Background technology
Microparticle thing in air is that visibility reduces the main cause producing gray haze sky, serious threat ground vapour
Car drives and the taking off of aircraft, lands, and is the main arch-criminal causing vehicle accident and air crash.Particle diameter exists
Fine particle (hereinafter referred to as PM2.5) below 2.5 μm, can be directly entered bronchus, deep lung, dry
Disturb the gas exchange of pulmonary, cause the disease including the aspects such as asthma, bronchitis and cardiovascular diseases.Additionally
These granules can also be carried harmful heavy metal and be dissolved in blood by bronchus and alveolar, thus to human body
Healthy injury is bigger, and then causes the generation of cancer.According to the ambient air quality of China, granule
The assay method of thing is divided into gravimetric method, trace oscillating balance method and β ray method, consults related data, granule
Thing research method also includes light scattering method and piezoquartz method.
Gravimetric method is the most traditional method, low cost, and automaticity is low, and workload is big and measurement result is
Meansigma methods in a period of time, poor real.Although trace oscillating balance method real-time is relatively good, accuracy
With highly sensitive, but measurement system works under 50 DEG C of constant temperature, must heat to remove by filter membrane and sampled air
Moisture, can make half volatile pollutant volatilize simultaneously, thus the data measured are on the low side, and bigger in humidity
Rainy day negative value easily occurs, be not suitable for the environment that outdoor air is changeable.β ray method utilizes β ray attenuation
Principle, measures the microparticle thing being deposited on filter membrane, obtains microparticle substrate concentration, be current most widely used general
Monitoring method.β ray method can realize automatically monitoring, should in 24 hours air quality automatic monitor for continuously
With extensively, but error is relatively big, especially when particulate matter diameter is less than 10 μm.Light scattering method has spirit in theory
Quick, good stability, the advantage such as easy and simple to handle, but particulate in air matter can be polluted optical element and cause sensitive
Degree reduces, and measurement result needs conversion coefficient to show, directly the particle concentration of detection air not yet becomes
Ripe.Piezoquartz method utilizes electrion pin and the Electrostatic collection device collection of quartz resonator composition, passes through stone
The quality of English axonometry microparticle thing, the method sensitivity in theory is higher, but particle sampling rate is the highest,
And electrion limits it and monitors in real time, exploitativeness is the highest.
For solving the deficiency of existing method and technology, the present invention proposes one and utilizes dielectrophoretic force principle and quartz-crystal
Body micro-balance technology combines and monitors the method and system of microparticle substrate concentration in air.
Dielectrophoresis phenomenon refers to that microgranule moves due to the orientation that stress produces by dielectric polarization in inhomogeneous field
Dynamic, its essence is owing to dielectric particle itself is induced eelctric dipole by extra electric field, this eelctric dipole with power up outward
The phenomenon produced under the reciprocal action of field.For microsphere particulate matter, the computing formula of dielectrophoretic force isWhereinω=2 π f, j2=-1, r
For the radius of particulate matter, εmAnd εpIt is respectively medium and the dielectric constant of granule, Re [fCM] represent fCMReality
Portion,For Hamiltonian, E is electric field intensity (being determined by applied voltage amplitude and electrode structure), and σ is
Electrical conductivity, ω is angular frequency, and f is frequency.From above formula, under identical electric field and solution condition, micro-
Dielectrophoretic force suffered by particulate matter and its radius cube proportional, can be used for different radii microparticle thing
Separation.
QCM (Quartz Crystal Microbalance, QCM) make use of quartz-crystal resonator
Piezoelectric property, according to QCM frequency displacement formula(Δ f is quartz resonator
The change of frequency, Δ m is the mass change of electrode surface, and A is quarts crystal electrode area, f0Humorous for quartz
Shake the fundamental frequency of device, μqFor the modulus of shearing of quartz crystal, ρqFor quartz density), by quartz crystal oscillator electrode surface
Mass change Δ m is converted into frequency changes delta f of the quartz crystal oscillator circuit output signal of telecommunication, and then by meter
Other auxiliary equipments such as calculation machine obtain high-precision data, are the sensitiveest a kind of quality testing instruments, its
Certainty of measurement is up to nanogram level, and in air, the measurement of microparticle substrate concentration has high accuracy feature.
The inventive method is using the electrolyte solution containing surfactant as detection environment, and sample rate is high, can
External environment is avoided to affect;Dielectrophoretic force is utilized to separate deposition microparticle thing and surveyed by QCM
Weight, separation detection speed is fast, measures highly sensitive, and exploitativeness is high, is not required to change filter membrane, and entirety reduces
Cost;Each step can be controlled by system run and change electrolyte solution in real time, be not required to cleaning electrode,
Monitoring process full automation and real-time can be realized.
Summary of the invention
The present invention proposes one and utilizes dielectrophoretic force principle and QCM technology to combine monitoring air
The method of middle microparticle substrate concentration, it is characterised in that said method comprising the steps of:
1) quantitative air is sent in electrolyte solution, make microparticle thing in air be dispersed in electrolyte solution
In;
2) utilize different size structure microelectrode to provide gradient electric field, make dielectrophoretic force act on and be dispersed in electrolysis
Microparticle thing in matter solution, different radii scope microparticle thing separates also because being varied in size by dielectrophoretic force
Deposition is gathered on the microelectrode of corresponding size structure respectively;
3) before and after QCM measures deposition, the mass change of corresponding size structure microelectrode, obtains institute
State different radii scope microparticle material amount;
4) according to sample introduction volume of air and surveyed different radii scope microparticle material amount, process and be calculated
Different radii scope microparticle substrate concentration in air.
Described method farther includes, and described electrolyte solution is electrolyte aqueous solution, and its electrical conductivity is 3 ×
10-4S/m~6 × 10-3S/m。
Described method farther includes, and containing surfactant in described electrolyte solution, is used for making in air
All hydrophobicity microparticle things are dispersed in electrolyte solution.
Described method farther includes, and described different size structure microelectrode is electrode gap size and/or electrode
The interdigitation microelectrode gradient array that width dimensions changes in gradient, described interdigitation microelectrode gradient array electricity
Pole shape includes any one in vertical bar type, sawtooth pattern, city wall buttress type, circular arc type or meander configuration.
Described method farther includes, and described interdigitation microelectrode gradient array is configured at QCM
Electrode detection district, QCM monitors electrode deposition mass change in real time, it is achieved in air micro-
The real-time monitoring of grain substrate concentration.
Described method farther includes, described interdigitation microelectrode gradient array and described QCM
Between depositing insulating layer, to prevent interdigitation microelectrode and QCM electric pole short circuit, described insulation
Layer is the inorganic or organic material good with described QCM electrode conductive material tack, including
SiO2、Al2O3、Cr2O3、ZnO、TiO2, any one in SU8, PMMA or PDMS.
Described method farther includes, and described method can configure a QCM and measure one and half
The microparticle material amount of footpath scope, it is achieved include that PM2.5 (diameter is less than or equal to 2.5 μm) or PM10 is (straight
Footpath be less than or equal to 10 μm) monitoring.
Described method farther includes, and described method can configure two or more QCMs
Measure two or more radius microparticle material amounts, it is achieved while including PM2.5 and PM10
Monitoring.
The present invention further proposes one and realizes approach described above, and in monitoring air, microparticle thing is dense in real time
The system of degree, it is characterised in that described system includes with lower part:
1) air sampling portion: include a air sampling module, air is also sent into detection cell by compressed air, and b flows
Amount control module, controls and detect the volume of sampled air and c air inlet and air vent, ensure monitor with
Carry out under extraneous identical atmospheric pressure;
2) test section: include a detection cell, equipped with the electrolyte solution containing surfactant, it is provided that detection
Electrolyte environment, b dielectrophoresis separation module, be made up of interdigitation microelectrode gradient array, it is provided that gradient electricity
Field environment separation also deposits the microparticle thing and c quartz crystal check weighing module being dispersed in electrolyte solution, profit
The mass change of described interdigitation microelectrode before and after deposition microparticle thing is measured with QCM;
3) data processing division: be connected with air sampling portion and test section, receive and process sampled air volume and
QCM frequency of oscillation changing value, derives and calculates the concentration of air microparticle thing;
4) manipulation portion: include that a drives module, drives the extra electric field work of interdigitation microelectrode gradient array
With b control module, drive QCM and measure transmission QCM frequency of oscillation change,
Control acquisition testing and transmit air sampling volume and the automatic operating of other parts of system.
Described system farther includes, and the concentration data that described data processing division obtains can be by wired or nothing
The mode of line is transferred to mobile communication equipment, is used for being viewed locally processing described concentration data and/or transmission to far
Journey data center.
Described system farther includes, and test section also includes inlet and liquid outlet, may be used for changing in real time
Liquid in detection cell, carries out next round detection, to realize whole system full automation.
The beneficial effect comprise that the inventive method using the electrolyte solution containing surfactant as
Detection environment, sample rate is high, and external environment can be avoided to affect;Dielectrophoretic force is utilized to separate deposition microparticle thing
And by QCM check weighing, separation detection speed is fast, it is highly sensitive to measure, exploitativeness is high,
Being not required to change filter membrane, entirety reduces cost;Each step can be controlled by system run and change electrolysis in real time
Matter solution, is not required to cleaning electrode, can realize monitoring process full automation and real-time.
Detailed description of the invention
Below by case study on implementation, the technical scheme in the present invention is clearly and completely described, it is clear that
Described embodiment and accompanying drawing are exemplary and nonrestrictive, and the scope of the present invention should be by not exemplary
Embodiment is limited, and should only be limited by claims and equivalency range thereof.Based in the present invention
Embodiment, those of ordinary skill in the art obtained under not making creative work premise all other
Embodiment, broadly falls into the scope of protection of the invention.
It should be noted that term "up" and "down" is unrelated with gravity direction, use for convenience of explanation.
Combine microparticle substrate concentration monitoring method in the accompanying drawing air to the present invention below by specific embodiment to enter
One step describes in detail, and what Fig. 1 illustrated the method realizes step, including:
Air sampling S101, sends into quantitative air in the electrolyte solution containing surfactant, makes sky
In gas, microparticle thing is dispersed in electrolyte solution.Set, by air compressor with constant flow speed Q
Sending into quantitative air sample in electrolyte solution, in certain embodiments, gas input volume range can
It is set as 10~100mL, flow-control S102 realizes.Set, control sampling time t by effusion meter,
Thus measure sampled air volume V.
Dielectrophoresis separates S201, utilizes different size structure microelectrode to provide gradient electric field, makes dielectrophoresis masterpiece
For the microparticle thing being dispersed in electrolyte solution, different radii scope microparticle thing is because of big by dielectrophoretic force
Little difference and separate and respectively deposition be gathered on the microelectrode of corresponding size structure.
In this step, dielectrophoresis implementation environment is the electrolyte solution containing surfactant, wherein: electricity
Electrolyte solution provides dielectric environment, preferably low concentration nontoxic electrolyte aqueous solution, and conductivity range is 3
×10-4S/m~6 × 10-3S/m;Surfactant makes all hydrophobicity microparticle things in air be dispersed in electrolyte
In solution, the mechanism of action as in figure 2 it is shown, surfactant hydrophobic group surround hydrophobicity microparticle thing,
Hydrophilic group makes microparticle thing be dispersed in electrolyte solution.
In dielectrophoresis separates S201 step, utilize different size structure microelectrode to provide gradient electric field, cause
Dielectrophoretic force acts on the microparticle thing being dispersed in electrolyte solution.Different radii microparticle thing is by dielectrophoresis
Power varies in size, different at dielectric environment move distance, thus separates and assembles to be deposited on and provide gradient electric
On the diverse location of the different size structure microelectrode of field.This step provide dielectrophoretic force voltage peak preferred
Scope is 1~5V, and the preferred scope of electric field frequency is 10kHz~20MHz, to ensure microparticle thing institute in air
Basically identical by dielectrophoretic force factor of influence, under identical electric field and solution condition, suffered by microparticle thing
Dielectrophoretic force is the most relevant with microparticle thing radius.
Fig. 3 represent electrode spacing be followed successively by 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm,
35 μm, the electric field strength change of 40 μm.It can be seen that the interdigitation microelectrode of different spacing size carries
The electric field strength of confession varies in size.Set, it is provided that the described different size structure microelectrode configuration of gradient electric field
The interdigitation microelectrode gradient array changed in gradient for electrode gap size.Fig. 4 is the micro-electricity of described interdigitation
Five kinds of advantageous version of pole shape, respectively vertical bar type, sawtooth pattern, city wall buttress type, circular arc type or meander configuration,
Feature according to actual particle radius determines that one of which optimum electrode shape forms interdigitation microelectrode gradient battle array
Row.
Quartz crystal check weighing S301, before and after utilizing QCM to measure different radii microparticle thing deposition
The mass change of described interdigitation microelectrode gradient array, obtains different radii scope microparticle material amount.Warp
Different radii microparticle thing after dielectrophoresis separates is respectively deposited at described interdigitation microelectrode gradient array not
Co-located, causes described interdigitation microelectrode gradient array diverse location mass change, QCM
Measuring the mass change of described interdigitation microelectrode gradient array, described mass change causes the micro-sky of quartz crystal
The change of flat frequency of oscillation, is changed by Δ f/ Δ m, draws the mass change of interdigitation microelectrode gradient array,
Its corresponding different radii scope microparticle material amount m i.e..In this step, can be by a quartz crystal
Micro-balance measurement is deposited on the microparticle material amount of a radius of described interdigitation microelectrode gradient array.
Further, this step can also be measured by multiple QCMs simultaneously be deposited on the micro-electricity of described interdigitation
The microparticle material amount of the different radii scope of pole gradient array diverse location.Setting, quartz crystal uses AT
Cut type quartz substrate, the preferred scope of natural frequency is 5~15MHz, and the preferred scope of thickness of crystal is
100~300 μm.
Described interdigitation microelectrode gradient array is configured at the electrode detection district of QCM, quartz-crystal
Electrode quality change before and after microparticle thing deposition monitored in real time by the micro-balance of body, it is achieved microparticle substrate concentration in air
Real-time monitoring.Deposit between the most described interdigitation microelectrode gradient array and described QCM
Insulating barrier, to prevent interdigitation microelectrode and QCM electric pole short circuit, its structure will have below
Body embodiment describes in detail.Insulating barrier described herein is preferably attached with QCM electrode conductive material
Inorganic or the organic material that the property is good, including SiO2、Al2O3、Cr2O3、ZnO、TiO2、SU8、PMMA
Or any one in PDMS.
Concentration computing S401, utilizes calculated different radii scope microparticle material amount m and sampled air
Volume V, complete the calculating of concentration.This method can include that concentration data shows, stores or transmits further
S402, including wired or wireless transmission to mobile communication equipment, is used for being viewed locally processing described concentration data
And/or transmission is to remote data center.
In one embodiment, setting, the air sampling flow that effusion meter records is Q, the sampling time is t,
Frequency be changed to Δ f, the mass change of electrode surface is Δ m, quarts crystal electrode area be A, quartz humorous
The fundamental frequency of device of shaking is f0, quartz crystal modulus of shearing is μq, quartz crystal density be ρq, then in air micro-
The concentration c of grain thing is represented by:
It follows that explain the system of microparticle concentration in approach described above monitoring air that realizes in conjunction with the embodiments.
This system can utilize the method for the invention to realize microparticle substrate concentration full automation and real-time prison in air
Survey.
Fig. 5 is shown as monitoring the system 100 of the example of microparticle concentration in air.System 100 may include that
Air sampling portion 110, test section 120, data processing division 130, manipulation portion 140 and/or other elements.
Air sampling portion 110 includes air sampling module, flow-control module, air inlet and gas outlet (not
Mark in the drawings), it is used for gathering air and air being sent into detection cell, detection simultaneously controls sampled air volume
Device, i.e. realize S101 and S102 step described in above method step.
Test section 120 is used to separate different radii microparticle thing in air, and it is micro-to detect different radii scope
The device of particulate matter quality, is the core of whole system, mainly includes with lower part:
Detection cell 121 is the case of described monitoring microparticle substrate concentration process.Set, detection cell 121
Volume be preferably 10~50cm3, pond is built with the electrolyte solution containing surfactant.Wherein, electrolysis
Matter solution provides dielectric environment, preferably low concentration nontoxic electrolyte aqueous solution, and conductivity range is 3 ×
10-4S/m~6 × 10-3S/m.The surfactant added makes all hydrophobicity microparticle things in air be scattered in electricity
In electrolyte solution.
Dielectrophoresis separation module 122, is made up of interdigitation microelectrode gradient array, it is provided that gradient electric field environment causes
Make dielectrophoretic force act on described microparticle thing, separate and deposit the microparticle thing being dispersed in electrolyte solution,
I.e. realize dielectrophoresis described in said method step and separate S201 step.
Quartz crystal check weighing module 123, utilizes QCM to measure described fork before and after deposition microparticle thing
The mass change of finger-type microelectrode gradient array, i.e. realizes quartz crystal check weighing S301 described in said method step
Step.
It addition, test section 120 can also include inlet and liquid outlet (mark the most in the drawings), in order in real time
Changing liquid in detection cell, carry out next round detection, feed liquor goes out the controlled device of liquid and controls, it is possible to achieve whole
Individual system full automation.
Data processing division 130 is connected with air sampling portion 110 and test section 120, receives and process sampling sky
Air volume and QCM frequency of oscillation changing value, derive and calculate different radii microparticle in air
The concentration of thing, i.e. realizes S401 step described in said method step.Data processing division 130 can be or include
It is capable of data acquisition process show and/or be delivered to by wired or wireless mode by the concentration data of gained
Mobile communication equipment, is used for being viewed locally processing described concentration data and/or transmission to teledata.
Manipulation portion 140 is connected driving and controls the operation of whole system each several part with other parts of system, including:
Drive module 141, drive the extra electric field work of interdigitation microelectrode gradient array, can be special or autonomous
The signal generator of exploitation;Control module 142 drives QCM to measure and transmits microparticle thing sinks
Before and after Ji QCM frequency of oscillation change, control acquisition testing and transmit air sampling volume and
The automatic operating of other parts of system.Control module 142 is by storing in a computer and one or more
The executable code run in system based on processor and instruction and/or hardwired electronic circuits realize.Pass through
Control module 142 control system each several part runs with the full automation and the real-time that realize whole monitoring process.
Fig. 6 illustrates dielectrophoresis separation module and a particular implementation of QCM check weighing module design
Example, the monitoring of PM2.5 in air.In Fig. 6, interdigitation microelectrode gradient array 601 is arranged on absolutely
On the upside of edge layer 602, QCM electrode 603 and 605 is separately positioned on quartz crystal substrate 604
Upper and lower sides.Described interdigitation microelectrode gradient array 601 is connected with driving module 141.Described quartz-crystal
The micro-nanobalance electrode of body 603 is connected with control module 142 with 605.
Air compressor compressed air air is sent into detection cell with constant speed in air sampling portion 110,
Being controlled by the effusion meter in flow-control module and the volume of detection sampled air, detection cell has air inlet simultaneously
Mouth is carried out to ensure to monitor with air vent under the atmospheric pressure identical with the external world.
Dielectrophoresis separation electrode 601 be electrode width be 2~20 μm, electrode gap a size of 2~20 μm and
Every the interdigitation microelectrode gradient array that size changes in gradient, manipulation portion 140 drive module 141 for fork
Finger-type microelectrode gradient array 601 provides extra electric field, drives described interdigitation microelectrode gradient array 601
Produce gradient electric field, cause and be dispersed in electrolyte solution different radii microparticle thing by dielectrophoretic force effect
Separate.Wherein, diameter is assembled less than or equal to the microparticle thing of 2.5 μm and deposits to interdigitation microelectrode ladder
On degree array 601, cause downside quartz crystal vibration corresponding to QCM electrode 605 area
The change of frequency.
Data processing division 130 receives and processes sampled air volume and the change of QCM frequency of oscillation
Value, derives and calculates PM2.5 concentration in air, be used for being viewed locally processing described concentration data and/or transmission
To teledata.
System above each several part runs and is controlled by the control module 142 in manipulation portion 140, it is achieved whole monitored
The full automation of journey and real-time.Test section 120 can also include inlet and liquid outlet, can be in order to
Change liquid in detection cell in real time, carry out next round detection.
Fig. 7 illustrates dielectrophoresis separation module and a particular implementation of QCM check weighing module design
Example, the monitoring of PM10 in air.In Fig. 7, interdigitation microelectrode gradient array 701 is arranged on absolutely
On the upside of edge layer 702, QCM electrode 703 and 705 is separately positioned on quartz crystal substrate 704
Upper and lower sides.Given an account of interdigitation microelectrode gradient array 701 is connected with driving module 141.Described quartz
Crystal microbalance electrode 703 is connected with control module 142 with 705.
Air compressor compressed air air is sent into detection cell with constant speed in air sampling portion 110,
Being controlled by the effusion meter in flow-control module and the volume of detection sampled air, detection cell has air inlet simultaneously
Mouth is carried out to ensure to monitor with air vent under the atmospheric pressure identical with the external world.
Dielectrophoresis separation electrode 701 be electrode width be 2~40 μm, electrode gap a size of 10~40 μm and
The interdigitation microelectrode gradient array that the size of space changes in gradient, in manipulation portion 140, driving module 141 is
Interdigitation microelectrode gradient array 701 provides extra electric field, drives described interdigitation microelectrode gradient array 701
Produce gradient electric field, cause and be dispersed in electrolyte solution different radii microparticle thing by dielectrophoretic force effect
Separate.Wherein, diameter is assembled less than or equal to the microparticle thing of 10 μm and deposits to interdigitation microelectrode gradient
On array 701, cause downside quartz crystal oscillation frequency corresponding to QCM electrode 705 area
The change of rate.
Data processing division 130 receives and processes sampled air volume and the change of QCM frequency of oscillation
Value, derives and calculates PM10 concentration in air, be used for being viewed locally processing described concentration data and/or transmission
To teledata.
System above each several part runs and is controlled by the control module 142 in manipulation portion 140, it is achieved whole monitored
The full automation of journey and real-time.Test section 120 can also include inlet and liquid outlet, can be in order to
Change liquid in detection cell in real time, carry out next round detection.
Fig. 8 illustrates dielectrophoresis separation module and a particular implementation of QCM check weighing module design
Example, monitors while PM2.5 and PM10 in air.In Fig. 8, interdigitation microelectrode gradient array
801a and 801b is arranged on the upside of insulating barrier 802, QCM electrode 803 and 805a, 805b
It is separately positioned on the upper and lower sides of quartz crystal substrate 804.Described interdigitation microelectrode gradient array 801 and driving
Dynamic model block 141 is connected.Described QCM electrode 803,805a and 805b and control module 142
It is connected.
Air compressor compressed air air is sent into detection cell with constant speed in air sampling portion 110,
Being controlled by the effusion meter in flow-control module and the volume of detection sampled air, detection cell has air inlet simultaneously
Mouth is carried out to ensure to monitor with air vent under the atmospheric pressure identical with the external world.
Dielectrophoresis separation electrode 801 be electrode width be 2~20 μm, electrode gap a size of 2~40 μm and
Every the interdigitation microelectrode gradient array that size changes in gradient, manipulation portion 140 drive module 141 for fork
Finger-type microelectrode gradient array 801a and 801b provides extra electric field, drives described interdigitation microelectrode gradient
Array 801a and 801b produces gradient electric field, causes and is dispersed in different radii microparticle thing in electrolyte solution
Separated by dielectrophoretic force effect.Wherein, diameter is assembled less than or equal to the microparticle thing of 2.5 μm and deposits
To interdigitation microelectrode gradient array 801a, cause downside QCM electrode 805a area institute right
The change of the quartz crystal frequency of oscillation answered;And diameter is assembled at the microparticle thing of 2.5~10 μ m and deposits
To interdigitation microelectrode gradient array 801b, cause lower section QCM electrode 805b area institute
The change of corresponding quartz crystal frequency of oscillation.
Data processing division 130 receives and processes sampled air volume and the change of QCM frequency of oscillation
Value, derives simultaneously and calculates PM2.5 and PM10 concentration in air, be used for being viewed locally processing described concentration
Data and/or transmission are to teledata.
System above each several part runs and is controlled by the control module 142 in manipulation portion 140, it is achieved whole monitored
The full automation of journey and real-time.Test section 120 can also include inlet and liquid outlet, can be in order to
Change liquid in detection cell in real time, carry out next round detection.