CN102549422A - Micro-thermal conductivity detector, method to fabricate such and chromatography system using such - Google Patents
Micro-thermal conductivity detector, method to fabricate such and chromatography system using such Download PDFInfo
- Publication number
- CN102549422A CN102549422A CN2010800453603A CN201080045360A CN102549422A CN 102549422 A CN102549422 A CN 102549422A CN 2010800453603 A CN2010800453603 A CN 2010800453603A CN 201080045360 A CN201080045360 A CN 201080045360A CN 102549422 A CN102549422 A CN 102549422A
- Authority
- CN
- China
- Prior art keywords
- heating element
- chamber
- heat flux
- fluid
- flux sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
- G01N27/18—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature caused by changes in the thermal conductivity of a surrounding material to be tested
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/66—Thermal conductivity detectors
Abstract
A heat flux sensor, a micro-scale gas chromatograph comprising the heat flux sensor, and method for measuring the thermal conductivity of a fluid using such are provided. The heat flux sensor comprises a chamber, a heating element suspended in the chamber, at least two current contacts configured to exchange a current with the heating element, and at least two measurement contacts configured to measure a voltage change along the heating element indicative of the thermal conductivity of the fluid.
Description
The cross reference of related application
The application based on and require the U.S. Provisional Application No.61/250 that submitted on October 9th, 2009,310 right of priority.
Technical field
The present invention relates to be used for the field of the sensor of chemical analysis instrument.More particularly, the present invention relates to be used for chromatographic analysis device, more particularly be used for the miniature pyroconductivity detector of miniature chromatographic analysis device.
Background technology
In the chemical analysis process, chromatographic analysis device is the main tool that is used for separating with the different compounds of surveying sample mixtures.Be used for carrying out a kind of use chromatography column of the common method of stratographic analysis, form compound sample fluid is separated into it.The inside surface of chromatographic column is inert material normally, and said inert material is coated with or is absorbed with on it the material that is called " stationary phase ".Sample fluid imports in the chromatographic column through the sample input media, and uses the inertia that is known as " moving phase " to carry fluid to be transmitted through chromatographic column.When sample fluid ran into stationary phase, the different component in the sample fluid differently was attracted to stationary phase, and this makes the different component in the sample fluid advance through system with friction speed.When the sample component was driven through chromatographic column by moving phase, the sample component was separated through producing with different delays that the interaction of stationary phase produces.Every kind of sample component imports that the moment and it in chromatographic system is flowed out from chromatography column and has the corresponding characteristic delay time between moment of being detected at its.This characteristic time is called " retention time ".The minimum phase residual quantity of some of retention time makes can distinguish the sample component through chromatogram analysis method.The plurality of color spectral analysis method is generally used in the analytical chemistry, wherein has stream phase and gas chromatography analysis method, carries fluid and correspondingly is inert fluid or gas.
One or more detectors in the exit of chromatographic column are surveyed the different compounds that flow out from chromatographic column, and provide and the proportional output signal of the amount of sample component.Different components is illustrated as " spike " on chromatogram, wherein, the area of height and spike below is corresponding with the amount of compound.
Can use various types of detectors, be favourable but the detector of the output signal corresponding with the pyroconductivity that is included in fluid wherein is provided, and this is because this detector is all sensitive to all fluids.
Pyroconductivity detector (TCD) used a lot of years as the detector in gas phase or the stream phase chromatographic system, so that described output signal to be provided.In simple form, the pyroconductivity detector comprises the unit with heated element, and said heated element is generally by electrically heated tinsel or thermistor, and is arranged in the chamber and remains in the mobile flow.The temperature of heated element changes according to the pyroconductivity of flowing fluid around it.When the output from chromatographic column flow through chamber, heat changed with the variation of the pyroconductivity of the fluid the chamber from the speed that heated element flows to the wall of chamber.The pyroconductivity that carries fluid is different with the pyroconductivity of sample fluid, and changes with the concentration that carries the sample fluid in the fluid with the pyroconductivity that carries the sample fluid that fluid mixes.The variation of pyroconductivity is surveyed and is measured as change in voltage as the changes in resistance that is heated in the element usually.
Fluid property can be confirmed through using a kind of operator scheme in two kinds of different operating modes.In constant voltage mode, the output of detector is relevant with the temperature variation of heating element.When the not so good fluid exposure of heat conductivity was given detector, less heat was transmitted away, thereby has increased temp of heating element.Under constant temperature mode, heating element is maintained under the scheduled operation temperature.For the variation that keeps the required power of this predetermined temperature measured.
At present, gas chromatography is mainly used in the lab investigation.The scientists and engineers has just expanded the use of gas chromatographic analysis through exploitation microscale gas chromatography system from the mid-term in the 1970's.Name according to J.H.Jerman and J.B.Angell is called " A gas chromatograph air analyzer fabricated on a silicon wafer "; IEEE Trans.Electron Devices; Vol.ED-26; P.1880,1979 open academic documents, the gas chromatography system of first kind of micro production is developed in Stanford University's electronic leaning laboratory.This system comprises and the integrated post of making separately of pyroconductivity detector.With the standard gas chromatograph compared with techniques in that period, this device has poor stratographic analysis resolution, and this most probable is because be used for the liquid deposition process of the stationary phase of chromatographic column.
Miniature chromatographic system has portable, reliable potentiality, and because in enormous quantities the making and scale economics is more cheap than traditional chromatographic system.The application scope of these systems can be from public medical Health Services, Homeland Security to industrial process control and geologic prospecting.The open No.2065703A1 of European patent has instructed an example of the gas chromatography system of miniaturization to the applicant/assignee, it particularly is designed in the oil and natural gas industry, this patent openly by reference integral body comprise in this application.
Obtain in the process of novel gas sensing and detection agency doing all one can, seldom work is put into and improved in the pyroconductivity detector.Yet the pyroconductivity detector is particularly suitable for miniaturization, and this is because they are responsive to the concentration of the material in the sample, and responsive unlike such gross mass to sample in the flame ionization detector (FID).Therefore, the miniaturization of pyroconductivity detector does not influence function sensitivity, and because reducing of quality can reduce power consumption and raising Mechanical Reliability simultaneously.
In limited miniature pyroconductivity detector (μ TCD) document,, some reports isolate the various trials that improve the sensitivity of gas concentration thereby having provided improvement heat.The name of Y.E.Wu, K.Chen, C.W.Chen and K.H.Hsu is called " Fabrication and characterization of thermal conductivity detectors (TCDs) of different flow channel and heater designs "; Sensors and Actuators A 100; Pp 37-45; 2002, people's such as Wu open academic documents relates to research flow channel and heater design and they Effect on Performance to detector.They are producing solid film and between two flow channels, are making membrane above the chamber, to attempt to increase hot isolation effect.Yet,, but also can cause the massive losses of potential sensitivity even film has obviously better heat conductivity than gas.
In addition; People's such as D.Cruz name is called " Microfabricated thermal conductivity detector for the micro-ChemMab "; Sensors and Actuators B 121; Pp.414-422,2007 open academic documents relate to design, computing machine prototype and the making and the sign of the pyroconductivity detector of micro production, to increase the detector detection sensitivity.The square pad silicon nitride that suspends has been described.This structure obtains through etching pyramid cavity, thereby obtains big dead space volume, and this possibly influence the performance of gas chromatographic analysis.
Traditional heat flux sensor is heated through heating element through electric current is advanced.Be used for also being used for voltage and detection output signal on the measurement mechanism to the identical joint of heating element supply of electrical energy.This configuration mode can produce mistake and noise in measuring voltage.
The principle of operation of pyroconductivity detector can be summarized as follows: energy is used for the heating quality body by input, and measures the thermal energy that is pulled away.As stated, with the chromatographic resolution column combination, but the chemicals in the pyroconductivity detector identification sample and its concentration.
The heat flux sensor of prior art has multiple deficiency, the resolution, unacceptable mistake and the noise in the voltage measurement of for example inadequate level of isolation, difference, thereby the pyroconductivity of fluid measure and the stratographic analysis process in loss of accuracy.
Summary of the invention
An aspect, the disclosure relate to a kind of heat flux sensor that is used to measure the pyroconductivity of fluid, and said heat flux sensor comprises: chamber; Be suspended at the heating element in the chamber; At least two current joints, said at least two current joints are configured for to the heating element supplying electric current; And at least two measurement joints, said at least two measurement joints are configured for measures the change in voltage along heating element that thermoflux that expression causes by fluid changes.
Another aspect, the disclosure relate to a kind of heat flux sensor that is used to measure the pyroconductivity of fluid, and said heat flux sensor comprises: chamber, and said chamber limits fluid flow direction therein; First heating element, said first heating element is suspended in the chamber, and the fluid that is configured for arrival preheats predetermined temperature; And second heating element; Said second heating element is suspended in the chamber; And on fluid flow direction, be positioned at the downstream of first heating element, wherein, second heating element is configured for detection to be changed by the thermoflux along second heating element that streaming flow causes.
Another aspect, the disclosure relate to a kind of microscale gas chromatography system, comprising: at least one injector, said injector are suitable for the fluid sample with multiple analytes is provided in the microscale gas chromatography system; At least one separating column, said separating column are suitable for isolating at least a portion of the multiple analytes of fluid sample; And heat flux sensor, said heat flux sensor is suitable for surveying at least a portion of isolated multiple analytes in said at least one separating column.This heat flux sensor comprises: chamber; Be suspended at the heating element in the chamber; At least two current joints, said at least two current joints are configured for and the heating element exchanging electric current; And at least two measurement joints, said at least two measurement joints are configured for the pyroconductivity of at least a portion of the multiple analytes of measuring fluid sample.
Another aspect, the disclosure relate to a kind of method that is used to measure the pyroconductivity of fluid, may further comprise the steps: fluid to be analyzed is provided; Heat flux sensor is provided, and said heat flux sensor comprises chamber and is suspended at the heating element in the chamber; At at least two current joint places to the heating element supplying electric current; And measure joints at least two and measure the change in voltage that thermoflux that expression causes by the fluid along heating element changes.
Another aspect, the disclosure relate to a kind of apparatus and method that are used to measure the pyroconductivity of fluid, comprising: the chamber that is limited a plurality of walls; Be suspended at first heating element in the chamber, spaced apart first distance of at least one in this first heating element and the chamber wall, first heating element is configured for the first thermoflux variation of detection along the fluid of first heating element; And second heating element; This second heating element is suspended in the chamber; And with at least one the spaced apart and different second distance of first distance in the chamber wall, second heating element is configured for the second thermoflux variation of detection along the fluid of second heating element.
Another aspect, the disclosure relate to a kind of method that is used to make the heat flux sensor of the pyroconductivity that is used to measure fluid, comprising: chamber is provided; Heating element is provided; Heating element is contained in the chamber, makes heating element be suspended in the chamber; At least two current joints are provided, and said at least two current joints are configured for to the heating element supplying electric current; And the change in voltage that changes of the thermoflux that provides at least two measurement joints, said at least two measurement joints to be configured for to measure expression to cause along heating element by fluid.
Another aspect, the disclosure relate to a kind of method that is used to make the microscale gas chromatography system, comprising: chamber is provided; At least one separating column is provided; Heating element is provided; Heating element is contained in the chamber, makes heating element be suspended in the chamber; At least two current joints are provided, and said at least two current joints are configured for to the heating element supplying electric current; And the change in voltage that changes of the thermoflux that provides at least two measurement joints, said at least two measurement joints to be configured for to measure expression to cause along heating element by fluid.
Another aspect, the disclosure relate to a kind of apparatus and method that are used to analyze the fluid sample (for example gas samples) that comprises multiple analytes.Said method comprising the steps of: the microscale gas chromatography system is provided; Fluid sample is injected the microscale gas chromatography system, and wherein, at least a portion of multiple analytes is separated in said at least one separating column; And according to changed by the pyroconductivity of the analyte surveyed, the thermoflux that causes by sample fluid, at least a portion of change detection isolated multiple analytes in said at least one separating column of the thermal resistance (K/W) of chamber or the knudsen number in the chamber.
Other aspects of the present disclosure and advantage will be obvious from the following description and claims.
Description of drawings
Fig. 1 is the electricity-hot loop model of simulation according to the operation of the heat flux sensor of embodiment of the present disclosure.
Fig. 2 is the schematic top view according to the heat flux sensor of an embodiment of the present disclosure.
Fig. 3 is the top view according to the heat flux sensor of an embodiment of the present disclosure.
Fig. 4 is the synoptic diagram according to a plurality of heat flux sensors of an embodiment of the present disclosure.
Fig. 5 a is the synoptic diagram according to the heat flux sensor of an embodiment of the present disclosure.
Fig. 5 b is the zoomed-in view of the heat flux sensor shown in Fig. 5 a.
Fig. 5 c is the cut-open view of the embodiment of Fig. 5 a of being done along line Va-Va.
Fig. 5 d is the cut-open view of another embodiment of Fig. 5 a of being done along line Va-Va.
Fig. 6 a, 6b, 6c and 6d are the indicative icons according to the making step of the heat flux sensor of an embodiment of the present disclosure.
Fig. 7 a, 7b, 7c, 7d, 7e, 7f and 7g are the indicative icons according to the making step of the chromatography column of an embodiment of the present disclosure and heat flux sensor.
Embodiment
The embodiment disclosed herein relates to the heat flux sensor of the pyroconductivity that is used to measure fluid.Especially; The embodiment disclosed herein relates to such heat flux sensor; Said heat flux sensor comprises chamber and is suspended at least one heating element in this chamber; Wherein, at least one heating element in the said heating element is configured for the pyroconductivity of measuring the fluid in the chamber.In embodiment more of the present disclosure; Heat flux sensor also comprises at least two current joints and at least two measurement joints; Said current joint is configured for and the heating element exchanging electric current, and said measurement joint is configured for the change in voltage along heating element of the pyroconductivity of measuring the expression fluid.In other embodiment of the present disclosure; Heat flux sensor comprises at least two heating elements: first heating element and second heating element; Wherein, at least one in first and second heating elements is configured for the thermoflux variation of detection along heating element.Other embodiment further of the present disclosure relate to the gas chromatography system that partially or even wholly comprises the microscale member.
Referring to Fig. 2, show heat flux sensor according to embodiment more of the present disclosure.Heat flux sensor comprises: be arranged on heating element 218 on the supporting pad 220, be used for to two current joints 226,228 of heating element 218 supplying electric currents and two measurement joints 222,224 of measuring voltage, make can be determined along the change in voltage of heating element 218.Heating element 218 is suspended in the passage 212 of heat flux sensor chamber 238 with supporting pad 220.Heating element 218 can Any shape be made.In certain embodiments, as shown in Figure 2, heating element 218 has serpentine shape.
In an embodiment of the present disclosure, be connected to the voltage finder 214,216 of measuring joint 222,224 and measure and write down the change in voltage on the whole heat flux sensor.Electric current passes through sensor stream to remittance portion 204 from power supply 202.Galvanometer measuring device 206 is used for measuring and Control current.
In another embodiment of the present disclosure, the finder line is connected to voltage finder 214,216 with sensor via measuring joint 222,224.The finder line can be directly connected to the heating element 218 in the passage 212 that is suspended at heat flux sensor chamber 238, and is as shown in Figure 2.Alternatively, the finder line can be connected to heating element 218 through medium line outside the passage 212 of heat flux sensor.Finder line according to embodiment of the present disclosure is not to be used for carries current, and therefore, the finder line can not disturb the electroresponse that is sent to voltage finder 214,216 from heat flux sensor by any way.
Temperature variation under the operating environment of said heat flux sensor will cause the impedance fluctuations of connecting line 208,210.These impedance fluctuations be difficult to or can not with the response decoupling zero of sensor to analyte.The joint (measure joint 222,224) that different joints is provided, promptly is used to utilize the joint (current joint 226,228) of power supply supply/exchanging electric current and is used for measuring voltage has advantageously been removed this noise source and error source.
In yet another embodiment, the number of measuring joint can increase, and they can be provided with along the heat flux sensor order.This has increased voltage and the information of corresponding Temperature Distribution on the relevant sensor.According to an embodiment of the present disclosure, use the feasible flow rate that can confirm fluid of plural measurement joint along heat flux sensor.In certain embodiments, heating element comprises at least two districts, and wherein, at least two measurement joints are provided with along each district, and are configured for the change in voltage of measuring in the respective area, and said change in voltage is represented the flow rate of fluid.Said district can be electrically connected to each other or be electrically connected independently of one another.Like this, an embodiment of the present disclosure relates to a kind of being used for through adopting heat flux sensor to measure the method for the flow rate of fluid, and said heat flux sensor comprises: chamber; Be suspended at the heating element in the chamber; At least two current joints, said current joint are configured for and the heating element exchanging electric current; And at least two measurement joints, said measurement joint is configured for the change in voltage along heating element of the flow rate of measuring the expression fluid.
Fig. 3 shows the heat flux sensor according to an embodiment of the present disclosure.This figure is top-down view, and it shows the heater pad that is suspended in the flow channel 310 that is formed in the supporting layer 302.Heater pad comprises heating element 316, and said heating element 316 has serpentine shape and is arranged on the supporting pad 308.Two current joints 314 that are connected to heating element 316 and are arranged on arbitrary end place of heating element 316 via power supply leg 312 are provided to the electric current of heating element 316.A pair of different joint, measurement joint 304 are connected to heating element 316 through measuring leg 306, and locate along the core of heating element 316, to be used to survey the change in voltage along the core of heating element 316.
Other embodiment of the present disclosure relate to the heat flux sensor of the pyroconductivity that is used to measure fluid; Said heat flux sensor comprises chamber and at least one heating element; Said heating element comprises at least two districts; Wherein, at least two measurement joints are provided with along each district, and are configured for the change in voltage of measuring in the respective area.Change in voltage is represented the flow rate of fluid.
Other embodiment of the present disclosure relate to the heat flux sensor of the pyroconductivity that is used to measure fluid; Said heat flux sensor comprises: the chamber and first heating element; Said chamber limits fluid flow direction therein, and said first heating element is suspended in the chamber and is configured for the fluid that arrives is preheated predetermined temperature; And comprise second heating element; Said second heating element is suspended in the chamber; And on fluid flow direction, be positioned at the downstream of first heating element, wherein, second heating element is configured for detection to be changed by the thermoflux along second heating element that streaming flow causes.In other embodiments; Said second heating element comprises at least two current joints and at least two measurement joints; Said current joint is configured for to the second heating element supplying electric current, and said measurement joint is configured for measures the change in voltage along heating element that thermoflux that expression causes by fluid changes.
The temperature range of heating element can be from the variation of ambient temperature to the heating element exercisable maximum temperature.In one embodiment, at least two heating elements and first heating element in series use, and said first heating element is used to preheat the fluid of arrival, so that set up the thermal gradient that is orthogonal to flow direction.In this way, element subsequently loses the effect of advection heat flux, so they only survey conduction thermoflux effect.
Referring to Fig. 4, comprise that the detection chamber 402 of more than one heating element 406,407,408 can make heat flux sensor possess additional function, for example, the detection of flow rate detection, the unchangeability that flows and molecular species.Survey the overall sensitivity that more than one heating element in the chamber 402 has improved system according to an embodiment of the invention, wherein, each heating element is used to survey the narrow spike from the chromatographic column elution.In this structure, each heating element can be made up of various types of suitable materials, for example silicon dioxide, silicon nitride or other any dielectric materials compatible with manufacturing process.
As shown in Figure 4, the analyte band moves through a plurality of heating elements 406,407,408 through fluid mobile 404, and the analyte tape leader is surveyed through first heating element 406 earlier, passes through heating element 407,408 detections subsequently then.Can set through the space between the heating element in the time delay between the detection at each heating element place, with the flow rate of the analyte band of confirming each heating element place.In one embodiment, at least two heating elements use with respect to flow direction 404 series connection, and they are can preset distance spaced apart.In another embodiment,, can use single heating element,, measure joint for every group and comprise at least two measurement joints as long as use at least two groups to measure joint along the length of sensor element in order to confirm the flow rate of fluid.
An embodiment of the present disclosure relates to a kind of heat flux sensor, and said heat flux sensor comprises two or more heating elements of the serial or parallel connection that is positioned at chamber 402.It is not too responsive that this can make that said heat flux sensor and existing heat flux sensor compare flow rate variation, and said existing heat flux sensor maybe be because the variation of convective thermal loss and all extremely sensitive to any variation of the flow rate of moving phase.According to embodiment of the present disclosure, heat flux sensor has obtained improvement at it aspect the response of the flow rate of variation.In essence, the fluid flow rate that do not changed of heat flux sensor influences.Have a plurality of independently heating elements heat flux sensor can to make flow rate be independently to the central section of heat flux sensor through having the adjacent elements that can be controlled to predetermined temperature.In an embodiment shown in Figure 4; Three heating elements; The use of can connecting with first heating element 406 of first heating element 406, second heating element 407 and the 3rd heating element 408, said first heating element 406 is used to preheat the fluid of arrival, to set up thermal gradient.Like this, element subsequently loses the effect of advection heat flux, so they only survey conduction thermoflux effect.Like this, the second and the 3rd heating element 407,408 and flow rate are irrelevant.
Referring to Fig. 2 and 3, heating element is suspended in the chamber 238,302 of heat flux sensor.In this manual with claims in, it is equal to statement " heating element suspends " and all replacement and is used for expression: heating element preferably supports through leg, at least one leg is connected with at least one support member outside being arranged on chamber.Preferably, heating element 218,316 is via power supply leg 234,236,312, and preferred two power supply legs are connected to power supply 202 and remittance portion 204, and through measuring leg 230,232,306, measures leg, be connected to voltage finder 214,216 for preferred two.Heater pad comprises heating element 218,316 and supporting pad 220,308, is connected to chamber 238,302 via the supporting leg 308 on the supporting pad that is arranged on heater pad 220,308.
According to the chamber of the heat flux sensor of embodiment of the present disclosure can be the structure of part hollow at least.This structure can form or form through a plurality of material components.The heat that material preferably can dissipate and produced by heating element.Material with high pyroconductivity is preferred.This material can be any suitable material that those skilled in the art knows, and is preferably in silicon, glass or the metal any.
According to embodiment more of the present disclosure, the chamber of heat flux sensor comprises first supporting layer and is arranged on second supporting layer on first supporting layer that wherein, heating element places between first and second supporting layers.And according to some embodiment, heating element is arranged on the supporting pad that comprises at least one supporting layer.
In embodiment more of the present disclosure, shown in Fig. 6 d and 7g, the chamber of heat flux sensor 622,722 can have the structure that two parts 602,616,702,716 of being formed by same material or different materials constitute.In certain embodiments, chamber can comprise first supporting layer 602,702 and be arranged on second supporting layer 616,716 on first supporting layer 602,702.Heater pad 614,714 places first and second supporting layers 602,702,616, between 716.
Still please referring to Fig. 6 d and 7g, in embodiment more of the present disclosure, heater pad 614,714 can comprise at least one supporting pad 604,704 and be arranged on the heating element on the supporting pad 604,704.Supporting pad 604,704 can comprise at least one supporting layer, and said supporting layer can be made up of at least one layer that silicon nitride, silicon dioxide or other any dielectric material form.
In certain embodiments, heating element can comprise one or more bonding coats 606,706 and be arranged on the one or more metal levels 608,708 on the bonding coat 606,706.Bonding coat 606,706 can be for ease of being adhered to metal level 608,708 on the layer of supporting layer 604,704.Bonding coat 606,706 can comprise the one or more elements that improve supporting layer 604,704 and metal level 608, the bond strength between 708.Bonding coat can be chromium or titanium layer.Metal level 608,708 can comprise with temperature can change one or more elements that any conductive material of resistance is processed, and can be nickel dam.
In certain embodiments, the surf zone of the heating element of heat flux sensor part at least can be capped through optionally depositing or grow nanotube, and heat is transmitted and/or the change mass transport to improve.
Heat flux sensor according to embodiment of the present disclosure can be miniature pyroconductivity detector.Heat flux sensor can be integrated in the chromatographic system, and said chromatographic system can be portable or miniature chromatographic system.Usually, the cross sectional dimensions of said heat flux sensor is less than 1mm, and this makes that heat flux sensor is miniature heat flux sensor.
The heat flux sensor of describing among the embodiment of the present disclosure makes that can handle the non-destructive method material surveys, thereby, the use of can connecting with the detector of other heat flux sensors of the present disclosure or other any kinds.
According to the heat flux sensor of embodiment of the present disclosure can but be not limited to and injector, pressure source, separating column and function software combination, said software comprises algorithm and database, with the component in the recognition sample fluid quantitatively.
In order to understand and simulate the operation of heat flux sensor, this system can the circuit component modeling.Thermal resistance can be measured through the resistance that applies known voltage and electric current to the heat flux sensor heating element and calculate heating element.Power consumption in the heating element causes a joule heating (with a watt measurement), increases the resistance of heating element.When temp of heating element was known, the impedance of hot-fluid and hot-fluid can be calculated.In order to carry out these calculating, power input (voltage X electric current) can be conditioned, up to reaching predetermined temperature.
The heat energy territory can be mapped to electric territory, and wherein, temperature (T) is equivalent to voltage (V), thermoflux (Q) replacement electric current (I), thermal resistance (R
T) corresponding with resistance (R).Thereby, equality V=IR can with T=QR
TCorresponding.In this case, Q equals VI, and intake is with a watt expression.Q and T are known, and therefore, entire thermal resistance can be passed through R
T=T/IV=T/Q calculates.
R
TBe the entire thermal resistance of system, this system is the parallel connection combination of all possible heat flow path.Fig. 1 shows the loop diagram of the relation between electric territory of expression and the hot territory.This system can be modeled as electricity-thermal converter 102, and this electricity-thermal converter has the circuit that comprises power source 108, the hot road with controlled current source 104 and quality 120.
Electricity-hot loop model comprises resistance element 106, and this resistance element 106 has the thermal resistance R corresponding with the heat flux sensor heating element
TCDThe hot coefficient of the impedance of the impedance variations of this heating element and heating element metal (TCR) is proportional.This depends on the temperature of heating element, because the impedance of TCR effect can be defined as R
TCD=R
0(1+ α
R(T
R+ T
0)), wherein, R
0Be cardinal temperature T
0Under impedance, T
RBe operating temperature, α
RBe metal TCR.
And electricity-hot loop model comprises resistance element 112, said resistance element 112 have with from the corresponding thermal resistance R of thermal-radiating thermoflux
Rad, this heat radiation is the heat that between heat flux sensor heating element and conduit wall, exchanges through radiation heat transfer.Radiation heat flux is defined as I
Q=σ
SBF
12A (T
2 4-T
1 4), wherein, I
QBe hot-fluid with watt expression, σ
SBBe Si Tepan-Boltzmann constant (5.67x10
-8W/m
2-K
4), F
12Be the constant of the energy absorption on the definite surface between 0-1, A is with m
2The heating element area of expression, for heat flux sensor, T
2Be heated detector element temperature, T
1It is the conduit wall temperature.Linearization provides to convert thermal resistance into: R
Rad=1/ (4 σ
SBF
12AT
2 3).
Electricity-hot loop model also comprises resistance element 114, this resistance element have with flow channel in the thermoflux, the hot corresponding thermal resistance R that promptly takes away from heated element of the forced convertion that causes of fluid through fluid convection
ConvThermal resistance R
ConvCan be defined as R
Conv=l/ (h
PlateA), wherein, A is the heating element area, h
PlateIt is the coefficient of the physical construction of the flow rate, type and heated element and the passage that depend on the fluid of Reynolds number, component ambient.Reynolds number equals Re=U*l/v, and wherein, U is an AFR, and l is a characteristic length, and v is the kinetic viscosity that is used for fluid.
Electricity-hot loop model also comprises resistance element 116, and said resistance element 116 has and the corresponding thermal resistance R of conduction thermoflux that passes through the heating element mechanical support structure
LegR
LegCan be defined as R
Leg=L/ κ A, wherein, L is the length of material, and A is a cross-sectional area, and κ is a pyroconductivity.
At last, this model comprises resistance element 118, and said resistance element 118 has and the corresponding thermal resistance R of conduction thermoflux that arrives conduit wall through fluid
FluidR
FluidHave and R
LegIdentical governing equation, wherein, conductive medium is a fluid, the thermmal storage capacity C of heat flux sensor
Thermal110 are defined as
Wherein, C
ThermalBe thermal capacitance,
Be the specific heat of material, ρ
mBe density of material, V is a volume.
The sensitivity of heat flux sensor depends on the energy stream in the system.When fluid sample flows through the heat flux sensor heating element, R
ConvAnd R
FluidValue confirm through the sample pyroconductivity.Peak response appears at R
FluidBe that main thermal loss path and other all heat loss paths are when being minimized.
Through the temperature difference (Δ T) between control heat flux sensor and the heating element, the performance of heat flux sensor can advantageously measured and modeling.All essential calculating depend on the measurement of thermal resistance, and said thermal resistance is defined as R
T=Δ T/IV=Δ T/Q.
Fig. 5 a shows the indicative icon according to the position of heater pad 514 in the chamber 520 of heat flux sensor 524 of an embodiment of the present disclosure.Fig. 5 b is the enlarged diagram of the heater pad 514 shown in Fig. 5 a.Fig. 5 c is the cut-open view of an embodiment of the heat flux sensor 524 shown in Fig. 5 a that is done along line Va-Va.Fig. 5 d is the cut-open view of another embodiment of the heat flux sensor 524 shown in Fig. 5 a that is done along line Va-Va.
Can further improve the performance of heat flux sensor 524 through the design of chamber 520 and heater pad 514, to increase the sensitivity of sensor 524.Heater pad 514 changes R with respect to the physical arrangement of the chamber 520 of sensor 524 and the variation of position
FluidValue.Therefore, the type of heater pad 514 and control of position are made the may command thermoflux therefore, improved the performance of heat flux sensor 524.Especially, the spacing 502,504,506,508 between chamber wall and the heating wall 514 can be selected, to improve the performance of heat flux sensor 524.
And the other type that improves heat flux sensor sensitivity can be that the heat that increases heating element is isolated.In certain embodiments, the hot increase of isolating can be through increasing bearing length and reducing the heat condition capacity realization that supporting pad width and thickness reduce supporting leg 230,232,234,236.In other embodiments, the raising of transducer sensitivity can realize through the induction electric energy transmission towards heating element.For example, through removing the metal trace on the heating element and remove metal trace, be reduced along the heat of supporting leg transmission from heating element.
Band broadening is corresponding with the broadening of analyte band before the analyte band reaches sensor; This effect has reduced the resolution of analyzing.According to embodiment more of the present disclosure, minimizing of band broadening can realize through making chamber size and connecting pipe coupling.In more special embodiment, the coupling of chamber size and connecting pipe realizes that through deformable connecting pipe is installed the shape of the connecting pipe of said distortion can be regulated through actuator.The cross-sectional area of connecting pipe can change, so that the approximate match with the cross-sectional area of the scope of chromatography column to be provided.In some the microscale chromatographic systems according to other embodiment, heating element can be placed in the flow channel of chamber, and the cross-sectional area of said flow channel and the cross-sectional area of at least one chromatography column are complementary.The coupling of channel size can prevent band broadening, has also improved the stratographic analysis performance.Should be appreciated that about 1%, 5%, 10% or the bigger manufacturing tolerance that allow to be formed integrally as the cross-sectional area between separating column, flow channel, connecting pipe, heating element and/or the heat flux sensor together in the term aspect the size of this use " coupling " considered.
Referring to Fig. 5 a-5d; If heat flux sensor is integrated in the chromatographic system; Passage 522 can have height 510 and width 512, makes height 510 and width 512 be matched with the cross-sectional area of given chromatography column, the 10 μ ms of the scope of this cross-sectional area under some embodiment
2Arrive the 1mm under other embodiment
2
Still please referring to Fig. 5 a-5d, the spacing 502,504,506,508 between heater pad 514 and the passage/chamber wall can be designed to make heater pad 514 to be suspended in the chamber 520.Spacing 502,504 is illustrated as with value after total chamber height 510 deducts the thickness of heater pad 514 and equates.Through using the thermal model of micro production and establishment, the size of spacing 502,504 can be selected to provides maximum response to analyte, thereby produces sensitiveer sensor.And passage 522 can have any such width 512: heater pad 514 can not contact chamber wall and be assemblied in the chamber width 512.
In other embodiments, still referring to Fig. 5 a-5d, heater pad 514 can have scope from several millimeters-several microns length 516.Heater pad 514 can have the length 516 of the about 20 μ m under other embodiment of about 2mm-under some embodiment.Although long length provides higher sensitivity, short pad can be surveyed short bands of a spectrum.In special embodiment, chamber 520 can have the length 518 greater than the length of heater pad 516, preferably from 100 μ m to several centimetres.
In other embodiments; Particularly referring to Fig. 5 d; A plurality of heater pad 514,514a, 514b are illustrated as and are suspended in the passage 522, and the pyroconductivity that can be used for the detection flows sample body is when owing to the dimensionless number of local knudsen number (Kn), expression molecule mean free path and the ratio of the physical size of chamber 520 changes.For example, compare with the mean free path of gas when big when plant bulk, pyroconductivity, gas physical property are constant.In Fig. 5 d, chamber 520 is shown as including a plurality of chamber wall 520a, 520b, 520c and 520d.Heater pad 514,514a, the 514b that has the one-tenth arranged in arrays of different distance 502,502a, 502b apart from chamber wall can be used for confirming the component/analyte of fluid sample.When distance 502,502a, 502b are reduced to when making them be in the point in the amplification level of molecule mean free path, the pyroconductivity of fluid begins to reduce.This reduces to depend on the mean free path of gas.Because all gas has different mean free paths, therefore, the Kn under the stationary installation parameter depends on the gas in the chamber.For example, in two component gas potpourris, for example hydrogen and water vapour, at least two heater pads 514,514a can be used for surveying the ratio of hydrogen and water vapour through obtain differential signal from two heating cushions 514,514a with different clearance distance.Hydrogen has much bigger mean free path, and therefore, the Kn of the given chamber of this gas is more a lot of greatly than the Kn of the identical chamber of water vapour.Two heater pads have similar response to water vapour, but hydrogen is had visibly different response.
In the embodiment shown in Fig. 5 d; In each heater pad 514,514a, 514b and the chamber wall at least one (promptly; Lid 520a and base portion 520c) spaced apart different distances 502,502a, 502b, survey and discern the molecular components of fluid with the pyroconductivity of measurement fluid.Heater pad 514 preferably is configured for first thermoflux of surveying fluid to be changed, and with spaced apart first distance 502 of lid 520a; Heater pad 514a preferably is configured for second thermoflux of surveying fluid to be changed, and with the spaced apart second distance 502a of lid 520a; Heater pad 514b preferably is configured for the 3rd thermoflux of surveying fluid to be changed, and with lid 520a the spaced apart the 3rd apart from 502b.Although this illustrate and described three heater pads, the present invention should not be limited to this embodiment.Can be according to multiple factor, for example the material etc. of size, heater pad or the heating element of temperature, the chamber/passage of fluid sample to be analyzed, detector silk has a plurality of heater pads in passage.Heater pad 514,514a, 514b preferably with the spaced apart predetermined fore-and-aft distance of section Va-Va, wherein, passage limits the longitudinal axis of chamber; Yet heater pad 514,514a, 514b can make the mode that each heater pad 514,514a, 514b are arranged in the identical section.Distance 502,502a, 502b can pass through to realize with the different depth etched channels.Distance 504 between heater pad 514,514a, 514b and the base portion 520c, 504a, 504b also can be used for optimizing the detection and the identification of the molecular components of fluid.Through use two or more heater pads 514,514a, the 514b of series connection with different distances 502,502a, 502b and 504,504a, 504b; When distance is in 2 powers of amplitude of mean free path the time, local Kn will be with the pyroconductivity of the gas in the given scale effect chamber 520.Like this, the ratio from the response of heater pad can be used for discerning gaseous species.Another advantage of present embodiment is, the fluid in the chamber or can flow maybe can be stagnated.
And in another aspect of the present disclosure, the microscale gas chromatography system can comprise at least one separating column, injector and heat flux sensor.Heat flux sensor can comprise chamber, be suspended at least one heating element in the chamber, be configured at least two current joints and at least two measurement joints to the heating element supplying electric current, and said measurement joint is configured for the change in voltage along heating element of the pyroconductivity of measuring the expression fluid.In certain embodiments, said at least one separating column and heat flux sensor form.In certain embodiments, the cross-sectional area of the cross-sectional area of the chamber of heat flux sensor and said at least one separating column is complementary.The microscale gas chromatography system can be used to analyze various analytes in the laboratory, for example be found in molecular weight in those analytes and the particularly gas samples in the gas samples less than the analyte of ethane.The microscale gas chromatography system may be implemented in the place, ground in well site, maybe can be comprised in the subsurface tool, and said subsurface tool is suitable for being connected to rig along the well deployment and via cable, drill string, tool string or oil pipe.
In certain embodiments, shown in Fig. 7 g, heat flux sensor 722 comprises chamber and heater pad 714.Chamber can have into the structure of two parts 702,716, and said two parts are formed by identical or different material.Chamber can comprise first supporting layer 702 and be arranged on second supporting layer 716 on first supporting layer 702.Heating element places first and second supporting layers 702 at this moment, between 716.In these embodiment, said at least one separating column 728 is shared first and second supporting layers 702,716 with chamber.Shown in Fig. 7 a-7g, heat flux sensor 722 separating columns 728 preferred and micro-scale gas chromatography system integrate, and their equal micro productions are on identical supporting layer 702.
According to another aspect of the present disclosure, a kind of method that is used to measure the pyroconductivity of fluid is provided, comprising: fluid to be analyzed is provided; Heat flux sensor is provided, and said heat flux sensor comprises chamber and is suspended at the heating element in the chamber; Near at least two current joints to the heating element supplying electric current; Near and the change in voltage that the measurement expression is changed by the thermoflux that causes along the heating element flowing fluid at least two measurement joints.
According to another aspect of the present disclosure, a kind of method that is used to make the heat flux sensor of the pyroconductivity that is used to measure fluid is provided.
Said method comprises: chamber is provided; Heating element is provided; Heating element is contained in the chamber, makes heating element be suspended in the chamber; At least two current joints are provided, and said current joint is configured for to the heating element supplying electric current; And the change in voltage that changes of the thermoflux that provides at least two measurement joints, said measurement joint to be configured for to measure expression to cause along heating element by fluid.
According to some embodiment, the said chamber that provides comprises: first supporting layer is provided and second supporting layer is arranged on first supporting layer.First and second supporting layers are configured to limit the cavity that holds heating element.
In other embodiments, said heating element is contained in the chamber comprises: at least one supporting layer is deposited on first supporting layer; At least one bonding coat is deposited on said at least one supporting layer; With at least one layer metal deposition at least one bonding coat; And etching first supporting layer and said at least one supporting layer, to limit heater pad and to be used for the passage that fluid flows.
In other embodiments, said at least one supporting layer was etched according to predetermined pattern before said at least one bonding coat of deposition.
Be used to make and describe referring to Fig. 6 a, 6b, 6c, 6d below the method for heat flux sensor 622.
Be more especially a referring to Fig. 6, first supporting layer 602 is provided at present.Then, supporting layer 604 is deposited on first supporting layer 602.Supporting layer 604 is covered by photoresist 620, thereby mask pattern is provided, to be used for deposit adhesion layer 606 and metal level 608.Supporting layer 604 is etched with mask pattern then.Bonding coat 606 and metal level 608 be deposited on then on the photoresist 620 with preparatory etched supporting layer 604 on, thereby fill preparatory etched groove.
Shown in Fig. 6 b, photoresist 620 is removed then, thereby on the top side of supporting layer 604, stays almost concordant surface, thereby in said method, allows to combine supporting layer 604.Flow channel 610 is defined through seeing through supporting layer 604 patterned and etching with heater pad 614.
In Fig. 6 c, first supporting layer 602 is etched, to form passage 612.At last, can find out from Fig. 6 d that heat flux sensor 622 comprises second supporting layer 616.Second supporting layer, 616 quilts are manufactured with the passage 618 with the first supporting layer passage, 612 symmetries.Combine first and second supporting layers 602, before 616, making passage 610,612,618 alignment.This alignment can realize through the key that use is placed in the passage 610,612,618 that is etched out.First and second supporting layers 602,616 anode ground then combine.This combination can apply the voltage execution through the supporting layer 602,616 of heating alignment and to hot plate and contact probe.
According to another aspect of the present disclosure, a kind of method that is used to make micro-scale gas chromatography system is provided, said micro-scale gas chromatography system comprises heat flux sensor and at least one separating column.
Said method comprises: chamber is provided; At least one separating column is provided; Heating element is provided; Heating element is contained in the chamber, makes heating element be suspended in the chamber; At least two current joints are provided, and said current joint is configured for to the heating element supplying electric current; And the change in voltage that changes of the thermoflux that provides at least two measurement joints, said measurement joint to be configured for to measure expression to cause along heating element by fluid.
According to some embodiment, the said chamber that provides comprises: first supporting layer is provided and second supporting layer is arranged on first supporting layer.First and second supporting layers are configured to limit the cavity that holds heater pad.
In other embodiments, said heater pad is contained in the chamber comprises: at least one supporting layer is deposited on first supporting layer; At least one bonding coat is deposited on said at least one supporting layer; With said at least one layer metal deposition on said at least one bonding coat; And etching first supporting layer and said at least one supporting layer, to limit heater pad and passage.
According to embodiment more of the present disclosure, said at least one separating column and chamber are shared first and second supporting layers and said at least one supporting layer.
In other embodiments, said at least one supporting layer was etched according to predetermined pattern before said at least one bonding coat of deposition.
Below, the method for making of micro-scale gas chromatography system will be described referring to Fig. 7 a, 7b, 7c, 7d, 7e, 7f and 7g.
Existing more particularly referring to Fig. 7 a, first supporting layer 702 is provided.Then, supporting layer 704 is deposited on first supporting layer 702.Referring to Fig. 7 b, supporting layer 704 is covered by photoresist 720, thereby mask pattern is provided, to be used for deposit adhesion layer 706 and metal level 708.Supporting layer 704 is etched with mask pattern then.
Shown in Fig. 7 c, bonding coat 706 and metal level 708 be deposited on then on the photoresist 720 with preparatory etched supporting layer 704 on, thereby fill preparatory etched groove.
In Fig. 7 d, supporting layer 704 is patterned processing with metal level 708 through being used for the etched photoresist sediment 720 of passage.In Fig. 7 e and 7f, flow channel 710,712,724 is etched out.
At last, shown in Fig. 7 g, after cleaning supporting layer surface 704 and metal surface 708, second supporting layer 716 is incorporated into said device.Said second supporting layer 716 be manufactured with the passage 718 of passage 712 symmetries of first supporting layer 702 and with the passage 726 of passage 724 symmetries of separating column 728.
Said layer the method that is used to deposit with etching chamber and heater pad can be any prior art that those skilled in the art can obtain.For example, the deposition of layer can be carried out through low pressure chemical vapor deposition (LPCVD).And etching for example can use CF4, use to combine the deep reactive ion etch (DRIE) of anisotropic etching and be exposed under the SF6 in the reactive ion etching machine, to realize.
Can make up with other data, for example gas chromatographic analysis data, optical measurement result and mass spectrometry results through the data of use according to the measuring method acquisition of heat flux sensor of the present disclosure.
Advantage of the present disclosure also can comprise one or more in the following advantage.The heat flux sensor that have different joints, promptly is used for the joint of supplying electric current and is used for the joint of measuring voltage has eliminated because noise and the error that the fluctuation of the impedance of electric current line causes.Advantageously, embodiment of the present disclosure provides a kind of improved heat flux sensor, and said heat flux sensor has the heat of increase isolates, thereby very sensitive owing to have very fast time constant.Heat flux sensor can make and reduce carrier gas consumption.
Although in order to have described various specific embodiments above the illustration purpose, the present invention is not limited to specific embodiments disclosed herein.For example; Although have one, two or three heating elements or heating cushion; But also can expect; In the various embodiments that conform to embodiments of the invention, also can implement, be provided with and turn up the soil at interval location four, five, six, ten, 50,100 or more a plurality of heating element or heating cushion.Without departing from the scope of the invention, those skilled in the art can carry out various modifications to disclosed embodiment.Therefore, the present invention is only limited the scope of claim at this.
Claims (21)
1. heat flux sensor that is used to measure the pyroconductivity of fluid, said heat flux sensor comprises:
Chamber;
Be suspended at the heating element in the chamber;
At least two current joints, said at least two current joints are configured for and the heating element exchanging electric current; And
At least two measurement joints, said at least two measurement joints are configured for the change in voltage along heating element of the pyroconductivity of measuring the expression fluid.
2. heat flux sensor as claimed in claim 1 is characterized in that heating element comprises at least two districts; Wherein, At least two measurement joints are provided with along each district, and are configured for the change in voltage of measuring in the respective area, and said change in voltage is represented the flow rate of fluid.
3. heat flux sensor as claimed in claim 1 is characterized in that, chamber comprises first supporting layer and be arranged on second supporting layer on first supporting layer that said heating element places between first and second supporting layers.
4. heat flux sensor as claimed in claim 3 is characterized in that heating element is arranged on the supporting pad that comprises at least one supporting layer.
5. heat flux sensor as claimed in claim 3 is characterized in that, heating element comprises at least one bonding coat and is arranged at least one metal level on the bonding coat.
6. heat flux sensor as claimed in claim 1 is characterized in that, heat flux sensor is miniature pyroconductivity detector.
7. heat flux sensor that is used to measure the pyroconductivity of fluid, said heat flux sensor comprises:
Chamber, said chamber limits fluid flow direction therein;
First heating element, said first heating element is suspended in the chamber, and the fluid that is configured for arrival preheats predetermined temperature; And
Second heating element; Said second heating element is suspended in the chamber; And on fluid flow direction, be positioned at the downstream of first heating element, wherein, second heating element is configured for detection to be changed by the thermoflux along second heating element that streaming flow causes.
8. heat flux sensor as claimed in claim 7 is characterized in that, said second heating element comprises:
At least two current joints, said at least two current joints be configured for first and second heating elements at least one exchanging electric current; And
At least two measurement joints, said at least two measurement joints are configured for the change in voltage of at least one in first and second heating elements of the pyroconductivity of measuring the expression fluid.
9. heat flux sensor as claimed in claim 7; It is characterized in that; Said chamber comprises a plurality of walls, wherein, and spaced apart first distance of at least one wall in the wall of first heating element and chamber; The spaced apart second distance of at least one wall in the wall of second heating element and chamber, and first distance is different with second distance.
10. microscale gas chromatography system, comprising: at least one injector, said injector are suitable for the fluid sample that comprises multiple analytes is provided in the microscale gas chromatography system; At least one separating column, said separating column are suitable for isolating at least a portion of the multiple analytes of fluid sample; And heat flux sensor, said heat flux sensor is suitable for surveying at least a portion of isolated multiple analytes in said at least one separating column, and said heat flux sensor comprises:
Chamber;
Be suspended at the heating element in the chamber;
At least two current joints, said at least two current joints are configured for and the heating element exchanging electric current; And
At least two measurement joints, said at least two measurement joints are configured for the change in voltage along heating element of the pyroconductivity of at least a portion of measuring the multiple analytes of representing fluid sample.
11. microscale gas chromatography system as claimed in claim 10 is characterized in that, said at least one separating column and heat flux sensor form.
12. microscale gas chromatography system as claimed in claim 11 is characterized in that, said sensor is miniature pyroconductivity detector.
13. microscale gas chromatography system as claimed in claim 11 is characterized in that, the cross-sectional area of the chamber of heat flux sensor and the cross-sectional area of said at least one separating column are complementary.
14. microscale gas chromatography system as claimed in claim 10; It is characterized in that said chamber comprises a plurality of walls, wherein; Said heat flux sensor comprises second heating element; Said second heating element is suspended in the chamber, and with the wall of chamber at least one spaced apart segment distance, second heating element has at least two current joints and at least two measurement joints; Said at least two current joints are configured for and the second heating element exchanging electric current, and said at least two measurement joints are configured for the change in voltage along second heating element of the pyroconductivity of at least a portion of measuring the multiple analytes of representing fluid sample.A kind of method that is used to analyze the fluid sample that comprises multiple analytes said method comprising the steps of:
The microscale gas chromatography system of claim 10 is provided;
The fluid sample that will comprise multiple analytes injects the microscale gas chromatography system;
Isolate at least a portion of the multiple analytes of fluid sample;
At at least two current joint places to the heating element supplying electric current; And
Measure the change in voltage that the thermoflux variation that is caused by the fluid along heating element is measured in the joint at least two.
15. a method that is used to measure the pyroconductivity of fluid may further comprise the steps:
Fluid to be analyzed is provided;
Heat flux sensor is provided, and said heat flux sensor comprises chamber and is suspended at the heating element in the chamber;
At at least two current joint places to the heating element supplying electric current; And
The change in voltage that the thermoflux that is caused by the fluid along heating element at least two measurement joints measurement expressions changes.
16. a method that is used to measure the pyroconductivity of fluid may further comprise the steps:
Fluid to be analyzed is provided;
Heat flux sensor is provided, and said heat flux sensor comprises chamber, and said chamber has longitudinal axis and around the laterally disposed a plurality of chamber walls of the longitudinal axis of chamber;
First and second heating elements that are suspended in the chamber are provided, wherein, at least one the spaced apart different distance in first and second heating elements and a plurality of chamber wall;
At least one supplying electric current at least two current joint places in first and second heating elements; And
Measure the pyroconductivity of fluid according to the preset distance between in chamber wall and said first and second heating elements at least one.
17. a method that is used to make the heat flux sensor of the pyroconductivity that is used to measure fluid comprises:
Chamber is provided;
Heating element is provided;
Heating element is contained in the chamber, makes heating element be suspended in the chamber;
At least two current joints are provided, and said at least two current joints are configured for to the heating element supplying electric current; And
At least two measurement joints are provided, and said at least two measurement joints are configured for measures the change in voltage along heating element that thermoflux that expression causes by fluid changes.
18. method as claimed in claim 17 is characterized in that, provides chamber to comprise:
First supporting layer is provided; And
Second supporting layer is arranged on first supporting layer;
Wherein, first and second supporting layers are configured to limit the cavity that holds heating element.
19. method as claimed in claim 17 is characterized in that, heating element is contained in the chamber comprise:
At least one supporting layer is deposited on first supporting layer;
At least one bonding coat is deposited on said at least one supporting layer;
With at least one layer metal deposition on said at least one bonding coat; And
Etching first supporting layer and said at least one supporting layer are to limit heating element and the round-robin passage that is used for fluid.
20. method as claimed in claim 19 is characterized in that, said at least one supporting layer was etched according to predetermined pattern before said at least one bonding coat of deposition.
21. a method that is used to make the microscale gas chromatography system comprises:
Chamber is provided;
At least one separating column is provided;
Heating element is provided;
Heating element is contained in the chamber, makes heating element be suspended in the chamber;
At least two current joints are provided, and said at least two current joints are configured for to the heating element supplying electric current; And
At least two measurement joints are provided, and said at least two measurement joints are configured for measures the change in voltage along heating element that thermoflux that expression causes by fluid changes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25031009P | 2009-10-09 | 2009-10-09 | |
| US61/250,310 | 2009-10-09 | ||
| PCT/US2010/052147 WO2011044547A2 (en) | 2009-10-09 | 2010-10-11 | Micro-thermal conductivity detector, method to fabricate such and chromatography system using such |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102549422A true CN102549422A (en) | 2012-07-04 |
Family
ID=43857430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800453603A Pending CN102549422A (en) | 2009-10-09 | 2010-10-11 | Micro-thermal conductivity detector, method to fabricate such and chromatography system using such |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2486398A4 (en) |
| CN (1) | CN102549422A (en) |
| CA (1) | CA2775583A1 (en) |
| WO (1) | WO2011044547A2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103675015A (en) * | 2012-09-19 | 2014-03-26 | 原子能和替代能源委员会 | Heat flux sensor with increased resolution |
| CN105136871A (en) * | 2015-06-19 | 2015-12-09 | 上海集成电路研发中心有限公司 | Micro thermal conductivity detector structure and processing and manufacturing method thereof |
| CN105283755A (en) * | 2013-06-04 | 2016-01-27 | 株式会社电装 | Vehicle abnormality determination device |
| CN105937877A (en) * | 2015-03-04 | 2016-09-14 | 株式会社三丰 | Chromatic range sensor including high sensitivity measurement mode |
| CN108181415A (en) * | 2016-12-08 | 2018-06-19 | 中国科学院上海微系统与信息技术研究所 | Micro- thermal conductivity detector (TCD) of film-type and preparation method thereof |
| CN108700533A (en) * | 2016-03-07 | 2018-10-23 | 株式会社岛津制作所 | thermal conductivity detector |
| CN109154581A (en) * | 2016-05-09 | 2019-01-04 | 日写株式会社 | Gas sensor device and its manufacturing method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8805614B2 (en) | 2010-08-31 | 2014-08-12 | Schlumberger Technology Corporation | Downhole sample analysis method |
| US8531422B2 (en) | 2011-09-12 | 2013-09-10 | Siemens Aktiengesellschaft | Intrinsically safe touch screen for process equipment |
| GB201421102D0 (en) | 2014-11-27 | 2015-01-14 | Cambridge Entpr Ltd | Thermal conductivity sensing device, methods for operation and uses of the same |
| FR3038982A1 (en) | 2015-07-16 | 2017-01-20 | Commissariat Energie Atomique | ANALYSIS DEVICE FOR ANALYZING A MIXTURE OF AT LEAST TWO GASES |
| FR3040489A1 (en) | 2015-08-28 | 2017-03-03 | Commissariat Energie Atomique | THERMAL FLOW SENSOR IMPLEMENTING AT LEAST ONE OPTICAL RESONATOR, GAS SENSOR AND PIRANI GAUGE COMPRISING AT LEAST ONE SUCH SENSOR. |
| FR3053793A1 (en) * | 2017-01-19 | 2018-01-12 | Commissariat Energie Atomique | GAS ANALYSIS DEVICE BY CATHAROMETRIC DETECTION |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000058723A2 (en) * | 1999-03-30 | 2000-10-05 | The Regents Of The University Of California | Micro-machined thermal conductivity detector |
| TW494233B (en) * | 2000-02-25 | 2002-07-11 | Chung Shan Inst Of Science | Thermal conductivity detector |
| CN2911684Y (en) * | 2006-03-21 | 2007-06-13 | 杨翌华 | Mini detector for heat conductivity of ceramic |
| US20070144238A1 (en) * | 2005-12-23 | 2007-06-28 | Serveron Corporation | Thermal conductivity detector |
| US20070169541A1 (en) * | 2005-09-22 | 2007-07-26 | Norbeck Joseph N | Gas sensor based on dynamic thermal conductivity and molecular velocity |
| US20080121016A1 (en) * | 2006-11-29 | 2008-05-29 | Schlumberger Technology Corporation | Gas chromatography system architecture |
| US20090031785A1 (en) * | 2007-07-31 | 2009-02-05 | Caviton, Inc. | Capacitively coupled dielectric barrier discharge detector |
| CN101443659A (en) * | 2006-03-15 | 2009-05-27 | 霍尼韦尔国际公司 | Three-wafer channel structure for a fluid analyzer |
| CN101501488A (en) * | 2004-07-30 | 2009-08-05 | 霍尼韦尔国际公司 | Phased VII micro fluid analyzer having a modular structure |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2992848B2 (en) * | 1991-08-21 | 1999-12-20 | 株式会社山武 | Thermal conductivity detector |
| US5772321A (en) * | 1995-10-25 | 1998-06-30 | Hewlett-Packard Company | Compensation for spacial and temporal temperature variations in a thermal conductivity detector |
-
2010
- 2010-10-11 WO PCT/US2010/052147 patent/WO2011044547A2/en active Application Filing
- 2010-10-11 CA CA2775583A patent/CA2775583A1/en not_active Abandoned
- 2010-10-11 EP EP10822815.6A patent/EP2486398A4/en not_active Withdrawn
- 2010-10-11 CN CN2010800453603A patent/CN102549422A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000058723A2 (en) * | 1999-03-30 | 2000-10-05 | The Regents Of The University Of California | Micro-machined thermal conductivity detector |
| TW494233B (en) * | 2000-02-25 | 2002-07-11 | Chung Shan Inst Of Science | Thermal conductivity detector |
| CN101501488A (en) * | 2004-07-30 | 2009-08-05 | 霍尼韦尔国际公司 | Phased VII micro fluid analyzer having a modular structure |
| US20070169541A1 (en) * | 2005-09-22 | 2007-07-26 | Norbeck Joseph N | Gas sensor based on dynamic thermal conductivity and molecular velocity |
| US20070144238A1 (en) * | 2005-12-23 | 2007-06-28 | Serveron Corporation | Thermal conductivity detector |
| CN101443659A (en) * | 2006-03-15 | 2009-05-27 | 霍尼韦尔国际公司 | Three-wafer channel structure for a fluid analyzer |
| CN2911684Y (en) * | 2006-03-21 | 2007-06-13 | 杨翌华 | Mini detector for heat conductivity of ceramic |
| US20080121016A1 (en) * | 2006-11-29 | 2008-05-29 | Schlumberger Technology Corporation | Gas chromatography system architecture |
| US20090031785A1 (en) * | 2007-07-31 | 2009-02-05 | Caviton, Inc. | Capacitively coupled dielectric barrier discharge detector |
Non-Patent Citations (1)
| Title |
|---|
| B.C.KAANTA ET AL: "High sensitivity micro-thermal conductivity detector for gas chromatography", 《MICRO ELECTRO MECHANICAL SYSTEMS IEEE 22ND INTERNATIONAL CONFERENCE, MEMS 2009》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103675015A (en) * | 2012-09-19 | 2014-03-26 | 原子能和替代能源委员会 | Heat flux sensor with increased resolution |
| US9746384B2 (en) | 2012-09-19 | 2017-08-29 | Commissariat à l'énergie atomique et aux énergies alternatives | Heat flux sensor with increased resolution |
| CN103675015B (en) * | 2012-09-19 | 2018-04-03 | 原子能和替代能源委员会 | The heat flux sensor of resolution ratio with raising |
| CN105283755A (en) * | 2013-06-04 | 2016-01-27 | 株式会社电装 | Vehicle abnormality determination device |
| CN105937877A (en) * | 2015-03-04 | 2016-09-14 | 株式会社三丰 | Chromatic range sensor including high sensitivity measurement mode |
| CN105937877B (en) * | 2015-03-04 | 2018-07-17 | 株式会社三丰 | Include the chromatography distance measuring sensor of high-sensitivity measurement pattern |
| CN105136871A (en) * | 2015-06-19 | 2015-12-09 | 上海集成电路研发中心有限公司 | Micro thermal conductivity detector structure and processing and manufacturing method thereof |
| CN108700533A (en) * | 2016-03-07 | 2018-10-23 | 株式会社岛津制作所 | thermal conductivity detector |
| CN109154581A (en) * | 2016-05-09 | 2019-01-04 | 日写株式会社 | Gas sensor device and its manufacturing method |
| CN108181415A (en) * | 2016-12-08 | 2018-06-19 | 中国科学院上海微系统与信息技术研究所 | Micro- thermal conductivity detector (TCD) of film-type and preparation method thereof |
| CN108181415B (en) * | 2016-12-08 | 2023-05-12 | 中国科学院上海微系统与信息技术研究所 | Thin film type micro heat conduction detector and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2486398A2 (en) | 2012-08-15 |
| WO2011044547A2 (en) | 2011-04-14 |
| CA2775583A1 (en) | 2011-04-14 |
| WO2011044547A3 (en) | 2011-09-09 |
| EP2486398A4 (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102549422A (en) | Micro-thermal conductivity detector, method to fabricate such and chromatography system using such | |
| CN103069272B (en) | System for analyzing a gas mixture including at least one chromatography column | |
| US4471647A (en) | Gas chromatography system and detector and method | |
| Noh et al. | Parylene gas chromatographic column for rapid thermal cycling | |
| Dziuban et al. | Portable gas chromatograph with integrated components | |
| Wu et al. | MEMS flow sensors for nano-fluidic applications | |
| Ali et al. | Tungsten-based SOI microhotplates for smart gas sensors | |
| Briand et al. | A low-power micromachined MOSFET gas sensor | |
| CN109844521A (en) | Multichannel Multidimensional Comprehensive gas-chromatography | |
| CN112119303A (en) | Method for analyzing hydrocarbons | |
| EP2304424A2 (en) | Chromatographic device and method of fabrication and chromatographic methods | |
| De Graaf et al. | Micro thermal conductivity detector with flow compensation using a dual MEMS device | |
| KR101867088B1 (en) | The Carbon Nano Tubes Integrated Micro Gas-Chromatography | |
| Xu et al. | A MEMS multi-sensor chip for gas flow sensing | |
| Zhao et al. | A microfluidic flow meter with micromachined thermal sensing elements | |
| Lorenzelli et al. | Development of a gas chromatography silicon-based microsystem in clinical diagnostics | |
| Kaanta et al. | Novel device for calibration-free flow rate measurements in micro gas chromatographic systems | |
| Legendre et al. | CMOS compatible nanoscale thermal conductivity detector for gas sensing applications | |
| CN102667465A (en) | Method and arrangement for gas chromatographic analysis of a gas sample | |
| Xue et al. | A silicon-glass-based microfabricated wide range thermal distribution gas flow meter | |
| Feng et al. | High sensitive micro thermal conductivity detector with sandwich structure | |
| De Graaf et al. | Flow compensation in a MEMS dual-thermal conductivity detector for hydrogen sensing in natural gas | |
| Kaanta et al. | Effect of forced convection on thermal distribution in micro thermal conductivity detectors | |
| Weiping et al. | Thermal distribution microfluidic sensor based on silicon | |
| De Graaf et al. | A MEMS flow compensated thermal conductivity detector for gas sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |