CN110018086B - Device and method for quantitatively measuring hysteresis force between solid surface and bubbles or liquid drops - Google Patents
Device and method for quantitatively measuring hysteresis force between solid surface and bubbles or liquid drops Download PDFInfo
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- CN110018086B CN110018086B CN201910395182.XA CN201910395182A CN110018086B CN 110018086 B CN110018086 B CN 110018086B CN 201910395182 A CN201910395182 A CN 201910395182A CN 110018086 B CN110018086 B CN 110018086B
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Abstract
The invention belongs to the field of physical and chemical measuring instruments, and particularly relates to a device and a method for quantitatively measuring hysteresis force between a solid surface and bubbles or liquid drops. The device comprises a fixed sample table, a camera, a light source, a sample injector, a sleeve actuating device and a push rod actuating device. Wherein the sample injector is in the form of an injector and comprises a sleeve, a needle communicated with the sleeve and a piston push rod inserted into the sleeve; the needle head is a bent needle head or a straight needle head; the center of the lens of the camera, the center of the light source and the center of the position of the sample table for placing the sample are arranged on the same straight line. The method calculates the hysteresis force between the solid surface and the bubbles for the first time, and solves the problem that the prior experimental operation is difficult to accurately and quantitatively measure. The device is simple and convenient to operate, high in accuracy, free of being coupled to more software instruments, more universal and easy to popularize.
Description
Technical Field
The invention belongs to the field of physical and chemical measuring instruments, and particularly relates to a device and a method for quantitatively measuring hysteresis force between a solid surface and bubbles or liquid drops.
Background
The gas-liquid-solid three-phase interface relates to the design of an interface structure and the research of the behavior of gas and liquid on the solid interface, and is widely applied to various fields, such as the fields of chemical three-phase mass transfer, photoelectrocatalysis, environmental protection and the like. The wettability of the three-phase interface has an important influence on the adhesion behavior of gases and liquids to solid surfaces, and the research on the wettability of the interface has not been paid attention in recent years, particularly on the behavior of bubbles adhering to solid interfaces underwater, whether based on industrial applications or basic research. For example, in some electrochemical reactions involving gas participation, the active sites of the electrode catalyst are blocked due to the massive adhesion of bubbles at the electrode interface, and the effective transmission and diffusion of the electrolyte at the electrode interface are inhibited, resulting in a significant reduction in reaction efficiency. In the environmental field, the emission of toxic gases in industry seriously pollutes the quality of air and water sources, and when the toxic gases are collected and waste water is treated in a foam flotation mode, the problem that the adhesion between bubbles and a solid interface is good or bad is often faced, which is related to whether the environmental pollution can be effectively treated. In addition, the study of the adhesion behavior of liquid droplets to solid surfaces is of practical value in various fields, for example, the study of the application effect of agricultural chemicals and the field of production of hydrophobic films.
However, achieving effective peeling of bubbles or liquid droplets adhered to the solid interface or rapid adhesion and collection of bubbles or liquid droplets on the solid interface often requires a clear judgment on the wettability of the interface and a deep understanding of the adhering behavior of the bubbles or liquid droplets. The contact angle is an important basic element for measuring the wettability of the interface, and the hydrophilicity and the hydrophobicity of the interface can be defined. However, the apparent contact angle, which is a measure of interfacial wettability, tends to randomly sit between the advancing and receding contact angles, leading to uncertainty in the assessment of interfacial wettability, and the problem of accurately characterizing interfacial wettability has not been solved. Besides, accurate assessment of the wettability of the solid interface is achieved, the adhesion behavior of gas and liquid on the solid interface is deeply understood, and the design and other problems of the three-phase interface can be effectively guided. For example, in some gas-consuming reactions, the attachment of bubbles to the solid surface is a prerequisite for the reaction, and the solid surface is usually subjected to affinity gasification treatment, but the problem of what degree of affinity gasification treatment is most beneficial for the reaction and the highest efficiency has not been answered. Therefore, if the adhesion force between the solid and the bubble or the liquid drop can be quantitatively represented, the problems of reasonable interface wettability modification degree, interface wettability design and the like can be solved.
The field of interfacial chemistry, generally utilizes hysteresis forces to represent the adhesive forces between a solid and a bubble or droplet. The hysteresis force is defined as the force generated on the three-phase contact interface to resist the relative motion when the three-phase contact interface generates the relative motion or has the tendency of generating the relative motion. The traditional method for measuring the hysteresis force between a liquid drop and a solid interface is to drop the liquid drop on the solid interface, insert a capillary into the liquid drop, move the solid at a constant speed until the capillary is just moved out of the liquid drop interface, record the position deviation of the capillary, and measure the hysteresis force. However, the capillary method for measuring the hysteresis force between the liquid droplet and the solid interface is influenced by the factors such as the gravity, viscosity, and moving speed of the solid interface of the liquid droplet, and it is very difficult to measure the hysteresis force between the liquid droplet and the solid interface by the capillary method due to the difference between the nature of the liquid droplet and the gas bubble and the difference between the surrounding environments (liquid around the gas bubble and air around the liquid droplet). Therefore, how to measure the retardation force between the bubble and the solid surface is a problem to be solved in the art.
The invention creatively provides a device and a method for quantitatively measuring the hysteresis force between the surface of a solid and bubbles. Similarly, the device and the method are also suitable for quantitatively measuring the hysteresis force between the solid surface and the liquid drop, are more accurate than the prior capillary method, and avoid the defects of high instrument cost, complex operation, large system error and the like.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide an apparatus and method for quantitatively measuring a retardation force between a solid surface and bubbles or droplets.
The purpose of the invention is realized by the following technical scheme:
in a first aspect the present invention discloses an apparatus for quantitative determination of the force of hysteresis between a solid surface and a gas bubble or liquid droplet, said apparatus comprising:
a fixed sample stage, a camera, a light source, a sample injector, a sleeve actuating device, a push rod actuating device,
wherein the sample injector is in the form of an injector and comprises a sleeve, a needle communicated with the sleeve and a piston push rod inserted into the sleeve; the needle head is a bent needle head or a straight needle head; the center of the lens of the camera, the center of the light source and the center of the position on the sample platform for placing the sample are arranged on the same straight line;
the cartridge actuation device is capable of controlling the distance between the injector needle end and the sample stage;
the push rod actuator is capable of controlling the amount of gas or liquid droplet extrusion in the injector.
Preferably, when the retardation force between the solid surface and the bubble is measured, the sample stage is a transparent quartz cylinder filled with a liquid, and the needle of the sample injector enters the transparent quartz cylinder, that is, the position of the sample stage where the sample is placed is exposed to the liquid.
Preferably, when the hysteresis force between the solid surface and the liquid drop is measured, the sample stage is a transparent quartz cylinder filled with gas, and the needle of the sample injector enters the transparent quartz cylinder, namely, the position of the sample stage where the sample is placed is exposed to the gas.
Preferably, the position on the sample stage where the sample is placed is exposed to air when measuring the hysteresis force between the solid surface and the liquid droplet.
Preferably, the injector is a microsyringe.
Preferably, the straight needle is used for determining the hysteresis force between the solid surface and the liquid drop,
the curved needle is used to determine the hysteresis force between the solid surface and the gas bubble.
The invention discloses a method for quantitatively determining the hysteresis force between a solid surface and bubbles or liquid drops in a second aspect, which is measured by the device of the first aspect and comprises the following steps:
(1) fixing a solid sample on the sample table, adjusting the position of a needle of the sample injector to plant a certain volume of bubbles or liquid drops on the surface to be measured of the solid sample, and keeping the needle of the sample injector inserted into the bubbles or liquid drops;
adjusting the push rod actuating device to drive a piston push rod of the sample injector to continuously increase the volume of the bubbles or the liquid drops in situ until a gas-liquid-solid three-phase contact line changes, recording the size change of the bubbles or the liquid drops by the camera, and measuring an advancing contact angle theta of the bubbles or the liquid dropsa；
Wherein the advancing contact angle thetaaThe included angle between the gas-liquid interface and the solid-gas interface of the increased bubble at the three-phase contact point is defined; or the included angle between the gas-liquid interface and the solid-liquid interface of the increased liquid drop at the three-phase contact point is defined;
then calibrating the size of the contact angle by using contact angle measurement software; adjusting the push rod actuating device to drive the piston push rod of the sample injector to continuously reduce the volume of the bubbles or the liquid drops in situ until the three-phase contact line changes, recording the size change of the bubbles or the liquid drops by the camera, and measuring the receding contact angle theta of the bubbles or the liquid dropsr；
Wherein the receding contact angle θrThe included angle between the gas-liquid interface and the solid-gas interface of the reduced bubble at the three-phase contact point is defined; or the included angle between the gas-liquid interface and the solid-liquid interface of the reduced liquid drop at the three-phase contact point is defined;
then calibrating the size of the contact angle by using contact angle measurement software;
(2) according to the formula
Calculating the forward retardation force f between the surface of the solid sample and the gas bubble or liquid dropleta；
According to the formula
Calculating the receding hysteresis force f between the surface of the solid sample and the bubble or dropletr；
Wherein the content of the first and second substances,
θifor ideal contact angle, thetai＝(θa+θr)/2，
The retardation angle is an average value of the difference between the advancing contact angle and the receding contact angle of a droplet or a bubble(θa-θr)/2；
γlgIs liquid-gas surface tension; is a known amount, which is known from experimental conditions;
the forward hysteresis force faOr receding hysteresis force frIs the hysteresis force between the solid surface and the bubble or droplet.
Preferably, in step (1), the first volume is a value in the range of 0.5u L-5 u L.
Preferably, in the step (1), when a certain volume of bubbles is planted on the surface to be measured of the solid sample, the surface to be measured of the solid sample faces upwards or downwards.
Preferably, in the step (1), when a liquid drop of a certain volume is planted on the surface to be measured of the solid sample, the surface to be measured of the solid sample faces upwards.
Wherein the forward retarding force f may be setaThe receding hysteresis force frThe retardation angle and the ideal contact angle thetaiBinding assays the degree of adhesion between the solid surface and the gas bubbles or liquid droplets.
The principle of the invention is as follows:
take example 4 and FIG. 4 as an example.
As shown in FIG. 4b, ideally, the bubble is in equilibrium, and the Young's equation γ is satisfiedlgcosθi+γgs＝γls. Wherein, γlgIs liquid-gas surface tension, gammagsIs gas-solid surface tension, gammalsIs the liquid-solid surface tension. This equation determines the unique ideal contact angle θi。
However, in most cases in reality, the bubbles pinned to the solid surface are always in a metastable state and the classical young's equation is no longer applicable. Therefore, in order to balance the state of the force balance which is destroyed by the change of the contact angle caused by the advance and retreat of the bubble, a force must be applied between the solid surface and the bubble at the three-phase contact point, parallel to the solid surface, i.e., a hysteresis force, which can also be understood as a frictional force.
The angle produced by the advancing process, as shown in fig. 4a and 4cDefined as advancing contact angle thetaaAnd the additional force is called the forward hysteresis force faNew equilibrium expression is gammalgcosθa+γgs+fa＝γls；
The angle produced by the receding process is defined as the receding contact angle θrAnd the additional force is called the receding hysteresis force frNew equilibrium expression is gammalgcosθr+γgs＝γls+fr。
For bubbles pinned to the surface of a real solid, we redefine the ideal contact angle as the average of the sum of the advancing and receding contact angles of the bubble, i.e., θi＝(θa+θr)/2. The retardation angle is an average value representing the difference between the advancing contact angle and the receding contact angle of a droplet or a bubble, and is (θ)a-θr)/2. Brought into the above balance, and further, the forward hysteresis force is expressed as
The force of receding hysteresis is expressed as
The invention has the following beneficial effects:
(1) the device for quantitatively measuring the hysteresis force between the solid surface and the bubbles or the liquid drops is creatively designed, is simple and convenient to operate, has high accuracy, does not need to be coupled to more software instruments, has higher universality and is easy to popularize.
(2) The invention accurately redefines an ideal contact angle and measures the ideal contact angle, the advancing contact angle, the rear leg contact angle and the lag angle. And the hysteresis force between the solid surface and the bubbles is calculated for the first time, so that the problem that the prior experimental operation is difficult to accurately and quantitatively measure is solved.
(3) The device and the method are also suitable for quantitatively measuring the hysteresis force between the solid surface and the liquid drop, are more accurate than the prior capillary method, and avoid the defects of high instrument cost, complex operation, large system error and the like.
(4) The method can combine a plurality of information of forward hysteresis force, backward hysteresis force, hysteresis angle and ideal contact angle to comprehensively represent the adhesion degree between the solid surface and the bubbles or liquid drops, and has high accuracy. Therefore, the theoretical basis of the problems of reasonable interface wettability modification degree, interface wettability design and the like can be provided aiming at some special reactions, such as gas consumption reaction.
(5) The device utilizes the sleeve actuating device to accurately control the distance between the end part of the syringe needle of the sample injector and the sample platform, utilizes the push rod actuating device to accurately control the amount of gas or liquid drop extruded, utilizes the same bubble or liquid drop to measure an advancing contact angle and a retreating contact angle through in-situ expansion and reduction, and calculates the hysteresis force, rather than the method of causing the liquid drop and the solid surface to generate relative displacement in the prior art to measure the hysteresis force, reduces moving parts, is easy to operate, greatly improves the accuracy of the experiment, and reduces the experiment error.
(6) The method has wide application range, and the problem related to the interface wettability characterization can be solved.
Drawings
FIG. 1 is a schematic diagram showing the detailed structure of the apparatus (with sample) for quantitatively determining the hysteresis force between the solid surface and the liquid droplet in example 2.
FIG. 2 is a schematic diagram showing the structure of the apparatus (with sample) for quantitatively determining the retardation force between the surface of the solid and the gas bubble in example 3.
FIG. 3 is a schematic diagram showing the structure of another design of the apparatus (with sample) for quantitatively determining the retardation force between the solid surface and the gas bubble in example 3.
FIG. 4 is a force analysis diagram of the bubble advancing in a), b) ideal state, and c) retreating process for a certain experiment of example 4. Wherein, γlgIs liquid-gas surface tension, gammagsIs gas-solid surface tension, gammalsIs the liquid-solid surface tension.
FIG. 5 shows the results of example 6 for planting on a solid surface of the same wettabilityI.e. advancing contact angle theta of the bubble on the substrate 6#, isaReceding contact Angle θrIdeal contact angle thetaiAnd apparent contact angle θtAnd (4) counting.
FIG. 6 shows the advancing contact angle θ of the bubbles planted on the same wetting solid surface, i.e., the substrate 6# in example 6aReceding contact Angle θrIdeal contact angle thetaiAnd apparent contact angle θtIs calculated (standard deviation is calculated based on the data of fig. 2).
FIG. 7 is a graph showing the relationship among the ideal contact angle, the retardation angle and the advancing retardation force of the bubbles planted on the solid surfaces with different wettability, namely substrates 1# -10# in the example 6, wherein the substrates used from left to right are substrates 1# -10# in sequence.
FIG. 8 is a graph showing the relationship among the ideal contact angle, retardation angle and receding retardation force of the bubbles planted on the substrates 1# -10# with different wettability of the solid surface in example 6, wherein the substrates used from left to right are substrates 1# -10# in sequence.
FIG. 9 is a graph showing the relationship among the ideal contact angle, the retardation angle and the advancing retardation force of a liquid drop planted on a solid surface with different wettability, namely a substrate 9# -1# in the example 8, wherein the substrate used from left to right is the substrate 9# -1# in sequence.
FIG. 10 is a graph showing the relationship among the ideal contact angle, retardation angle and receding retardation force of a droplet planted on a solid surface of different wettability, i.e., a substrate No. 9-1 # in the example 8, wherein the substrate used from left to right is the substrate No. 9-1 # in the figure.
List of reference numerals:
1. a fixed sample stage; 2. a camera; 3. a light source; 4. a microsyringe; 5. a fixed block; 6. a holder; 7. a slider; 8. a sliding table; 9. a first guide rail; 10. a first knob; 11. a second guide rail; 12. a second knob; 13. a support; 14. a base; 15. a solid sample; 16. a quartz cylinder cover; 17. and a through hole.
Detailed Description
The invention is further illustrated by the following detailed description.
Example 1
The preparation of smooth substrates with different wettability comprises the following steps:
(1) first, before depositing a metal layer, a silicon wafer, a cadmium rod (purity 99.99%) and gold particles (purity 99.999%) were ultrasonically cleaned with ethanol and deionized water, respectively, for 10 minutes, and used as raw materials. Then, a 5nm thick cadmium layer was deposited as an adhesion layer on the silicon wafer by vacuum sputtering, followed by sputter deposition of a 50nm thick gold film.
(2) Preparing a series of hexadecyl mercaptan solutions with different concentrations (3 mol/L, 2 mol/L, 1 mol/L, 0.5 mol/L, 0.1 mol/L, 0.01 mol/L, 0.001 mol/L, 0.0001 mol/L, 0 mol/L and 0 mol/L), soaking the silicon wafer deposited with the cadmium layer and the gold film prepared in the step (1) in the hexadecyl mercaptan solutions with different concentrations for 1 hour respectively, taking out the silicon wafer, performing vacuum drying at 30 ℃ to obtain smooth substrates with different wettability treatments, wherein the smooth substrates are named as a substrate # 1, a substrate # 2, a substrate # 3, a substrate # 4, a substrate 5, a substrate # 6, a substrate # 7, a substrate # 8, a substrate # 9 and a substrate # 9A # in sequence, and then treating the substrate # 9A for 5 minutes to obtain the gas-repellent substrate # 10.
The above substrates 1# -10# (excluding 9A) each represent 10 substrates of different wettability, and were used as solid samples in the following examples, and the side of the solid sample on which the cadmium layer and the gold film were deposited was used as the surface to be measured.
Example 2
FIG. 1 is a detailed block diagram of an apparatus for quantitatively determining the hysteresis force between a solid surface and a liquid droplet, the apparatus comprising:
the device comprises a fixed sample table 1, a camera 2, a light source 3, a microsyringe 4, a holder 6, a fixed block 5, a sliding block 7, a sliding table 8, a first guide rail 9, a first knob 10, a second guide rail 11 and a second knob 12; a support 13, a base 14;
the needle head of the sample injector 4 is a straight needle head, the center of the lens of the camera 2, the center of the light source 3 and the center of the position on the sample table 1 for placing the sample are arranged on the same straight line, and the end part of the needle head of the micro sample injector 4 is arranged right above the sample table 1; the micro sample injector 4 is in an injector form and is provided with a sleeve, a needle communicated with the sleeve and a piston push rod inserted into the sleeve;
the micro sample injector 4 is fixed on the fixing block 5, and the fixing block 5 is fixed on the sliding table 8; the sliding table 8 can move up and down along the first guide rail 9 by rotating the first knob 10, so that the fixed block 5 and the microsyringe 4 are driven to move up and down, namely, the distance between the needle end of the microsyringe 4 and the sample table 1 is controlled; the piston push rod of microsyringe 4 with holder 6 is together fixed, holder 6 is fixed on slider 7, second guide rail 11 is fixed on the slip table 8, rotates second knob 12 can make slider 7 is followed second guide rail 11 reciprocates, thereby drives holder 6 reaches the piston push rod of microsyringe 4 reciprocates to the volume that the control liquid drop was extruded, camera 2 the light source 3 with sample platform 1 is fixed on base 14, first guide rail 9 is fixed on support 13, support 13 is fixed on base 14.
It is clear that the sleeve actuator and the push rod actuator can also have other designs as long as the movement of the sleeve and the push rod is controlled.
Example 3
An apparatus for quantitatively determining the force of hysteresis between a solid surface and a gas bubble, as illustrated in fig. 2, with the following differences from fig. 1:
the syringe needle of the microsyringe 4 is a bent syringe needle, the sample table 1 is a transparent quartz cylinder which is covered with a quartz cylinder cover 16 and is filled with water, a through hole 17 is arranged on the quartz cylinder cover 16, and the bent syringe needle of the microsyringe 4 penetrates through the through hole 17 to enable the end part to be positioned under the quartz cylinder cover 16. When the measurement is performed, the solid sample 15 is fixed below the quartz cylinder head 16 and above the bent needle of the micro-injector 4 by a holding structure, and the surface to be measured of the solid sample 15 faces downward. Thus, this device is for measuring the hysteresis force between the submerged solid surface and the gas bubble, wherein the clamping structure is omitted in fig. 2 and not shown.
Obviously, there may be other designs for the sample stage 1 and the substrate 6#, for example, as shown in fig. 3, the sample stage 1 is a transparent quartz cylinder filled with water, the substrate 6# is fixed below the cylinder bottom of the quartz cylinder and the straight needle of the microsyringe 4, and the surface to be measured of the substrate 6# faces upward.
Example 4
A method for quantifying the hysteresis force between a solid surface and a gas bubble, using the device of fig. 2, comprising the steps of:
(1) fixing a substrate 6# on the sample table 1 to be positioned right above a bent needle of the microsyringe 4, enabling the surface to be measured of the substrate 6# to face downwards, planting a bubble of 4u L on the surface to be measured of the solid sample 15 through the microsyringe 4, enabling the needle to remain in the bubble, recording the size of the bubble by a camera 2, and then automatically calibrating the apparent contact angle theta of the bubble by using contact angle measurement softwaret；
The second knob 12 is rotated to drive the microsyringe 4 to continuously increase the volume of the bubbles in situ until the three-phase contact line changes, the camera 2 records the size change of the bubbles, and then contact angle measurement software is used for calibrating the advancing contact angle thetaa；
The second knob 12 is rotated reversely to drive the microsyringe 4 to continuously reduce the volume of the bubbles in situ until the three-phase contact line changes, the camera 2 records the size change of the bubbles or liquid drops, and then contact angle measurement software is used for automatically calibrating the receding contact angle theta of the microsyringe 4r。
The sample table 1 is a transparent quartz cylinder which is covered with a quartz cylinder cover 16 and filled with water, and a substrate 6# is fixed below the quartz cylinder cover 16 and above a bent needle of the micro-sampler 4 through a clamping structure.
(2) According to the formula
Calculating the forward hysteresis force f between the substrate No. 6 underwater surface and the bubblea；
According to the formula
Calculating the receding hysteresis force f between the substrate No. 6 underwater surface and the bubbler；
Wherein the content of the first and second substances,
θifor ideal contact angle, thetai＝(θa+θr) Accurately characterizing the wettability of the interface;
the retardation angle means an average value of the difference between the advancing contact angle and the receding contact angle of the bubble, i.e., (θ)a-θr)/2；
γlgIs the surface tension of water vapor; gamma raylg＝72mN/m；
Then, the forward hysteresis force faOr receding hysteresis force frIs the hysteresis force between the solid surface and the gas bubbles.
Example 5
A method for quantifying the hysteresis force between a solid surface and a liquid droplet, using the device of fig. 1, comprising the steps of:
(1) respectively fixing substrates 9# -1# on the sample table 1 to be positioned under the straight needle of the microsyringe 4, enabling the surface to be measured of the substrates to face upwards, planting a 2u L water drop on the surface to be measured of the solid sample 15 through the microsyringe 4, exposing the water drop in the air, recording the size of the water drop by a camera 2, and then automatically calibrating the apparent contact angle theta by using contact angle measurement softwaret；
The second knob 12 is rotated to drive the microsyringe 4 to continuously increase the volume of the liquid drop in situ until the three-phase contact line changes, the camera 2 records the size change of the water drop, and then contact angle measurement software is used for calibrating the advancing contact angle thetaa；
The second knob 12 is rotated reversely to drive the microsyringe 4 to continuously reduce the volume of the liquid drop in situ until the three-phase contact line changes, the camera 2 records the size change of the liquid drop, and then contact angle measurement software is used for automatically calibrating the receding contact angle theta of the liquid dropr。
(2) According to the formula
Calculating the forward hysteresis force f between the substrate surface and the dropleta。
According to the formula
Calculating the receding hysteresis force f between the substrate surface and the dropletr。
Wherein the content of the first and second substances,
θifor ideal contact angle, thetai＝(θa+θr) Accurately characterizing the wettability of the interface;
the retardation angle means an average value of the difference between the advancing contact angle and the receding contact angle of the droplet, and is (θ)a-θr)/2；
γlgIs the surface tension of water vapor; gamma raylg＝72mN/m；
Then, the forward hysteresis force faOr receding hysteresis force frIs the hysteresis force between the solid surface and the liquid droplet.
Example 6
Verifying the evaluation accuracy of the interface wettability by using the ideal contact angle defined by the invention:
the experiment described in example 4 was performed using the substrate # 6 prepared in example 1 as a solid sample, and 13 times of repetition, the advancing contact angle θ of the bubbles on the solid surface was counted and calculatedaReceding contact Angle θrIdeal contact angle thetaiAnd apparent contact angle θtSee fig. 5. It can be seen that the bubble advancing contact angle θaThe value is 110-rThe value is 75-85 DEG, apparent contact angle thetatThe value is 90-110 deg..
At the same time, the advancing contact angle θ for the above-mentioned bubble is calculatedaReceding contact Angle θrIdeal contact angle thetaiAnd apparent contact angle θtSee fig. 6 (amplitude i.e. standard deviation calculated based on the data of fig. 5).
And (4) conclusion:
fig. 5 and 6 show that by measuring and comparing the advancing contact angle, receding contact angle, ideal contact angle and apparent contact angle of bubbles planted on the same wetting solid surface, it can be found that the standard deviation of the ideal contact angle, i.e., the amplitude of deviation from the mean value, is minimal, i.e., the evaluation of the interface wettability is most accurate using the ideal contact angle defined in the present invention.
Example 7
The degree of adhesion between the solid surface and the gas bubbles is accurately characterized by using a combination of forward hysteresis force, backward hysteresis force, hysteresis angle and ideal contact angle:
the experiment described in example 4 was repeated using substrates # 1 to # 10 having different wettability in example 1 as solid samples, respectively, and forward hysteresis force, backward hysteresis force, hysteresis angle and ideal contact angle were calculated to obtain a graph 7 of the relationship among ideal contact angle, hysteresis angle and forward hysteresis force of bubbles planted on the surfaces of the solid having different wettability and a graph 8 of the relationship among ideal contact angle, hysteresis angle and backward hysteresis force of bubbles planted on the surfaces of the solid having different wettability. In fig. 7 and 8, the bases used from left to right are bases 1# -10 #.
And (4) conclusion:
fig. 7 and 8 show that when the ideal contact angle is close to 90 °, the hysteresis angle of the bubbles and the hysteresis force between the bubbles and the solid surface both show a maximum value, and the super-adhesion state of the bubbles on the solid surface is realized. Therefore, for some gas consumption reactions, the design of the interface wettability can be effectively guided.
Example 8
The degree of adhesion between the solid surface and the liquid drop is accurately characterized by using a combination of forward hysteresis force, backward hysteresis force, hysteresis angle and ideal contact angle:
the experiment described in example 5 was repeated using substrates 9# -1# having different wettability in example 1 as solid samples, respectively, to calculate the advancing retardation force, the receding retardation force, the retardation angle, and the ideal contact angle, and to obtain a graph 9 of the relationship among the ideal contact angle, the retardation angle, and the advancing retardation force for a liquid droplet planted on a surface of a solid having different wettability and a graph 10 of the relationship among the ideal contact angle, the retardation angle, and the receding retardation force for a liquid droplet planted on a surface of a solid having different wettability. In fig. 9 and 10, the bases used from left to right are bases 9# -1 #.
And (4) conclusion:
fig. 9 and 10 show that when the ideal contact angle is close to 90 °, the hysteresis angle of the liquid drop and the hysteresis force between the liquid drop and the solid surface both show a maximum value, namely, the super-adhesion state of the liquid drop on the solid surface is realized.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A method for quantifying the hysteresis force between a solid surface and a gas bubble or a liquid droplet, characterized in that it is measured with a device comprising:
a fixed sample stage, a camera, a light source, a sample injector, a sleeve actuating device, a push rod actuating device,
wherein the sample injector is in the form of an injector and comprises a sleeve, a needle communicated with the sleeve and a piston push rod inserted into the sleeve; the needle head is a bent needle head or a straight needle head; the center of the lens of the camera, the center of the light source and the center of the position on the sample platform for placing the sample are arranged on the same straight line;
when the hysteresis force between the solid surface and the bubbles is measured, the sample stage is a transparent quartz cylinder, the transparent quartz cylinder is filled with liquid, and the needle head of the sample injector enters the transparent quartz cylinder;
when the hysteresis force between the solid surface and the liquid drop is measured, the sample stage is a transparent quartz cylinder, the inside of the sample stage is filled with gas, and a needle head of the sample injector enters the transparent quartz cylinder;
the method comprises the following steps:
(1) fixing a solid sample on the sample table, adjusting the position of a needle of the sample injector to plant a certain volume of bubbles or liquid drops on the surface to be measured of the solid sample, and keeping the needle of the sample injector inserted into the bubbles or liquid drops;
adjusting the push rod actuating device to drive a piston push rod of the sample injector to continuously increase the volume of the bubbles or the liquid drops in situ until a gas-liquid-solid three-phase contact line changes, recording the size change of the bubbles or the liquid drops by the camera, and measuring an advancing contact angle theta of the bubbles or the liquid dropsa(ii) a Wherein the advancing contact angle thetaaThe included angle between the gas-liquid interface and the solid-gas interface of the increased bubble at the three-phase contact point is defined; or the included angle between the gas-liquid interface and the solid-liquid interface of the increased liquid drop at the three-phase contact point is defined;
adjusting the push rod actuating device to drive the piston push rod of the sample injector to continuously reduce the volume of the bubbles or the liquid drops in situ until the three-phase contact line changes, recording the size change of the bubbles or the liquid drops by the camera, and measuring the receding contact angle theta of the bubbles or the liquid dropsr(ii) a Wherein the receding contact angle θrThe included angle between the gas-liquid interface and the solid-gas interface of the reduced bubble at the three-phase contact point is defined; or the included angle between the gas-liquid interface and the solid-liquid interface of the reduced liquid drop at the three-phase contact point is defined;
(2) according to the formula
Calculating the forward retardation force f between the surface of the solid sample and the gas bubble or liquid dropleta；
According to the formula
Calculating the receding hysteresis force f between the surface of the solid sample and the bubble or dropletr；
Wherein the content of the first and second substances,
θifor ideal contact angle, thetai＝(θa+θr)/2，
The retardation angle means an average value of the difference between the advancing contact angle and the receding contact angle of a droplet or a bubble, and is (θ)a-θr)/2；
γlgIs liquid-gas surface tension;
the forward hysteresis force faOr receding hysteresis force frIs the hysteresis force between the solid surface and the bubble or droplet.
2. The method of claim 1, wherein in step (1), the certain volume is a value in the range of 0.5u L-5 u L.
3. The method according to claim 1, wherein in step (1), the surface to be measured of the solid sample faces upward or downward while a volume of bubbles is planted on the surface to be measured of the solid sample.
4. The method according to claim 1, wherein in step (1), the surface to be measured of the solid sample faces upward when a volume of the liquid droplet is planted on the surface to be measured of the solid sample.
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