CN103575630B - A kind of Simultaneously test combination gas respectively forms the assay method of the membrane permeability of gas - Google Patents
A kind of Simultaneously test combination gas respectively forms the assay method of the membrane permeability of gas Download PDFInfo
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Abstract
The invention discloses assay method and device that a kind of Simultaneously test combination gas respectively forms the membrane permeability of gas, the present invention realizes the coupling of the gas osmotic cell of gas chromatograph and survey membrane permeability, can once quick and precisely measure simultaneously mixed gas through time film and the Multiple components perviousness of sheeting, and this method of attachment of the present invention does not need to build sweep gas system, do not need through quantitative sampling device, can be used for the film that test diameter 8mm is even less, test infiltration 5 minutes had enough sensitivity through gas gas chromatographic flame ionization detector.Utilize the present invention, can study mixed gas through time various compositions influencing each other to infiltration rate, conveniently can record coefficient of diffusion and the solubility coefficient of film and sheeting.
Description
Technical field:
The present invention relates to and belong to membrane material analysis and gas chromatographic analysis field, be specifically related to assay method and device that a kind of Simultaneously test combination gas respectively forms the membrane permeability of gas.
Background technology:
At present, the method measuring film and thin slice gas penetration potential is existing many, and common have different platen press and equal-pressure method.Different platen press includes pressure application and volumetric method, and equal-pressure method includes electrode method and thermistor detects method etc.Wherein, pressure application is comparatively conventional.The U.S. test with materialogy can test method ASTMD1434-82 (2009) e1 " standard method of plastic sheeting and thin slice ventilation characteristic measuring " (StandardMethodforDeterminingGasPermeabilityCharacteristi csofPlasticFilmandSheeting), and the standard GB/T/T1038-2000 of China " plastic sheeting and thin slice gas-premeable test method pressure differential method " apply be pressure application.The gas penetration potential that these methods measure film and thin slice uses the device or the similar device that are called gas osmotic cell (GasTransmissionCell), film or thin slice are sandwiched in wherein, allow gas to be measured pass into diaphragm side, opposite side measures the gas flow through diaphragm by surveying instrument.But there is a common deficiency in these methods, can only measure a kind of gas penetration potential of gas at every turn, or mixed gas simultaneously through gas penetration potential, can not Simultaneously test mixed gas through time mixed gas respectively form the gas penetration potential of gas permeation film.When reality uses, many films are all be in atmospheric environment or mixed-gas environment, and mixed gas infiltration is owing to may exist influencing each other of gas, and ventilative speed might not with single composition through completely the same during film.
Another deficiency of gas-premeable method of testing conventional at present is that test period is long, often needs a few hours to arrive tens of hours.
Gas chromatograph is a kind of reproducible, highly sensitive and modern analysis and test instrument that separating power is strong.
If gas osmotic cell is received on gas chromatograph, the carrier gas of gas chromatograph is utilized the gas through film to be blown into the separation column cap of gas chromatograph, then suitable method and chromatographic condition is selected, quick and precisely can measure the gas penetration potential of film and thin slice, can also once quick and precisely measure simultaneously mixed gas through time film or the perviousness of the various constituent of mixed gas of sheeting.
Mixed gas through time simultaneously the various composition gases of rapid and accurate determination mixed gas permeance property be separately reality need, be also a difficult problem of measuring technology.
Patent CN102297827A discloses a kind of method of testing of fuel cell film battery gas penetration potential and test pool and proving installation.The side in experimental test pond is provided with the import and export passage of gas, and opposite side then forms test channel; Pass into tested gas and carrier gas respectively in the both sides in test examination pond, and the gas vent of its carrier gas side is passed in gas chromatography, by the content of tested gas in gas chromatography test carrier gas, thus calculate the air penetrability of membrane electrode.The air permeability test device of membrane electrode is primarily of experimental test pond and air penetrability test macro composition.Experimental test pond is made up of two pieces of plate jigs with gas feed and outlet and corresponding encapsulant.
The disclosed gas permeation rate proving installation principle of work such as patent CN202994616U and UCN201314906Y is similar to patent CN102297827A.
The common Problems existing of above-mentioned patent has: the test gas cell cavity of (1) osmotic cell is not specially for vapor-phase chromatography designs, and dead volume is unfavorable for clean through gas purging greatly; (2) method of testing be by stable through time bring gas chromatograph quantity tube through gas into by the inert gas of continuous flow and purge again into gas chromatograph for determination, for reaching the quantitative limit that gas chromatograph is enough to measure, the infiltrating area of film is enough large, is not suitable for measuring the film of small size or the slow film of infiltration rate; (3) need to set up stability of flow, flow velocity slow and can the more complicated inert gas air supply system of Accurate Measurement pressure and flow velocity, flow velocity can make to bring the not enough through gas flow of quantity tube into too soon.
Summary of the invention:
The object of this invention is to provide assay method and device that a kind of Simultaneously test combination gas respectively forms the membrane permeability of gas, solve dead volume large, the test duration is long, cannot accurate quantitative analysis; Easy not with gas chromatography connected mode, the problems such as inconvenient operation.
The present invention is achieved by the following technical solutions:
A kind of gas osmotic cell, comprise osmotic cell base, with osmotic cell base, there is the osmotic cell upper cover of symmetrical structure, the sealing gasket arranged between osmotic cell base and osmotic cell upper cover, osmotic cell base is connected by stationary installation with osmotic cell upper cover, described osmotic cell base and osmotic cell upper cover are the reeded flat board of side band and groove is relative fastens, the surrounding of groove is amplexiformed mutually with membrane material to be measured, disconnected two cell cavities are mutually formed in the both sides of membrane material to be measured, be respectively the sample gas cell cavity of osmotic cell base and the test gas cell cavity of osmotic cell upper cover, the both sides, sample gas cell cavity bottom of described osmotic cell base are communicated with the gas piping running through osmotic cell base respectively, the both sides, test gas cell cavity bottom of described osmotic cell upper cover are communicated with the gas piping running through osmotic cell upper cover respectively, it is characterized in that described sample gas cell cavity and test gas cell cavity all (test gas cell cavities in narrow strip, long 1mm-300mm, wide 0.2mm-5mm, high 0.2mm-5mm, sample gas cell cavity, long 1mm-300mm, wide 0.2mm-5mm, high 1mm-30mm) and the gas piping of sample gas cell cavity and test gas cell cavity both sides is all located at the most edge, bottom of groove, make through gas all blow into, reduce dead volume, go out peak sharp-pointed.
The sealing gasket arranged between described osmotic cell base and osmotic cell upper cover is preferably silicone rubber O-ring.
Described gas piping can be the plastic tube such as the metal tubes such as stainless steel, copper, aluminium or nylon, polypropylene, tygon, and echoing condensation to prevent test aspiration can be pipeline set temperature control device as required.
The present invention also provides a kind of Simultaneously test combination gas respectively to form the assay method of the membrane permeability of gas, adopt the device measuring combination gas and respectively form the membrane permeability of gas, this device comprises foregoing gas osmotic cell, pressure control device system, temperature control equipment, sample gas cylinder, four-way valve and gas chromatograph, comprises the following steps:
A, film to be measured to be arranged in foregoing gas osmotic cell, to obtain the gas osmotic cell assembled;
B, one end gas piping be provided with the groove bottom of gas osmotic cell base are communicated with sample gas cylinder through tensimeter, sample gas gas admittance valve, and other end gas piping is communicated with air; The gas piping that the two ends of gas osmotic cell upper cover are provided with is connected respectively wherein two joints of four-way valve, one of them joint in two other joint of four-way valve is communicated with the gas-carrier pipeline of gas chromatograph, another joint is communicated with the chromatographic column of gas chromatograph, obtain the device that mensuration combination gas respectively forms the membrane permeability of gas, be placed in thermostatic bath constant temperature;
C, first pass into sample gas and drive other gases in gas osmotic cell sample gas cell cavity and gas piping away, turn four-way valve handle enters chromatographic column after the carrier gas of gas chromatograph being switched to gas coming through osmotic cell test gas cell cavity again, after the gas in test gas cell cavity is driven in logical carrier gas away, the carrier gas of gas chromatograph switches back and directly enters chromatographic column by turn four-way valve handle again, starts to calculate time of penetration simultaneously; After sample gas infiltration certain hour infiltration rate is stable, the carrier gas of gas chromatograph is switched to and flows through osmotic cell test gas cell cavity and enter chromatographic column again by turn four-way valve handle, sweeps penetrating film gas chromatograph with carrier gas and carries out gas chromatographic analysis to the test air-blowing in test gas cell cavity; Record thickness, film infiltrating area, sample gas pressure, room temperature, thermostatic bath temperature, gas chromatography test condition, calculate membrane permeability.
Calculate membrane permeability to carry out according to chromatogram and following formula:
Wherein, q is transit dose (standard state, the state namely under 0 DEG C and 1 atmospheric pressure, cm
3); P is gas permeability coefficient (cm
3.cm.cm
-2.s
-1.cmHg
-1); p
1for the partial pressure (cmHg) of sample gas cell cavity; p
2for the partial pressure (cmHg) of test gas cell cavity, because steady seepage speed is that this value is approximately zero in the test of shorter time of penetration; A is film infiltrating area (cm
2); T is through the time (s); L is thickness (cm).
In order to increase the infiltrating area of membrane material, the series connection of the gas osmotic cell of two or more (comprising two) can be used if desired.
Described thermostatic bath can be liquid bath, air bath, semiconductor attemperator, infrared temperature regulating device, heat-generating pipe etc. can realize thermostatically controlled device.
The present invention also provides a kind of determinator measuring combination gas and respectively form the membrane permeability of gas, comprises foregoing gas osmotic cell, pressure control device, temperature control equipment, sample gas cylinder, four-way valve and gas chromatograph; One end gas piping that the sample gas cell cavity bottom of described gas osmotic cell base is provided with is sample gas air inlet pipeline, sample gas air inlet pipeline is communicated with sample gas cylinder through tensimeter, sample gas admittance valve, the other end gas piping of sample gas cell cavity bottom is sample gas outlet pipe, and sample gas outlet pipe is communicated with air through sample gas vent valve; The test air pipe that gas osmotic cell upper cover test both sides, gas cell cavity bottom are provided with connects wherein two joints of four-way valve respectively, one of them joint in two other joint of four-way valve is communicated with the gas-carrier pipeline of gas chromatograph, and another joint is communicated with by the chromatographic column of gas-carrier pipeline with gas chromatograph; Connection gas piping between sample gas cylinder, gas osmotic cell is respectively equipped with valve, tensimeter forms pressure control device, is provided with temperature control equipment in addition.
Described four-way valve is external plane four-way sampling valve, or the gas chromatograph first wife standby six-way valve four-way valve that sample gas inlet, outlet converts through shutoff, again or the good four-way valve of other gas tightness.
Described gas osmotic cell is one or more (comprising two).
Beneficial effect of the present invention: the present invention utilizes gas chromatograph reproducible, highly sensitive, there is the feature of configuration the strong and many testing laboratories of separating power, realize the coupling of the gas osmotic cell of gas chromatograph and survey membrane permeability, can once quick and precisely measure simultaneously mixed gas through time film and the Multiple components perviousness of sheeting, and this method of attachment of the present invention does not need to build sweep gas system, by turn four-way valve handle switching gas circuit, the carrier gas of gas chromatograph is switched to and flows through osmotic cell test gas cell cavity and enter chromatographic column again, utilize the carrier gas of gas chromatography by quick from test gas cell cavity for the test gas through film, all be blown into chromatographic column and carry out gas chromatographic analysis, do not need through quantitative sampling device, can be used for the film that test diameter 8mm is even less, test infiltration 5 minutes had enough sensitivity through gas gas chromatographic flame ionization detector.Utilize the present invention, can study mixed gas through time various compositions influencing each other to infiltration rate, conveniently can record coefficient of diffusion and the solubility coefficient of film and sheeting.
Accompanying drawing illustrates:
Fig. 1 is vapor-phase chromatography special gas osmotic cell schematic diagram of the present invention;
Fig. 2 is the connection diagram that the present invention measures combination gas and respectively forms the device of the membrane permeability of gas;
Fig. 3 is process of osmosis of the present invention and sample introduction analytic process schematic diagram;
Fig. 4 is the liquefied petroleum gas (LPG) chromatogram in the embodiment 1 obtained under optimum analytical conditions for gas chromatography;
Fig. 5 be in the liquefied petroleum gas (LPG) in embodiment 1 each alkane through the graph of a relation of time and transit dose;
Fig. 6 is single alkane calibrating gas in embodiment 1 through the graph of a relation of time and transit dose;
Fig. 7 is that the gas osmotic cell series connection of embodiment 3 uses schematic diagram;
Wherein: 1. sample gas vent valve, 2. sample gas outlet pipe, 3. osmotic cell, 4. air pipe is tested, 5. four-way valve, 6. gas-carrier pipeline, 7. sample gas gas admittance valve, 8. tensimeter, 9. sample gas air inlet pipeline, 10. osmotic cell attemperating unit, 11. test air pipes, 12. gas-carrier pipeline, 13. gas chromatographs, 14. test gas cell cavities, 15. sample gas cell cavities, 16. films to be measured, 17. sealing gaskets, 18. osmotic cell upper covers, 19. osmotic cell bases, 20. chromatographic columns, 21. test gas connecting pipes, 22. sample gas connecting pipes.
Embodiment:
Below further illustrate of the present invention, instead of limitation of the present invention.
Embodiment 1:
Liquefied petroleum gas (LPG) is through the wherein infiltrative Gas Chromatographic Method of propane, normal butane and isobutane of Simultaneously test during polyethylene film
The present embodiment adopts the vapor-phase chromatography special gas osmotic cell of a fillet type cell cavity, sees Fig. 1.This gas osmotic cell 3 comprises the osmotic cell upper cover 18 that osmotic cell base 19 and osmotic cell base 19 have symmetrical structure, the sealing gasket 17 arranged between osmotic cell base 19 and osmotic cell upper cover 18, osmotic cell base 19 and osmotic cell upper cover 18 are equipped with screw, are fixed by screw bolt and nut; Described osmotic cell base 19 and osmotic cell upper cover 18 are the reeded flat board of side band, and groove fastens relatively, the surrounding of groove is amplexiformed mutually with membrane material to be measured, disconnected two cell cavities are mutually formed in the both sides of membrane material to be measured, be respectively the sample gas cell cavity 15 of osmotic cell base 19 and the test gas cell cavity 14 of osmotic cell upper cover 18, the both sides, sample gas cell cavity 15 bottom of described osmotic cell base 19 are communicated with the gas piping 2 and 9 running through osmotic cell base 19 respectively; The both sides, test gas cell cavity 14 bottom of described osmotic cell upper cover 18 are communicated with the gas piping 4 and 11 running through osmotic cell upper cover respectively; Described sample gas cell cavity and test gas cell cavity are all in narrow strip, length × wide × height=8.12mm × 0.90mm × 2.00mm, and the gas piping of sample gas cell cavity 15 and test gas cell cavity 14 both sides is all located at the most edge, bottom of groove, make through gas all blow into, reduce dead volume, go out peak sharp-pointed.
During use, vacuum grease is coated at gas osmotic cell base 19 inside surface, load onto the silicone rubber seal gasket 17 having through hole at infiltration chamber correspondence position, film 16 to be measured is put after sealing gasket 17 upper side coats vacuum grease, be loaded on the osmotic cell upper cover 18 that inside surface scribbles vacuum grease, with fastened by screw, obtain the gas osmotic cell assembled; Be placed in thermostatic bath 10 and carry out constant temperature test.When making liquefied petroleum permeability to gas with the PE film of thickness 0.04mm and measuring, gas chromatography hydrogen flame detector can obviously measure be not more than 15 minutes through the minimum time of penetration of liquefied petroleum gas components.
The device that described mensuration combination gas respectively forms the membrane permeability of gas connects by Fig. 2.Comprise gas osmotic cell 3, pressure control device, temperature control equipment, sample gas cylinder, four-way valve 5 and gas chromatograph 13.
One end gas piping that sample gas cell cavity 15 bottom of described gas osmotic cell base 19 is provided with is sample gas air inlet pipeline 9, sample gas air inlet pipeline 9 is communicated with sample gas cylinder through tensimeter 8, sample gas gas admittance valve 7, the other end gas piping of sample gas cell cavity bottom is sample gas outlet pipe 2, and sample gas outlet pipe 2 is communicated with air through sample gas vent valve 1; Gas osmotic cell upper cover 18 tests wherein two joints that test air pipe 4 and 11 that both sides, gas cell cavity 14 bottom are provided with is connected four-way valve 5 respectively, one of them joint in two other joint of four-way valve 5 is communicated with the gas-carrier pipeline 6 of gas chromatograph 13, another joint is communicated with the device obtaining measuring combination gas and respectively form the membrane permeability of gas with the chromatographic column of gas chromatograph 13 by gas-carrier pipeline 12, be placed in thermostatic bath constant temperature.
Connection gas piping between sample gas cylinder, gas osmotic cell is respectively equipped with valve, tensimeter forms pressure control device, is provided with temperature control equipment in addition.
During test, first open sample gas gas admittance valve 7 to pass into sample gas and drive other gases in gas osmotic cell sample gas cell cavity 15 and gas piping 2 and 9 away, turn four-way valve 5 handle enters chromatographic column after the carrier gas of gas chromatograph 13 being switched to gas coming through osmotic cell test gas cell cavity 14 again, after logical carrier gas 30s drives the gas in test gas cell cavity 14 away, the carrier gas of gas chromatograph 13 switches back and directly enters chromatographic column by turn four-way valve 5 handle again, starts to calculate time of penetration simultaneously.After sample gas infiltration certain hour infiltration rate is stable, the carrier gas of gas chromatograph 13 is switched to and flows through osmotic cell test gas cell cavity 14 and enter chromatographic column again by turn four-way valve 5 handle, sweeps penetrating film gas chromatograph with carrier gas and carries out gas chromatographic analysis (Fig. 3 is shown in by process of osmosis and sample introduction analytic process schematic diagram) to the test air-blowing in test gas cell cavity; Record thickness, film infiltrating area, sample gas pressure, room temperature, thermostatic bath temperature, gas chromatography test condition, calculate film infiltration coefficient according to chromatogram and following formula:
Wherein, q is transit dose (standard state, the state namely under 0 DEG C and 1 atmospheric pressure, cm
3); P is gas permeability coefficient (cm
3.cm.cm
-2.s
-1.cmHg
-1); p
1for the partial pressure (cmHg) of sample gas cell cavity; p
2for the partial pressure (cmHg) of test gas cell cavity, because steady seepage speed is that this value is approximately zero in the test of shorter time of penetration; A is film infiltrating area (cm
2); T is through the time (s); L is thickness (cm).
Tested by analytical conditions for gas chromatography, utilize orthogonal experimental design method to determine following optimum analytical conditions for gas chromatography:
Chromatographic column: SE-30 capillary column (50mm × 0.32mm × 1um);
Carrier gas: nitrogen;
Detecting device: flame ionization detector;
Detector temperature: 200 DEG C;
Injector temperature: 150 DEG C;
Column temperature: 35 DEG C;
Post flow: 1.0ml/min;
Input mode: split sampling, split ratio 30:1;
Tail blows: 25ml/min.
The liquefied petroleum gas (LPG) chromatogram obtained by above optimum analytical conditions for gas chromatography is shown in Fig. 4.
Thermostatic bath temperature is 35 DEG C, under optimum analytical conditions for gas chromatography, and thickness 0.0038cm, film infiltrating area 0.071cm
2, sample gas pressure is that through during polyethylene film, wherein propane, normal butane and isobutane infiltration coefficient are 3.17,3.49,4.82 × 10 to the liquefied petroleum gas (LPG) that records of atmospheric pressure respectively
-9.cm
3.cm
.cm
-2s
-1cmHg
-1.
By above optimum analytical conditions for gas chromatography, with propane, isobutane, the normal butane Criterion curve of variable concentrations, sample size.Propane sample size is good in 1.4749ng ~ 198200ng scope internal linear relation, and related coefficient is 0.9993; Isobutane sample size is good in 1.8782ng ~ 1259460ng scope internal linear relation, and related coefficient is 0.9990; Normal butane sample size is good in 1.9222ng ~ 1259460ng scope internal linear relation, and related coefficient is 0.9996.
Respectively sample introduction 0.00,0.10,0.20,0.25,0.50,0.70,1.00 μ L dilute after concentration be the propane calibrating gas of 1.338 μ g/mL, the normal butane calibrating gas of concentration to be the isobutane calibrating gas of 1.719 μ g/mL and concentration be 1.776 μ g/mL, carry out gas chromatographic analysis, repeat sample introduction 6 times, average.Calculate its detection limit (LOD) with the tested component amount corresponding to blank test signal to noise ratio (S/N ratio) S/N=3, the tested component amount corresponding to blank test signal to noise ratio (S/N ratio) S/N=10 calculates its lower limit of quantitation (LOQ).When obtaining analyzing by above analytical conditions for gas chromatography, the LOD of propane is 0.472ng, LOQ is 1.573ng; The LOD of isobutane is 0.534ng, LOQ is 1.779ng; The LOD of normal butane is 0.692ng, LOQ is 2.307ng.
The stable of membrane material should carry out when infiltration rate reaches steady state (SS) through test.In order to determine the stable through the time of membrane material different temperatures, the osmotic cell 3 installing film is placed in thermostatic bath 10 constant temperature that temperature is respectively 25 ± 1 DEG C, 35 ± 1 DEG C, 45 ± 1 DEG C, measured the infiltration rate of a sample gas every 15 minutes after osmotic cell base sample gas cell cavity 15 passes into sample gas, take infiltration rate as ordinate time of penetration be horizontal ordinate curve plotting, curve forms time corresponding to horizontal flex point place for stable through the time.The each component of the liquefied petroleum gas (LPG) seepage stability time at different temperatures obtained.Also can simple process, the change of infiltration rate in the time of penetration interval of 10 minutes is kept constant be considered as reaching stable through.
The input mode of this method is for the test air-blowing penetrating film is swept into gas chromatograph 13 by sweep gas with the carrier gas of gas chromatograph 13, for guaranteeing that all test gas penetrating film is all blown into gas chromatograph 13 and carries out gas chromatographic analysis, after 35 ± 1 DEG C time, membrane material infiltration rate reaches steady state (SS), fixing time of penetration is 15 minutes, purge time is set to 5s, 10s, 15s, 20s respectively, observation infiltration rate changes, and is defined as the purge time be applicable to the purge time that infiltration rate is substantially constant.Show the correlation analysis of the infiltration coefficient of purge time and liquefied petroleum gas (LPG) 3 kinds of alkane, the infiltration coefficient correlativity of purge time and 3 kinds of alkane is not remarkable.Because the dead volume of osmotic cell is little, each alkane detected value of the liquefied petroleum gas (LPG) that different purge time records does not have notable difference.Purge time is enough to allow sample all enter gas chromatographic column analysis for 15 seconds.
Infiltration reaches stable through rear at test temperature, set different time of penetration respectively, purge with fixed purge time, observe each component of liquefied petroleum gas (LPG) and single alkane infiltration capacity and time of penetration relation, with gas chromatography signal by force and also chromatographic peak be separated the time of penetration that good time of penetration determines to be applicable to.In liquefied petroleum gas (LPG), each alkane is shown in Fig. 5 through the relation of time and transit dose, and single alkane calibrating gas is shown in Fig. 6 through the graph of a relation of time and transit dose.As seen from Figure 5, in 5 to 20 minutes, each alkane time of penetration and the linear and linear relationship of transit dose good, the related coefficient of propane, isobutane and normal butane is respectively 0.9978,0.9985 and 0.9998.Consider test gas cell cavity dividing potential drop and purge time on the impact of error, adopt time of penetration be 15 minutes comparatively suitable.
Embodiment 2: utilize gas chromatograph first wife six-way valve reequip for mixed gas through time Simultaneously test film, the infiltrative method of testing of sheet material multicomponent
Present gas chromatograph polygamy has six-way valve, can simple refit become four-way valve for mixed gas through time Simultaneously test film, sheet material multicomponent perviousness.Backing out first wife's six-way valve for connecing two collar nuts of sample tracheae, with silicon rubber plug, these two joints of six-way valve being blocked respectively.Pull down the quantitative loop of six-way valve, replace quantitative loop with osmotic cell in Fig. 1, osmotic cell is tested air pipe 4 and 11 and be connected to the former joint connecing quantitative loop of six-way valve.All the other analytical approachs and operation steps are with embodiment 1.
Embodiment 3: the series connection of gas osmotic cell be used for mixed gas through time Simultaneously test film, the infiltrative method of testing of sheet material multicomponent
If measure the film that perviousness is lower, the infiltrating area of membrane material can be increased, two gas osmotic cell series connection are used.Be connected with sample gas connecting pipe 22 with the sample gas air intake opening of another pond body the sample gas gas outlet of a pond body, test gas gas outlet is connected with testing gas connecting pipe 21 with test gas air intake opening, as shown in Figure 7.The operation steps of all the other analytical approachs is with embodiment 1..
Embodiment 4: utilize thermal conductivity cell detector to measure the Gas Chromatographic Method of film permeability
In the present embodiment, the film of test is polyethylene film, and sample gas is carbon dioxide calibrating gas, and gas chromatography detector is both arms TCD detecting device, is tested by analytical conditions for gas chromatography, determines following optimum analytical conditions for gas chromatography:
Chromatographic column: GDX-502 packed column;
Detector temperature: 80 DEG C;
Injector temperature: 50 DEG C;
Carrier gas: hydrogen;
Column temperature: 50 DEG C;
Post flow: A post 20ml/min, B post 20ml/min;
All the other analytical approachs and operation steps are with embodiment 1.Sample gas pressure 101.70kPa, 26 DEG C time, recording the poly carbon dioxide permeability coefficient of 0.039mm thickness is 4.5 × 10
-9.cm
3.cm
.cm
-2s
-1cmHg
-1.
Claims (5)
1. Simultaneously test combination gas respectively forms an assay method for the membrane permeability of gas, comprises the following steps:
A, film to be measured to be arranged in gas osmotic cell, to obtain the gas osmotic cell assembled, described gas osmotic cell, comprise osmotic cell base, with osmotic cell base, there is the osmotic cell upper cover of symmetrical structure, the sealing gasket arranged between osmotic cell base and osmotic cell upper cover, osmotic cell base is connected by stationary installation with osmotic cell upper cover, described osmotic cell base and osmotic cell upper cover are the reeded flat board of side band and groove is relative fastens, the surrounding of groove is amplexiformed mutually with membrane material to be measured, disconnected two cell cavities are mutually formed in the both sides of membrane material to be measured, be respectively the sample gas cell cavity of osmotic cell base and the test gas cell cavity of osmotic cell upper cover, both sides, described sample gas cell cavity bottom are communicated with the gas piping running through osmotic cell base respectively, both sides, described test gas cell cavity bottom are communicated with the gas piping running through osmotic cell upper cover respectively, described sample gas cell cavity and test gas cell cavity are all in narrow strip and sample gas cell cavity and the gas piping of testing gas cell cavity both sides are all located at the most edge, bottom of groove,
B, one end gas piping be provided with the groove bottom of gas osmotic cell base are communicated with sample gas cylinder through tensimeter, sample gas gas admittance valve, and other end gas piping is communicated with air; The gas piping that the two ends of gas osmotic cell upper cover are provided with is connected respectively wherein two joints of four-way valve, one of them joint in two other joint of four-way valve is communicated with the gas-carrier pipeline of gas chromatograph, another joint is communicated with the chromatographic column of gas chromatograph, obtain the device that mensuration combination gas respectively forms the membrane permeability of gas, be placed in thermostatic bath constant temperature;
C, first pass into sample gas and drive other gases in gas osmotic cell sample gas cell cavity and gas piping away, turn four-way valve handle enters chromatographic column after the carrier gas of gas chromatograph being switched to gas coming through osmotic cell test gas cell cavity again, after the gas in test gas cell cavity is driven in logical carrier gas away, the carrier gas of gas chromatograph switches back and directly enters chromatographic column by turn four-way valve handle again, starts to calculate time of penetration simultaneously; After sample gas infiltration rate is stable, the carrier gas of gas chromatograph is switched to and flows through osmotic cell test gas cell cavity and enter chromatographic column again by turn four-way valve handle, sweeps penetrating film gas chromatograph with carrier gas and carries out gas chromatographic analysis to the test air-blowing in test gas cell cavity; Record thickness, film infiltrating area, sample gas pressure, room temperature, thermostatic bath temperature, gas chromatography test condition, calculate membrane permeability.
2. Simultaneously test combination gas according to claim 1 respectively forms the assay method of the membrane permeability of gas, it is characterized in that, described gas osmotic cell is one or more.
3. Simultaneously test combination gas according to claim 1 respectively forms the assay method of the membrane permeability of gas, it is characterized in that, described sealing gasket is silicone rubber O-ring.
4. Simultaneously test combination gas according to claim 1 respectively forms the assay method of the membrane permeability of gas, it is characterized in that, described gas piping is metal tube or plastic tube and is provided with temperature control equipment.
5. Simultaneously test combination gas according to claim 1 respectively forms the assay method of the membrane permeability of gas, it is characterized in that, described test gas cell cavity, long 1mm-300mm, wide 0.2mm-5mm, high 0.2mm-5mm, described sample gas cell cavity, long 1mm-300mm, wide 0.2mm-5mm, high 1mm-30mm.
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