CN103575630A - Measuring method and device for simultaneously measuring membrane permeability of each gas mixed gas - Google Patents
Measuring method and device for simultaneously measuring membrane permeability of each gas mixed gas Download PDFInfo
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Abstract
The invention discloses a measuring method and a device for simultaneously measuring the membrane permeability of each gas in mixed gas. According to the measuring method and device, the combination of a gas chromatograph and a gas permeation tank for measuring the membrane permeability is realized, and the permeabilities of multiple components of a thin film and a flake material when the mixed gas permeates through the thin film and the flake material can be simultaneously and rapidly measured accurately one time; furthermore, in a connecting method disclosed by the invention, an air blowing system does not need to be arranged, the measuring method can be used for measuring the thin film with the diameter of 8mm or even smaller without that the gas passes through a quantitative feeding device, and a gas chromatography flame ionization detector has the enough sensitivity for measuring penetration gas after permeating for 5 minutes. By utilizing the measuring method and device, the interaction effect of each component to the permeation rate can be researched when the mixed gas permeates, and the diffusion coefficients of the solubility coefficients of the thin film and the flake material can be conveniently measured.
Description
Technical field:
The present invention relates to belong to membrane material analysis and gas chromatographic analysis field, be specifically related to a kind of assay method and device that combination gas respectively forms the membrane permeability of gas of simultaneously measuring.
Background technology:
At present, the method for measuring film and thin slice gas penetration potential is existing many, and common have different platen press and an 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.Test method ASTM D1434-82 (2009) e1 " standard method of plastic sheeting and thin slice ventilation characteristic measuring " (Standard Method for Determining Gas Permeability Characteristics of Plastic Film and Sheeting) of U.S.'s test and materialogy meeting, and the applied pressure application that is of the standard GB/T/T1038-2000 of China " plastic sheeting and thin slice gas-premeable test method pressure differential method ".These methods are measured the gas penetration potential of film and thin slice and are used device or the similar device that is called gas permeation pond (Gas Transmission Cell), film or thin slice are sandwiched in wherein, allow gas to be measured pass into diaphragm one side, opposite side is measured the gas flow that sees 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, or the gas penetration potential that simultaneously sees through of mixed gas at every turn, in the time of can not once measuring mixed gas simultaneously and see through, mixed gas respectively forms the gas penetration potential of gas permeation film.When reality is used many films be all in atmospheric environment or mixed-gas environment in, and mixed gas infiltration is owing to may there being influencing each other of gas, ventilative speed might not be in full accord while seeing through film with single composition of planting.
Another deficiency of at present conventional gas-premeable method of testing 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 permeation pond is received on gas chromatograph, utilize the carrier gas of gas chromatograph the gas that sees through film to be blown into the separated column cap of gas chromatograph, then select suitable method and chromatographic condition, can quick and precisely measure the gas penetration potential of film and thin slice, the perviousness of the various constituents of mixed gas of film or sheeting in the time of can also be once quick and precisely measuring mixed gas and see through simultaneously.
When mixed gas sees through, the various composition gas of rapid and accurate determination mixed gas permeance property is separately reality needs simultaneously, is also a difficult problem of measuring technology.
Patent CN102297827A discloses a kind of method of testing and test pool and proving installation of fuel cell film battery gas penetration potential.One side in experimental test pond is provided with the import and export passage of gas, and opposite side forms test channel; Both sides in test examination pond pass into respectively tested gas and carrier gas, and the gas vent of its carrier gas side is passed in gas chromatography, test the content of tested gas in carrier gas by gas chromatography, thereby calculate the air penetrability of membrane electrode.The air permeability test device of membrane electrode is mainly comprised of experimental test pond and air penetrability test macro.Experimental test pond is comprised of two blocks of plate jig and corresponding encapsulants with gas feed and outlet.
Patent CN202994616U is similar to patent CN102297827A with disclosed gas permeation rate proving installation principle of work such as UCN201314906Y.
The common problem 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 greatly clean through gas purging; (2) method of testing is that the gas that sees through during by stable seeing through is brought gas chromatograph quantity tube into by the inert gas of continuous flow and purged into gas chromatograph for determination again, for reaching gas chromatograph, be enough to the quantitative limit of measuring, it is enough large that the infiltrating area of film is wanted, and is not suitable for measuring film or the slow film of infiltration rate of small size; (3) need to set up stability of flow, flow velocity slow and can Accurate Measurement pressure and the more complicated inert gas air supply system of flow velocity, flow velocity can make too soon to bring into quantity tube to see through gas flow not enough.
Summary of the invention:
The object of this invention is to provide a kind of assay method and device that combination gas respectively forms the membrane permeability of gas of simultaneously measuring, solved 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 permeation pond, comprise osmotic cell base, there is the osmotic cell upper cover of symmetrical structure with osmotic cell base, the sealing gasket arranging 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 is the reeded flat board of a side band with osmotic cell upper cover and groove is relative fastens, the surrounding of groove is amplexiformed mutually with membrane material to be measured, in the both sides of membrane material to be measured, form disconnected two cell cavities mutually, 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 respectively the gas piping that runs through osmotic cell base, the both sides, test gas cell cavity bottom of described osmotic cell upper cover are communicated with respectively the gas piping that runs through osmotic cell upper cover, it is characterized in that described sample gas cell cavity and test gas cell cavity are all narrow strip (test gas cell cavity, 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 be all located at the edge, bottom of groove, the gas seeing through is all blown into, reduce dead volume, go out peak sharp-pointed.
The sealing gasket arranging between described osmotic cell base and osmotic cell upper cover is preferably silicone rubber O-ring.
Described gas piping, can be the plastic tubes such as the metal tubes such as stainless steel, copper, aluminium or nylon, polypropylene, tygon, and in order to prevent from testing aspiration, to echo condensation can be pipeline set temperature control device as required.
The present invention also provides a kind of assay method that combination gas respectively forms the membrane permeability of gas of simultaneously measuring, adopt and measure the device that combination gas respectively forms the membrane permeability of gas, this device comprises foregoing gas permeation pond, 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 is arranged in foregoing gas permeation pond to the gas permeation pond that obtains assembling;
B, one end gas piping that the groove bottom of gas permeation pond base is provided with are communicated with sample gas cylinder through tensimeter, sample gas gas admittance valve, and other end gas piping is communicated with atmosphere; The gas piping that the two ends of gas permeation pond upper cover are provided with connects 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 measuring the device that 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 permeation pond sample gas cell cavity and gas piping away, turn four-way valve handle enters chromatographic column after the carrier gas of gas chromatograph is switched to gas coming through osmotic cell test gas cell cavity again, logical carrier gas is driven away after the gas in test gas cell cavity, turn four-way valve handle switches back the carrier gas of gas chromatograph directly to enter chromatographic column again, starts to calculate time of penetration simultaneously; After sample gas infiltration certain hour infiltration rate is stable, turn four-way valve handle is switched to by the carrier gas of gas chromatograph the osmotic cell test gas cell cavity of flowing through and enters chromatographic column again, with carrier gas, by penetrating film, sweeps gas chromatograph carry 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.
Calculating membrane permeability can carry out according to chromatogram and following formula:
Wherein, q is transit dose (standard state, i.e. state under 0 ℃ and 1 atmospheric pressure, cm
3); P is gas permeability coefficient (cm
3.cm.cm
-2.s
-1.cmHg
-1); p
1partial pressure (cmHg) for 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 shorter time of penetration test; A is film infiltrating area (cm
2); T is for seeing through the time (s); L is thickness (cm).
In order to increase the infiltrating area of membrane material, the gas permeation pond series connection of two above (comprising two) can be used if desired.
Described thermostatic bath can be that liquid bath, air bath, semiconductor attemperator, infrared temperature regulating device, heat-generating pipe etc. can be realized thermostatically controlled device.
The present invention also provides a kind of determinator that combination gas respectively forms the membrane permeability of gas of measuring, and comprises foregoing gas permeation pond, 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 permeation pond 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 atmosphere through sample gas vent valve; The test air pipe that upper cover test both sides, gas cell cavity bottom, gas permeation pond are provided with connects 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, and another joint follows the chromatographic column of gas chromatograph to be communicated with by gas-carrier pipeline; Connection gas piping between sample gas cylinder, gas permeation pond is respectively equipped with valve, tensimeter forms pressure control device, is provided with in addition temperature control equipment.
Described four-way valve is external plane four-way sampling valve, or the six-way valve of the former outfit of gas chromatograph through shutoff the four-way valve that converts of sample gas inlet, outlet, again or the good four-way valve of other gas tightness.
Described gas permeation pond 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, the coupling that realizes gas chromatograph and survey the gas permeation pond of membrane permeability, the Multiple components perviousness of film and sheeting simultaneously in the time of can be once quick and precisely measuring mixed gas and see through, 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 the osmotic cell test gas cell cavity of flowing through and enters again chromatographic column, utilize the carrier gas of gas chromatography that the test gas that sees through film is quick from test gas cell cavity, 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, the test infiltration gas that sees through of 5 minutes has had enough sensitivity with gas chromatographic flame ionization detector.Utilize the present invention, in the time of can studying mixed gas and see through, various compositions, to the influencing each other of infiltration rate, can conveniently record coefficient of diffusion and the solubility coefficient of film and sheeting.
Accompanying drawing explanation:
Fig. 1 is vapor-phase chromatography special gas osmotic cell schematic diagram of the present invention;
Fig. 2 is that the present invention measures the connection diagram of device that combination gas respectively forms 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 obtaining under optimum analytical conditions for gas chromatography;
Fig. 5 is the graph of a relation that in the liquefied petroleum gas (LPG) in embodiment 1, each alkane sees through time and transit dose;
Fig. 6 is the graph of a relation that the single alkane calibrating gas in embodiment 1 sees through time and transit dose;
Fig. 7 is that schematic diagram is used in the gas permeation pond series connection of embodiment 3;
Wherein: 1. sample gas vent valve, 2. sample gas outlet pipe, 3. osmotic cell, 4. test air pipe, 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 to further illustrate of the present invention, rather than limitation of the present invention.
Embodiment 1:
When seeing through polyethylene film, liquefied petroleum gas (LPG) measures the wherein infiltrative Gas Chromatographic Method of propane, normal butane and isobutane simultaneously
The present embodiment adopts the vapor-phase chromatography special gas osmotic cell of a fillet type cell cavity, sees Fig. 1.This gas permeation pond 3 comprise osmotic cell base 19, and osmotic cell base 19 there is the sealing gasket 17 arranging between osmotic cell upper cover 18, osmotic cell base 19 and the osmotic cell upper cover 18 of symmetrical structure, osmotic cell base 19 and osmotic cell upper cover 18 are equipped with screw, by screw bolt and nut, fix; Described osmotic cell base 19 and osmotic cell upper cover 18 are the reeded flat board of a side band, and groove fastens relatively, the surrounding of groove is amplexiformed mutually with membrane material to be measured, in the both sides of membrane material to be measured, form disconnected two cell cavities mutually, 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, sample gas cell cavity 15 both sides, bottom of described osmotic cell base 19 are communicated with respectively the gas piping 2 and 9 that runs through osmotic cell base 19; Test gas cell cavity 14 both sides, bottom of described osmotic cell upper cover 18 are communicated with respectively the gas piping 4 and 11 that runs through osmotic cell upper cover; Described sample gas cell cavity and test gas cell cavity are all 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 edge, bottom of groove, and the gas seeing through is all blown into, reduce dead volume, go out peak sharp-pointed.
During use, in gas permeation pond, base 19 inside surfaces are coated vacuum grease, load onto the silicone rubber seal gasket 17 that has through hole at infiltration chamber correspondence position, sealing gasket 17 upper sides are put film 16 to be measured after coating vacuum grease, be loaded on the osmotic cell upper cover 18 that inside surface scribbles vacuum grease, with fastened by screw, the gas permeation pond that obtains assembling; Be placed in thermostatic bath 10 and carry out constant temperature test.When the PE film with thickness 0.04mm is made liquefied petroleum permeability to gas mensuration, the minimum time of penetration that gas chromatography hydrogen flame detector can obviously be measured seen through liquefied petroleum gas (LPG) composition is not more than 15 minutes.
The device that described mensuration combination gas respectively forms the membrane permeability of gas connects by Fig. 2.Comprise gas permeation pond 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 bottoms of described gas permeation pond base 19 are 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 atmosphere through sample gas vent valve 1; The test air pipe 4 and 11 that upper cover 18 test gas cell cavity 14 both sides, bottom in gas permeation pond are provided with is connected respectively wherein two joints of four-way valve 5, 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, by gas-carrier pipeline 12, the chromatographic column connection with gas chromatograph 13 obtains measuring the device that combination gas respectively forms the membrane permeability of gas another joint, is placed in thermostatic bath constant temperature.
Connection gas piping between sample gas cylinder, gas permeation pond is respectively equipped with valve, tensimeter forms pressure control device, is provided with in addition temperature control equipment.
During test, first opening sample gas gas admittance valve 7 passes into sample gas and drives other gases in gas permeation pond sample gas cell cavity 15 and gas piping 2 and 9 away, turn four-way valve 5 handles enter chromatographic column after the carrier gas of gas chromatograph 13 is switched to gas coming through osmotic cell test gas cell cavity 14 again, logical carrier gas 30s drives away after the gas in test gas cell cavity 14, turn four-way valve 5 handles switch back the carrier gas of gas chromatograph 13 directly to enter chromatographic column again, start to calculate time of penetration simultaneously.After sample gas infiltration certain hour infiltration rate is stable, turn four-way valve 5 handles are switched to by the carrier gas of gas chromatograph 13 the osmotic cell test gas cell cavity 14 of flowing through and enter chromatographic column again, with carrier gas, by penetrating film, sweep gas chromatograph carry 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, according to chromatogram and following formula, calculate film infiltration coefficient:
Wherein, q is transit dose (standard state, i.e. state under 0 ℃ and 1 atmospheric pressure, cm
3); P is gas permeability coefficient (cm
3.cm.cm
-2.s
-1.cmHg
-1); p
1partial pressure (cmHg) for 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 shorter time of penetration test; A is film infiltrating area (cm
2); T is for seeing through the time (s); L is thickness (cm).
By analytical conditions for gas chromatography, test, 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 ℃;
Injector temperature: 150 ℃;
Column temperature: 35 ℃;
Post flow: 1.0ml/min;
Input mode: split sampling, split ratio 30:1;
Tail blows: 25ml/min.
The liquefied petroleum gas (LPG) chromatogram obtaining by above optimum analytical conditions for gas chromatography is shown in Fig. 4.
Thermostatic bath temperature is 35 ℃, under optimum analytical conditions for gas chromatography, and thickness 0.0038cm, film infiltrating area 0.071cm
2, sample gas pressure is that wherein propane, normal butane and isobutane infiltration coefficient are respectively 3.17,3.49,4.82 * 10 to the liquefied petroleum gas (LPG) that records of atmospheric pressure while seeing through polyethylene film
-9.cm
3.cm
.cm
-2s
-1cmHg
-1.
By above optimum analytical conditions for gas chromatography, with variable concentrations, the propane of sample size, isobutane, normal butane Criterion curve.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.
Propane calibrating gas, the concentration that the rear concentration of sample introduction 0.00,0.10,0.20,0.25,0.50,0.70,1.00 μ L dilution is 1.338 μ g/mL is respectively that isobutane calibrating gas and the concentration of 1.719 μ g/mL is the normal butane calibrating gas of 1.776 μ g/mL, carry out gas chromatographic analysis, repeat sample introduction 6 times, average.With the corresponding tested one-tenth component of blank test signal to noise ratio (S/N ratio) S/N=3, calculate its detection limit (LOD), the corresponding tested one-tenth component of blank test signal to noise ratio (S/N ratio) S/N=10 calculates its lower limit of quantitation (LOQ).While obtaining analyzing by above analytical conditions for gas chromatography, the LOD of propane is 0.472ng, and LOQ is 1.573ng; The LOD of isobutane is 0.534ng, and LOQ is 1.779ng; The LOD of normal butane is 0.692ng, and LOQ is 2.307ng.
Stable the seeing through of membrane material tested and should when infiltration rate reaches steady state (SS), be carried out.In order to determine the stable through the time of membrane material different temperatures, the osmotic cell 3 that installs film is placed in to thermostatic bath 10 constant temperature that temperature is respectively 25 ± 1 ℃, 35 ± 1 ℃, 45 ± 1 ℃, osmotic cell base sample gas cell cavity 15 was measured the infiltration rate of a sample gas after passing into sample gas every 15 minutes, take infiltration rate as ordinate time of penetration be horizontal ordinate curve plotting, curve forms the corresponding time of horizontal flex point place and sees through the time for stable.The seepage stability time of each component of liquefied petroleum gas (LPG) obtaining under different temperatures.Also can simple process, the variation of infiltration rate in the time of penetration interval at 10 minutes is kept to constant and be considered as reaching stable and see through.
The input mode of this method is to take the carrier gas of gas chromatograph 13 the test air-blowing that penetrates film to be swept into gas chromatograph 13 as sweep gas, for guaranteeing that all test gas that penetrates film is all blown into gas chromatograph 13 and carries out gas chromatographic analysis, in the time of 35 ± 1 ℃, membrane material infiltration rate reaches after steady state (SS), fixedly time of penetration is 15 minutes, purge time is made as respectively to 5s, 10s, 15s, 20s, observation infiltration rate changes, and with the substantially constant purge time of infiltration rate, is defined as applicable purge time.Correlation analysis to the infiltration coefficient of purge time and 3 kinds of alkane of liquefied petroleum gas (LPG) shows, 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 times record does not have notable difference.Purge time is enough to allow sample all enter gas chromatographic column analysis for 15 seconds.
Under probe temperature, infiltration reaches after stable seeing through, set respectively different times of penetration, with fixed purge time, purge, observe each component of liquefied petroleum gas (LPG) and single alkane infiltration capacity and time of penetration relation, with gas chromatography signal, the strong and separated good time of penetration of chromatographic peak is determined applicable time of penetration.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 sees through the graph of a relation of time and transit dose and sees Fig. 6.As seen from Figure 5, in 5 to 20 minutes, each alkane time of penetration and transit dose is linear and linear relationship is 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 the impact of purge time on error, adopt time of penetration be 15 minutes comparatively suitable.
Embodiment 2: while utilizing the repacking of gas chromatograph first wife six-way valve to see through for mixed gas, measure film, the infiltrative method of testing of sheet material multicomponent simultaneously
Now gas chromatograph polygamy has six-way valve, measures film, sheet material multicomponent perviousness while can simple refit becoming four-way valve to see through for mixed gas simultaneously.Back 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 are blocked respectively.Pull down the quantitative ring of six-way valve, with osmotic cell in Fig. 1, replace quantitatively ring, osmotic cell is tested to air pipe 4 and 11 and be connected to the former joint that connects quantitative ring of six-way valve.All the other analytical approachs and operation steps are with embodiment 1.
Embodiment 3: when the series connection of gas permeation pond sees through for mixed gas, measure film, the infiltrative method of testing of sheet material multicomponent simultaneously
If measure the lower film of perviousness, can increase the infiltrating area of membrane material, two gas permeation pond series connection are used.The sample gas gas outlet of a pond body is connected with sample gas connecting pipe 22 with the sample gas air intake opening of another pond body, and test gas gas outlet is connected with test 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 permeation
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, by analytical conditions for gas chromatography, tests, and has determined following optimum analytical conditions for gas chromatography:
Chromatographic column: GDX-502 packed column;
Detector temperature: 80 ℃;
Injector temperature: 50 ℃;
Carrier gas: hydrogen;
Column temperature: 50 ℃;
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 ℃ time, recording the poly carbon dioxide infiltration coefficient of 0.039mm thickness is 4.5 * 10
-9.cm
3.cm
.cm
-2s
-1cmHg
-1.
Claims (9)
1. a gas permeation pond, comprise osmotic cell base, there is the osmotic cell upper cover of symmetrical structure with osmotic cell base, the sealing gasket arranging 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 is the reeded flat board of a side band with osmotic cell upper cover and groove is relative fastens, the surrounding of groove is amplexiformed mutually with membrane material to be measured, in the both sides of membrane material to be measured, form disconnected two cell cavities mutually, 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 respectively the gas piping that runs through osmotic cell base, both sides, described test gas cell cavity bottom are communicated with respectively the gas piping that runs through osmotic cell upper cover, it is characterized in that gas piping that described sample gas cell cavity and test gas cell cavity are all narrow strip and sample gas cell cavity and test gas cell cavity both sides is all located at the edge, bottom of groove.
2. gas permeation according to claim 1 pond, is characterized in that, described sealing gasket is silicone rubber O-ring.
3. gas permeation according to claim 1 pond, is characterized in that, described gas piping is metal tube or plastic tube and is provided with temperature control equipment.
4. gas permeation according to claim 1 pond, 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.
5. measure the assay method that combination gas respectively forms the membrane permeability of gas simultaneously, comprise the following steps:
A, film to be measured is arranged in the arbitrary described gas permeation pond of claim 1-4 to the gas permeation pond that obtains assembling;
B, one end gas piping that the groove bottom of gas permeation pond base is provided with are communicated with sample gas cylinder through tensimeter, sample gas gas admittance valve, and other end gas piping is communicated with atmosphere; The gas piping that the two ends of gas permeation pond upper cover are provided with connects 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 measuring the device that 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 permeation pond sample gas cell cavity and gas piping away, turn four-way valve handle enters chromatographic column after the carrier gas of gas chromatograph is switched to gas coming through osmotic cell test gas cell cavity again, logical carrier gas is driven away after the gas in test gas cell cavity, turn four-way valve handle switches back the carrier gas of gas chromatograph directly to enter chromatographic column again, starts to calculate time of penetration simultaneously; After sample gas infiltration rate is stable, turn four-way valve handle is switched to by the carrier gas of gas chromatograph the osmotic cell test gas cell cavity of flowing through and enters chromatographic column again, with carrier gas, by penetrating film, sweeps gas chromatograph carry 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.
6. according to claim 5ly measure the assay method that combination gas respectively forms the membrane permeability of gas simultaneously, it is characterized in that, described gas permeation pond is one or more.
7. measure the device that combination gas respectively forms the membrane permeability of gas for one kind, it is characterized in that, comprise the gas permeation pond described in arbitrary claim, pressure control device, temperature control equipment, sample gas cylinder, four-way valve and gas chromatograph in the claims 1～4; The sample gas air inlet pipeline that the sample gas cell cavity bottom of described gas permeation pond base is provided with is communicated with sample gas cylinder through tensimeter, sample gas admittance valve, and the sample gas outlet pipe of sample gas cell cavity bottom is communicated with atmosphere; The test air pipe that upper cover test both sides, gas cell cavity bottom, gas permeation pond are provided with connects 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, and another joint follows the chromatographic column of gas chromatograph to be communicated with by gas-carrier pipeline; Connection gas piping between sample gas cylinder, gas permeation pond is respectively equipped with valve, tensimeter forms pressure control device, is provided with in addition temperature control equipment.
8. mensuration combination gas according to claim 7 respectively forms the device of the membrane permeability of gas, it is characterized in that, described four-way valve is external plane four-way sampling valve, or the six-way valve of the former outfit of gas chromatograph through shutoff the four-way valve that converts of sample gas inlet, outlet, again or the good four-way valve of other gas tightness.
9. mensuration combination gas according to claim 7 respectively forms the device of the membrane permeability of gas, it is characterized in that, described gas permeation pond is one or more.
Priority Applications (1)
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| CN104034699A (en) * | 2014-06-19 | 2014-09-10 | 同济大学 | Device for automatically detecting transmissivity of collected sample |
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| CN106644886A (en) * | 2016-12-28 | 2017-05-10 | 中国石油天然气集团公司 | Method for testing seepage performance of thermoplastic plastic mixed gas and test device thereof |
| CN107422046A (en) * | 2016-05-24 | 2017-12-01 | 李向辉 | A kind of screening technique of packaging material |
| CN108051352A (en) * | 2017-12-08 | 2018-05-18 | 成都迈德克科技有限公司 | A kind of bandage device for checking air permeability and method |
| CN108279198A (en) * | 2017-12-18 | 2018-07-13 | 广州番禺职业技术学院 | A kind of packaging material gas permeability detection method based on pressure differential method |
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| CN114152682A (en) * | 2020-09-07 | 2022-03-08 | 中国科学院青岛生物能源与过程研究所 | Oxygen permeation membrane permeator system heated by solar energy |
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| CN116735456A (en) * | 2023-08-16 | 2023-09-12 | 煤炭科学技术研究院有限公司 | Device and method for measuring coal rock permeability |
| CN117169088A (en) * | 2023-11-03 | 2023-12-05 | 大连理工大学 | High-pressure hydrogen permeation continuous monitoring device and testing method thereof |
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