm, k is the slope, and b is the liquid bridge system resistance when the liquid bridge neck radius is 1 μm.
Preferably, the end-capped polymeric surfactant is an aminated polymer or a polyvinylpyridine polymer.
Preferably, the aminated polymer is at least one of mono-amino polydimethylsiloxane, di-amino polydimethylsiloxane and penta-amino polydimethylsiloxane; the polyvinyl pyridine polymer is polystyrene-poly (2-vinyl pyridine).
Preferably, the nanoparticle is at least one of a polyoxometalate nanoparticle, a carboxylated silica nanoparticle, and a sulfonated cellulose nanocrystal.
Preferably, the oil phase is toluene, chloroform or methylene chloride.
Preferably, the hydrophilic substrate is a glass cuvette, a quartz cuvette or a metal electrode.
Preferably, the concentration of the end-capped polymeric surfactant in the oil phase is from 0.1mg/mL to 0.5mg/mL and the concentration of the nanoparticles in the aqueous phase is from 0.1mg/mL to 0.5mg/mL.
According to another aspect of the invention, a micro-nano scale all-liquid-phase fluid channel prepared by any one of the methods is provided.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) According to the invention, a liquid bridge quasi-static stretching model is used for replacing the traditional jet model to be combined with a nanoparticle-polymer interface assembly system, nanoparticles and polymer ligands are cooperatively assembled on 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 the balance between the hydrodynamic speed and the chemical interface assembly rate, the quasi-static stretching process ensures that the interface state of the liquid bridge is always in a metastable state in the construction process, the time scale of the rupture of the fluid approaches infinity, and the time scale of the particle interface assembly is far smaller than the time scale of the rupture of the fluid. The restriction of dynamic conditions is removed. And thus breaks through the size limit (d=10μm) of the existing full liquid phase fluid channel construction at present, and a brand new full liquid phase fluid channel (d=800 nm) with micro-nano scale is constructed.
(2) The application scene applied by the invention is more universal, the quasi-static stretching process ensures that the whole fluid structure is stable, the auxiliary support of the high-viscosity external phase environment is not needed, and the construction of the micro-nano scale full-liquid-phase fluid channel can be realized in the low-viscosity toluene phase. Meanwhile, compared with the traditional 3D printing jet model, the method for constructing the fluid channel of the full liquid phase is constructed, and complex 3D printing equipment is not needed.
(3) The invention selects to determine the size of the liquid phase fluid channel by measuring the resistance change of the system, approaches the diffraction limit of an optical microscope under the micro-nano scale, and images and blurs, while in the liquid phase system, the scanning electron microscope is difficult to characterize the in-situ size of the liquid phase fluid channel, and the invention determines that a good logarithmic linear relation exists between the system resistance and the size of the fluid channel, and gives a relational expression of the system resistance and the fluid channel, namely: lg r=klgr+b, where R is the liquid bridge system resistance, in Ω, R is the liquid bridge neck radius, in μm, k is the slope, and b is the liquid bridge system resistance when the liquid bridge neck radius is 1 μm. The size of the all liquid phase fluid channel can be accurately calculated through measuring the system resistance.
Drawings
FIG. 1 is { Mo } 72 V 30 }(0.1mg mL -1 ) Immersed in a solution containing PDMS-NH 2 (0.01mg mL -1 ) Dynamic interfacial tension curve of water dispersed phase droplets in toluene solution.
Fig. 2 is a graph showing the self-wrinkling behavior observed when the nanoparticle-polymer interface assembly system is assembled at the interface.
FIG. 3 is a cross-sectional view of symmetric fracture kinetics of an all-liquid phase fluid channel when the system is present in a nanoparticle-polymer interface assembly system.
FIG. 4 is a graph of system resistance versus size for all liquid phase fluid channels.
FIG. 5 is a graph of the (water: { Mo) when the system is free of nanoparticle-polymer interface assembled system 72 V 30 }(0.1mg mL -1 ) /oil: pure toluene) all liquid phase fluid channel symmetric fracture kinetics cross-section.
FIG. 6 is a graph of the symmetrical breaking kinetics of an all liquid phase fluid channel when the system is free of nanoparticle-polymer interface assembly system (water: pure water/oil: pure toluene).
FIG. 7 is a graph of the water/oil PDMS-NH when the system is free of nanoparticle-polymer interface assembly systems 2 (0.1mg mL -1 ) Toluene solution) symmetric fracture kinetics cross-section of the all-liquid phase fluid channel.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention combines the quasi-static stretching of the liquid bridge and the assembling of the nanoparticle-polymer interface, and combines the nano-structureThe aqueous solution of the rice particles is fixed between the substrate and the needle head to form a liquid bridge; and then adding an oil phase immersed water phase of the polymer ligand dissolved with the end group functionalization, wherein the nanoparticles and the polymer ligand with the end group functionalization are rapidly assembled at an oil-water interface due to electrostatic interaction, a liquid bridge is stretched, and the drainage process of the liquid bridge is completely dependent on the retraction of a needle head. The substrate and needle are hydrophilic to ensure that the three-phase contact line is fixed to the interface during needle retraction, the interface force effectively limiting the stability of the liquid bridge structure before Plateau-Rayleigh instability occurs, and when the Plateau-Rayleigh instability limit is reached, stretching is suspended, allowing enough time for the nanoparticle-polymer interface assembly network to assemble at the interface until maximum surface bulk density is reached
Interface blocking phase transition to give interface shear modulus +.>
Is sufficient to inhibit Plateau-Rayleigh instability. Then the needle is retracted for a certain distance dL, the center of the liquid bridge can leak out a new oil-water interface, the bulk density of the particle surface is reduced, and the retraction distance is controlled only to ensure that
The system is still in a metastable state. And then waiting for the nanoparticle-polymer interface assembly network to assemble completely on the new interface, the surface bulk density of the particles +.>
Reach maximum areal bulk Density->
The needle can be retracted again. And (5) circularly reciprocating to obtain the nanoscale full liquid phase fluid channel.
According to the object of the present invention, there is provided a method for preparing a micro-nano scale all liquid phase fluid channel which is stable in structure and controllable in size by inhibiting Plateau-Rayleigh instability, comprising the steps of:
(1) Dissolving a polymer surfactant with a functionalized end group in an oil phase, dispersing nano particles with complementary functional groups in an aqueous phase, wherein the nano particles with the complementary functional groups and the polymer surfactant with a functionalized end group can perform electrostatic interaction at an oil-water interface;
(2) Fixing the aqueous phase between a substrate and a needle to form a liquid bridge;
(3) Adding the oil phase immersed liquid bridge, and forming a nanoparticle-polymer interface assembly network on the liquid bridge interface;
(4) And stretching the liquid bridge in a quasi-static state to obtain the micro-nano scale full liquid phase fluid channel.
In some embodiments, the dissolution of the end-group functionalized polymeric surfactant in step (1) is achieved using a vortex mixer, and the dissolution of the nanoparticle having a complementary functional group in step (1) is achieved using a vortex mixer.
In some embodiments, the micro-nano scale all-liquid phase fluid channel in step (4) can control the size of the fluid channel by regulating the concentration of the polymer surfactant and the nanoparticles and the topology of the polymer surfactant.
Preferably, the end group functionalized polymer surfactant is an amino polymer or a polyvinyl pyridine polymer, preferably, the end group functionalized polymer surfactant is mono-amino polydimethylsiloxane (PDMS-NH) 2 ) Bis-amino polydimethylsiloxane (PDMS-2 NH) 2 ) Pentaamino polydimethylsiloxane (PDMS-5 NH) 2 ) Any one of polystyrene-poly (2-vinylpyridine) (PS-b-PVP).
Preferably, the nanoparticle with complementary functional groups is polyoxometalate { 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 which are not miscible with water, and preferably, the organic solvents are any one of toluene, chloroform and methylene chloride.
Preferably, the substrate is selected from any one of a glass cuvette, a quartz cuvette and a metal electrode.
Preferably, the dissolution of the end group functionalized polymer surfactant in step (1) is achieved using a vortex mixer.
Preferably, the nanoparticle dissolution with complementary functional groups in step (1) is achieved using a vortex mixer.
Preferably, in the step (4), the micro-nano scale full liquid phase fluid channel is controlled in size by regulating the concentration of the polymer surfactant and the nano particles and the topological structure of the polymer surfactant.
Preferably, in the step (4), the quasi-static stretching liquid bridge ensures that the interface state of the liquid bridge is always in the process of stretching,
i.e. the blocking phase change occurs, the liquid bridge is in a metastable state, wherein Ca is the capillary number, eta e Is the viscosity of oil phase, the unit is cSt, v e For tensile shear rate in mm s -1 ，ν 0w Is interfacial tension between oil and water, and has unit of mN m -1 τ is the time scale of the break of the liquid bridge in s.
Preferably, the size characterization of the micro-nano scale all-liquid-phase fluid channel in the step (4) is obtained by the resistance of a system, and the relation between the system resistance and the liquid bridge size 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 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 neck is 1 mu m, alpha is the morphology factor, and sigma is the conductivity of the water phase. Wherein the morphology α of the inclined k and the liquid bridge is related to the conductivity α of the aqueous phase.
The monoaminodimethicone of the invention(PDMS-NH 2 ) Bis-amino polydimethylsiloxane (PDMS-2 NH) 2 ) Pentaamino polydimethylsiloxane (PDMS-5 NH) 2 ) Polystyrene-poly (2-vinylpyridine) (PS-b-P2 VP), carboxylated Silica (SiO) 2 -COOH), sulfonated cellulose nanocrystals (CNC-OHSO 3 ) Rubidium chloride (Rbcl) is commercially available. Polyoxometalates { Mo 72 V 30 The preparation was performed experimentally by mixing 35mL VOSO 4 ·5H 2 O(2.53g,10mmol，H 2 O) aqueous solution was added 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 closed with a rubber stopper) and then Kcl (0.65 g,8.72 mmol) was added. 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 diamond crystal, washing with cold water, and air drying to obtain polyoxometallate { Mo 72 V 30 }. Wherein vanadyl sulfate (VOSO) 4 ·5H 2 O), sodium molybdate (Na 2 MoO 4 ·2H 2 O) and potassium chloride (Kcl) are commercially available.
Example 1
(1) Weighing 2mg of polyoxometallate { Mo 72 V 30 Stirring and mixing for 5 minutes at the rotating speed of 800 revolutions per minute in a reagent bottle filled with 20mL of deionized water by using a vortex mixer to obtain a solution { Mo (molybdenum) of 0.1mg/mL 72 V 30 Aqueous dispersion.
(2) 2mg of monoaminopolydimethylsiloxane (PDMS-NH) was weighed out 2 ) In a reagent bottle filled with 20mL of toluene, stirring and mixing for 5 minutes at the rotating speed of 800 revolutions per minute by using a vortex mixer to obtain a solution of 0.1mg/mL of PDMS-NH 2 Toluene solution.
(3) Deionized water was placed in the pure toluene phase and the interfacial tension between the two phases was measured using an interfacial viscoelastic meter.
(4) And (3) 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 viscoelastometer.
(5) Deionized water is placed in PDMS-NH prepared in the step (2) 2 In toluene solution, the interfacial tension between two phases was measured using an interfacial viscoelastic meter.
(6) Placing the aqueous phase solution prepared in the step (1) in the PDMS-NH prepared in the step (2) 2 In toluene solution, the interfacial tension between two phases was measured using an interfacial viscoelastic meter.
Interfacial tension is shown in FIG. 1, { Mo compared to pure water/pure toluene system 72 V 30 No interfacial activity is present, where { Mo } is 72 V 30 }(0.1mg mL -1 ) The interfacial tension of the aqueous solution in toluene was the same as that of pure water in toluene, γ=34 mN m -1 。PDMS-NH 2 In toluene (0.01 mg mL) -1 ) Medium dissolution, γ=28 mN 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 ) In toluene of (c), γ=18 mN m-1, the interfacial energy decreases rapidly and significantly, indicating the formation and assembly of nanoparticle-polymer interfacial assembled networks at the interface.
Example 2
(1) 0.0386g of rubidium chloride (Rbcl) was weighed into a reagent bottle containing 20mL of deionized water, and stirred and mixed for 5 minutes at a rotational speed of 800 rpm by a vortex mixer to obtain a solution of 1.93mg/mL of Rbcl aqueous dispersion.
(2) 0.2mg/mL { Mo in example 1 was taken 72 V 30 10mL of the aqueous dispersion was mixed with 10mL of the aqueous Rbcl dispersion in step (1) of this example in a reagent bottle, and the mixture was stirred and mixed for 5 minutes at a rotational speed of 800 rpm by a vortex mixer to give a solution of 0.1mg/mL { Mo 72 V 30 Aqueous dispersion (containing 0.97mg/mL Rbcl).
(3) Taking { Mo } prepared in the step (2) 72 V 30 An aqueous dispersion of PDMS-NH was suspended at 0.1mg/mL in example 1 2 In toluene solution, the morphology of the droplet interface was observed.
As shown in fig. 2, the pendant drop interface forms 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 self-crimping films indicates that the areal bulk density of the particles at the interface has been close to the maximum areal bulk density and that a blocking phase change has occurred.
Example 3
(1) 0.1mg/mL { Mo } prepared in example 2 was taken 72 V 30 An aqueous dispersion (containing 0.97mg/mL of Rbcl) was placed in a 100. Mu.L syringe.
(2) Drip 1.5. Mu.L of { Mo.0.1 mg/mL prepared in example 2 72 V 30 The aqueous dispersion was applied to the substrate of a glass cuvette, and the droplet coverage size was the same as that of the syringe needle.
(3) Overhang 3.5. Mu.L { Mo 72 V 30 And (3) contacting the water phase liquid drops with the liquid drops on the cuvette substrate in the step (2), connecting the two water phase liquid drops into a section of liquid bridge, and adjusting the height of the needle head of the injector to ensure that the liquid bridge is kept uniform up and down.
(4) 2mL of PDMS-NH prepared as in example 1 at 0.1mg/mL was added to the cuvette in step (2) 2 Toluene solution, oil phase completely immersed in water phase.
(5) Standing for 20 seconds, and when the assembly network of the nano-particles and the polymer interface of the liquid bridge interface is completely assembled, the surface packing density of the particles reaches the maximum value, the needle dL is slowly moved upwards, and the upward movement ensures that the liquid bridge only has ductile action and does not have capillary action.
(6) Standing for 10 seconds, and after the liquid bridge interface nanoparticle-polymer interface assembly network is completely reassembled, the particle surface bulk density reaches the maximum again, the needle dL is slowly moved upwards, and the upward movement ensures that the liquid bridge only has ductile action and does not have capillary action.
(7) Repeating the step (6) until the target size (less than 1 μm) is reached. The diameter of the liquid bridge neck is smaller than 1 mu m.
As shown in fig. 3, in the process of quasi-static stretching of the liquid bridge, the formation of the nanoparticle-polymer interface assembly network completely inhibits the development of the Plateau-Rayleigh unstable process, and the stretching process of the whole liquid bridge only has ductile effect and has no influence of capillary effect. The size of the liquid bridge center thin neck, namely the full liquid phase fluid channel, can reach the nano scale, and the structure is stable.
Example 4
(1) 0.1mg/mL { Mo } prepared in example 2 was taken 72 V 30 An aqueous dispersion (containing 0.97mg/mL of Rbcl) was placed in a 100. Mu.L syringe.
(2) Drip 1.5. Mu.L of { Mo.0.1 mg/mL prepared in example 2 72 V 30 The aqueous dispersion was applied to the substrate of the metal electrode, and the droplet coverage size was the same as that of the syringe needle.
(3) Overhang 3.5. Mu.L { Mo 72 V 30 And (3) contacting the water phase liquid drops with the liquid drops on the cuvette substrate in the step (2), wherein the two water phase liquid drops are connected into a section of liquid bridge, and the height of the needle head of the injector is adjusted so that the liquid bridge is kept uniform up and down.
(4) 2mL of PDMS-NH prepared as in example 1 at 0.1mg/mL was added to the cuvette in step (2) 2 Toluene solution, oil phase completely immersed in 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 passage.
(6) The construction method of the nanoscale full 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 clear log-linear relationship between the system resistance and the size of the all liquid phase fluid channel, which can be related by fitting, i.e
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 neck, the unit is mu m, k is the slope, and b is the resistance value of the liquid bridge system when the radius of the liquid bridge neck is 1 mu m. The final system resistance was determined to be 11.27mΩ, and the radius of the all liquid phase fluid channel was 400nm, taking into account this relationship.
Comparative example 1
(1) 0.1mg/mL { Mo } prepared in example 2 was taken 72 V 30 An aqueous dispersion (containing 0.97mg/mL of Rbcl) was placed in a 100. Mu.L syringe.
(2) Drip 1.5. Mu.L of { Mo.0.1 mg/mL prepared in example 2 72 V 30 The aqueous dispersion was applied to the substrate of a glass cuvette, and the droplet coverage size was the same as that of the syringe needle.
(3) Overhang 3.5. Mu.L { Mo 72 V 30 And (3) contacting the water phase liquid drops with the liquid drops on the cuvette substrate in the step (2), wherein the two water phase liquid drops are connected into a section of liquid bridge, and the height of the needle head of the injector is adjusted so that the liquid bridge is kept uniform up and down.
(4) Adding a pure toluene solution into the cuvette in the step (2), and completely immersing the oil phase into the water phase.
(5) The liquid bridge was stretched quasi-statically and the radius of the central thin neck fluid channel of the liquid bridge break was recorded.
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 the Plateau-Rayleigh unstable process, the liquid bridge breaks under the combined action of the ductile effect and the capillary effect, and the breaking radius is 0.375mm, which is more than 1000 times 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 was dropped onto the substrate of the glass cuvette, and the droplet coverage size thereof was consistent with that of the syringe needle.
(3) Suspending 3.5 mu L of ultrapure water drops, contacting the drops of the cuvette substrate in the step (2), connecting the two water phase drops into a section of liquid bridge, and adjusting the height of the needle head of the injector to ensure that the liquid bridge is kept uniform up and down.
(4) Adding a pure toluene solution into the cuvette in the step (2), and completely immersing the oil phase into the water phase.
(5) The liquid bridge was stretched quasi-statically and the radius of the central thin neck fluid channel of the liquid bridge break was recorded.
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 the Plateau-Rayleigh unstable process, and the liquid bridge breaks under the combined action of the ductile effect and the capillary effect.
Comparative example 3
(1) Ultrapure water was taken in a 100. Mu.L syringe.
(2) 1.5. Mu.L of ultrapure water was dropped onto the substrate of the glass cuvette, and the droplet coverage size thereof was consistent with that of the syringe needle.
(3) Suspending 3.5 mu L of ultrapure water drops, contacting the drops of the cuvette substrate in the step (2), connecting the two water phase drops into a section of liquid bridge, and adjusting the height of the needle head of the injector to ensure that the liquid bridge is kept uniform up and down.
(4) PDMS-NH of example 1 at 0.1mg/mL was added to the cuvette in step (2) 2 Toluene solution, oil phase completely immersed in water phase.
(5) The liquid bridge was stretched quasi-statically and the radius of the central thin neck fluid channel of the liquid bridge break was recorded.
As shown in fig. 7, when the liquid phase interface cannot form a nanoparticle-polymer interface assembly system, the system cannot inhibit the development of the Plateau-Rayleigh unstable process, and the liquid bridge breaks under the combined action of the ductile effect and the capillary effect.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A method of preparing micro-nano scale all liquid phase fluid channels by inhibiting Plateau-Rayleigh instability, comprising the steps of:
(1) Dissolving an end-capped polymeric surfactant in the oil phase, and dispersing the nanoparticles in the water phase; the end-capped polymer surfactant is mono-amino polydimethylsiloxane, di-amino polydimethylsiloxane, penta-amino polydimethylsiloxane or polystyrene-poly (2-vinyl pyridine); the nano particles are polyoxometallate nano particles, carboxylated silicon dioxide nano particles or sulfonated cellulose nano crystals;
(2) Dropping the water phase dispersed with the nano particles obtained in the step (1) on a hydrophilic substrate, and enabling the water phase liquid drop suspended by a needle head and dispersed with the nano particles to contact with the liquid drop on the hydrophilic substrate so as to enable the two liquid drops to be connected into a section of liquid bridge;
(3) Adding the oil phase of the polymer surfactant dissolved with the end groups obtained in the step (1) into a hydrophilic substrate to immerse a liquid bridge, wherein the nano particles and the polymer surfactant with the end groups can perform electrostatic interaction on an oil-water interface, so that a nano particle-polymer interface assembly network is formed on the liquid bridge interface;
(4) And (3) carrying out quasi-static stretching on the liquid bridge, and obtaining the micro-nano-scale all-liquid-phase fluid channel when the diameter of the liquid bridge neck reaches the micro-nano level.
2. The method for preparing a micro-nano scale all-liquid-phase fluid channel by inhibiting Plateau-Rayleigh instability according to claim 1, wherein the interface state of the liquid bridge is always in a blocking phase change state and the liquid bridge is in a metastable state during the stretching process of quasi-static stretching in the step (4).
3. The method for preparing a micro-nano scale all-liquid-phase fluid channel by suppressing Plateau-Rayleigh instability according to claim 1 or 2, wherein the size of the micro-nano scale all-liquid-phase fluid channel in step (4) is obtained by a liquid bridge system resistance, and the relationship between the liquid bridge system resistance and the liquid bridge size is: lgr=klgr+b, where R is the liquid bridge system resistance, in Ω, R is the liquid bridge neck radius, in μm, k is the slope, and b is the liquid bridge system resistance when the liquid bridge neck radius is 1 μm.
4. The method of preparing micro-nano scale all liquid phase fluid channels by inhibiting Plateau-Rayleigh instability according to claim 1, wherein the oil phase is toluene, chloroform or methylene chloride.
5. The method of preparing a micro-nano scale all liquid phase fluid channel by inhibiting Plateau-Rayleigh instability according to claim 1, wherein the hydrophilic substrate is a glass cuvette, a quartz cuvette or a metal electrode.
6. The method of preparing a micro-nano scale all liquid phase fluid channel by inhibiting Plateau-Rayleigh instability according to claim 1, wherein the concentration of end-capped polymeric surfactant in the oil phase is 0.1mg/mL to 0.5mg/mL and the concentration of nanoparticles in the aqueous phase is 0.1mg/mL to 0.5mg/mL.
7. The micro-nano scale all-liquid-phase fluid channel prepared by the method of any one of claims 1-6.
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