CN110975772A - Non-equilibrium self-assembly system and method based on self-driven colloid system - Google Patents
Non-equilibrium self-assembly system and method based on self-driven colloid system Download PDFInfo
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Abstract
The invention discloses a self-driven colloid system-based unbalanced self-assembly system and a self-driven colloid system-based unbalanced self-assembly method, which are characterized in that the unbalanced self-assembly system comprises a first electrode plate and a second electrode plate which are oppositely arranged, a partition plate packaged between the first electrode plate and the second electrode plate, and a power supply electrically connected between the first electrode plate and the second electrode plate, wherein a closed space for accommodating colloid particles and diluent is formed among the first electrode plate, the second electrode plate and the partition plate, the power supply is used for applying an alternating electric field to the first electrode plate and the second electrode plate, and the colloid particles are automatically assembled in the closed space in an unbalanced manner under the alternating electric field applied by the power supply. The invention combines the self-driving system and the periodic driving force, can realize the non-equilibrium self-assembly of the self-driving colloid system, generates a time-space self-assembly structure with the coexistence of space periodicity and time periodicity, and has higher controllability and dynamic adaptability.
Description
Technical Field
The invention belongs to the technical field of colloid self-assembly, and particularly relates to a non-equilibrium self-assembly system and a non-equilibrium self-assembly method based on a self-driven colloid system.
Background
Dynamic self-assembly is the basic process of life, and the ordered functional structure formed by dynamic self-assembly is the basis for organism to realize various biological functions and maintain life activities. Inspired by life systems, the structure is dynamically variable, and intelligent materials which can adapt to the change of external environment are more and more emphasized by people.
The self-assembly of colloidal particles has unique structural characteristics, and the self-assembly of colloids has also developed a lot of important technical applications, for example, the application in developing photonic crystals and porous materials; also plays a key role in the technologies of energy storage and conversion, biological detection and the like. However, in these applications, the structure formed by the self-assembly of the colloid is mostly static and difficult to control.
In the prior art, in 2013 Konstatin et al reported the magnetic fluid dynamic self-assembly technology, as shown in FIG. 1a, when the magnet starts to rotate, the magnetic disk also rotates at the same angular velocity, and the rotating magnetic disk drives the surrounding liquid to form vortex, as shown in FIGS. 1b and 1 c. In addition, the rotating disk will self-assemble into a different, stable, multi-state structure by competing magnetic and hydrodynamic forces, as shown in FIG. 1 d.
However, the dynamic self-assembly in the prior art has no long-range order, and is poor in controllability and dynamic adaptability, and a long-range ordered dynamic space structure cannot be formed.
Therefore, in order to solve the above technical problems, it is necessary to provide a non-equilibrium self-assembly system and method based on a self-driven colloid system.
Disclosure of Invention
The invention aims to provide a non-equilibrium self-assembly system and a non-equilibrium self-assembly method based on a self-driven colloid system so as to form a long-range ordered dynamic space structure.
In order to achieve the above object, an embodiment of the present invention provides the following technical solutions:
the utility model provides a non-equilibrium self-assembly system based on self-driven colloid system, non-equilibrium self-assembly system is including relative first plate electrode and the second plate electrode that sets up, encapsulates baffle between first plate electrode and second plate electrode and the power of electric connection between first plate electrode and second plate electrode, be formed with the confined space that is used for acceping colloidal particles and diluent between first plate electrode, second plate electrode and the baffle, the power is used for applying the alternating electric field to first plate electrode and second plate electrode, under the alternating electric field that the power was applied colloidal particles carries out non-equilibrium automatic assembly in the confined space.
In one embodiment, the density of the colloidal particles is greater than that of the diluent, the viscosity coefficient of the diluent is greater than or equal to a predetermined threshold, and the conductivity of the diluent is greater than that of the colloidal particles.
In one embodiment, the colloidal particles are polystyrene non-conductive beads, and the diluent is a mixed solution of docusate sodium and n-hexadecane.
In one embodiment, the alternating electric field is a high electric field E1And low electric field E2Alternating periodically varying square-wave electric field, wherein E2＜E0＜E1，E0Critical electric field, E0The colloidal particles are subjected to a high electric field E for the electric field intensity when part of the particles move continuously1Lower continuous motion, colloidal particles under low electric field E2The lower part is static.
In one embodiment, the power supply is an alternating power supply and the power supply voltage is a high voltage V1And a low voltage V2Alternating periodically varying square wave voltage, wherein V1＝E1*H，V2＝E2H, H is the distance between the first and second electrode plates.
In one embodiment, the motion of the colloidal particles under the alternating electric field is a "converging-diverging" reciprocating motion based on the Quincke rotation, and the formed non-equilibrium automatic assembly structure is a dynamic ordered self-assembly grid structure with alternately changing high-density regions and low-density regions.
In one embodiment, the average size D of clusters and the average distance L between clusters in the dynamically ordered self-assembled lattice structure are linear with the period T, and satisfy:
wherein the content of the first and second substances,
and
the average colloidal particle density when the colloidal particles are initially uniformly distributed and the average colloidal particle density in the range of D in the stable grid structure are respectively shown, S is the average distance of the colloidal particles moving in one period T, S is vT/2, and v is the average moving speed of the colloidal particles.
The technical scheme provided by another embodiment of the invention is as follows:
a method of non-equilibrium self-assembly based on a self-driven colloidal system, the method comprising:
s1, encapsulating colloid particles and diluent in a closed space between the first electrode plate and the second electrode plate;
and S2, applying an alternating electric field to the first electrode plate and the second electrode plate, and carrying out unbalanced automatic assembly on the colloid particles in the closed space.
In one embodiment, in the step S2, the non-equilibrium automatic assembly of the colloidal particles in the enclosed space specifically includes:
the motion of colloid particles under an alternating electric field is 'gathering-diverging' reciprocating motion based on Quincke rotation, and the formed non-equilibrium automatic assembly structure is a dynamic ordered self-assembly grid structure with alternately changed high-density areas and low-density areas.
In one embodiment, the average size D of clusters and the average distance L between clusters in the dynamically ordered self-assembled lattice structure are linear with the period T, and satisfy:
wherein the content of the first and second substances,
and
the average colloidal particle density when the colloidal particles are initially uniformly distributed and the average colloidal particle density in the range of D in the stable grid structure are respectively shown, S is the average distance of the colloidal particles moving in one period T, S is vT/2, and v is the average moving speed of the colloidal particles.
Compared with the prior art, the invention has the following advantages:
the invention combines the self-driving system and the periodic driving force, can realize the non-equilibrium self-assembly of the self-driving colloid system, generates a time-space self-assembly structure with the coexistence of space periodicity and time periodicity, and has higher controllability and dynamic adaptability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1a is a schematic diagram of the dynamic self-assembly of a magnetic fluid in the prior art;
FIGS. 1b and 1c are schematic diagrams illustrating a liquid whirlpool formed by a magnetic disk according to the prior art;
FIG. 1d is a schematic diagram of a prior art self-assembled structure formed on a disk;
FIG. 2 is a schematic structural diagram of an unbalanced self-assembled system according to an embodiment of the present invention;
FIG. 3 is a schematic illustration of an alternating electric field in one embodiment of the present invention;
FIG. 4 is a schematic diagram of a Quincke-based rotation of colloidal particles in an embodiment of the present invention;
FIGS. 5a, 5b, and 5c are schematic diagrams of an initial disordered state structure, a disordered heterogeneous state structure with density fluctuation beginning, and a stable dynamic structure of colloidal particles according to an embodiment of the present invention;
FIGS. 6a, 6b, and 6c illustrate a high electric field E according to an embodiment of the present invention1The dynamic change process of the grid structure is shown in the graph when the frequency f is 1.98 v/mum and 10 Hz;
FIG. 7a shows a high electric field E in an embodiment of the present invention1A schematic diagram of a stable grid structure formed at 1.98v/μm and a frequency f of 12 Hz;
FIG. 7b is a graph of grid size D, L as a function of frequency f in an embodiment of the present invention;
fig. 7c is a graph of grid size D, L as a function of half cycle T/2 in an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to embodiments shown in the drawings. The embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to the embodiments are included in the scope of the present invention.
The invention discloses a non-equilibrium self-assembly system based on a self-driven colloid system, which comprises a first electrode plate and a second electrode plate which are oppositely arranged, a partition plate packaged between the first electrode plate and the second electrode plate, and a power supply electrically connected between the first electrode plate and the second electrode plate, wherein a closed space for accommodating colloid particles and diluent is formed among the first electrode plate, the second electrode plate and the partition plate, the power supply is used for applying an alternating electric field to the first electrode plate and the second electrode plate, and the colloid particles are subjected to non-equilibrium automatic assembly in the closed space under the alternating electric field applied by the power supply.
The invention also discloses a non-equilibrium self-assembly method based on the self-driven colloid system, which comprises the following steps:
s1, encapsulating colloid particles and diluent in a closed space between the first electrode plate and the second electrode plate;
and S2, applying an alternating electric field to the first electrode plate and the second electrode plate, and carrying out unbalanced automatic assembly on the colloid particles in the closed space.
The present invention is further illustrated by the following specific examples.
Referring to fig. 2, a schematic structural diagram of an unbalanced self-assembly system based on a self-driven colloid system according to an embodiment of the present invention includes a first electrode plate 11 and a second electrode plate 12 which are disposed opposite to each other, a partition plate 13 enclosed between the first electrode plate and the second electrode plate, and a power supply 14 electrically connected between the first electrode plate and the second electrode plate, wherein a closed space 10 for accommodating colloid particles 20 and a diluent (not shown) is formed between the first electrode plate, the second electrode plate, and the partition plate, and the power supply 14 is configured to apply an alternating electric field to the first electrode plate 11 and the second electrode plate 12, and the colloid particles 20 are automatically assembled in the closed space in an unbalanced manner under the alternating electric field applied by the power supply 14.
In the invention, the following points are ensured when the colloidal particles and the diluent are selected:
1. the density of the colloidal particles is higher than that of the diluent, so that the colloidal particles are deposited and distributed on the surface of the lower electrode plate (second electrode plate) under the action of a gravity field;
2. the light refraction coefficient of the colloidal particles is obviously different from that of the diluent, so that the colloidal particles can be distinguished from the background of the diluent under an optical microscope;
3. the diluent has a high viscosity coefficient (greater than or equal to a preset threshold value) to ensure that the colloidal particles do not slide in the rolling process;
4. the electric conductivity of the diluent is larger than that of the colloidal particles, and the response time of the free charges in the diluent to the electric field is shorter than that of the bound charges in the colloidal particles, so that the colloidal particles are ensured to generate reverse polarization under the action of an external field.
Preferably, the colloidal particles in this embodiment are 4.8 μm non-conductive polystyrene beads, the diluent is a conductive solution prepared by mixing docusate sodium and n-hexadecane, and the first electrode plate and the second electrode plate in this embodiment are both conductive glass.
The prepared colloidal particles and the diluent are injected into a closed space 10 formed by two electrode plates, and the colloidal particles are deposited on the surface of a second electrode plate 12 at the bottom under the action of gravity. In the solution, the small balls of the insulating medium can generate polarization opposite to the electric field under the action of the external field, the thermal fluctuation can generate a polarization component in the horizontal direction, and the horizontal couple component can generate a rotating torque under the action of the external field.
An alternating voltage V is applied by a power supply, thereby forming an alternating electric field E between the first electrode plate 11 and the second electrode plate 12. The power supply is an alternating power supply, and the power supply voltage is high voltage V1And a low voltage V2Alternating periodically varying square wave voltages. Referring to FIG. 3, the alternating electric field is a high electric field E1And low electric field E2Alternating periodically varying square-wave electric field, wherein E2＜E0＜E1，E0Critical electric field, E0The electric field intensity of part of the particles (most of the particles, such as 75-90%) in continuous motion is high, and the colloid particles are under high electric field E1Lower continuous motion, colloidal particles under low electric field E2At rest, the relationship between the supply voltage V and the alternating electric field is:
V1＝E1*H，V2＝E2*H；
wherein H is the distance between the first electrode plate and the second electrode plate.
Preferably, the critical electric field in this embodiment is E01.43 v/. mu.m, high electric field E11.98 v/. mu.m, low electric field E20.64v/μm, the frequency f of the alternating electric field is 10Hz, corresponding to a period of 0.1 s.
The distance H between the first electrode plate and the second electrode plate was 60 μm, and thus, according to the formula V1＝E1*H、V2＝E2H can obtain the magnitude of the corresponding power supply voltage V as V1＝118.8v，V2＝38.4v。
Low electric field E in the invention2Is only required to ensure that the electric field is obviously lower than the critical electric field E0That is, the specific value thereof has no influence on the result, but the high electric field E1The value of (a) is the key of the invention. When the electric field intensity is higher than the critical electric field E0When the electric field intensity is lower than the critical electric field E, the colloid particles can move continuously0When the colloidal particles are at rest.
And observing the experimental phenomenon by using an inverted optical microscope after the electric field is started, and recording the experimental phenomenon by using a high-speed imaging camera. The motion mechanism of the balls in the system is based on Quincke rotation. Referring to fig. 4, colloidal particles suspended in a diluent are polarized in opposite directions under a constant external electric field to form an electric dipole moment in parallel with the direction of the electric field, and the electric dipole moment deviates from the direction of the external electric field due to thermal vibration of the colloidal particles. At this time, the surface charges of the colloidal particles themselves and the charges accumulated in the solution near the surface of the colloidal particles are redistributed, and once the polarization state is restored to the equilibrium state, the electric dipole moment has an instantaneous in-plane polarization component perpendicular to the external electric field within a limited time of the redistribution of the charges. The interaction of the electric field and the in-plane polarization component forms a rotation moment to drive the colloid particles to rotate.
The following is a detailed description of the characteristics of the self-assembled lattice structure of the colloidal particles in this example.
1. By applying a periodic alternating electric field between the two electrode plates, the colloidal particles can spontaneously form a disordered to ordered structure transition.
Referring to FIG. 5a, initially, the colloidal particles are uniformly and randomly dispersed in the system;
when an alternating electric field is applied, the local density of the colloidal particles in the system will rapidly fluctuate, as shown in fig. 5b, and after several cycles, the colloidal particles show a reciprocating behavior pattern of "aggregation-divergence" and have formed prototypes of the mesh structure in a partial region;
after a certain time evolution, an ordered spatial regular structure will appear in the final system as shown in fig. 5 c.
2. By applying a periodic alternating electric field between the two electrode plates, the structure formed by the colloidal particles is a dynamic, oscillating, self-assembled structure.
A series of dynamic changes of the mesh structure in the steady state is shown with reference to fig. 6.
High electric field E11.98 v/. mu.m, low electric field E2The frequency can form a stable grid structure under the condition of f being 1-20Hz under the electric field intensity of 0.64 v/mum and H being 60-65 μm, and the assembly results are shown in the embodiment when the frequency is 60 μm and f is 10 Hz.
By applying an alternating electric field, the colloidal particles will eventually show an ordered spatially regular structure as shown in fig. 6a, over a period of time;
because the electric field intensity of the alternating electric field is periodically changed, when the field intensity of the alternating electric field is higher than the critical electric field, the colloid particles move from the high-density area to the low-density area, and when the electric field intensity is lower than the critical electric field, the colloid particles start to decelerate, and the middle structure is shown in fig. 6 b;
finally, when the colloidal particles were at rest, an ordered spatially regular structure was observed as shown in fig. 6 c.
Comparing the particle distributions in fig. 6a and 6c, it is found that the high-density region and the low-density region of the grid structure alternate with each other (exchange positions) every time a period passes, and the structure is dynamically oscillated, and the structure is switched between fig. 6a and 6 c.
3. By applying a periodic alternating electric field between the two electrode plates, the resulting structure is a real-time controllable stable dynamic ordered self-assembled structure.
FIG. 7a shows a high electric field E1A stable grid structure is formed when the frequency f is 12Hz at 1.98v/μm, D in the figure indicates the average size of clusters in the grid, and L indicates the average distance between clusters.
By calculating the spatial correlation function of the direction of the velocity of the colloidal particles, both the average size D of the clusters in the grid and the average distance L between clusters decrease with increasing frequency, as shown in fig. 7 b. However, when this is converted into a relationship with the period T, it is found that both the average size of clusters in the grid and the average distance between clusters are linearly related to the period T, i.e., the time of the colloidal particle movement, as shown in fig. 7 c.
In addition, the average size D of clusters in the grid and the average distance L between clusters are linearly related to the electric field intensity, which indicates that the moving distance of colloidal particles in a single period changes, resulting in the change of the grid size. L, D, the dependence on electric field and frequency is theoretically constrained by the local density of the particles and the average distance S the particles move during a cycle. Under the condition of conservation of population, the following relations are satisfied by the several parameters:
wherein the content of the first and second substances,
and
the average colloid particle density when colloid particles are initially uniformly distributed and the average colloid particle density in a D range in a stable grid structure are respectively shown, S is the average distance of colloid particle movement in a period T, S is vT/2, v is the average movement speed of colloid particles, and theoretically v is determined by the electric field intensity,
in this embodiment, the non-equilibrium self-assembly method based on a self-driven colloid system specifically includes:
s1, encapsulating colloid particles and diluent in a closed space between the first electrode plate and the second electrode plate;
and S2, applying an alternating electric field to the first electrode plate and the second electrode plate, and carrying out unbalanced automatic assembly on the colloid particles in the closed space.
The process and features of the non-equilibrium automatic assembly of colloidal particles in a closed space are discussed in detail above, and are not further described herein.
According to the technical scheme, the invention has the following beneficial effects:
the invention combines the self-driving system and the periodic driving force, can realize the non-equilibrium self-assembly of the self-driving colloid system, generates a time-space self-assembly structure with the coexistence of space periodicity and time periodicity, and has higher controllability and dynamic adaptability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The utility model provides a non-equilibrium self-assembly system based on self-driven colloid system, its characterized in that, non-equilibrium self-assembly system is including relative first plate electrode and the second plate electrode that sets up, encapsulation in the baffle between first plate electrode and second plate electrode, and the power of electric connection between first plate electrode and second plate electrode, be formed with the confined space that is used for acceping colloidal particles and diluent between first plate electrode, second plate electrode and the baffle, the power is used for applying the alternating electric field to first plate electrode and second plate electrode, under the alternating electric field that the power was applied colloidal particles carries out non-equilibrium automatic assembly in the confined space.
2. The self-propelled colloidal system based unbalanced self-assembly system of claim 1, wherein the colloidal particles have a density greater than a density of the diluent, a viscosity coefficient of the diluent is greater than or equal to a predetermined threshold, and a conductivity of the diluent is greater than a conductivity of the colloidal particles.
3. The self-driven colloid system-based nonequilibrium self-assembly system as claimed in claim 2, wherein the colloid particles are polystyrene non-conductive pellets and the diluent is a mixed solution of docusate sodium and n-hexadecane.
4. The self-propelled colloidal system-based non-equilibrium self-assembly system of claim 1, wherein the alternating electric field is a high electric field E1And low electric field E2Alternating periodically varying square-wave electric field, wherein E2＜E0＜E1，E0Critical electric field, E0The colloidal particles are subjected to a high electric field E for the electric field intensity when part of the particles move continuously1Lower continuous motion, colloidal particles under low electric field E2The lower part is static.
5. The self-propelled colloidal system-based unbalanced self-assembly system of claim 4, wherein the power supply is an alternating power supply and the power supply voltage is a high voltage V1And a low voltage V2Alternating periodically varying square wave voltage, wherein V1＝E1*H，V2＝E2H, H is the distance between the first and second electrode plates.
6. The self-driven colloid system-based unbalanced self-assembly system as claimed in claim 1, wherein the colloid particles move under the alternating electric field in a "converging-diverging" reciprocating motion based on Quincke rotation, and the formed unbalanced self-assembly structure is a dynamic ordered self-assembly grid structure with alternately changing high-density regions and low-density regions.
7. The self-driven colloid system-based nonequilibrium self-assembly system according to claim 1, characterized in that the average size D of clusters and the average distance L between clusters in the dynamically ordered self-assembled lattice structure are linear with the period T, and satisfy:
wherein the content of the first and second substances,
and
the average colloidal particle density when the colloidal particles are initially uniformly distributed and the average colloidal particle density in the range of D in the stable grid structure are respectively shown, S is the average distance of the colloidal particles moving in one period T, S is vT/2, and v is the average moving speed of the colloidal particles.
8. A non-equilibrium self-assembly method based on a self-driven colloid system is characterized by comprising the following steps:
s1, encapsulating colloid particles and diluent in a closed space between the first electrode plate and the second electrode plate;
and S2, applying an alternating electric field to the first electrode plate and the second electrode plate, and carrying out unbalanced automatic assembly on the colloid particles in the closed space.
9. The method for non-equilibrium self-assembly based on self-driven colloid system according to claim 8, wherein the step S2 is to perform non-equilibrium self-assembly of colloid particles in the enclosed space specifically as follows:
the motion of colloid particles under an alternating electric field is 'gathering-diverging' reciprocating motion based on Quincke rotation, and the formed non-equilibrium automatic assembly structure is a dynamic ordered self-assembly grid structure with alternately changed high-density areas and low-density areas.
10. The method according to claim 9, wherein the average size D of clusters and the average distance L between clusters in the dynamically ordered self-assembled lattice structure are linear with the period T, and satisfy:
wherein the content of the first and second substances,
and
the average colloidal particle density when the colloidal particles are initially uniformly distributed and the average colloidal particle density in the range of D in the stable grid structure are respectively shown, S is the average distance of the colloidal particles moving in one period T, S is vT/2, and v is the average moving speed of the colloidal particles.
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