WO2012119274A1 - 表面张力检测装置及方法 - Google Patents

表面张力检测装置及方法 Download PDF

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Publication number
WO2012119274A1
WO2012119274A1 PCT/CN2011/000763 CN2011000763W WO2012119274A1 WO 2012119274 A1 WO2012119274 A1 WO 2012119274A1 CN 2011000763 W CN2011000763 W CN 2011000763W WO 2012119274 A1 WO2012119274 A1 WO 2012119274A1
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Prior art keywords
liquid medium
surface tension
light
tested
light source
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PCT/CN2011/000763
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English (en)
French (fr)
Inventor
蔡利锋
刘克良
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中国人民解放军军事医学科学院毒物药物研究所
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Publication of WO2012119274A1 publication Critical patent/WO2012119274A1/zh

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02Investigating surface tension of liquids
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02Investigating surface tension of liquids
    • G01N2013/0208Investigating surface tension of liquids by measuring contact angle

Definitions

  • the present invention relates to detection techniques, and more particularly to a surface tension detecting apparatus and method. Background technique
  • the interfacial properties of liquids are of great importance in research, technology development and product manufacturing.
  • the surface tension of the liquid and the liquid-solid interfacial tension are the key to understanding the properties of the liquid interface, so the determination of the surface tension is very important.
  • the classical surface tension measurement method can obtain accurate surface tension values, but the measurement is time-consuming and labor-intensive, and the technical requirements for the measurement personnel are also relatively high.
  • the rapid surface tension measurement method developed has been improved in speed, but since the method used is sequence measurement, each measurement requires a long balance time to obtain reliable results.
  • Liquids of different interfacial properties can form different solution surfaces or different liquid column heights in the micropores, a common capillary phenomenon.
  • the surface shape of the solution is determined by the surface tension of the liquid, the surface tension of the solid, the tension of the liquid-solid interface, the gravity and the size and shape of the pores. These relationships can be accurately described by the classical Young's equation and the Laplace equation.
  • the plate pore diameter is close to the capillary size, and the capillary phenomenon becomes remarkable, so that the liquids with different interface properties are different.
  • the radius of curvature of the liquid surface are different spectral detection signal.
  • Patent publication GB2408572A provides another rapid surface tension detection method. This method determines the surface curvature radius of the medium in the micro-hole by capturing the pattern of the preset mode image through the medium in the micro-hole, and by matching the degree of deformation of the comparison image, which has great obstacles in technical implementation. , and accurate quantitative results are not available, and it is difficult to ensure the accuracy and accuracy of surface tension measurement. Summary of the invention
  • the present invention provides a surface tension detecting apparatus comprising:
  • a light source disposed on one side of the sample cell for emitting light to the liquid medium to be tested in the sample cell;
  • a detector having a sensing area disposed on the other side of the sample cell for detecting a position of a light spot projected into the sensing area after the light is transmitted through the liquid medium to be tested in the sample cell;
  • a computing device connected to the detector, configured to calculate a surface curvature radius of the liquid medium to be tested according to the received spot position, and calculate a surface tension of the liquid medium to be tested according to the surface curvature radius.
  • the light emitted by the light source enters the liquid medium to be tested to be refracted at an angle deviating from the normal, and the refracted light returns to the air from the liquid medium to undergo secondary refraction, and the light projected on the detector
  • the position of the point is offset, and the position of the spot after the offset can calculate the surface curvature of the liquid medium according to the principle of refraction of light.
  • the radius of the radius further calculated by the Young's and Laplace equations can be used to calculate the surface tension of the liquid medium. This approach eliminates the need to rely on existing surface tension measurement techniques to calibrate the instrument and enables quantitative detection with high accuracy and accuracy.
  • the sample cell has a hollow structure for causing a significant capillary phenomenon of the liquid medium to be tested, and the bottom of the sample cell is transparent.
  • the surface tension is calculated by virtue of the relationship between the shape of the liquid surface and the associated force, which is based on the capillary phenomenon of the liquid medium in the micropores.
  • the diameter of the sample cell should be as small as a certain size, such as below 7 mm, the influence of gravity begins to retreat, and the capillary phenomenon begins to become significant to ensure the accuracy and accuracy of the calculation.
  • the bottom of the sample cell is transparent, ensuring that light can penetrate the liquid medium onto the detector.
  • the detection pool should have a cylindrical structure.
  • it is not limited to a cylindrical structure, and is also suitable for other suitable structures.
  • the sample cell is a single-well plate or a multi-well array plate.
  • the present invention can employ a single orifice plate as a sample cell, and in order to facilitate high throughput detection, a porous array plate can also be used, which is also coupled with a positioning and stepping mechanism. Continuous scanning of different holes is achieved by connecting the positioning and stepping mechanisms to the porous array plate.
  • the porous array plate is a 96, 394 or 1536-well microplate, and the microplate is further connected with a positioning and stepping mechanism.
  • the disposable array plate can be used with a single-well microplate. Common specifications for microplates include 96, 394 or 1536 wells, with different pore sizes.
  • the light source is disposed vertically above the sample cell, and the light emitted by the light source is vertically incident into the sample cell, and the incident point is offset from the sample center center preset distance.
  • the light incident from the center of the offset sample cell passes through the non-horizontal liquid medium to be tested, it will be offset from the vertical direction.
  • the light re-enters the air it will be further offset from the vertical direction.
  • the detector is an array type photosensitive detector or a digital camera.
  • the light source is a linear light source
  • the computing device includes: a spot offset determining unit, configured to determine a spot offset value according to the received spot position;
  • a first radius of curvature calculation unit configured to calculate a surface curvature radius of the liquid medium to be tested according to the spot offset value
  • a surface tension calculating unit configured to calculate a surface tension of the liquid medium to be tested according to the radius of curvature of the surface.
  • the light beam emitted by the linear light source is relatively thin, and the sensing area projected to the detector can be regarded as a light spot.
  • the light spot offset value can be further determined, and then the light refraction principle is used to calculate The radius of curvature of the surface of the liquid medium to be tested.
  • the light source is a column light source
  • the computing device comprises: a light receiving area determining unit, configured to integrate the light spot emitted by the received column light source in the sensing area to determine a light receiving area;
  • a second radius of curvature calculating unit configured to calculate a surface curvature radius of the liquid medium to be tested according to the light receiving area
  • a surface tension calculating unit configured to calculate a surface tension of the liquid medium to be tested according to the radius of curvature of the surface.
  • the beam emitted by the columnar light source is a beam with a wider diameter. When it is projected into the sensing area, it is actually a large spot. Therefore, the position of the spot is not calculated when calculating, but the beam is split into multiple rays, and then the pair is passed. These rays are integrated at the position of the spot projected by the sensing area of the detector to obtain the area of the spot formed by the spots, and then the corresponding relationship is determined according to the relationship between the light receiving area and the surface curvature derived from the principle of light refraction. The radius of curvature of the surface of the liquid medium to be tested.
  • the light source is a controllable column light source of known light intensity
  • the computing device comprises:
  • the light intensity determining unit is configured to integrate the product of the light spot and the light intensity coefficient of the light emitted by the controllable column light source of the received known light intensity in the sensing area to determine the light Strong
  • a third radius of curvature calculating unit configured to calculate a surface curvature radius of the liquid medium to be tested according to the light intensity
  • a surface tension calculating unit configured to calculate a surface tension of the liquid medium to be tested according to the radius of curvature of the surface.
  • the ratio of the intensity of the refracted light to the incident light intensity is determined by the angle of refraction, and finally determined by the radius of curvature of the surface 'R, which can be calculated by the Fresnel equation. .
  • the intensity coefficient caused by these factors is multiplied and integrated with the spot projected by the detector to obtain the intensity information of the light, and the detector can be the most commonly used light intensity detector. Since the quantitative relationship between the light intensity and the surface curvature of the liquid medium can be established, the quantitative relationship is established by the capillary principle and the surface tension. The method can theoretically determine the surface tension without other technical calibration.
  • the computing device further includes:
  • a critical micelle concentration determining unit configured to record a change curve of a surface curvature radius of the liquid medium to be tested by gradually increasing a surfactant concentration of the liquid medium to be tested, and determine the surface activity according to an inflection point in the change curve
  • the critical micelle concentration of the agent When measuring the surface tension of the liquid medium to be tested, by increasing the surfactant concentration of the liquid medium to be tested, it is found that when a certain concentration is reached, the radius of curvature of the surface will not change significantly, and the concentration is the critical glue of the surfactant. Beam concentration. This method can be used to measure the critical micelle concentration of a high throughput probeless surfactant, the computing device comprising:
  • control unit for issuing control commands to the light source, the sample cell, and/or the detector.
  • the computing device can also issue control commands directly to the source, sample cell, and/or detector.
  • the present invention provides a surface tension detection based on the foregoing
  • the method for detecting the surface tension of the device includes:
  • the light source emits light to the liquid medium to be tested filled in the sample pool
  • the detector detects that the light is transmitted through the liquid medium to be tested in the sample cell and is projected at a spot position of the sensing region;
  • the computing device calculates a surface curvature radius of the liquid medium based on the received spot position and calculates a surface tension of the liquid medium based on the surface radius of curvature.
  • the operation of the light source to emit light to the liquid medium to be tested filled in the sample pool is specifically as follows:
  • the light emitted by the light source into the liquid medium to be tested filled in the sample cell is vertically incident into the sample cell, and the incident point is offset from the center of the sample cell by a predetermined distance.
  • the light source is a linear light source
  • the calculating device calculates a surface curvature radius of the liquid medium according to the received spot position, and calculates an operation specificity of the surface tension of the liquid medium according to the surface curvature radius.
  • the computing device determines a spot offset value according to the received spot position; the calculating device calculates a surface curvature radius of the liquid medium to be tested according to the spot offset value, and calculates a radius of curvature according to the surface The surface tension of the liquid medium to be tested.
  • the light is a column light source
  • the computing device calculates a surface curvature radius of the liquid medium according to the received spot shape and position, and senses the light emitted by the computing device according to the received column light source.
  • the spot projected by the zone is integrated to determine the light receiving area;
  • the computing device calculates a surface curvature radius of the liquid medium to be tested according to the light receiving area, and calculates a surface tension of the liquid medium to be tested according to the surface curvature radius.
  • the light is a controllable column light source of known light intensity
  • the calculation The device calculates a surface curvature radius of the liquid medium according to the received light intensity, and includes: ' ⁇ , ⁇ ,
  • the computing device integrates the product of the light spot and the intensity coefficient of the light emitted by the controllable columnar light source of the received known light intensity in the sensing area to determine the light intensity; the computing device calculates the light intensity The surface curvature radius of the liquid medium to be tested, and calculating the surface tension of the liquid medium to be tested according to the surface curvature radius.
  • the method further includes the following steps:
  • the critical micelle concentration of the surfactant is determined based on the inflection point in the profile.
  • the light emitted by the light source in the present invention enters the liquid medium to be tested to be refracted at an angle deviating from the normal, and the refracted light returns to the air from the liquid medium to undergo secondary refraction, which is projected on the detector.
  • the position of the spot is offset, and the position of the spot after the offset can calculate the radius of curvature of the surface of the liquid medium according to the principle of refraction of light, and the surface tension of the liquid medium can be calculated by the Young's and Laplace equations.
  • FIG. 1 is a schematic view showing the principle of an embodiment of a surface tension detecting method of the present invention.
  • FIG. 3 is a schematic structural view of an embodiment of a surface tension detecting device of the present invention.
  • 4 is a schematic flow chart of an embodiment of a surface tension detecting method of the present invention.
  • Fig. 5 is a schematic view showing the principle of still another embodiment of the surface tension detecting method of the present invention.
  • Figure 6 is a schematic view of the light beam projection of Figure 5.
  • Fig. 7 is a schematic view showing the application of the surface tension detecting method of the present invention to the determination of the critical micelle concentration.
  • Fig. 8 is a view showing the configuration of a computing device in an embodiment of the surface tension detecting device of the present invention.
  • Figure 9 is a schematic view showing the structure of a computing device in still another embodiment of the surface tension detecting device of the present invention.
  • FIG. 10 is a block diagram showing the construction of a computing device in another embodiment of the surface tension detecting device of the present invention. detailed description
  • the inventors have found that in the case where the detection beam deviates from the center of the micropore, the refracted light will deviate from the original vertical position according to the principle of refraction of light, thereby deflecting the transmitted spot from the predetermined detection position.
  • the deviation of the transmitted light has a direct and simple geometric relationship with the radius of curvature of the surface of the liquid, which can be resolved by simple calculation.
  • the invention quantitatively detects the deviation of the position of the light spot caused by the refraction of the light beam on the surface of the microporous liquid with different radius of curvature of the surface, thereby determining the radius of curvature of the surface of the liquid, thereby achieving quantitative determination of the surface tension of the liquid, or detecting the property of the liquid interface. The change.
  • FIG. 1 is a schematic diagram showing the principle of the embodiment of the surface tension detecting method of the present invention.
  • the detection light When the detection light is incident on the micropore from the center of the hole, the detection ray has different normals on the liquid surface of different radii of curvature.
  • the direction of the detected light incident perpendicularly overlaps the normal line, and the direction of the refracted light does not change when passing through the liquid surface, and after refracting, reaches the detector origin position zo corresponding to the vertical direction of the light source.
  • the normal line points to the center B of the curved surface; when the detected light deviates from the center of the sample hole, the normal line deviates from the vertical direction, so that the detected light deviates from the first time into the solution. Incident direction; When the refracted detection light re-enters the air from the solution, a second refraction occurs, further deviating from the vertical direction.
  • the transmitted light forms a spot of light at the Z1 position of the detector.
  • the offset distance Shi between Z0 and ⁇ can be calculated according to the principle of light refraction in Figure 1.
  • the present invention quantitatively describes the relationship between the position or offset value of the light spot after the refracting and the surface curvature radius R of the liquid medium, and develops new uses based on this.
  • the quantitative relationship between shift and R can be obtained by solving the following simultaneous equations:
  • ct is the angle of incidence
  • is the exit angle into the liquid surface
  • is the offset angle after refraction
  • is the angle of refraction from liquid to air!
  • ⁇ 2 is the refractive index of light in the liquid medium and air
  • offset is the offset value of the detection light to the center of the micropore
  • h2 is the distance from the bottom of the sample cell to the detector plane
  • hi is the liquid medium in the micropore Depth
  • nl, n2, offset, h2 are instrument constants, in fixed sample volume and The offset is 0.7 times the micropore radius
  • hi is basically unchanged, and can be regarded as a constant.
  • the position of the spot and the shift have a certain relationship with R, which is shown in Fig. 2.
  • hl, h2, offset, nl, and n2 are set to 5 mm, 10 mm, 1.2 mm, 1.33, and 1, respectively.
  • different relationship curves can be obtained. From this curve, the surface curvature radius R of the corresponding liquid medium can be quickly obtained from the spot offset value shift. From the figure, from the horizontal liquid surface (R infinity) to the maximum curvature liquid surface (R equals the radius of the sample cell), the measurable shift range is 0 ⁇ 4 mm, which is easily determined by the prior art.
  • the present invention is based on the capillary phenomenon of a solution in a micropore.
  • the liquid forms a liquid surface of different curvature in the micropores due to surface tension including liquid surface tension, solid surface tension, and liquid-solid interfacial tension and gravity.
  • the relationship between the shape of the liquid surface and the associated force can be determined by the classical Young's equation and the Laplace equation, and has a great relationship with the pore size of the micropore; when the pore size is small to a certain extent, the influence of gravity is rapidly reduced, and the surface tension is small.
  • the capillary phenomenon became noticeable.
  • the surface tension detecting device mainly comprises: a sample cell 1, a light source 2, a detector 3, and a computing device 4.
  • the sample cell 1 is used to fill the liquid medium to be tested 5 .
  • the sample cell 1 may have a suitable radius of less than 7 mm for causing significant capillary phenomenon of the liquid medium 5 to be tested, the bottom of the sample cell is transparent, and the surface coating layer should be hydrophilic and hydrophobic so that the sample containing pure water is in the micro A near horizontal level is formed in the pores.
  • Sample cell 1 can be designed as a multi-well array to facilitate high-throughput detection, but not Exclude the form of a single orifice plate as needed.
  • the multi-well array plate can also be connected to a positioning and stepping mechanism that allows for controlled adjustment and movement of the sample cell to a specific position in a horizontal position for continuous scanning detection of different wells.
  • Current porous array plates are available with widely used 96, 394 or 1536 well microplates.
  • the sample cell 1 can be placed on a test rack 8, which is integrated or connected to the positioning and stepping mechanism.
  • microporous array plates with different micropore shapes and surface coating materials, as well as stepping systems can be selected to improve the quality of the inspection.
  • the surface of the plate can be coated with a material with the same liquid-solid interfacial tension as most aqueous solutions, which makes it easier to determine the absolute surface tension of the solution; a special micropore shape is designed to improve signal quality.
  • Porous array boards are designed for single-use and fixed devices depending on cost and application. Since the liquid surface tension and the liquid-solid interfacial tension are both interfacial properties with the solution, the light source 2 is disposed on one side of the sample cell 1, as above, for emitting light to the liquid medium 5 to be tested in the sample cell 1.
  • the light source can be a very thin linear light source, for example, the light diameter is less than 10 microns, can be used for spot position or offset displacement measurement, or can be a columnar light source with a relatively large diameter, and the spot portion can match or exceed the diameter of the sample cell.
  • the light-receiving part of the device can be used for spot area or light intensity measurement.
  • the light source can be used with a common non-monochromatic source, or a single source can be selected to expand and optimize the detection. Matching with the detector 3, the light source can also emit other detectable light (such as ultraviolet light, etc.) outside the visible range, as long as the detector 3 can detect the corresponding spot position or offset displacement.
  • the light source can also emit other detectable light (such as ultraviolet light, etc.) outside the visible range, as long as the detector 3 can detect the corresponding spot position or offset displacement.
  • the light source 2 can be placed vertically above the sample cell 1, and the light emitted by the light source 2 is directed into the sample cell 1 and the incident point is offset from the center of the sample cell by a predetermined distance. In this way, the geometric relationship between the offset distance and the surface curvature has been given in the foregoing, and will not be described in detail here.
  • the detector 3 has a sensing area 6 disposed on the other side of the sample cell 1, for example, below. It is used to detect the position of the light spot projected on the sensing area 6 after the light is transmitted through the liquid medium to be tested in the sample cell 1.
  • the detector 3 can be an array type photosensitive detector or a digital camera, and other types of detectors that meet the detection requirements are also applicable.
  • the detector 3 can be set to a detection area of 1 cm X lcm, 4 million black and white pixels or higher, wherein the origin position (gray) is perpendicular to the incident light. After passing through the sample cell, the light forms a spot at the corresponding location of the sensing area of the detector and thereby induces an optical signal.
  • the spot offset value shift is directly obtained according to the position of the light signal in the sensing area and the fixed origin position.
  • the sensing area of the detector covers all possible spots occurrence positions as much as possible, and the exact position or shift value of the spot can be determined according to the array photodetector; for spot position offset detection, detector sensing The area should be matched with the original spot without refraction so that the light-receiving area is reduced by the spot shift when bending the liquid surface, and the surface curvature of the liquid is determined according to the change of the light-receiving area shown in Fig. 5; if possible, the sensitization of the detector The area is designed to coincide with the maximum possible offset spot predicted according to the above principle and coincide with a minimum amount to improve the dynamic range and detection accuracy of the detector.
  • the spot shape and position are as shown in Fig. 6.
  • the light receiving area can be calculated by integrating each light ray emitted from the column light source onto the light spot of the light receiving surface. According to the principle of light refraction, a part of the light will be reflected back during the two refractions. The ratio of the intensity of the refracted light to the incident light intensity is determined by the angle of refraction, and finally determined by the radius of curvature of the surface 'R, which can be calculated by the Fresnel equation. . Combining these factors with the methods shown in Figures 1 and 5, the detector can also use the widely used light absorption detector, which can also obtain the quantitative relationship between the surface intensity of the light intensity signal and the liquid medium (refer to Figure 2, not shown here).
  • This detection mode determines the surface curvature of the liquid medium based on the most common light intensity detection.
  • the absolute relationship between the surface curvature of the solution and the light intensity signal can be resolved to determine the absolute surface curvature and thereby Determining absolute surface tension without relying on calibration with samples of known surface tension, although in conventional use of the apparatus of the invention This calibration is not excluded.
  • the computing device 4 is connected to the detector 3.
  • the basic function is to calculate the surface curvature radius of the liquid medium to be tested according to the received spot position, and calculate the surface tension of the liquid medium to be tested according to the radius of curvature of the surface.
  • the computing device 4 can include a control unit that can issue control commands to the light source 2, the detector 3, and the sample plate 1 as needed.
  • the computing device 4 can also be configured with an array plate stepping. Controller; for different porous array plates (such as different specifications of microporous microplates) can also set the plate selection and adapter. If you are also involved with a single-color source and multiple sources, you can also set up a light source switcher and wavelength selector in your computing device.
  • the computing device can be a computer with a corresponding computing function software or a microcontroller with a computing function hardware.
  • the surface tension detecting device of the present invention can integrate the above components into one instrument, or separately design the instrument according to the detection of the spot position, the light receiving area, or the detection principle according to the light intensity.
  • the surface tension detecting device of the present invention can also be upgraded and modified by referring to the existing microplate reader for absorption detection, and the instrument itself can also retain the absorption detecting function, making it a multifunctional microplate reader including the detecting function described in the present invention.
  • an existing microplate reader for detecting light absorption can quantitatively measure the surface curvature change of the solution on an existing microplate. Although it is difficult to obtain a quantitative relationship between the surface curvature of the solution and the light absorption signal, it has been difficult to obtain an instrument setting.
  • the use of the present invention on existing instruments is suitable for determining the relative change in surface tension due to good precision and dynamic range.
  • the surface tension detecting method includes: Step 101: The light source is emitted into the sample cell to be filled with the liquid medium to be tested. Step 102: The detector detects that the light is transmitted through the liquid medium to be tested in the sample pool and is projected at a spot position of the sensing area;
  • Step 103 The computing device calculates a surface curvature radius of the liquid medium according to the received spot position, and calculates the liquid medium according to the surface curvature radius. Surface tension.
  • the light emitted by the light source into the liquid medium to be tested filled in the sample cell can be vertically injected into the sample cell, and the incident point is offset from the center of the sample cell by a predetermined distance.
  • the light source in FIG. 1 is a linear light source, and the calculation process corresponding to the computing device in step 103 can be specifically as follows:
  • the computing device determines a light spot offset value according to the received light spot position, and calculates the light spot offset value according to the light spot offset value. Describe the surface curvature radius of the liquid medium to be measured, and calculate the surface tension of the liquid medium to be tested according to the surface curvature radius.
  • Figure 2 shows the relationship between the shift value of the spot offset and the radius of curvature R of the liquid medium. «According to this curve, the corresponding radius of curvature R can be quickly determined. tension.
  • the light source is a columnar light source
  • the columnar beam emitted by the light source is a spot when it is incident on the liquid surface of the sample pool, and different edge lines are formed according to the curvature of the surface.
  • a horizontal liquid surface whose spot is a spot A.
  • different edge lines are calculated according to the calculation method corresponding to the linear light source, and the spot B in the detector can be obtained.
  • the quantitative relationship between the light receiving area and the surface curvature of the liquid medium to be tested is calculated in advance (refer to Fig. 2, which is not shown here).
  • the light-receiving area can be determined by integrating the light emitted by the columnar light source at the spot projected by the sensing area.
  • Calculating, by the computing device, the surface curvature radius of the liquid medium according to the received spot position, and calculating the surface tension of the liquid medium according to the surface radius of curvature comprises: calculating, by the computing device, the light emitted by the received columnar light source Integrating the spot projected in the sensing area to determine the spot area, calculating the surface radius of curvature of the liquid medium to be tested, and calculating the surface tension of the liquid medium to be tested according to the surface radius of curvature.
  • the above-mentioned columnar light source is designed to have a known and controllable light intensity (most of the current light sources have such a function), and the light intensity coefficient of the refracted light and the above-mentioned light receiving surface are according to the principle of FIG.
  • the surface tension detection of the present invention can also be achieved by integrating the calculations. Calculating a quantitative relationship between the light intensity and the surface curvature of the liquid medium according to the calculation (refer to FIG. 2, not shown here), determining the surface curvature according to the detected light intensity, and calculating the liquid medium to be tested according to the surface curvature Surface Tension.
  • the method further includes the following steps: recording the change curve of the surface curvature radius of the liquid medium to be tested by gradually increasing the concentration of the surfactant of the liquid medium to be tested; The inflection point in the profile determines the critical micelle concentration of the surfactant.
  • FIG. 7 it is a schematic diagram of applying the embodiment of the surface tension detecting method of the present invention to the determination of the critical micelle concentration.
  • the existing 384-well black bottom transparent ELISA plate was used to measure on an existing microplate reader.
  • Surfactant (in mM) includes: anionic surfactant sodium n-octyl sulfate (c 8 so 4 ), sodium decyl sulfate (C 10 SO 4 ), sodium 12- sulfonate (C 12 S0) 4 ), sodium n-decyl sulfonate (C 1 () S0 3 ); positive ion surfactant brominated n-decyl 3 methyl quaternary ammonium salt (C 1 () NBr), brominated n- 12 alkyl 3 ⁇ A quaternary ammonium salt (C 12 NBr), a n-alkyl 3 decyl quaternary ammonium bromide (C 14 NBr),
  • Surfactant solutions tend to accumulate on the surface of the solution to reduce the surface tension of the liquid.
  • the surfactant When the surfactant is dissolved in the liquid, it causes the surface curvature of the micropores to change, which causes the change of the light signal.
  • the critical micelle concentration When the critical micelle concentration is reached, the surface concentration tends to be saturated, the surface curvature is no longer reduced, and more surfactants are dissolved.
  • the surfactant When liquid is introduced, the surfactant will form micelles while the surface curvature remains unchanged. Therefore, the surface tension and surfactant concentration curve will have an inflection point at the critical micelle concentration, and the table will be determined accordingly.
  • the critical micelle concentration of the surfactant Through studies of different surfactants, the present inventors have found that the method can accurately and rapidly determine the critical micelle concentration of these surfactants. This method is theoretically applicable to all surfactants which form clear or partially transparent solutions.
  • the light source in this embodiment is a linear light source
  • the computing device 4 includes: a spot shift determining unit 41, a first radius of curvature calculating unit 42, and a surface tension calculating unit 43.
  • the spot offset determining unit 41 is configured to determine a spot offset value according to the received spot position.
  • the first radius of curvature calculation unit 42 is configured to calculate a surface curvature radius of the liquid medium to be tested according to the spot offset value.
  • the surface tension calculating unit 43 is configured to calculate the surface tension of the liquid medium to be tested based on the radius of curvature of the surface.
  • the light source in this embodiment is a columnar light source
  • the computing device 4 includes: a light receiving area determining unit 44, a second radius of curvature calculating unit 46, and a surface tension calculating unit 43.
  • the light receiving area determining unit 44 is configured to integrate the light spot projected by the received column light source in the sensing area to determine the light receiving area.
  • the second radius of curvature calculation unit 46 is configured to calculate a surface curvature radius of the liquid medium to be tested according to the light receiving area.
  • the surface tension calculating unit 43 is configured to calculate the surface tension of the liquid medium to be tested based on the radius of curvature of the surface.
  • the light source in this embodiment is a controllable column light source of known light intensity
  • the computing device 4 comprises: a light intensity determining unit 47, a third radius of curvature calculating unit 48 and a surface tension calculation.
  • the light intensity determining unit 47 is configured to integrate the product of the light spot emitted by the controllable columnar light source of the received known light intensity in the sensing area and the light intensity coefficient to determine the light intensity.
  • the third radius of curvature calculation unit 49 is configured to calculate a surface curvature radius of the liquid medium to be tested according to the light intensity.
  • the surface tension calculating unit 50 is configured to calculate a surface tension of the liquid medium to be tested according to the surface curvature radius.
  • the computing device may further include: a critical micelle concentration determining unit, configured to record a surface curvature radius of the liquid medium to be tested by gradually increasing a surfactant concentration of the liquid medium to be tested A curve of variation, determining a critical micelle concentration of the surfactant based on an inflection point in the curve.
  • a critical micelle concentration determining unit configured to record a surface curvature radius of the liquid medium to be tested by gradually increasing a surfactant concentration of the liquid medium to be tested A curve of variation, determining a critical micelle concentration of the surfactant based on an inflection point in the curve.

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Description

Figure imgf000003_0001
技术领域
本发明涉及检测技术, 尤其涉及一种表面张力检测装置及方 法。 背景技术
液体的界面性质在科研、技术开发和产品制造上具有重要意 义。 液体的表面张力和液-固界面张力是了解液体界面性质的关 键, 因此表面张力的测定具有非常重要的意义。 经典表面张力测 定方法能够得到精确的表面张力值, 但测定费时费力, 对测定人 员的技术要求也比较高。 而已开发的快速表面张力测定方法在速 度方面有所提高, 但因其所采用的方法属于序列测定, 每一次测 定均需要较长的平衡时间才能够得到可靠结果。
不同界面性质的液体可在微孔中形成不同的溶液表面或不 同的液柱高度, 即常见的毛细现象。 溶液表面形状由液体表面张 力、 固体表面张力、液-固界面张力、重力和孔的大小和形状决定, 这些关系可由经典的杨氏方程和拉普拉斯方程精确描述。 在目前 高通量筛选广泛使用的微孔酶标板上 (如 384孔和 1536孔酶标 板) , 板孔直径接近毛细管尺寸, 毛细现象变得显著起来, 从而 使不同界面性质的液体具有不同的液体表面曲率半径。 这些不同 反 和折射, 从而影响光谱检测信号。
目前, 已有针对多孔酶标板微孔中表面曲率半径不同引起的 光吸收信号差异的专利公开文本 WO01/53798 , 可望用于开发快 速表面张力检测。 其通过检测微孔内不同溶液表面对透射和反射 光强度的影响来检测表面张力。 这种方式缺乏有效的理论描述, 无法合理解释信号变化, 因此需要依赖现有表面张力测定技术来 校准仪器, 这缩小了这种方式的应用范围和使用效率。
专利公开文本 GB2408572A提供了另一种快速表面张力检 测方法。 这种方法通过拍摄透过微孔内介质的预设模式图像的图 形, 并通过匹配比对图像的变形程度来确定微孔内介质的表面曲 率半径, 这种方式在技术实现上有较大障碍, 且无法获得精确的 定量结果, 难以保证表面张力测量的精度和准确性的要求。 发明内容
本发明的目的是提出一种表面张力检测装置及方法, 能够根 测出表面张力, 且无需依靠现有表面张力测试技术进行标定。
为实现上述目的, 本发明提供了一种表面张力检测装置, 包 括:
样品池, 用于填充待测液态介质;
光源, 设于所述样品池的一方, 用于向所述样品池中的待测 液态介质发射光线;
检测器, 具有感应区, 设于所述样品池的另一方, 用于检测 所述光线透射过所述样品池中的待测液态介质后投射在所述感应 区的光点位置;
计算设备, 与所述检测器相连, 用于根据接收到的光点位置 计算所述待测液态介质的表面曲率半径, 并根据所述表面曲率半 径计算所述待测液态介质的表面张力。
在上述技术方案中,光源发出的光线在偏离法线的角度下进 入待测液态介质中发生折射, 而折射后的光线从液态介质中返回 空气后发生二次折射, 其投射在检测器的光点位置发生偏移, 而 偏移后的光点位置可根据光的折射原理计算出液态介质的表面曲 率半径, 进一步通过杨氏和拉普拉斯方程可计算出液态介质的表 面张力。 这种方式无需依赖现有表面张力测定技术来校准仪器, 而且可实现较高精度和准确度的定量检测。
进一步的, 所述样品池具有使待测液态介质发生明显毛细现 象的中空结构, 所述样品池底部为透明。 本发明中凭借液体表面 形状与相关作用力的关系来计算表面张力, 其基于液体介质在微 孔中的毛细现象。 , 而样品池的直径应小到一定尺寸, 如 7毫米 以下, 重力的影响开始退居次要, 而毛细现象开始变得显著, 以 保障其计算精度和准确度越高。 样品池的底部为透明, 保障光线 能够穿透液体介质投射到检测器上。
优选的, 所述检测池应为圆柱形结构。 但并不限于圆柱形结 构, 也适于采用其他合适结构。
进一步的, 所述样品池为单孔板或多孔阵列板。 本发明可采 用单孔板作为样品池, 同时为了方便高通量检测, 也可采用多孔 阵列板, 所述多孔阵列板还连有定位和步进机构。 通过在多孔阵 列板连接定位和步进机构, 实现对不同孔进行持续性的扫描。
进一步的, 所述多孔阵列板为 96、 394或 1536孔微量酶标 板, 所述微量酶标板还连有定位和步进机构。 根据成本和应用范 围, 多孔阵列板可选用一次性使用的微孔酶标板。 微量酶标板的 常用规格包括 96、 394或 1536孔, 各种规格的孔径有所不同。
进一步的, 所述光源设于所述样品池垂直上方, 所述光源发 射的光线竖直射入所述样品池, 且入射点偏移所述样品池中心预 设距离。 偏移样品池中心射入的光线经过非水平的待测液态介质 后会偏移竖直方向, 光线重新进入空气后, 会进一步的偏移竖直 方向。
进一步的, 所述检测器为阵列式光敏检测器或数码照相机。 进一步的, 所述光源为线状光源, 所述计算设备包括: 光点偏移确定单元,用于根据接收到的光点位置确定光点偏 移值;
第一曲率半径计算单元,用于根据所述光点偏移值计算所述 待测液态介质的表面曲率半径;
表面张力计算单元, 用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
线状光源所发射出的光束比较细,投射到检测器的感应区可 视为一个光点, 通过获取该光点的位置信息可以进一步的确定光 点偏移值, 再利用光折射原理计算出待测液态介质的表面曲率半 径。
进一步的, 所述光源为柱状光源, 所述计算设备包括: 受光面积确定单元,用于对接收到的柱状光源发出的光线在 感应区投射的光点进行积分确定受光面积;
第二曲率半径计算单元,用于根据所述受光面积计算所述待 测液态介质的表面曲率半径;
表面张力计算单元, 用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
柱状光源发出的光束为具有较宽直径的光束,投射到感应区 时实际是一个大的光斑, 因此在计算时就不再计算光点位置, 而 是将光束分解成多条光线, 然后通过对这些光线在检测器的感应 区投射的光点位置进行积分,得到这些光点所枸成的光斑的面积, 再根据由光的折射原理推出的受光面积与表面曲率之间的关系曲 线来确定对应的待测液态介质的表面曲率半径。
进一步的, 所述光源为已知光强的可控柱状光源, 所述计算 设备包括:
光强确定单元, 用于对接收到的已知光强的可控柱状光源发 出的光线在感应区投射的光点和光强系数的乘积进行积分确定光 强;
第三曲率半径计算单元, 用于将所述光强计算所述待测液态 介质的表面曲率半径;
表面张力计算单元,用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
根据光的折射原理, 两次折射过程中都还将有一部分光反射 回去, 折射的光强度与入射光强的比值由折射角确定, 也最终由 表面曲率半径 'R, 决定, 可由 Fresnel方程算出。 将这些因素引 起的光强系数与上述光斑在检测器投影的光点相乘并积分, 即可 得到光的强度信息, 检测器可为最常用的光强度检测器。 由于可 建立光强与液体介质表面曲率的定量关系曲线, 从而通过毛细现 象原理与表面张力建立确定定量关系, 该方法理论上可不经过其 它技术标定进行表面张力的测定。
进一步的, 所述计算设备还包括:
临界胶束浓度确定单元, 用于通过逐步增加待测液态介质的 表面活性剂浓度, 记录所述待测液态介质的表面曲率半径的变化 曲线, 根据所述变化曲线中的拐点确定所述表面活性剂的临界胶 束浓度。 在测量待测液态介质的表面张力时, 通过增加待测液态 介质的表面活性剂浓度会发现当达到一定浓度时, 表面曲率半径 将不再明显变化, 而该浓度即为表面活性剂的临界胶束浓度。 这 种方法可以用于高通量无探针的表面活性剂临界胶束浓度的测 进一步的, 所述计算设备包括:
控制单元, 用于向所述光源、 样品池和 /或检测器发出控制 指令。 为了提高测量精度和使操作更便利, 计算设备还可以直接 向光源、 样品池和 /或检测器等发出控制指令。
为实现上述目的,本发明提供了一种基于前述表面张力检测 装置的表面张力检测方法, 包括:
光源向样品池中填充的待测液态介质发射光线;
所述检测器检测所述光线透射过所述样品池中的待测液态 介质后投射在所述感应区的光点位置;
计算设备根据接收到的光点位置计算所述液态介质的表面 曲率半径, 并根据所述表面曲率半径计算所述液态介质的表面张 力。
进一步的, 所述光源向样品池中填充的待测液态介质发射光 线的操作具体为:
所述光源向样品池中填充的待测液态介质发射的光线竖直 射入所述样品池, 且入射点偏移所述样品池中心预设距离。
进一步的, 所述光源为线状光源, 所述计算设备 据接收到 的光点位置计算所述液态介质的表面曲率半径, 并根据所述表面 曲率半径计算所述液态介质的表面张力的操作具体包括:
所述计算设备根据接收到的光点位置确定光点偏移值; 所述计算设备根据所述光点偏移值计算所述待测液态介质 的表面曲率半径, 并根据所述表面曲率半径计算所述待测液态介 质的表面张力。
进一步的, 所述光线为柱状光源, 所述计算设备根据接收到 的光斑形状和位置计算所述液态介质的表面曲率半径, 并根据所 所述计算设备对接收到的柱状光源发出的光线在感应区投 射的光点进行积分确定受光面积;
所述计算设备将所述受光面积计算所述待测液态介质的表 面曲率半径, 并根据所述表面曲率半径计算所述待测液态介质的 表面张力。
进一步的, 所述光线为已知光强的可控柱状光源, 所述计算 设备根据接收到的光强计算所述液态介质的表面曲率半径, 并根 括: ' < 、 β
所述计算设备对接收到的已知光强的可控柱状光源发出的 光线在感应区投射的光点和强度系数的乘积进行积分确定光强; 所述计算设备将所述光强计算所述待测液态介质的表面曲 率半径, 并根据所述表面曲率半径计算所述待测液态介质的表面 张力。
进一步的, 还包括以下步骤:
通过逐步增加待测液态介质的表面活性剂的浓度,记录所述 待测液态介质的表面曲率半径的变化曲线;
根据所述变化曲线中的拐点确定所述表面活性剂的临界胶 束浓度。
基于上述技术方案,本发明中光源发出的光线在偏离法线的 角度下进入待测液态介质中发生折射, 而折射后的光线从液态介 质中返回空气后发生二次折射, 其投射在检测器的光点位置发生 偏移, 而偏移后的光点位置可根据光的折射原理计算出液态介质 的表面曲率半径, 进一步通过杨氏和拉普拉斯方程可计算出液态 介质的表面张力。 这种方式无需依赖现有表面张力测定技术来校 准仪器, 而且可实现较高精度和准确度的定量检测。 附图说明
此处所说明的附图用来提供对本发明的进一步理解,构成本 申请的一部分,本发明的示意性实施例及其说明用于解释本发明, 并不构成对本发明的不当限定。 在附图中:
图 1为本发明表面张力检测方法实施例的原理示意图。
图 2 为本发明表面张力检测方法实施例中光点偏移值 shift 与液态介质的表面曲率半径 R之间的关系曲线。
图 3为本发明表面张力检测装置的一实施例的结构示意图。 图 4为本发明表面张力检测方法的一实施例的流程示意图。 图 5 为本发明表面张力检测方法的又一实施例的原理示意 图。
图 6为图 5中光柱投射的示意图。
图 7为本发明表面张力检测方法实施例应用于临界胶束浓度 测定的示意图。
图 8为本发明表面张力检测装置的一实施例中计算设备的结 构示意图。
图 9为本发明表面张力检测装置的又一实施例中计算设备的 结构示意图。
图 10为本发明表面张力检测装置的另一实施例中计算设备 的结构示意图。 具体实施方式
下面通过附图和实施例,对本发明的技术方案做进一步的详 细描述。
发明人分析发现在检测光束偏离微孔中心的情况下,根据光 的折射原理, 折射光将偏离原来的垂直位置, 从而使透射光点偏 离预定的检测位置。 而在一定的仪器设置下, 透射光的偏离值与 液体的表面曲率半径有直接的简单几何关系, 可通过简单计算解 析出来。 本发明将定量检测光束在不同表面曲率半径的微孔液体 表面上折射导致的光点位置偏离值, 以此确定液体的表面曲率半 径, 从而达到对液体表面张力的定量测定, 或检测液体界面性质 的变化。
如图 1所示, 为本发明表面张力检测方法实施例的原理示意 图。 当检测光线射入微孔中偏离孔中心位置时, 该检测光线在不 同曲率半径的液面上具有不同的法线。 在高表面张力液体形成的 近水平溶液表面上, 垂直射入的检测光线方向与法线重叠, 在通 过液面时折射光线方向不变, 折射后到达与光源垂直对应的检测 器原点位置 zo。 在低表面张力液体引起的弯曲溶液表面上, 法线 指向弯曲表面的圆心 B; 当检测光线偏离样品孔中心时, 法线将 偏离垂直方向, 从而使检测光线经第一次折射进入溶液时偏离入 射方向; 折射后的检测光线从溶液中重新进入空气时, 发生第二 次折射, 进一步偏离垂直方向。 透射光线在检测器的 Z1 位置上 形成光点。 Z0和 ΖΓ间的偏移距离 shift可通过图一根据光的折射 原理计算出。
本发明将折射后检测光线光点的位置或偏移值 shift与液体 介质的表面曲率半径 R的关系进行定量描述, 并基于此开发新用 途。 根据光的折射原理, shift和 R的定量关系可通过解以下联立 方程组得出:
sin ( o ) = offset/R;
sin( a )/sin( β ) = n2/nl;
Υ = - β ;
I sin( γ )/sin( θ ) = nl/n2;
dl = hl*tg( Y );
d2 = h2*tg( θ );
hift = dl + d2。
其中, ct为入射角, β为进入液面的出射角, γ为折射后的 偏移角, Θ为从液体到空气的折射角, !^、 η2分别为光在液体介 质中和空气中的折射系数, offset 为检测光线对微孔中心的偏移 值, h2 为样品池底部到检测器平面的距离, hi 为微孔中液体介 质的深度; nl、 n2、 offset, h2 为仪器常数, 在固定样品体积和 offset为 0.7倍微孔半径下, hi基本保此不变, 可视为常数。
在一定仪器参数的设置下, 光点位置和 shift与 R具有确定 的关系, 该关系曲线如图 2所示。 在图 2中 hl、 h2、 offset, nl、 n2分別被设为 5毫米、 10毫米、 1.2毫米、 1.33和 1。 设置不同 的上述仪器参数, 可以得到不同的关系曲线, 通过该曲线就可以 由光点偏移值 shift快速获得对应液态介质的表面曲率半径 R。从 图上看, 从水平液体表面 (R 无穷大) 到最大曲率液体表面 (R 等于样品池的半径) , 可测定的 shift变化范围为 0 ~ 4毫米, ί艮 容易通过现有技术精确测定。
前面已经提到, 本发明是基于溶液在微孔中的毛细现象来进 行检测的。 在液-固和液体界面上, 由于表面张力包括液体表面 张力、 固体表面张力、 和液-固界面张力和重力的作用, 液体在 微孔中形成不同曲率的液体表面。 液体表面形状和相关作用力的 关系可由经典的杨氏方程和拉普拉斯方程确定, 与微孔的孔径有 很大关系; 当孔径小到一定程度时, 重力的影响迅速减小, 表面 张力开始占主导地位, 毛细现象就变得显著起来。对于水相溶液, 当孔径小于 7毫米时, 重力开始不占主导地位, 毛细现象开始显 示出来。 当孔径小于 3.5 毫米时, 毛细现象开始变得显著起来。 上述两种孔径接近目前广泛使用的 96孔和 384孔板的孔径。
下面结合前面的原理提供一种表面张力检测装置的实施例 的结构示意图, 参见图 3。 在本实施例中, 表面张力检测装置主 要包括: 样品池 1、 光源 2、 检测器 3和计算设备 4。 其中样品池 1 用于填充待测液态介质 5。 样品池 1 可具有使待测液态介质 5 发生明显毛细现象的小于 7毫米的合适半径,样品池底部为透明, 表面涂层应亲水性和疏水性适中, 以使含纯水的样品在微孔中形 成近水平的液面。
样品池 1可设计为多孔阵列板, 以方便高通量检测, 但也不 排除根据需要设计为单孔板的形式。 多孔阵列板还可连接定位和 步进机构,使其可在水平位置可控调节和移动样品池到特定位置, 以便对不同孔进行连续的扫描检测。 目前的多孔阵列板可选用广 泛使用的 96、 394或 1536孔微量酶标板。样品池 1可被安置在检 测板架 8上, 检测板架 8与定位和步进机构一体整合或相连接。
对于不同的检测要求,还可以选用包括不同微孔形状和表面 涂层材料, 以及与步进系统匹配的微孔阵列板, 以提高检测质量。 例如可将酶标板表层涂抹一层和大多数水相溶液具有相同的液- 固界面张力的材料, 可更方便测定溶液的绝对表面张力; 设计特 殊的微孔形状以改善信号质量。
多孔阵列板可视成本和应用范围设计成一次性使用和固定 器件。 因为液体表面张力和液-固界面张力都与溶液的界面性质相 光源 2设于样品池 1的一方, 如上方, 用于向样品池 1中的 待测液态介质 5发射光线。 光源可为非常细的线状光源, 例如光 线直径小于 10微米, 可用于光点位置或偏移位移测量, 也可以为 直径较粗的柱状光源, 光斑部分可达到与样品池直径匹配或超出 检测器的受光部分, 可用于光斑面积或光强测量。 光源可釆用普 通非单色光源,也可以根据需要选择单色光源来扩展和优化检测。 与检测器 3相匹配, 光源还可以发射可见光范围之外的其他可检 测的光线 (例如紫外光等) , 只要检测器 3能够检测出对应的光 点位置或偏移位移即可。
为了简化计算, 光源 2可设于样品池 1的垂直上方, 光源 2 发射的光线竖直射入样品池 1 , 且入射点偏移样品池中心预设距 离。 这种方式在前文已经给出了该偏移距离与表面曲率之间的几 何关系推导, 这里就不再详述了。
检测器 3具有感应区 6,设于样品池 1的另一方, 例如下方, 用于检测光线透射过样品池 1中的待测液态介质后投射在感应区 6的光点位置。检测器 3可采用阵列式光敏检测器或数码照相机, 其他满足检测要求的各类型检测器也同样适用。 检测器 3可设为 lcm X lcm检测面积、 400万黑白像素或更高, 其中原点位置(灰 色) 与入射光线垂直相对。 光线经过样品池后在检测器的感应区 的相应位置形成光点并从而引发一光信号。 根据感应区中光信号 的位置和固定的原点位置直接得到光点偏移值 shift。
对于光点位置或偏移位移检测,检测器的感应区尽量覆盖全 部可能的光点出现位置, 可根据阵列光敏检测器确定光斑的确切 位置或 shift值; 对于光斑位置偏移检测,检测器感应区应和无折 射的原始光斑相匹配, 以便在弯曲液面时因光斑偏移使受光面积 减少, 根据图 5所示受光面积的变化确定液体的表面曲率; 如有 可能, 将检测器的感光区域设计为与根据上述原理预测的最大可 能偏移光斑有一定重合且为最小量重合, 以提高检测器的动态范 围和检测精度。
光斑形状和位置如图 6所示,其受光面积可由柱状光源发出 的每一条光线投射在受光面的光点进行积分算出。 根据光的折射 原理, 两次折射过程中都还将有一部分光反射回去, 折射的光强 度与入射光强的比值由折射角确定, 也最终由表面曲率半径 'R, 决定, 可由 Fresnel方程算出。 将这些因素与图 1及图 5所示的 方法综合起来, 检测器还可选用目前广泛使用的光吸收检测器, 这样还可得到光强信号与液态介质的表面曲率的定量关系曲线 (可参考图 2, 这里就不示出了) 。 这种检测模式可根据最常用 的光强度检测确定液态介质的表面曲率, 然而根据本发明描述的 原理可以解析出溶液表面曲率和光强信号的绝对关系, 从而用于 测定绝对表面曲率以及由此测定绝对表面张力, 而无需依靠通过 已知表面张力的样品进行标定, 虽然本发明仪器的常规使用中也 不排除这种标定。
计算设备 4与检测器 3相连,基本功能为根据接收到的光点 位置计算待测液态介质的表面曲率半径, 并根据表面曲率半径计 算待测液态介质的表面张力。 计算设备 4可包括控制单元, 可根 据需要向光源 2、 检测器 3和样本板 1发出控制指令, 对于多孔 阵列板连有定位和步进机构的, 计算设备 4中还可以设置阵列板 步进控制器; 针对于不同的多孔阵列板 (例如不同规格的微孔酶 标板) 则还可以设置酶标板选择和适配器。 如果还涉及到利用单 色光源和多种光源, 还可以在计算设备中设置光源切换器和波长 选择器。 计算设备可为安装相应计算功能软件的计算机或者计算 功能硬件化的单片机等。
本发明表面张力检测装置可将上述部件集成为一台仪器,或 者将根据光点位置的检测、 根据受光面积或根据光强的检测原理 单独设计仪器。 本发明表面张力检测装置还可参照现有的用于吸 收检测的酶标仪进行升级改造 ,仪器本身也可保留吸收检测功能 , 使之成为包括本发明描述检测功能的多功能酶标仪。 在将检测光 线偏置的情况下, 已有的检测光吸收的酶标仪可在已有的酶标板 上定量测出溶液的表面曲率变化。 虽然已有仪器设置很难得到溶 液表面曲率和光吸收信号的定量关系。 由于有良好的精度和动态 范围,本发明在现有仪器上的使用适合测定表面张力的相对变化。
基于上述的表面张力检测装置, 下面给出一种表面张力检测 方法实施例的流程示意图,如图 4所示,表面张力检测方法包括: 步骤 101、 光源向样品池中填充的待测液态介质发射光线; 步骤 102、 检测器检测所述光线透射过所述样品池中的待测 液态介质后投射在感应区的光点位置;
步骤 103、 计算设备根据接收到的光点位置计算所述液态介 质的表面曲率半径, 并根据所述表面曲率半径计算所述液态介质 的表面张力。
参照图 1原理图, 光源向样品池中填充的待测液态介质发射 的光线可竖直射入样品池, 且入射点偏移样品池中心预设距离。 图 1中光源为线状光源, 对应着步骤 103中的计算设备的计算过 程可具体为: 计算设备根据接收到的光点位置确定光点偏移值, 根据所述光点偏移值计算所述待测液态介质的表面曲率半径, 并 根据所述表面曲率半径计算所述待测液态介质的表面张力。 图 2 中已经给出了一种光点偏移值 shift与液态介质的表面曲率半径 R 之间的关系曲线, «据该曲线就可以快速确定对应的曲率半径 R。 张力。
图 5及图 6示出了本发明表面张力检测方法的另一实施例的 原理。 在本实施例中, 光源为柱状光源, 该光源发出的柱状光束 在射入样本池的液面时为一光斑, 根据表面曲率形成不同的边缘 线。 水平液体表面, 其投射的光斑为光斑 A。 对于待测液态介质, 将不同边缘线按照线状光源所对应的计算方法进行计算, 即可得 到在检测器中的光斑 B。 预先计算出受光面积与待测液态介质的 表面曲率之间的定量关系曲线(可参考图 2, 这里就不示出了) 。 而受光面积可由柱状光源发出的光线在感应区投射的光点进行积 分来确定。 计算设备据接收到的光点位置计算所述液态介质的表 面曲率半径, 并根据所述表面曲率半径计算所述液态介质的表面 张力的操作具体包括: 计算设备对接收到的柱状光源发出的光线 在感应区投射的光点进行积分确定光斑面积, 将所述光斑面积计 算所述待测液态介质的表面曲率半径, 并根据所述表面曲率半径 计算所述待测液态介质的表面张力。
将上述柱状光源设计为光强已知和可控(现大多数光源都具 有这种功能) , 根据图 1原理将折射光的光强系数和上述受光面 积计算结合, 也可实现本发明的表面张力检测。 预先根据计算确 定光强与液态介质的表面曲率的定量关系曲线 (可参考图 2, 这 里就不示出了) , 根据检测光强确定表面曲率, 再根据表面曲率 计算所述待测液态介质的表面张力。
在上述三种光源对应的实施例中, 均可以进一步包括以下步 骤, 即通过逐步增加待测液态介质的表面活性剂的浓度, 记录所 述待测液态介质的表面曲率半径的变化曲线; 根据所述变化曲线 中的拐点确定所述表面活性剂的临界胶束浓度。 这些步驟可以将 表面张力变化检测方法应用在高通量无探针的表面活性剂临界胶 束浓度的检测之中。
如图 7所示, 为本发明表面张力检测方法实施例应用于临界 胶束浓度测定的示意图。 采用已有的 384孔黑色底部透明酶标板 在已有酶标仪上测定。 表面活性剂 (surfactant, 单位为 mM ) 包 括: 负离子表面活性剂正辛基硫酸钠(c8so4)、 正癸基硫酸钠 (C10SO4), 正 12烷基硫酸钠(C12S04), 正癸基磺酸钠(C1()S03); 正 离子表面活性剂溴化正癸基 3甲基季铵盐 (C1()NBr)、溴化正 12烷 基 3曱基季铵盐 (C12NBr)、溴化正 14烷基 3曱基季铵盐 (C14NBr)、 溴化正 16烷基 3甲基季铵盐 (C16NBr)、 溴化正 18烷基 3甲基季 铵盐 (C18NBr); 两亲表面活性剂 3 - (氮, 氮二申基正 16烷铵) -正丙基磺酸盐(SB3-16); 非离子型表面活性剂吐温 20 ( Tween20 ) 和曲拉通 100 (Triton)。
表面活性剂溶液倾向于在溶液表面聚集从而降低液体表面 张力。 表面活性剂溶于液体时引起微孔中液体表面曲率变化, 从 而引起光信号的变化, 当达临界胶束浓度时,表面浓度趋向饱和, 表面曲率不再降低, 当更多的表面活性剂溶入液体时, 表面活性 剂将形成胶束, 而表面曲率则保持不变。 因此表面张力和表面活 性剂浓度变化曲线将在临界胶束浓度出现一个拐点, 据此确定表 面活性剂的临界胶束浓度。 通过对不同表面活性剂进行的研究, 本发明发现该方法可精确快速测定这些表面活性剂的临界胶束浓 度。 该方法理论上适用于所有能形成透明或部分透明溶液的表面 活性剂。
本领域普通技术人员可以理解: 实现上述方法实施例的全部 或部分步驟可以通过程序指令相关的硬件来完成, 前述的程序可 以存储于一计算机可读取存储介质中, 该程序在执行时, 执行包 括上述方法实施例的步骤;而前述的存储介质包括: ROM、RAM、 磁碟或者光盘等各种可以存储程序代码的介质。
如图 8所示, 为本发明表面张力检测装置的另一实施例中计 算设备的结构示意图。 与前面的表面张力检测装置实施例相比, 本实施例中光源为线状光源, 计算设备 4包括: 光点偏移确定单 元 41、 第一曲率半径计算单元 42和表面张力计算单元 43。 其中 光点偏移确定单元 41 用于根据接收到的光点位置确定光点偏移 值。第一曲率半径计算单元 42用于根据所述光点偏移值计算所述 待测液态介质的表面曲率半径。表面张力计算单元 43用于根据所 述表面曲率半径计算所述待测液态介质的表面张力。
如图 9所示, 为本发明表面张力检测装置的又一实施例中计 算设备的结构示意图。 与前面的表面张力检测装置实施例相比, 本实施例中光源为柱状光源, 计算设备 4包括: 受光面积确定单 元 44、 第二曲率半径计算单元 46和表面张力计算单元 43。 其中 受光面积确定单元 44 用于对接收到的柱状光源发出的光线在感 应区投射的光点进行积分确定受光面积。 第二曲率半径计算单元 46 用于根据所述受光面积计算所述待测液态介质的表面曲率半 径。表面张力计算单元 43用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
如图 10所示, 为本发明表面张力检测装置的另一实施例中 计算设备的结构示意图。与前面的表面张力检测装置实施例相比, 本实施例中光源为已知光强的可控柱状光源, 计算设备 4包括: 光强确定单元 47、 第三曲率半径计算单元 48和表面张力计算单 元 43。 其中光强确定单元 47用于对接收到的已知光强的可控柱 状光源发出的光线在感应区投射的光点和光强系数的乘积进行积 分确定光强。第三曲率半径计算单元 49用于根据所述光强计算所 述待测液态介质的表面曲率半径。表面张力计算单元 50用于根据 所述表面曲率半径计算所述待测液态介质的表面张力。
在上述三个实施例中, 计算设备还可以包括: 临界胶束浓度 确定单元, 该单元用于通过逐步增加待测液态介质的表面活性剂 浓度, 记录所述待测液态介质的表面曲率半径的变化曲线, 根据 所述变化曲线中的拐点确定所述表面活性剂的临界胶束浓度。
最后应当说明的是:以上实施例仅用以说明本发明的技术方 案而非对其限制; 尽管参照较佳实施例对本发明进行了详细的说 明, 所属领域的普通技术人员应当理解: 依然可以对本发明的具 体实施方式进行修改或者对部分技术特征进行等同替换; 而不脱 离本发明技术方案的精神, 其均应涵盖在本发明请求保护的技术 方案范围当中。

Claims

权 利 要 求
1. 一种表面张力检测装置, 包括:
样品池, 用于填充待测液态介质;
光源, 设于所述样品池的一方, 用于向所述样品池中的待测 液态介质发射光线;
检测器, 具有感应区, 设于所述样品池的另一方, 用于检测 所述光线透射过所述样品池中的待测液态介质后投射在所述感应 区的光点位置;
计算设备, 与所述检测器相连, 用于根据接收到的光点位置 计算所述待测液态介质的表面曲率半径, 并根据所述表面曲率半 径计算所述待测液态介质的表面张力。
2. 如权利要求 1所述的表面张力检测装置, 其中, 所述样 品池具有使待测液态介质发生明显毛细现象的中空结构, 所述样 品池底部为透明。
3. 如权利要求 2所述的表面张力检测装置, 其中, 所述中 空结构为圓柱形中空结构。
4. 如权利要求 3所述的表面张力检测装置, 其中, 所述样 品池为单孔板或多孔阵列板, 所述多孔阵列板还连有定位和步进 机构。
5. 如权利要求 4所述的表面张力检测装置, 其中, 所述多 孔阵列板为 96、 394或 1536孔微量酶标板。
6. 如权利要求 1所述的表面张力检测装置, 其中, 所述光 源设于所述样品池垂直上方, 所述光源发射的光线竖直射入所述 样品池, 且入射点偏移所述样品池中心预设距离。
7. 如权利要求 1所述的表面张力检测装置, 其中, 所述检 测器为阵列式光敏检测器或数码照相机。
8. 如权利要求 6所述的表面张力检测装置, 其中, 所迷光 源为线状光源, 所述计算设备包括: , ; 光点偏移确定单元, 用于根据接收到的光点位置确定光点偏 移值;
第一曲率半径计算单元, 用于根据所述光点偏移值计算所述 待测液态介质的表面曲率半径;
表面张力计算单元, 用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
9. 如权利要求 6所述的表面张力检测装置, 其中, 所述光 源为柱状光源, 所述计算设备包括:
光斑面积确定单元, 用于对接收到的柱状光源发出的光线在 感应区投射的光点进行积分确定受光面积;
第二曲率半径计算单元, 用于将所述受光面积计算所述待测 液态介质的表面曲率半径;
表面张力计算单元, 用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
10. 如权利要求 6所述的表面张力检测装置, 其中, 所述光 源为已知光强的可控柱状光源, 所述计算设备包括:
光强确定单元, 用于对接收到的已知光强的可控柱状光源发 出的光线在感应区投射的光点和光强系数的乘积进行积分确定光 强;
第三曲率半径计算单元, 用于将所述光强计算所述待测液态 介质的表面曲率半径;
表面张力计算单元, 用于根据所述表面曲率半径计算所述待 测液态介质的表面张力。
11. 如权利要求 8、 9或 10所述的表面张力检测装置, 其中 所述计算设备还包括: 临界胶束浓度确定单元, 用于通过逐步增加待测液态介质的 表面活性剂浓度, 记录所述待测液态介质的表面曲率半径的变化 曲线, 根据所述变化曲线中的拐点确定所述表面活性剂的临界胶 束浓度。
12. 如权利要求 1所述的表面张力检测装置, 其中所述计算 设备包括:
控制单元, 用于向所述光源、 样品池和 /或检测器发出控制指令。
13. 基于权利要求 1〜12 任一所述的表面张力检测装置的表 面张力检测方法, 包括:
光源向样品池中填充的待测液态介质发射光线;
检测器检测所述光线透射过所述样品池中的待测液态介质后 投射在感应区的光点位置;
计算设备根据接收到的光点位置计算所述液态介质的表面曲 率半径,并根据所述表面曲率半径计算所述液态介质的表面张力。
14. 如权利要求 13 所述的表面张力检测方法, 其中, 所述 光源向样品池中填充的待测液态介质发射光线的操作具体为: 所述光源向样品池中填充的待测液态介质发射的光线竖直射 入所述样品池, 且入射点偏移所述样品池中心预设距离。
15. 如权利要求 14 所述的表面张力检测方法, 其中, 所述 光源为线状光源, 所述计算设备根据接收到的光点位置计算所述 液态介质的表面曲率半径, 并根据所述表面曲率半径计算所述液 态介质的表面张力的操作具体包括:
所述计算设备根据接收到的光点位置确定光点偏移值; 所述计算设备根据所述光点偏移值计算所述待测液态介质的 表面曲率半径, 并根据所述表面曲率半径计算所述待测液态介质 的表面张力。
16. 如权利要求 14 所述的表面张力检测方法, 其中, 所述 光线为柱状光源, 所述计算设备根据接收到的光点位置计算所述 液态介质的表面曲率半径, 并根据所述表面曲率半径计算所述液 态介质的表面张力的操作具体包括:
所述计算设备对接收到的柱状光源发出的光线在感应区投射 的光点进行积分确定受光面积;
所述计算设备将所述受光面积计算所述待测液态介盾的表面 曲率半径, 并根据所述表面曲率半径计算所述待测液态介质的表 面张力。
17、 如权利要求 14 所述的表面张力检测方法, 其中, 所述 光线为已知光强的可控柱状光源, 所述计算设备根据接收到的光 点位置计算所述液态介质的表面曲率半径, 并根据所述表面曲率 半径计算所述液态介质的表面张力的操作具体包括:
所述计算设备对接收到的已知光强的可控柱状光源发出的光 线在感应区投射的光点和强度系数的乘积进行积分确定光强; 所述计算设备将所述光强计算所述待测液态介质的表面曲率 半径, 并根据所述表面曲率半径计算所述待测液态介质的表面张 力。
18、 如权利要求 15、 16或 17所述的表面张力检测方法, 其 中, 还包括以下步骤:
通过逐步增加待测液态介质的表面活性剂的浓度, 记录所述 待测液态介质的表面曲率半径的变化曲线;
根据所述变化曲线中的拐点确定所述表面活性剂的临界胶束 浓度。
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