CN101701895B - Device and method capable of measuring liquid-liquid diffusion coefficient at different temperatures - Google Patents
Device and method capable of measuring liquid-liquid diffusion coefficient at different temperatures Download PDFInfo
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Abstract
The invention relates to a device and method capable of measuring liquid-liquid diffusion coefficient at different temperatures. In the invention, solution in different concentrations is injected into a micro fluid control chip 2 by inject pumps 1 and 5, concentration distribution of mixing runner in the micro fluid control chip 2 is measured by a Raman spectroscopy, and further liquid-liquid diffusion coefficient is inverted. The micro fluid control chip is placed on a soaking block 4, and the soaking block is connected with a metering pump 7 and a thermostatic waterbath 8, so as to realize measurement at different temperatures. The micro fluid control chip 2 realizes high-accuracy measurement by design of winding micro runner structure before mixing, mixing runner section designed as a rectangle with high crown proportion and aluminizing at the bottom of runner. The device and method of the invention can realize continuous measurement of liquid-liquid diffusion coefficient at different temperatures and has the advantages of less sample usage, low cost, non contact, high sensibility, high repeatability, high efficiency, small error, safety and reliability and easy operation.
Description
Technical field
The present invention relates to a kind of apparatus and method that can under different temperatures, measure liquid-liquid diffusion coefficient, the particularly a kind of apparatus and method that can under different temperatures, measure liquid-liquid diffusion coefficient based on Raman spectrum and micro-fluidic chip.
Background technology
Liquid Phase Diffusion plays important effect in research mass transport process, calculating mass transfer rate and Chemical Engineering Design and exploitation, coefficient of diffusion is the key of unit operations and reaction design.About the measurement of liquid liquid mass transfer and diffusion aspect and theoretical description more than gas and solid difficulty.At present, Liquid Diffusion Coefficient mainly is to adopt experiment measuring to obtain, and mainly contains barrier film pond method (quasi-stable state), real time laser holographic interferometry method (unstable state), Talyor dispersion (impulse attenuation).
Barrier film pond method is widely used because device is simple.But about being injected into, solution can measurement result is caused certain error, and error will strengthen under higher probe temperature with diffusion in the two chamber processes.When measuring the coefficient of diffusion under the different temperatures, device need be cleaned, equilibrium temperature again after the drying, conventional efficient is low.
The real time laser holographic interferometry method by set up liquid liquid mass transfer and and the laser holographic interferometry device, Real Time Observation is taken the interface phenomena and the distribution of concentration of liquid liquid mass transfer, and, obtain the direct interpretation method of the striped formula of Liquid Diffusion Coefficient, and then calculate Liquid Diffusion Coefficient through the theoretical formula derivation.Similar to barrier film pond method, can't eliminate the diffusion couple measurement result influence of in forming liquid liquid initial interface process, following in the measuring process.And can't realize the measurement of liquid-liquid diffusion coefficient under the different temperatures.The metering of laser hologram reflection simultaneously system operation complexity is had relatively high expectations to operating personnel.
Talyor dispersion method is that the pulse of solute drop is injected in the elongated tubular, and solvent carries out laminar flow continuous flow in elongated tubular, and drop is disperseed after being injected into elongated tubular, measures and disperses the CONCENTRATION DISTRIBUTION that is caused and then calculate coefficient of diffusion.But the method is only applicable to lean solution, and can not realize the measurement of liquid-liquid diffusion coefficient under the different temperatures.
Micro-fluidic chip is as a kind of analysis device fast and efficiently rapid rising in nearly ten years, a large amount of patented technologies occurred, included cell qualitative analysis (CN200310105075.8), Separation of Proteins analysis (CN200410020971.9), be used for small and dense low-density lipoprotein analysis (CN200810032532.8) of diagnosis of coronary heart disease or the like based on micro-fluidic chip.Because the micro-fluidic chip runner is small, the runner inner fluid is the laminar flow stable-state flow, and diffusion becomes the major control factor of mass transport process, and it is feasible coming inverting and obtain liquid-liquid diffusion coefficient by the concentration field in the measurement runner.Micro-fluidic chip is easy to make in batches, and measurement and experimental cost are lower.So, measure for realizing the quick, efficient of liquid-liquid diffusion coefficient, adopting micro-fluidic chip (microfluidic chip) technology is a kind of desirable scheme.US7233865 has disclosed a kind of method of the measurement coefficient of diffusion based on micro-fluidic chip, utilize the structure of a right-angled intersection, to contain the solution of measured matter is in an angle of 90 degrees introducing runner with the damping fluid that does not contain this material, converge diffusion at infall, measured matter is labeled to record the CONCENTRATION DISTRIBUTION that it spreads in damping fluid, separate at once after infall converges, eliminate the influence of the background signal of indiffusion molecule when detecting.This method is simple in structure, but only considers the diffusion of particle, is not suitable for the measurement of neat liquid.
Raman spectrum can be realized non-contacting qualitative and quantitative analysis as a kind of chemical analysis method efficiently.People such as Lee utilize Raman spectrum to observe the interior imines forming process (Journal of Raman Spectroscopy, 34,737) of micro-fluidic chip; People such as Fletcher utilize Raman spectrum to study the process of ethanol and acetate synthesizing ethyl acetate (Electrophoresis, 24,3239) in T type micro-fluidic chip; People such as Sarrazin have utilized raman study based on the diffusion and the H of drop on micro-fluidic chip
2O and D
2The building-up process of O (Analytical Chemistry, 80,1689); People such as Yin utilize Raman spectrum to carry out original position to contain mineral screening (Analytical Chemistry, 81,473).CN1878875A has disclosed and has utilized nanochannel or microchannel to fill nm of gold or silver-colored particulate aggregate, and nucleotide is detected by Raman spectrum through the nano particle meeting point, thereby realizes dna sequencing.
Salmon (Appl.Phys.Lett, 86,3) has proposed the measuring method based on the liquid-liquid diffusion coefficient of Raman spectrum and micro-fluidic chip first.On Y type micro-fluidic chip, measured the interdiffusion coefficient of dimethyl sulfoxide (DMSO), acetonitrile, dimethyl formamide and chloroform under the normal temperature.But there is following problem in its method and apparatus: only limit to normal temperature, can not realize the measurement of coefficient of diffusion under the different temperatures; Fail to consider the disturbance of raman laser heating to measurement result, measuring accuracy is low.
How fast, efficient, high precision, the liquid-liquid diffusion coefficient measured under the different temperatures at low cost be problem demanding prompt solution as everyone knows, temperature is very big to the influence of liquid-liquid diffusion coefficient, so.
Summary of the invention
At the problem that exists in the existing liquid-liquid diffusion coefficient measuring method, the invention provides a kind of measurement mechanism and method of the liquid-liquid diffusion coefficient based on Raman spectrum and micro-fluidic chip, has following advantage: can obtain the liquid-liquid diffusion coefficient under the different temperatures, but the continued operation of precision height, efficient height, reagent dosage are little, simple to operate, safe and reliable.
The present invention is achieved by the following technical solutions:
A kind of device that can under different temperatures, measure liquid-liquid diffusion coefficient, it is characterized in that, described device comprises: microfluidic system, soaking system and confocal laser Raman spectrometer 3, described microfluidic system comprises the micro-fluidic chip 2 that a base material is a silicon, micro-fluidic chip 2 is provided with two sinuous fluid channel 9 and 10 through etching, syringe pump 1 and syringe pump 5 enter the mouth 15 with two sinuous fluid channel respectively, 16 link to each other, article two, connect thermopair T1 respectively on the sinuous fluid channel, compile behind the T2 and form a mixing diffusion straight channel 11, article two, the incident angle of sinuous fluid channel inlet is 0 °, thermopair T1, T2 is positioned at the meet upstream apart from point 0.5～2mm place, mixes the diffusion straight channel and exports 17 places and connect a thermopair T3 and link to each other with waste liquid tank 6;
Wherein, the xsect that mixes diffusion straight channel 11 is a rectangle, and width is 600～1200 μ m, and the degree of depth is 10～50 μ m; The fluid channel 9 of wriggling and 10 the degree of depth are 10～50 μ m, and length is greater than 5cm, and flow channel cross-section is a rectangle, and width is for mixing half of diffusion straight channel 11;
Described soaking system comprises one by three copper sheets soaking copper billet 4 that is welded, be processed with annular channel 14 at the middle copper sheet upper surface between two copper sheets up and down, the width of annular channel is 1～5mm, the annular channel length overall is 0.3～1m, and annular channel is provided with annular channel import 12 and annular channel outlet 13 respectively; Annular channel import 12 links to each other with volume pump 7 outlets, and the import of volume pump 7 links to each other with constant water bath box 8;
In the technique scheme, in the sinuous fluid channel 9 of micro-fluidic chip 2 and 10 and mix the runner bottom of diffusion straight channel 11, have the silver of one deck deposition or the metallic film of aluminium, film thickness is 150～400nm, preferred 200～300nm.
In the technique scheme, mix preferred 700～900 μ m of width of the xsect of diffusion straight channel 11, highly preferred 25～35 μ m.
In the technique scheme, the preferred 2～3mm of the width of the annular channel of soaking copper billet 4, the preferred 0.5～0.8m of total length.
It is base material that micro-fluidic chip 2 is selected silicon for use, to guarantee good thermal conductivity.Adopt dark silicon etching technology on silicon chip, to process as shown in Figure 2 runner.Laser thermal effect when testing for eliminating Raman is at the metallic film of silicon chip runner bottom deposit one deck high reflectance.Earlier by magnetron sputtering with the silicon chip surface of deposit metal films after etching, adopt again negative adhesive process with the metallic film beyond the runner peel off with guarantee its can with send the encapsulation of Simon Rex glass anode linkage, and keep aluminium film bottom the runner with reflector laser irradiation.
The high-reflectivity metal film is selected high reflectance materials such as silver, aluminium for use, and preferred aluminium has high cost performance.Film thickness is 150～400nm, preferred 200～300nm.
The manufacture craft of described depositing metal films is made as example with the thick aluminium film of 200nm, carries out magnetron sputtering behind photoetching shown in Figure 3, dark silicon etching process.Use the aluminium target,, be evacuated to 1e at 22 ℃
-6Pa feeds argon gas again, behind the pre-sputter 120s, and abundant again sputter 540s.The aluminium lamination that this is deposited on the etching water passage surface, recording reflectivity is 97%, and the naked silicon runner of sputter not, recording reflectivity is 37.7%.
Described negative adhesive process, as Fig. 4, the negative glue glue that preferably reverses, counter-rotating glue AZ5214E through exposing after, reverse baking and general exposure, performance is similar to bears glue, and is more conducive to peel off.Even glue on the slice, thin piece behind the depositing operation, place again carry out on 95 ℃ of hot plates before baking 1 minute, use the mask plate exposure 4s that uses in the etching technics, again in 100 ℃ of bakings 1.5 minutes down, take down the mask 50s that exposes to the sun entirely at last, develop.Glue beyond the runner is removed, and correspondingly the aluminium lamination beyond the runner comes out.Use metal etch IBE (ion beam etching) at last, 2.1 * 10
-2Under Pa working pressure and the 16 ℃ of working temperatures, feed argon gas, ion energy is adjusted into 351V, electronic beam current 99mA, in and 127mA, anode imposes 0.95A45V, and finally adds to 180V, negative electrode 5.7A, bombardment aluminium lamination 18 minutes is removed runner aluminium film in addition fully.
Soaking piece of the present invention is made by red copper, by diffusion welding three copper sheets is welded, as shown in Figure 5.Wherein, a middle copper sheet is processed with the runner of annular.The annular channel length overall is 0.3～1m, and preferred 0.5～0.8m, the width of runner are 1～5mm, preferred 2～3mm.Soaking piece area is greater than micro-fluidic chip and be convenient to be placed on the Raman microscope objective table.The soaking piece is provided with imports and exports the pipeline connection annular channel.
The present invention also provides a kind of method based on liquid-liquid diffusion coefficient under the measurement different temperatures of said apparatus, comprises the steps:
1) the water bath temperature is set in below the boiling point of sample, open syringe pump, behind the temperature stabilization of water bath with thermostatic control, in micro-fluidic chip, feed the solution of variable concentrations to be measured through volume pump, when the deviation of reading of three thermopairs less than 0.5K, calculate the mean value of three measured values and measure corresponding temperature as coefficient of diffusion;
2) described Raman spectrometer configures wave-number range, laser power and the sweep time that comprises the test substance characteristic peak, guarantee that the signal that Raman scanning obtains is enough to quantitative test, the tested xsect of test section is apart from two inlet 0.5～2cm place, joint downstream xsects, autoscan after on the Width sweep span being set, scanning needs the zone that concentration change is arranged on the cover width direction;
3) the spectrogram information that Raman spectroscopy scans is obtained is related with concentration, thereby obtain testing the concentration and the position data of xsect, match obtains a coefficient of diffusion value, when the two solution concentration differences of injecting less, can think that diffusion coefficient D is a constant under this concentration, promptly obtain liquid-liquid diffusion coefficient D by formula (1) inverting, wherein, (x is y) for the solution concentration (being obtained by Raman spectroscopy scans) at measuring point place for c; c
1, c
2Be the initial mole fraction (known) of two solution; Y is that measuring point is in the distance (control Raman spectrum automatic mobile platform obtain) of width of flow path direction apart from diffuse interface; X is the vertical range (the automatic mobile platform of control Raman spectrum obtains and immobilizes, and is known) of tested cross-sectional distance joint, and U is mean flow rate (being calculated by the syringe pump input flow rate, known), and erf is an error function.
4) change two concentration of injecting solution to record the coefficient of diffusion under the variable concentrations, change the water bath temperature to record the coefficient of diffusion under the different temperatures.
Beneficial effect
The present invention is based on micro-fluidic chip and Raman spectrum, realize the high-acruracy survey of the liquid-liquid diffusion coefficient under the different temperatures.Be processed with the copper billet of annular channel and be aided with water-bath, volume pump and guarantee that copper billet upper surface temperature is even.Micro-fluidic chip is fixed on the copper billet upper surface by heat-conducting glue.Basic structure is the Y type structure that crosses, and two access roades make the abundant preheating of sample for long serpentine flow-channels.The micro-fluidic chip straight channel is the rectangularl runner with big the ratio of width to height, with deflection that suppresses diffuse interface and the homogeneity that guarantees test section xsect temperature.Realize the measurement of the liquid-liquid diffusion coefficient under the different temperatures by the temperature that changes water-bath.Laser thermal effect when testing for eliminating Raman, the nano metal aluminium at silica-based runner bottom sputter high reflectance has improved the precision of measuring.Compare with the method for Salmon report, can realize the measurement of liquid-liquid diffusion coefficient under the different temperatures and eliminate the influence of laser thermal effect.
Compare with conventionally test method such as barrier film Chi Fa, this device has following several characteristics: adopt the micro-fluidic chip amount of samples few, for the measurement of the coefficient of diffusion of a temperature, chip method expends reagent and is about 1 μ L, and barrier film pond method is about 10mL; Cost is low; Safe for hypertoxic hazardous chemical; Noncontact; High sensitivity; Can realize the continuous coverage of liquid-liquid diffusion coefficient under the different temperatures easily by changing bath temperature; The efficiency of measurement height, for the measurement of the coefficient of diffusion of a temperature, chip method 10min consuming time approximately is more than the barrier film pond method 1h consuming time; Avoided the routine measurement method when forming the initial propagations interface, to ignore the error that existing diffusion is caused, easy operating.
The invention has the advantages that the structural design by micro-fluidic chip also realizes the continuous coverage of the liquid-liquid diffusion coefficient under the different temperatures in conjunction with soakage device, and with runner bottom sputtered aluminum film to improve measuring accuracy.With respect to prior art be a kind of fast, the measurement mechanism and the method for efficient, high precision, low cost, easy operating, be with a wide range of applications.
Description of drawings
Fig. 1 is an installation drawing of measuring liquid-liquid diffusion coefficient under the different temperatures
Wherein, 1,5: syringe pump, 2: micro-fluidic chip, 3: Raman spectrometer, 4: the soaking copper billet, 6: waste liquid tank, 7: volume pump, 8: constant water bath box, 9,10: the fluid channel of wriggling, 11: mixed DC road, 12: import, 13: outlet, T1, T2, T3: thermopair.
Fig. 2 is the microfluidic chip structure synoptic diagram
Wherein, 2: micro-fluidic chip, 9,10: the fluid channel of wriggling, 11: mixed DC road, 15,16: the fluid channel of wriggling inlet, 17: the outlet of mixed DC road, T1, T2, T3: thermopair.
Fig. 3 is the manufacture craft process flow diagram of silica-based micro-fluidic chip substrate
Wherein: 18: silicon dioxide layer, 19: silicon substrate, 20: eurymeric photoresist, 21: light source, 22: mask.
Fig. 4 is negative adhesive process process flow diagram
Wherein: 23: aluminium film, 24: negative photoresist.
Fig. 5 is a soaking copper billet structural representation
Wherein, 12: annular channel import, 13: annular channel outlet, annular channel 14.
Fig. 6 is the coefficient of diffusion matched curve figure of room temperature carapax et plastruw testudinis benzene mole mark 0.347 correspondence of the present invention's embodiment 1
Fig. 7 is the present invention's the embodiment 1 and the toluene and the cyclohexane coefficient of diffusion measurement data figure of Comparative Examples 1
Wherein, ▲ embodiment 1 (328K), ● embodiment 1 (313K), ■ embodiment 1 (298K), △ Comparative Examples 1 (328K), zero Comparative Examples 1 (313K), △ Comparative Examples 1 (298K).
Fig. 8 measures the data plot of toluene and cyclohexane coefficient of diffusion on ordinary silicon-glass-chip for the present invention's Comparative Examples 2
Wherein, * Comparative Examples 2 (25mW 10s), ◇ Comparative Examples 2 (12.5mW 20s),
Comparative Examples 2 (2.5mW 100s), ■ embodiment 1 (25mW 10s), Comparative Examples 1.
Embodiment
For purpose of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and conjunction with figs. is described in detail below.
The present invention can realize the continuous coverage of the liquid-liquid diffusion coefficient under the different temperatures, adopt the confocal microscopy Raman spectrometer to realize the sample concentration test that micro-fluidic chip is interior, bottom surface, microchannel sputter high reflectance nano metal aluminium weakens laser thermal effect, the soaking piece is provided with the required even steady temperature of sample in the chip, and the last revised function match of nonlinear fitting Fick's second law gets under the different temperatures and concentration dependent coefficient of diffusion.Below especially exemplified by embodiment and be aided with Comparative Examples, but do not represent that this system only is confined to this embodiment.
Comparative Examples 1: the coefficient of diffusion of toluene and cyclohexane is measured (barrier film pond method)
People such as Sanni utilized barrier film pond method to measure the coefficient of diffusion (Sanni, J.Chem.Eng.Data, 1971,16,424) of toluene and cyclohexane in 1971.Device is the airtight diffusion cell of glass, has two Room up and down, and the centre is separated by perforated membrane.The effect of perforated membrane is to avoid the convection current of two Room solution up and down, and guarantees that sufficient molecular diffusion takes place.The perforated membrane two sides add magnetic agitation to avoid near solution density unevenness film.The sample of two Room is introduced to guarantee that sample is stablized by polyfluortetraethylene pipe and is entered and avoid measuring preceding unnecessary mixing up and down.Before measuring, need to demarcate the barrier film pond, with the system KCl/H of known coefficient of diffusion
2O determines the membrane cisterna coefficient.Utilize the membrane cisterna coefficient to come the measured value of modified diffusion coefficient again.Before each group is measured, inject the solution of variable concentrations in chamber up and down, inject the lighter solution in the upper strata heavier solution of lower floor that reinjects earlier, the concentration change of continuous detecting two Room finally can obtain the integration coefficient of diffusion between two initial concentrations.Because magnetic agitation causes the shakiness of continuous coverage, before regularly measuring each time, stop to stir several seconds to finish measurement of concetration.After one group of measurement, thoroughly clean perforated membrane, diffusion cell and pipeline thereof, the coefficient of diffusion that enters next concentration section is again measured.The barrier film pond places water bath with thermostatic control, and the control bath temperature can be measured the coefficient of diffusion under the different temperatures.The resulting data of this method will compare with the result of embodiment 1.
The used sample total amount of coefficient of diffusion that this Comparative Examples is measured a concentration section is about 80mL, and diffusion process will continue 1-3 days.
Embodiment 1: the coefficient of diffusion of toluene and cyclohexane is measured (the method for the invention)
Silica-based micro-fluidic chip at first obtains to have the silicon base of figure as shown in Figure 2 by dark silicon etching, utilizes negative adhesive process to stay the thick aluminium film of 200nm in the runner bottom again, last and glass anode linkage.Chip is bonded at soaking copper billet surface.800 μ m are wide for main diffusion straight channel sectional dimension, the degree of depth 30 μ m.
The mole fraction of preparation toluene is respectively toluene-cyclohexane solution of 0.247 and 0.447, utilize syringe pump with the solution of two concentration respectively with 10 μ Lmin
-1Inject two inlets of chip, select joint downstream axial 1cm distance cross section for measuring the cross section, with 30 μ m is the transversal scanning interval, Raman spectrum is each position scanning seven times, data are the mean value of seven measurement of concetrations, Raman spectrum is selected the 514.5nm Argon ion laser for use, and power is 25mW, unitary sampling 10s sweep time.With the concentration value of the correspondence position that obtains, and two entrance concentrations (actual measurement two wriggle the concentration in the preheating sections), axial distance, known parameters match formulas (1) such as mean flow rate, matched curve as shown in Figure 6, the diffusion coefficient D that inverting obtains under the 298K is 1.86 * 10
-9m
2S
-1
Carry out the coefficient of diffusion of variable concentrations measures with aforesaid same procedure, change temperature and promptly adjust bath temperature, treat to carry out identical measurement again after the electric thermo-couple temperature demonstration of arranging in the chip is stablized, data mean deviation＜10% of coefficient of diffusion measurement result and barrier film pond method, as shown in Figure 7.As seen, it is fine to adopt apparatus and method gained result of the present invention and classic method to coincide, and has higher precision.And this method is measured for the coefficient of diffusion of a concentration section, and amount of samples is about 10 μ L, and Measuring Time then only needs 10 minutes.Twice measurement only need change sample introduction concentration, need not the cleaning of complicated operations and trouble.
Advantages such as this embodiment demonstrated fully apparatus and method of the present invention and have fast, efficient, high precision, low cost, easy operating.
Comparative Examples 2: measure with ordinary silicon-glass-chip
Ordinary silicon-glass-chip method for making is earlier by the silicon base of dark silicon etching acquisition with Fig. 2 same structure, again with the glass anode linkage.It and unique not being both of chip of the present invention, the runner bottom does not have the aluminium film.People such as Salmon adopt identical silicon-glass-chip to carry out the measurement (Appl.Phys.Lett, 86,3) of liquid-liquid diffusion coefficient under the room temperature.
The mole fraction of preparation toluene is respectively toluene-cyclohexane solution of 0.621 and 0.819, under the room temperature condition, utilize syringe pump with the solution of two concentration respectively with 10 μ Lmin
-1Two inlets of injection chip select joint downstream axial 1cm distance cross section for measuring the cross section, are the transversal scanning interval with 30 μ m, and Raman spectrum is each position scanning seven times, and data are the mean value of seven measurement of concetrations.Raman spectrum is selected the 514.5nm Argon ion laser for use, for showing the influence degree of laser thermal effect, power is set to 25mW, 12.5mW, 2.5mW respectively, still can obtain identical signal intensity for guarantee reducing power, and corresponding unitary sampling is respectively 10s, 20s, 100s sweep time.The data that obtain after the match are seen Fig. 8.
As seen, measure, still can't obtain reliable result, can't guarantee measuring accuracy in the short period of time even reduce power with common silicon-glass-chip.
Embodiment 2: measure with the silicon that has the aluminium film-glass-chip
Silicon-the glass-chip that has the aluminium film is chip used for embodiment 1.Chip sticks at soaking copper billet surface.800 μ m are wide for main diffusion straight channel sectional dimension, the degree of depth 30 μ m.
The mole fraction of preparation toluene is respectively toluene-cyclohexane solution of 0.609 and 0.811, under the room temperature condition, utilize syringe pump with the solution of two concentration respectively with 10 μ Lmin
-1Two inlets of injection chip select joint downstream axial 1cm distance cross section for measuring the cross section, are the transversal scanning interval with 30 μ m, and Raman spectrum is each position scanning seven times, and data are the mean value of seven measurement of concetrations.Raman spectrum is selected the 514.5nm Argon ion laser for use, and power 25mW, unitary sampling are respectively 10s sweep time.The data that obtain after the match are seen Fig. 8, with data deviation under the measured room temperature in barrier film pond only be 10%.
Comparative Examples 2 is measured on common silicon-glass-chip, also can't obtain result more accurately in the short period of time even reduce power.And this embodiment has realized the measurement of degree of precision with the highest laser power.As seen, provided by the invention is to guarantee to measure quick, efficient, high-precision necessary condition at silica-based runner bottom sputter nano metal aluminium.
Claims (6)
1. the device that can under different temperatures, measure liquid-liquid diffusion coefficient, it is characterized in that, described device comprises: microfluidic system, soaking system and confocal laser Raman spectrometer (3), described microfluidic system comprises that a base material is the micro-fluidic chip of silicon (2), micro-fluidic chip (2) is provided with two the first sinuous fluid channel (9) and second sinuous fluid channel (10) through etching, first syringe pump (1) links to each other with the first sinuous fluid channel inlet (15) and the second sinuous fluid channel inlet (16) respectively with second syringe pump (5), article two, compile a mixing diffusion of formation straight channel (11) after connecting the first thermopair T1 and the second thermopair T2 on the sinuous fluid channel respectively, article two, the incident angle of sinuous fluid channel inlet is 0 °, the first thermopair T1 and the second thermopair T2 are positioned at the meet upstream apart from point 0.5～2mm place, and mixing diffusion straight channel outlet (17) is located to connect a three thermocouple T3 and linked to each other with waste liquid tank (6);
Wherein, the xsect that mixes diffusion straight channel (11) is a rectangle, and width is 600～1200 μ m, and the degree of depth is 10～50 μ m; The degree of depth of first, second sinuous fluid channel (9,10) is 10～50 μ m, and length is greater than 5cm, and xsect is a rectangle, and width is for mixing half that spreads straight channel (11) width;
Described soaking system comprises one by three copper sheets soaking copper billet (4) that is welded, be processed with annular channel (14) at the middle copper sheet upper surface between two copper sheets up and down, the width of annular channel (14) is 1～5mm, the annular channel length overall is 0.3～1m, and annular channel (14) is provided with annular channel import (12) and annular channel outlet (13) respectively; Annular channel import (12) links to each other with volume pump (7) outlet, and the import of volume pump (7) links to each other with constant water bath box (8);
Micro-fluidic chip (2) is bonded in the upper surface of soaking copper billet (4) by heat-conducting glue, and soaking copper billet (4) is placed on the microscope stage of Raman spectrometer (3).
2. the device that can under different temperatures, measure liquid-liquid diffusion coefficient as claimed in claim 1, it is characterized in that, first, second sinuous fluid channel (9 at described micro-fluidic chip (2), 10) and mix the runner bottom of diffusion straight channel (11), have the silver of one deck deposition or the metallic film of aluminium, film thickness is 150～400nm.
3. the device that can measure liquid-liquid diffusion coefficient under different temperatures as claimed in claim 2 is characterized in that described thickness of metal film is 200～300nm.
4. the device that can measure liquid-liquid diffusion coefficient under different temperatures as claimed in claim 1 is characterized in that, the cross-sectional width of mixing diffusion straight channel (11) is 700～900 μ m, and the degree of depth is 25～35 μ m.
5. the device that can measure liquid-liquid diffusion coefficient under different temperatures as claimed in claim 1 is characterized in that the width of the annular channel of soaking copper billet (4) is 2～3mm, and total length is 0.5～0.8m.
6. the method based on liquid-liquid diffusion coefficient under the measurement different temperatures of the described device of claim 1 is characterized in that described method comprises the steps:
1) the water bath temperature is set in below the boiling point of sample, open syringe pump, behind the temperature stabilization of water bath with thermostatic control, in micro-fluidic chip, feed the solution of variable concentrations to be measured through syringe pump, the deviation of reading of three thermopairs is calculated the mean value of three measured values and is measured corresponding temperature as coefficient of diffusion during less than 0.5K;
2) described Raman spectrometer configures wave-number range, laser power and the sweep time that comprises the test substance characteristic peak, guarantee that the signal that Raman scanning obtains is enough to quantitative test, the tested xsect of test section is apart from two inlet 0.5～2cm place, joint downstream xsects, autoscan after on the Width sweep span being set, scanning needs to have on the cover width direction zone of concentration change;
3) the spectrogram information that Raman spectroscopy scans is obtained is related with concentration, obtain testing the concentration and the position data of xsect, match obtains a coefficient of diffusion value, less when the two solution concentration differences of injecting, diffusion coefficient D is a constant under this concentration, promptly obtains liquid-liquid diffusion coefficient D by formula (1) inverting, wherein, (x y) is the solution concentration at measuring point place, c to c
1, c
2Be the initial mole fraction of two solution; Y be measuring point in the distance of width of flow path direction apart from diffuse interface, x is the vertical range of tested cross-sectional distance joint,
Be mean flow rate, this mean flow rate is calculated by the syringe pump input flow rate, and is known, and erf is an error function;
4) concentration of change two injection solution record the coefficient of diffusion under the variable concentrations, and change water bath temperature records the coefficient of diffusion under the different temperatures.
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| CN101907549B (en) * | 2010-07-06 | 2013-03-13 | 南京工业大学 | Test method and test device for obtaining saturated solubility and diffusion coefficients of solid solute in liquid phase simultaneously |
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