The content of the invention
It is an object of the invention to propose a kind of measuring method of the adherent boundary-layer transmissivity of liquid under External Electrical Field, energy
Enough solve the problems, such as the transmissivity measurement in ER fluid under DC Electric Field/ionic liquid boundary-layer.
The measuring method of the adherent boundary-layer transmissivity of liquid under External Electrical Field according to the present invention, including:
S1, according to the liquid thickness in electric field strength and incident ray direction, determine the adherent boundary-layer region of liquid,
And incoming position of the incident ray on sample cell is determined according to the adherent boundary-layer region;
S2, make incident ray along perpendicular to the direction of liquid levels and electric field, it is incident from the incoming position, obtain into
The first transmitted intensity after the incident intensity of light and the empty sample cell of incident ray transmission is penetrated, according to incident intensity
The photon absorbing intensity of empty sample cell is determined with the first transmitted intensity;
S3, make incident ray along perpendicular to the direction of liquid levels and electric field, it is incident from the incoming position, obtain into
It penetrates the incident intensity of light and incident ray penetrates the second transmitted intensity being equipped with after the sample cell of testing liquid;
S4, photon absorbing intensity and the second transmitted intensity based on incident intensity, empty sample cell, determine the saturating of testing liquid
Penetrate rate;
Wherein, sample cell includes:Pedestal and two electrode plates;The both sides of pedestal raise up so that pedestal has concave
Cross section;The both ends of pedestal set an electrode plate respectively;Electrode plate is " ┣ " type boss structure, including:Perpendicular to pedestal
Electrode plate body and the horizontal projection for being arranged on electrode plate main body side;The concave cavity shape of horizontal projection and base end is matched somebody with somebody
It closes;Two electrode plates are connected respectively with the positive and negative anodes of power supply, for generating electric field.
Preferably, the extension elongation l of horizontal projection in the horizontal direction meets following relation:
L=1.25/d
In formula, μ is the viscosity of sample tank liquid, and unit is:Pa·s;ρ is the density of sample tank liquid, and unit is:
g/cm3;L is the distance between two electrode plates, and unit is:cm;E is electric field strength, and unit is:v/m.
Preferably, sample cell further includes cover board;The horizontal projection of electrode plate thickness in vertical direction and chassis side
Height of projection it is equal, in the same plane, cover board is covered in for the upper surface of horizontal projection and the upper surface of chassis side protrusion
On the raised and described horizontal projection of chassis side.
Preferably, the one side chromium plating contacted with liquid of the cover board and focusing mark is provided with, conduct during for focusing on
The benchmark of position adjustment.
Preferably, the thickness of cover board is no more than 3mm.
Preferably, the material of bottom plate and/or cover board is:CaF2Or BaF2。
Preferably, electrode plate is the titanium or niobium of surface platinum plating.
Preferably, the depth of parallelism between the depth of parallelism between two electrode plates and cover board and bottom plate is not more than 0.5%;
The processing roughness of electrode plate is less than Ra1.6;Bottom plate and the finish of cover board processing are 60-40, and 3, aperture, the depth of parallelism is little
In 0.5%, bottom plate and cover board bubble-free, without scattering particles.
Preferably, the thickness of horizontal projection in vertical direction is no more than 3mm.
Preferably, measuring system according to the present invention further comprises:
Chopper between incident light source and sample cell is set, specific frequency is intercepted in the light generated from incident light source
Wavelength signals are as incident ray;
Two lock-in amplifiers between sample cell and measuring unit are set, are respectively used to eliminate the modulating frequency of chopper
The influence brought with ac frequency change, and the optical signal to being emitted from sample cell is amplified processing.
Advantageous effect according to the present invention:
(1) both ends of sample cell pedestal set the electrode plate being connected with power positive cathode respectively, can be in sample cell
Liquid improves electric field, and then measures the variation of liquid refractivity under External Electrical Field;
(2) both sides of pedestal are raised up, electrode plate is designed as to " ┣ " type boss structure so that horizontal projection and bottom
The concave cavity shape cooperation of seat end, convenient for accurately obtaining the thickness of sample tank liquid, improves the accuracy of measurement structure;
(3) thickness of the horizontal projection of electrode plate in vertical direction is equal with the height of projection of chassis side, horizontal convex
The upper surface risen and the upper surface of chassis side protrusion in the same plane, one are covered on chassis side protrusion and horizontal projection
A cover board can avoid the liquid level injustice problem caused by surface tension of liquid;
(4) chopper is set between incident light source and sample cell, and the wavelength signals that can intercept specific frequency are used as
Penetrate light source;Two lock-in amplifiers between sample cell and measuring unit are set, on the one hand can eliminate the modulating frequency of chopper
With the influence that brings of ac frequency change, on the other hand can and amplify the optical signal being emitted from sample cell, prevent because from
The optical signal of sample cell outgoing is too weak and can not obtain or can not accurately analyze liquid refractivity.
Specific embodiment
Exemplary embodiments of the present invention are described in detail with reference to the accompanying drawings.Illustrative embodiments are retouched
It states merely for the sake of demonstration purpose, and is definitely not to the present invention and its application or the limitation of usage.
The measuring method of the adherent boundary-layer transmissivity of liquid under External Electrical Field according to the present invention, including:
S1, according to the liquid thickness in electric field strength and incident ray direction, determine the adherent boundary-layer region of liquid,
And incoming position of the incident ray on sample cell is determined according to the adherent boundary-layer region;
S2, make incident ray along perpendicular to the direction of liquid levels and electric field, it is incident from the incoming position, obtain into
The first transmitted intensity after the incident intensity of light and the empty sample cell of incident ray transmission is penetrated, according to incident intensity
The photon absorbing intensity of empty sample cell is determined with the first transmitted intensity;
S3, make incident ray along perpendicular to the direction of liquid levels and electric field, it is incident from the incoming position, obtain into
It penetrates the incident intensity of light and incident ray penetrates the second transmitted intensity being equipped with after the sample cell of testing liquid;
S4, photon absorbing intensity and the second transmitted intensity based on incident intensity, empty sample cell, determine the saturating of testing liquid
Penetrate rate.
Measuring method according to the present invention uses measuring system as shown in Figure 1, including:Incident light source 10, sample cell 20,
Power supply 30 and measuring unit 40.The present invention holds testing liquid using sample cell, and sample cell 20 includes:Pedestal 21 and two electricity
Pole plate 22.Wherein, the both sides of pedestal 21 raise up so that pedestal 21 has concave cross-sectional;The both ends of pedestal 21 are set respectively
Put an electrode plate 22.Fig. 2 a are the front views of sample cell pedestal according to the present invention, and Fig. 2 b are sample cells according to the present invention
The top view of pedestal, Fig. 2 c are the left views of sample cell pedestal according to the present invention.Two protrusions of 21 both sides of pedestal and bottom
Two electrode plates at seat both ends form four sides of sample cell 20, and the semi-closed structure that this four sides are formed can be used for containing
Put testing liquid.Due to absorption of the sample cell 20 to optical signal, optical signal can be weakened after penetrating sample cell 20, if from sample
The optical signal that slot 20 is emitted is excessively weak, easily so that measuring unit 40 can not accurately analyze sample cell according to weaker optical signal
The refractive index of liquid in 20, even more so that measuring unit 40 is obtained less than optical signal.It, can be in order to avoid the generation of such case
Make the transmitance of the optical signal of the designated wavelength range of sample cell 20 not less than a certain threshold value, such as 90%.Preferably, for the ease of
The transmission of optical signal, the material of the bottom plate 21 of bottom plate 21 can be CaF2Or BaF2。
Electrode plate 22 is " ┣ " type boss structure, including:Perpendicular to pedestal 21 electrode plate body 221 and be arranged on electrode
The horizontal projection 222 of 221 side of plate body.Fig. 3 a are the front views of sample cell electrode plate according to the present invention, and Fig. 3 b are bases
The top view of the sample cell electrode plate of the present invention, Fig. 3 c are the left views of sample cell electrode plate according to the present invention.Horizontal projection
222 coordinate with the concave cavity shape of 21 end of pedestal, and the semi-closed structure formed can be used for holding testing liquid.Two
Positive and negative anodes of the electrode plate 22 respectively with power supply 30 are connected, and when opening power supply 30, electric field is generated between two electrode plates 22 so that
Liquid in sample cell 20 is under External Electrical Field.
Common metal can constantly dissolve during being used as anode so that there are gap, surfaces between coating for it
Coating can rapidly depart from the dissolving of the metal anode.Since titanium, niobium etc. belong to valve metal, make directly as electrode anode
Used time can be passivated and stop reaction and conductive, so itself will not dissolve and corrode, when using the valve metals such as titanium, niobium as electrode
It is not easy during anode because substrate dissolving causes platinum coating to come off, conductive coating lasts a long time.Therefore, it is according to the present invention preferred
Embodiment.Electrode plate 22 is the titanium or niobium of surface platinum plating.
The extension elongation of horizontal projection is mainly determined by the boundary layer thickness of liquid, final again by the electrochemistry physical property of liquid
Matter is determined, i.e., the size of field strength inhomogeneities determines under DC Electric Field.Boundary layer thickness is big, and the level of counter electrode plate is convex
The extension elongation risen can be smaller, as long as can guarantee enough testing distances.Preferably, horizontal projection is in the horizontal direction
Extension elongation l meet following relation:
L=1.25/d
In formula, μ is the viscosity of sample tank liquid, and unit is:Pa·s;ρ is the density of sample tank liquid, and unit is:
g/cm3;L is the distance between two electrode plates, and unit is:cm;E is electric field strength, and unit is:v/m.
The thickness of horizontal projection in vertical direction is mainly determined that horizontal projection is more thin more is difficult to by the absorption coefficient of liquid
Processing.If horizontal projection is too thick and sample cell in liquid thickness be less than horizontal projection thickness, be not easy to adding for testing liquid
Add, while be also unfavorable for accurately obtaining the liquid thickness in sample cell;If liquid thickness and level in horizontal projection sample cell
Projection thickness is equal, then the thickness of sample tank liquid can be accurately obtained by the thickness of horizontal projection, but horizontal at this time
The thickness of protrusion is bigger, and the liquid thickness in sample cell can accordingly increase, if the excessive easy weakening transmitted light of liquid absorption coefficient
Signal so that measuring unit can not obtain optical signal transmissive or the optical signal transmissive of acquisition is too weak, so that liquid can not be obtained
The transmissivity of adherent boundary-layer.Therefore according to different types of liquid, the thickness of horizontal projection can as far as possible be existed with respective change
Can reach do under conditions of machining accuracy it is thinner.According to a preferred embodiment of the invention, horizontal projection is in vertical direction
Thickness be no more than 3mm.
Theoretically between two electrode plates 22 should keeping parallelism, but actual processing or make sample cell when, due to adding
Work error is extremely difficult to be substantially parallel between two electrode plates.If electrode plate 22 is not parallel will to cause liquid electric field intensity inside high point
Cloth is uneven, causes the fluid transmittance measurement result in certain area inconsistent, causes larger measurement error.In addition, passing through
When the liquid volume and the cross-sectional area of sample cell added in sample cell determines the liquid thickness on incident ray direction, if sample
The electrode plate 22 at product slot both ends is not parallel, then the liquid thickness obtained according to the method described above is inaccurate, and also measurement result can be produced
It is raw to influence.Therefore, in order to ensure the accuracy of measurement result, it is necessary to two electrode plates 22 be made to keep certain depth of parallelism.
For influence size of the machining accuracy to field strength uniformity of the Electrode depth of parallelism, the present invention for 50mm ×
The rectangular duct of 5mm using numerical simulation the technique study Different electrodes depth of parallelism when, electric field strength during additional 1V voltages
Distribution situation, the spacing between two electrode plates is 5mm.Numerical simulation shows by the testpieces size designed in this figure, figure
4a-4e shown in preferred embodiment according to the present invention, the relation between the depth of parallelism and field uniformity of two electrode plates, figure
In, the depth of parallelism from Fig. 4 a- Fig. 4 d be respectively in 5%, 2.5%, 1% and 0.5%, Fig. 4 e two electrode plates be substantially parallel, electricity
The unit of field intensity is V/m, and gray value more large surface electric field strength is bigger, and the uniformity of gray value difference more large surface electric field is more
Difference.When can be seen that two electrode plates from Fig. 4 a-4e and being substantially parallel, the uniformity of electric field strength is best, when two electrode plates it
Between not exclusively it is parallel when, the depth of parallelism is smaller, and the uniformity of electric field strength is better.When the depth of parallelism is less than 0.5% between two electrodes,
The numerical fluctuations (maximum/minimum value compares situation during uniform electric field) of field strength are less than 0.5% inside incident light direction upper liquid body,
And light path upper and lower ends region is concentrated mainly on, field strength has almost no change with uniform electric field in the middle part of light path.
In order to investigate influence of the numerical fluctuations 0.5% of liquid internal field strength to transmittivity measurement results, in the item of Fig. 4 d
Under part, continue to investigate influence of the field strength variation to transmittivity measurement results by taking methyl-propyl iodonium imidazolide salts as an example.The multiple folding of medium
Penetrate rateWith complex phase to permittivity ε (ω)=ε1(ω)+iε2Relation between (ω) is [n (ω)+i κ
(ω)]2=ε1(ω)+iε2(ω) has real part equal with imaginary part difference, obtains
n(ω)2-κ(ω)2=ε1(ω) 2n (ω) κ (ω)=ε2(ω)
And absorption coefficient (ω) is directly proportional to extinction coefficient κ (ω), lower relation of plane is presented in the two:
Wherein ω is angular frequency, and f is frequency, and c is the light velocity;
When wavelength is 1520nm, and voltage is 0V, refractive index 1.56292, absorption coefficient 0.474cm-1, electrical conductivity is
0.8ms/cm-1, the value of κ (ω) is calculated at this time as 1.52 × 10-4 × 0.474/2/3.14=1.132 × 10-5cm-1, by
This calculates to obtain ε1The value of (ω) is 2.44272-1.28 × 10-10=2.44272, ε2The value of (ω) is 0.00000035845;
When wavelength is 1520nm, and voltage is 1V, refractive index 1.56287, absorption coefficient 0.775cm-1, electrical conductivity is
0.8ms/cm, the value that κ (ω) is calculated at this time are 1.52 × 10-4 × 0.775/2/3.14=1.875 × 10-5cm-1, thus
ε is calculated1The value of (ω) is 2.44256-3.515 × 10-10=2.44256, ε2The value of (ω) is 0.00000058607;
When wavelength is 1520nm, and voltage is 2V, refractive index 1.56276, absorption coefficient 0.852cm-1, electrical conductivity is
0.8ms/cm, the value that κ (ω) is calculated at this time are 1.52 × 10-4 × 0.852/2/3.14=2.062 × 10-5cm-1, thus
Calculate to obtain ε1The value of (ω) is 2.44222-4.252 × 10-10=2.44222, ε2The value of (ω) is 0.00000064448;
When wavelength is 1520nm, and voltage is 3V, refractive index 1.56266, absorption coefficient 0.945cm-1, electrical conductivity is
0.8ms/cm, the value that κ (ω) is calculated at this time are 1.52 × 10-4 × 0.945/2/3.14=2.287 × 10-5cm-1, thus
Calculate to obtain ε1The value of (ω) is 2.4419-5.23 × 10-10=2.4419, ε2The value of (ω) is 0.00000071476;
Due to more than voltage be for the distance between two electrode plates be 5cm, supply voltage is exemplified by 1V changes to 3V,
Field strength increases twice (field strength variation is 200%) at this time, and ε1(ω) has only changed 1.392 × 10-4, ε2(ω) also just becomes
Change 9.96%, analyzed accordingly, the error caused by experimental result of field strength variation 0.5% can be ignored.Therefore, according to the present invention
Preferred embodiment, the depth of parallelism of two electrode plates is maintained within 0.5%.
Electrode plate 22 can be connected by conducting wire with power supply 30.For example, one end of conducting wire is welded on electrode plate, conducting wire
The other end be connected with the positive or negative pole of power supply;For another example, set on electrode plate and stretch out unit, one end of conducting wire passes through admittedly
Clamp be connected with electrode plate or the stretching unit on open up aperture for connecting wire, one end of conducting wire is directly wound in
On the aperture.According to a preferred embodiment of the invention, be provided on electrode plate with electrode plate it is integrated stretch out unit 50, so as to
It is connected in power supply, as shown in Fig. 3 a, 3b.Tiny platinum filament is connected by argon arc welding with platinized platinum, in the one layer of protection of platinum filament housing
Layer, so as to prevent the wall surface of platinum filament and optical spectrometer sample chamber is in contact in measurement process from causing to leak electricity;Alternatively, use electrode holder
The part that platinized platinum has more glass guide channel is clamped, and electrode holder is connected with external power supply 40 with conducting wire.
The pedestal of sample cell and two electrode plates can be bonded together by optics cold glue, should be noted that optics is cold when bonding
Glue cannot ooze out glued horizontal plane, in order to avoid must assure that two electrode plates begin to microscope by having an impact, while during gluing
The state vertical with pedestal is kept eventually.Testing liquid is poured into after drying box drying 12h is put into after gluing is complete, then stands 6h, with true
Protect the liquid No leakage in sample cell.According to a preferred embodiment of the present invention, when measuring, sample cell is put first
It puts on the mobile platform of Bruker-hypersion infrared microscopes, places clay in the surrounding of sample cell to fix sample cell
Position.
Liquid close to electrode plate is due to the presence of surface tension, and liquid is uneven, so as to be generated to incident ray
Refraction and/or reflection problems influence the accuracy of measurement result.In addition, when the liquid thickness in sample cell is smaller, in liquid
Under the action of surface tension, the liquid level of liquid is easily uneven so that the liquid thickness at different incoming positions is inconsistent, influences to survey
Measure the accuracy of result.In order to eliminate surface tension of liquid to the preferred of measurement result, a cover board can be designed for sample cell
23, and so that the thickness of the horizontal projection of electrode plate in vertical direction is equal with the height of projection of chassis side, horizontal projection
Upper surface and chassis side protrusion upper surface in the same plane, liquid thickness and horizontal projection in guarantee sample cell
Thickness is equal, then covers cover board on the upside of liquid level on chassis side protrusion and horizontal projection, i.e. so that liquid level is convex with level
The extension risen is parallel, can so ensure the consistent of liquid thickness in sample cell, avoid drawing due to surface tension of liquid
The liquid level injustice problem risen.
In order to improve the accuracy of multiple measurement results and accuracy, needed before every measurement by adjusting sample cell
Position be focused.According to a preferred embodiment of the invention, cover board 23 the one side chromium plating contacted with liquid and be provided with
Mark is focused on, benchmark during for focusing on as position adjustment, for example, the thickness according to the adherent boundary-layer of the liquid actually measured
Scope or according to it is fixed distance be spaced, in the cross shape marks processed on one side contacted with liquid of cover board 23.The thickness of cover board 23
Degree is bigger, stronger to the absorption of optical signal, so as to weaken the intensity for the optical signal being emitted from sample cell 20, is not easy to standard
Really obtain the refractive index of liquid boundary-layer.According to a preferred embodiment of the invention, the thickness of cover board 23 is no more than 3mm.Cover board 23
If thickness it is too small, easily swum under the buoyancy of liquid on the upside of liquid, surface tension of liquid can not be completely eliminated
Influence to liquid thickness homogeneity.Preferably, the thickness of cover board 23 is 3mm.Preferably, for the ease of the transmission of optical signal,
The material of the bottom plate 21 of bottom plate 21 can be CaF2Or BaF2。
Incident light source 10 generate incident ray from close to electrode plate 22 liquid boundary-layer position at, along perpendicular to liquid
Body fluid face and the direction of electric field are incident.Measuring unit 40 is located in the light path of incident ray, is emitted for receiving from sample cell 20
Optical signal and analyze obtain External Electrical Field under the adherent boundary-layer of liquid transmissivity.
The incident ray that incident light source 10 generates is it is possible that the clutter including its all band, influences the accurate of measurement result
Property.The appearance of this problem in order to prevent can set chopper between incident light source 10 and sample cell 20, specific to intercept
The wavelength signals of frequency are as incident light source.Two lock-in amplifiers are set between sample cell 20 and measuring unit 40 simultaneously,
On the one hand the modulating frequency and ac frequency that chopper can be eliminated change the influence brought, on the other hand can and amplify from sample
The optical signal of product slot outgoing prevents from not obtaining because the optical signal being emitted from sample cell is too weak or can not accurately analyzing liquid
Body refractive index.Fig. 5 shows the flow chart that the adherent boundary-layer transmissivity of liquid is measured in preferred embodiment according to the present invention, figure
In, the incident ray that continuous spectrum light source 11 is sent forms monochrome after plus lens group 12, chopper 13 and monochromator 14
Light penetrates the liquid in sample cell, is emitted from sample cell after then being focused on by infrared surface focus lamp 15 and infrared microscope 16
Optical signal enter infrared detector 41, infrared detector 41 enters level-one lock phase according to the electric current that the optical signal received generates
Amplifier 42 enters back into two level lock-in amplifier 43 after electric current is accordingly amplified, after being handled through two level lock-in amplifier 43
Optical signal enter computer 44, computer 44 carries out analysis calculating according to the optical signal of reception, determines the adherent boundary-layer of liquid
Transmissivity.Level-one lock-in amplifier 42 is mainly used to eliminate the influence that the modulating frequency of chopper 13 is brought, and secondary latch is mutually put
Big device 43 is mainly used for elimination ac frequency and changes the influence brought to measurement.By the effect of the two lock-in amplifiers,
The measured signal of specific frequency can be extracted, excludes noise signal, and enhances the optical signal of input computer to be convenient for measuring.
Chopper controller 60 in figure is used to control chopper 13, level-one lock-in amplifier 42 and two level lock-in amplifier 43.
Since influence of the electric field to liquid refractivity is little, and the thickness of liquid boundary-layer is smaller, in order to accurately measure
The transmissivity of the adherent boundary-layer of liquid under External Electrical Field, it is necessary to assure measuring device has higher measurement accuracy.According to this
The preferred embodiment of invention, the depth of parallelism between the depth of parallelism and cover board and bottom plate between two electrode plates are not more than
0.5%;The processing roughness of electrode plate is less than Ra1.6;Bottom plate and the finish of cover board processing are 60-40, and 3, aperture is parallel
Degree is no more than 0.5%, bubble-free in bottom plate and cover board, without scattering particles.
Measuring method according to the present invention can be used for the transmissivity of liquid under measurement non-electrical field action.Work as testing liquid
Thickness it is smaller when, be difficult to ensure that the liquid level of testing liquid is consistent using conventional measuring system.By using the present invention
Sample cell, can accurately obtain the thickness of testing liquid, and the liquid level caused by surface tension of liquid can be avoided not
Flat problem.Based on this, the present invention can also be applied to the survey of gradient liquid (liquid i.e. with non-uniform transmission rate) transmissivity
The fields such as measurement of fluid transmittance at different position in amount, the solution with concentration difference.The biofilm thickness of organism is smaller,
And there is substantial amounts of biochemical reactions for the both sides and inside of biomembrane.Since the present invention can measure miniature scale scope
Interior fluid transmittance, therefore can also use and be applied to biofilm thickness inverting and its optical characteristic measurement, different type cell
Ir transmissivity measurement etc. fields.
Although with reference to illustrative embodiments, invention has been described, but it is to be understood that the present invention does not limit to
The specific embodiment that Yu Wenzhong is described in detail and shows, in the case of without departing from claims limited range, this
Field technology personnel can make various changes to the illustrative embodiments.