# Patent

## Title
Valve system for a coulometric analyte sensing instrument

## Abstract

A valve system that includes (i) first and second longitudinally facing members defining a gap therebetween in fluid communication with transversely offset first and second orifices through the members, (ii) a primary biasing means longitudinally biasing the members away from one another, (iii) an elastic element positioned within the gap between the first and second orifices, and (iv) a repositioning means for longitudinally repositioning one of the members towards the other member against the bias of the primary biasing means for adjusting the longitudinal height of the gap. The members can be repositioned between (a) a first position wherein the elastic element does not seal the gap so as to allow fluid flow from the first orifice to the second orifice through the gap, and (b) a second position wherein the elastic element is compressed between the members and seals the gap so as to prevent fluid flow from the first orifice to the second orifice through the gap.

## Background
BACKGROUND
Permeation instruments are used to measure the transmission rate of a target analyte, such as oxygen, carbon dioxide or water vapor, through a film of interest. Typical films subjected to permeation testing are polymeric packaging films such as those constructed from low density polyethylene (LDPE), high density polyethylene (HDPE), oriented polypropylene (OPP), polyethylene terepthalate (PET), polyvinylidene chrloride (PVTDC), etc. Typically, the film to be tested is positioned within a test chamber to sealing separate the chamber into first and second cells. The first cell (commonly referenced as the sensing cell) is flushed with an inert gas to remove any target analyte from the cell and the second cell (commonly referenced as the analyte cell) filled with a gas containing a known concentration of the target analyte. A sensor for the target analyte detects the presence of target analyte that has migrated into the sensing cell from the analyte cell through the film.
Permeation instruments typically employ a flow-through method or an accumulation method for sensing the presence of target analyte in the sensing cell. Briefly, the flow-through method uses an inert flushing gas to continuously pick up any target analyte that has migrated into the sensing cell and deliver it to a remote sensor. The accumulation method allows target analyte to build up in the sensing cell for an accumulation period, with the sensor either positioned within the sensing cell or the sensing cell flushed with a flushing gas after the accumulation period for delivery of accumulated target analyte to a remote sensor.
Both methods require precision in timing the opening and closing of fluid flows through the instrument, as well as opening and closing access to the analyte sensor. In addition, when sensing cell is sealed to fluid flow during a testing period, such as occurs with the accumulation technique, the instrument is relying solely upon diffusion to move analyte molecules within the sensing cell into sensing contact with the sensor, and the valving system should not seal the sensing cell too far upstream or downstream from the cell as this causes an increase in the effective volume of the sensing cell, thereby reducing the responsiveness and accuracy of the instrument.
Accordingly, a substantial need exists for a valving system for permeation testing instruments capable of reliably and consistently opening and closing the various cells within the instrument to fluid flow with a limited increase in the effective volume of the sensing cell of the instrument.
SUMMARY OF THE INVENTION
The invention is directed to a valve system. One embodiment of the valve system includes (i) first and second longitudinally facing members defining a gap therebetween in fluid communication with transversely offset first and second orifices through the members, (ii) a primary biasing means longitudinally biasing the members away from one another, (iii) an elastic element positioned within the gap between the first and second orifices, and (iv) a repositioning means for longitudinally repositioning one of the members towards the other member against the bias of the primary biasing means for adjusting the longitudinal height of the gap. The members can be repositioned between (a) a first position wherein the elastic element does not seal the gap so as to allow fluid flow from the first orifice to the second orifice through the gap, and (b) a second position wherein the elastic element is compressed between the members and seals the gap so as to prevent fluid flow from the first orifice to the second orifice through the gap.
Another embodiment of the valve system includes (i) first and second longitudinally facing members defining a gap therebetween in fluid communication with a first inlet and a first outlet orifice through one member and a second inlet and a second outlet orifice through the other member, wherein (a) the inlet orifices are transversely offset, (b) the outlet orifices are transversely offset, and (c) one of the members is longitudinally repositionable relative to the other member for adjusting the longitudinal height of the gap, (ii) an inlet larger-diameter elastic O-ring positioned within the gap and encompassing both the first and second inlet orifices, (iii) an inlet smaller-diameter elastic O-ring positioned within the gap and surrounding only one of the first or second inlet orifices, (iv) an outlet larger-diameter elastic O-ring positioned within the gap and encompassing both the first and second outlet orifices, (v) an outlet smaller-diameter elastic O-ring positioned within the gap and surrounding only one of the first or second outlet orifices, and (vi) a repositioning means for longitudinally repositioning the repositionable member towards the other member against the bias of the larger-diameter elastic O-rings. The members can be repositioned between (a) a first position wherein the larger-diameter O-rings are compressed between the members and seal the gap so as to prevent fluid flow through the gap from the inlet orifices to the outlet orifices without compressing the smaller-diameter O-rings between the members so as to allow fluid flow from the first inlet orifice to the second inlet orifice through the gap and from the first outlet orifice to the second outlet orifice through the gap, and (b) a second position wherein both larger-diameter O-rings are compressed between the members and seal the gap so as to prevent fluid flow through the gap from the inlet orifices to the outlet orifices, the inlet smaller-diameter O-ring is compressed between the members so as to prevent fluid flow from the first inlet orifice to the second inlet orifice through the gap, and the inlet smaller-diameter O-ring is compressed between the members so as to prevent fluid flow from the first outlet orifice to the second outlet orifice through the gap.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic overview of one embodiment of a testing system useful for performing the testing process of the present invention.
FIG. 2 is a side view of the measurement unit component of the testing system shown in FIG. 1.
FIG. 3 is a top view of the measurement unit component of the testing system shown in FIG. 2.
FIG. 4A is a cross-sectional side view of the measurement unit shown in FIG. 3 taken along line 4-4 with the upper mounting plate in the open position spaced a distance away from the upper portion of the housing.
FIG. 4A1 is an enlarged cross-sectional side view of the encircled inlet area of the gap in the measurement unit shown in FIG. 4A.
FIG. 4A2 is an enlarged cross-sectional side view of the encircled outlet area of the gap in the measurement unit shown in FIG. 4A.
FIG. 4A3 is an enlarged cross-sectional side view of the encircled sensor passageway area of the gap in the measurement unit shown in FIG. 4A.
FIG. 4B is a cross-sectional side view of the measurement unit shown in FIG. 3 taken along line 4-4 with the upper mounting plate in the closed position immediately adjacent the upper portion of the housing.
FIG. 4B1 is an enlarged cross-sectional side view of the encircled inlet area of the gap in the measurement unit shown in FIG. 4B.
FIG. 4B2 is an enlarged cross-sectional side view of the encircled outlet area of the gap in the measurement unit shown in FIG. 4B.
FIG. 4B3 is an enlarged cross-sectional side view of the encircled sensor passageway area of the gap in the measurement unit shown in FIG. 4B.
FIG. 5A is a cross-sectional side view of the measurement unit shown in FIG. 3 taken along line 5-5 with the upper mounting plate in the open position spaced a distance away from the upper portion of the housing.
FIG. 5A1 is an enlarged cross-sectional side view of the encircled humidity control window in the measurement unit shown in FIG. 5A.
FIG. 5B is a cross-sectional side view of the measurement unit shown in FIG. 3 taken along line 5-5 with the upper mounting plate in the closed position immediately adjacent the upper portion of the housing.
FIG. 5B1 is an enlarged cross-sectional side view of the encircled humidity control window in the measurement unit shown in FIG. 5B.
FIG. 6A is a cross-sectional side view of the measurement unit shown in FIG. 3 taken along line 6-6 with the upper mounting plate in the open position spaced a distance away from the upper portion of the housing.
FIG. 6B is a cross-sectional side view of the measurement unit shown in FIG. 3 taken along line 6-6 with the upper mounting plate in the closed position spaced a distance away from the upper portion of the housing.
FIG. 7 is a grossly enlarged side view of the encircled portion of the testing chamber shown in FIG. 3 depicting individual molecules of an analyte of interest on each side of a test film being tested with the measurement unit shown in FIG. 4B.
FIG. 8 is a graph of the O2 transmission rate over time obtained from the permeation testing conducted in Example 1.



DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
Nomenclature


    10 Testing System
    21 Source of Inert Gas
    22 Source of Test Gas
    31a Inlet Shutoff Valve for Source of Inert Gas
    31b Outlet Shutoff Valve for Source of Inert Gas
    32a Inlet Shutoff Valve for Source of Test Gas
    32b Outlet Shutoff Valve for Source of Test Gas
    41a Inlet Conduit for Directing Gas From the Source of Inert Gas Into the Upper Cell
    41b Outlet Conduit for Venting Gas From the Upper Cell
    42a Inlet Conduit for Directing Gas From the Source of Test Gas Into the Lower Cell
    42b Outlet Conduit for Venting Gas From the Lower Cell
    50 Computer or CPU
    60 Monitor
    70 Printer
    80 Electrical Leads from the Sensor to the CPU
    100 Measurement Unit
    110 Housing
    111 Upper Section of Housing
    111i Lower Surface of Upper Section of Housing
    112 Lower Section of Housing
    119 Retention Chamber Defined by Housing
    120 Mounting Plates
    121 Upper Mounting Plate
    121u Upper Surface of Upper Mounting Plate
    121n Pin On Upper Mounting Plate
    122 Lower Mounting Plate
    125 O-ring Between Mounting Plates
    129 Testing Chamber Defined by Mounting Plates
    1291 Upper Cell of Testing Chamber
    1292 Lower Cell of Testing Chamber
    130 Actuator
    131 Actuator Shaft
    140 Valve for Passageway to Analyte Sensor
    141 Valve Body
    142 Valve Stem
    151a Inlet Channel to Lower Cell Through Upper Section of Housing
    151b Inlet Channel to Lower Cell Through Upper Mounting Plate
    151c Inlet Channel to Lower Cell Through Lower Mounting Plate
    151w Larger O-ring within Gap Encircling Inlet Passageways into the Lower Cell
    152a Outlet Channel from Lower Cell Through Upper Section of Housing
    152b Outlet Channel from Lower Cell Through Upper Mounting Plate
    152c Outlet Channel from Lower Cell Through Lower Mounting Plate
    152w Larger O-ring within Gap Encircling Outlet Passageways from the Lower Cell
    160 Gap Between Upper Section of Housing and Upper Mounting Plate
    170 Flow Control Channels and Passageways Through the Upper Section of the Housing and the Upper Mounting Plate
    171a Inlet Channel to Gap Through Upper Section of Housing
    171b Inlet Channel from Gap to Upper Cell Through Upper Mounting Plate
    172a Outlet Channel from Gap Through Upper Section of Housing
    172b Outlet Channel from Upper Cell to Gap Through Upper Mounting Plate
    173a Passageway from Gap to Analyte Sensor Through Upper Section of Housing
    173b Passageway from Upper Cell to Gap Through Upper Mounting Plate
    180 O-Ring Seals within the Gap
    181v Smaller O-ring within Gap Encircling Inlet Channel through Upper Mounting Plate
    181w Larger O-ring within Gap Encircling Both Inlet Channels
    182v Smaller O-ring within Gap Encircling Outlet Channel through Upper Mounting Plate
    182w Larger O-ring within Gap Encircling Both Outlet Channels
    183w Larger O-ring within Gap Encircling Passageways Leading to the Sensor
    190 Humidity Control System
    191a Inlet Channel to Humidity Control Chamber Through Upper Section of Housing
    192a Outlet Channel from Humidity Control Chamber Through Upper Section of Housing
    193 Selectively Permeable Film
    194 O-ring
    195 Washer
    196 Inset Ring
    197 Locking Ring
    198w Larger O-ring within Gap Encircling Both Inlet and Outlet Channels for a Humidity Control Chamber
    199 Humidity Control Chambers in the Upper Mounting Plate
    200 Analyte Sensor
    A Analyte Molecules
    F Film Being Tested
    x Lateral Direction
    y Longitudinal Direction
    z Transverse Direction


DESCRIPTION
Overview
Referring generally to FIG. 1, the invention is directed to a valve system for an analyte measurement unit 10. The valve system ensures that the flow of various fluids through the unit 10 occur in the properly sequence as necessary and appropriate for measuring the effective volume of the sensing cell 1291 of the measurement unit 10.
The method includes the steps of (i) separating a testing chamber 129 into a first or upper cell 1291 and a second or lower cell 1292 with a known area of a film F, (ii) flushing the first cell 1291 with an inert gas to remove any target analyte A from the first cell 1291, (iii) introducing a gas (not shown) containing a known concentration of an analyte A into the lower cell 1292, (iv) sealing the upper cell 1291 to gas flow (not shown) through the upper cell 1291, and (v) sensing any analyte A in the upper cell 1291 with an analyte sensor 200 that consumes the analyte A at a rate greater than the rate at which the analyte A is passing through the film F, until a steady state rate of analyte A consumption is measured by the analyte sensor 200. The analyte sensor 200 preferably consumes analyte A at least ten times faster than the rate at which the analyte A is transmitted through the film F, more preferably twenty times faster, and most preferably one hundred times faster.
Referring to FIGS. 4A and 4B, the valve system includes (i) an upper section 111 of a housing 110 and an upper mounting plate 121 defining a gap 160 therebetween, (ii) a means for reposition the mounting plate 121 relative to the upper section 111 of the housing 110 as between an open position with a “thicker” gap 160 and a closed position with a “thinner” gap 160, (iii) flow control channels and passageways 170 through the upper section 111 of the housing 110 and the upper mounting plate 121 and (iv) o-ring seals 180 of different diameters and different thicknesses positioned within a gap 160, encircling the various channels and passageways 170.
Referring to FIGS. 4A and 4A1, fluid flow into the upper cell 1291 is provided by laterally x and/or transversely z offset inlet channels 171a and 171b in the upper section 111 of the housing 110 and the upper mounting plate 121 respectively. In similar fashion, referring now to FIGS. 4A and 4A2, fluid flow out from the upper cell 1291 is provided by laterally x and/or transversely z offset outlet channels 172a and 172b in the upper section 111 of the housing 110 and the upper mounting plate 121 respectively.
Referring to FIGS. 4A and 4A1, a small diameter o-ring 181v is positioned within the gap 160 encircling just one of the inlet channels 171b, while a large diameter o-ring 181w, also positioned within the gap 160, encircles both inlet channels 171a and 171b. In similar fashion, referring now to FIGS. 4A and 4A2, a small diameter o-ring 182v is positioned within the gap 160 encircling just one of the outlet channels 172b, while a large diameter o-ring 182w, also positioned within the gap 160, encircles both the outlet channels 172a and 172b. 
Referring to FIGS. 4A, 4A1, 4A2, 4A3, 5A, 5A1, the thickness or longitudinal y height of the o-rings 181 and 182 are selected so that the large diameter o-rings 181w and 182w are sealingly engaged within the gap 160 regardless of whether the gap 160 is thicker or thinner, while the smaller diameter o-rings 181v and 182v are sealingly engaged within the gap 160 only when the gap is thinner. Such positioning of the larger (181w and 182w) and smaller (181v and 182v) o-rings, in combination with the different thicknesses of the larger (181w and 182w) and smaller (181v and 182v) o-rings, permits the inlet (171a and 171b) and outlet (172a and 172b) channels to be simultaneously opened to fluid flow for flushing of the upper cell 1291 prior to a testing period by longitudinally y moving the mounting plates 120 into the downward or open position as shown in FIGS. 4A, 4A1 and 4A2, and simultaneously closed to fluid flow for sealing-off the upper cell 1291 during a testing period by longitudinally y moving the mounting plates 120 into the upward or closed position as shown in FIGS. 4B, 4B1 and 4B2.
The film F can be a perforated or nonperforated film F, and can be porous or nonporous with respect to the target analyte A, so long as the analyte sensor 200 can consume the target analyte A at a rate greater than the rate at which the analyte A is passing through the film F. To ensure that the analyte sensor 200 is consuming all target analyte A that is passing through the film F, the analyte sensor 200 is preferably selected so that it consumes target analyte A at a rate that is at least ten times greater, preferably twenty times greater and most preferably 100 times greater, than the rate at which the target analyte A is likely to be transmitted through the film F.
Specific Embodiment
Testing System
Construction
An exemplary embodiment of a testing system 10 capable of measuring the transmission rate of an analyte A through a film F in accordance with the present invention is depicted in FIG. 1. A measurement unit 100 defines a testing chamber 129 sealingly divided by a film F to be tested into an upper cell 1291 and a lower cell 1292. A source of an inert gas 21 communicates with the upper cell 1291 via inlet conduit 41a and outlet conduit 41b for flushing the upper cell 1291 prior to testing. Suitable inert gases include specifically, but not exclusively, nitrogen, argon, helium, krypton or a blend of nitrogen and hydrogen, etc. A source of test gas 22 containing a known concentration of an analyte A, communicates with the lower cell 1292 via inlet conduit 42a and outlet conduit 42b for continuously providing the lower cell 1292 with test gas to ensure that the concentration of analyte A within the lower cell 1292 remains constant throughout a test period. Shutoff valves 31a and 31b are provided in inlet conduit 41a and outlet conduit 41b respectively, for controlling the flow of inert gas through the upper cell 1291. Similarly, shutoff valves 32a and 32b are provided in inlet conduit 42a and outlet conduit 42b respectively, for controlling the flow of gas through the lower cell 1292.
An analyte sensor 200 for the target analyte A is placed in fluid communication with the upper cell 1291 for sensing the presence of target analyte A within the upper cell 1291. Typical target analytes include oxygen, carbon dioxide, carbon monoxide and water vapor. The analyte sensor 200 may be selected from any of the wide variety of commercially available consuming sensors capable of detecting and consuming the target analyte A, with electrochemical sensors generally preferred based upon the high sensitivity and low cost of such sensors and the fact that such sensors, when employed in the present invention, follow Faraday's Law—eliminating the need to calibrate the sensor.
The analyte sensor 200 communicates via electrical leads 80 with a suitable central processing unit 50 equipped with electronic memory (not shown), and optionally but preferably attached to a monitor 60 and/or printer 70 for storing and reporting analyte A concentrations detected by the analyte sensor 200.
Use
A film F to be tested is “loaded” into the testing chamber 129 so as to sealingly separate the testing chamber 129 into an upper cell 1291 and a lower cell 1292 with a known area of the film F exposed to both cells 1291 and 1292. Shutoff valves 31a and 31b are then opened to permit the flow of inert gas through the upper cell 1291 for flushing analyte A from the upper cell 1291. After flushing, the shutoff valves 31a and 31b are closed to seal-off the upper cell 1291 from the surrounding environment. Shutoff valves 32a and 32b are then opened to permit the flow of gas containing a known concentration of analyte A into the lower cell 1292. The presence of analyte A within the upper cell 1291 is then detected and recorded by the analyte sensor 200. By ensuring that the only route through which analyte A can enter into the upper cell 1291 is through the “exposed” area of the film F, and by selecting an analyte sensor 200 that consumes analyte A faster than the analyte A is transmitted through the film F, then the rate at which the analyte sensor 200 detects analyte A, once a steady state rate is attained, can be equated directly to the analyte transmission rate for the known “exposed” area of the film F.
Measurement Unit Including Valve System
Construction
An exemplary embodiment of a measurement unit 100 capable of quickly and accurately measuring the transmission rate of an analyte A through a film F in accordance with the present invention is depicted in FIGS. 2-6.
The measurement unit 100 includes (i) a housing 110, (ii) mounting plates 120, (iii) an actuator 130, (iv) a valve 140 for controlling fluid communication with an analyte sensor 200, (v) channels 151a, 151b, 151c, 152a, 152b, and 152c in the housing 110 and mounting plates 120 for directing test gas (not shown) into a lower cell 1292 in the mounting plates 120, and (vi) a flow control system (not collectively numbered) including flow control channels 170 and o-ring seals 180 for selectively opening and sealing closing an upper cell 1291 in the mounting plates 120 to fluid flow. The measurement unit 100 optionally, but preferably, also includes a humidity control system 190.
The housing 110 includes an upper section 111 and a lower section 112 that cooperatively define a retention chamber 119.
Referring to FIGS. 4A, 4B, 5A, 5B, 6A and 6B, upper and lower mounting plates 121 and 122 (collectively referenced as mounting plates 120) are retained within the retention chamber 119 defined by housing 110 with the upper surface 121u of the upper mounting plate 121 longitudinally y offset a distance from the lower surface 111i of the upper section 111 of the housing 110 so as to define a gap 160 therebetween. The upper and lower mounting plates 121 and 122 define a testing chamber 129 therebetween. An o-ring 125 encircling the testing chamber 129 is provided between the mounting plates 120. The testing chamber 129 can be sealingly divided into an upper cell 1291 and a lower cell 1292 by placement of a test film F between the mounting plates 120 overlaying the o-ring 125, and compressing the mounting plates 120 together so as to sealingly compress the entire periphery of the o-ring 125 between the mounting plates 120.
It is generally preferred to configure the testing chamber 129 to provide an upper cell 1291 of about 1 cm3 to about 3 cm3. An upper cell 1291 larger than about 3 cm3 is too slow to respond as molecules of analyte A within the upper cell 1291 can be consumed and detected by the analyte sensor 200 only when the molecules enter the analyte sensor 200 and the upper cell 1291 relies solely upon diffusion to move molecules within the upper cell 1291. An upper cell 1291 smaller than about 1 cm3 tends to cause areas of the film F to contact with the upper surface (not numbered) of the upper mounting plate 121 during the testing period, thereby introducing error into the test results as analyte A cannot readily pass through the film F into the upper cell 1291 through these “covered” areas.
Referring to FIGS. 4A, 4B, 5A, 5B, 6A and 6B, the lower mounting plate 122 is mounted onto the distal end (unnumbered) of an actuator shaft 131 for longitudinally repositioning of the mounting plates 120 by an actuator 130 as between a lower or open position creating a longitudinally thicker gap 160 between the upper surface 121u of the upper mounting plate 121 and the lower surface 111i of the upper section 111 of the housing 110, as shown in FIG. 4 (collectively 4A, 4A1, 4A2 and 4A3), and an upper or closed position creating a longitudinally thinner gap 160 between the upper surface 121u of the upper mounting plate 121 and the lower surface 111i of the upper section 111 of the housing 110, as shown in FIG. 5 (collectively 5A, 5A1, 5A2 and 5A3). Suitable actuators 130 include specifically, but not exclusively, pneumatic and hydraulic pistons.
Referring to FIGS. 6A and 6B, fluid flow into the lower cell 1292 is provided by aligned inlet channels 151a, 151b and 151c in the upper section 111 of the housing 110, the upper mounting plate 121 and the lower mounting plate 122 respectively. In similar fashion, fluid flow out from the lower cell 1292 is provided by aligned outlet channels 152a, 152b and 152c in the upper section 111 of the housing 110, the upper mounting plate 121 and the lower mounting plate 122 respectively. A large diameter o-ring 151w is positioned within the gap 160 encircling the inlet channels 151a and 151b in the upper section 111 of the housing 110 and the upper mounting plate 121 for preventing testing gas from flowing throughout the gap 160. In similar fashion, a large diameter o-ring 152w is positioned within the gap 160 encircling the outlet channels 152a and 152b in the upper section 111 of the housing 110 and the upper mounting plate 121 for preventing testing gas from flowing throughout the gap 160.
Referring to FIGS. 4A and 4B, the flow control system (not collectively numbered) includes (i) flow control channels and passageways 170 through the upper section 111 of the housing 110 and the upper mounting plate 121, and (ii) o-ring seals 180 of different diameters and different thicknesses positioned within the gap 160 and encircling the various channels and passageways 170. The flow control system provides a quick, simple and reliable method of opening and closing the upper cell 1291 and the analyte sensor 200 to fluid flow at the appropriate times.
Referring to FIGS. 4A and 4A1, fluid flow into the upper cell 1291 is provided by laterally x and/or transversely z offset inlet channels 171a and 171b in the upper section 111 of the housing 110 and the upper mounting plate 121 respectively. In similar fashion, referring now to FIGS. 4A and 4A2, fluid flow out from the upper cell 1291 is provided by laterally x and/or transversely z offset outlet channels 172a and 172b in the upper section 111 of the housing 110 and the upper mounting plate 121 respectively.
Referring to FIGS. 4A and 4A1, a small diameter o-ring 181v is positioned within the gap 160 encircling the inlet channel 171b in the upper mounting plate 121. A large diameter o-ring 181w is also positioned within the gap 160 for encircling both the inlet channel 171a in the upper section 111 of the housing 110 and the inlet channel 171b in the upper mounting plate 121 as well as fully encircling the small diameter o-ring 181v. In similar fashion, referring now to FIGS. 4A and 4A2, a small diameter o-ring 182v is positioned within the gap 160 encircling the outlet channel 172b in the upper mounting plate 121, with a large diameter o-ring 182w positioned within the gap 160 and encircling both the outlet channel 172a in the upper section 111 of the housing 110 and the outlet channel 172b in the upper mounting plate 121 as well as encircling the small diameter o-ring 182v. 
Referring to FIGS. 4A, 4A1, 4A2, 4A3, 5A, 5A1, the thickness or longitudinal y height of the large diameter o-rings 181w and 182w is selected so that these o-rings 181w and 182w are sealingly engaged within the gap 160 regardless of whether the mounting plates 120 are in the open or closed longitudinally y position so as to prevent fluid from flowing freely within the gap 160. The thickness or longitudinal y height of the smaller diameter o-rings 181v and 182v is selected so that these o-rings 181v and 182v are sealingly engaged within the gap 160 only when the mounting plates 120 are in the closed longitudinally y position. Such positioning of the larger (181w and 182w) and smaller (181v and 182v) o-rings, in combination with the different thicknesses of the larger (181w and 182w) and smaller (181v and 182v) o-rings, permits the inlet (171a and 171b) and outlet (172a and 172b) channels to be simultaneously opened to fluid flow for flushing of the upper cell 1291 prior to a testing period by longitudinally y moving the mounting plates 120 into the downward or open position as shown in FIGS. 4A, 4A1 and 4A2, and simultaneously closed to fluid flow for sealing-off the upper cell 1291 during a testing period by longitudinally y moving the mounting plates 120 into the upward or closed position as shown in FIGS. 4B, 4B1 and 4B2.
Referring to FIGS. 4A, 4A3, 5A, the analyte sensor 200 communicates with the upper cell 1291 via longitudinally y aligned passageways 173a and 173b in the upper section 111 of the housing 110 and the upper mounting plate 121 respectively. A large diameter o-ring 183w is positioned within the gap 160 encircling both passageways 173a and 173b for ensuring that fluid diffusing into the analyte sensor 200 from the upper cell 1291 is not contaminated by fluid from the gap 160.
In order to extend the useful life of the analyte sensor 200, especially when an electrochemical sensor is employed, the passageway 173a should be closed at all times except during testing periods (i.e., only after the upper cell 1291 has been flushed with an inert gas and sealed so that the only analyte A in the upper cell 1291 is analyte A that has permeated through a test film F). Referring to FIGS. 4A, 4A3, 5A, an expedient technique for providing such limited access to the analyte sensor 200 is to position a normally closed tire valve 140 within the passageway 173a, with the body 141 of the tire valve 140 sealingly wedged into the passageway 173a and the stem 142 of the tire valve 140 extending longitudinally y downward towards the gap 160. An upwardly extending pin 121n is provided on the upper mounting plate 121 for pressing longitudinally y upward against the valve stem 142 and thereby opening the valve 140 only when the mounting plates 120 are in the upper or closed position.
The transmission rate of analyte A through most plastic films F is sensitive to humidity, with an increase in humidity tending to result in an increase in the transmission rate. Most analyte sensors 200 are also somewhat sensitive to humidity, especially if permitted to “dry out”. Hence, in order to obtain consistent and comparable test results it is important to maintain a constant relative humidity within the testing chamber 129, especially within the closed upper cell 1291. To maintain a constant humidity within the upper cell 1291, a humidity control system 190 can be provided. A suitable humidity control system 190 is shown in FIGS. 5A, 5A1, 5B and 5B1. The humidity control system 190 include a pair of humidity control chambers 199 in the upper mounting plate 121 diametrically positioned relative to the analyte sensor 200 and in fluid communication with both the upper cell 1291 and the gap 160. Inlet 191a and outlet 192a channels are provided in the upper section 111 of the housing 110 for placing each of the humidity control chambers 199 in fluid communication with a source of a gas (not shown) having a known humidity, typically 0% or 100% relative humidity. A large diameter o-ring 198w is positioned within the gap 160 encircling each of the humidity control chambers 199 and the corresponding set of inlet 191a and outlet 192a channels. A film 193 permeable to water vapor and impermeable to the target analyte A, such as a Nafion® film, is provided over the opening of each humidity control chamber 199 into the upper cell 1291 for purposes of allowing transpiration between the humidity control chamber 199 and the upper cell 1291 without introducing extraneous analyte A into the upper cell 1291 or allowing analyte A to escape from the upper cell 1291 undetected. The selectively permeable film 193 can be sealingly held in position within each humidity control chamber 199 by an o-ring 194, washer 195, inset ring 196 and locking ring 197 as shown in FIGS. 5A1 and 5B1.
Use
The mounting plates 120 are removed from the retention chamber 129 by activating the actuator 130 to lower the actuator shaft 131 into a removal position (not shown) where the o-ring seals 180 within the gap 160 no longer contact the upper section 111 of the housing 110, and sliding the mounting plates 120 out through an open side (not numbered) of the lower section 112 of the housing 110.
The upper mounting plate 121 is then separated from the lower mounting plate 122, and a sample of the film F to be tested placed atop the lower mounting plate 122 over the test chamber 129 so as to fully engage the entire periphery of the o-ring 125 encircling the test chamber 129.
The upper mounting plate 121 is then placed back atop the lower mounting plate 122 and secured to the lower mounting plate 122 so as to sealingly clamp the film F between the plates 121 and 122, thereby sealingly separating the testing chamber 129 into an upper cell 1291 and a lower cell 1292 with a known area of the film F exposed to both cells 1291 and 1292. The “loaded” mounting plates 120 are then slid back into the retention chamber 119.
Referring to FIGS. 4A, 4A1, 4A2 and 4A3, the actuator 130 is activated to move the loaded mounting plates 120 into an “open” position wherein the larger diameter o-rings 181w, 182w, 183w and 198w located within the gap 160 sealingly engage the lower surface 111i of the upper section 111 of the housing 110 while the smaller diameter o-rings 181v and 182v within the gap 160 do not. With the mounting plates 120 in the “open” position, the upper cell 1291 is flushed with an inert gas to remove any target analyte A from the upper cell 1291 by placing the inlet channel 171a in the upper section 111 of the housing 110 in fluid communication with a pressurized source of inert gas 21 and allowing the inert gas to flow sequentially through the inlet channel 171a in the upper section 111 of the housing 110, through that portion of the gap 160 surrounded by the larger diameter o-ring 181w, through the inlet channel 171b in the upper mounting plate 121, through the upper cell 1291, through the outlet channel 172b in the upper mounting plate 121, through that portion of the gap 160 surrounded by the larger diameter o-ring 182w, and out from the measurement unit 100 through the outlet channel 172a in the upper section 111 of the housing 110.
Referring to FIGS. 4B, 4B1, 4B2 and 4B3, after flushing, the actuator 130 is activated to move the loaded mounting plates 120 into a “closed” position wherein both the larger diameter o-rings 181w, 182w, 183w and 198w and smaller diameter o-rings 181v and 182v within the gap 160 sealingly engage the lower surface 111i of the upper section 111 of the housing 110 so as to seal-off the upper cell 1291 from the surrounding environment.
Referring to FIG. 4A3, movement of the loaded mounting plates 120 into the “closed” position also causes the pin 121n on the upper mounting plate 121 to engage the stem 142 on the valve 140 within the passageway 173a in the upper section 111 of the housing 110 so as to open the passageway 173a and thereby place the analyte sensor 200 in fluid communication with the upper cell 1291.
With the mounting plates 120 in the “closed” position, the lower cell 1292 is flushed with a test gas containing a known concentration of target analyte A and continuously supplied with “fresh” test gas throughout the testing period to ensure that the concentration of target analyte A within the lower cell 1291 remains constant. Test gas is introduced into the lower cell 1292 by placing the inlet channel 151a in the upper section 111 of the housing 110 in fluid communication with a pressurized source of test gas 22 and allowing the test gas to flow sequentially through the inlet channel 151a in the upper section 111 of the housing 110, through that portion of the gap 160 surrounded by the larger diameter o-ring 151w, through the inlet channel 151b in the upper mounting plate 121, through the inlet channel 151c in the lower mounting plate 122, through the lower cell 1292, through the outlet channel 152c in the lower mounting plate 122, through the outlet channel 152b in the upper mounting plate 121, through that portion of the gap 160 surrounded by the larger diameter o-ring 152w, and out from the measurement unit 100 through the outlet channel 152a in the upper section 111 of the housing 110.
Target analyte A will permeate through the film F as the analyte A seeks to diffuse through the film F from a region of higher concentration (i.e., the lower cell 1292) to a region of lower concentration (i.e., the upper cell 1291). Since test gas continuously flows through the lower cell 1292 the concentration of target analyte A in the region of higher concentration remains constant throughout the relevant test period. Similarly, since the analyte sensor 200 consumes target analyte A within the upper cell 1291 faster that the target analyte A permeates through the film F, the concentration of target analyte A in the region of lower concentration also remains constant at essentially zero throughout the relevant test period.
Eventually, the system will reach a steady state condition where the rate at which analyte A is detected in the upper cell 1291 by the analyte sensor 200 and reported by the central processing unit 50 remains constant. This steady state rate equates directly to the permeation rate for the film F for the “exposed” area of the film.
EXAMPLES
Example 1
A 1.0 mil thick polyethylene terephthalate mylar film is placed between the mounting plates of the permeation testing system depicted in FIGS. 1-7 so as to provide a 50 cm2 area of the film exposed to both the upper and lower cells. Permeation testing is conducted in accordance with ASTM D3985 employing the following testing parameters:
















Gas In Upper Cell:




Type:
100% N2



RH:
 10%



Gas In Lower Cell:




Type:
100% O2



RH:
 10%



Testing Chamber Temp: 
23° C.



Barometer:
742.3 mmHg










Oxygen within the upper cell is continuously sensed with a high-sensitivity standard electrochemical oxygen sensor covered with a porous membrane. Utilizing a reporting cycle of five (5) minutes, the transmission rate of oxygen through the film (O2TR) is calculated from the amperes sensed by the sensor each reporting cycle utilizing EQUATION A. The O2TR calculated for each reporting cycle throughout the testing period is depicted in FIG. 8 and set forth in Table One below. The O2TR for the film, reported after fifty (50) reporting cycles (4 hours and 10 minutes) is 60.975 cm3/(m2)(day).

O2TR=Amperes/(Area)(k1)(k2)(k3)  (EQUATION A)

Wherein:

    O2TR=Transmission Rate of Oxygen (cm3/(m2)(sec))
    Amperes=Amperes generated at the sensor (coulombs/second)
    Area=Exposed area of the film (m2)
    k1=Molecules of Oxygen per cm3 at Standard Temperature and Pressure (2.6876*1019 molecules/cm3)
    k2=Electrons involved in covalent bonding @ the sensor per molecule of Oxygen (4 e−/molecule)
    k3=Coulombs generated per electron (1.6*10−19 coulombs/e-)












TABLE ONE







Time
O2TR



(hrs:min)
cm3/(m2)(day)



















  5
0.1



  10
5.078



  15
15.105



  20
25.023



  25
33.235



  30
39.666



  35
47.96



  40
51.218



  45
53.614



  50
55.399



  55
56.72



1:00
57.732



1:05
58.499



1:10
59.073



1:15
59.491



1:20
59.844



1:25
60.086



1:30
60.254



1:35
60.397



1:40
60.51



1:45
60.592



1:50
60.67



1:55
60.715



2:00
60.769



2:05
60.785



2:10
60.807



2:15
60.84



2:20
60.857



2:25
60.843



2:30
60.858



2:35
60.858



2:40
60.896



2:45
60.9



2:50
60.935



2:55
60.952



3:00
60.957



3:05
60.973



3:10
60.97



3:15
60.966



3:20
60.954



3:25
60.959



3:30
60.948



3:35
60.98



3:40
60.984



3:45
60.978



3:50
60.974



3:55
60.973



4:00
60.984



4:05
60.968



4:10
60.975

## Claims

1. A valve system, comprising:
(a) first and second longitudinally facing members defining a gap therebetween in fluid communication with transversely offset first and second orifices through the members, wherein one of the members is longitudinally repositionable relative to the other member for adjusting the longitudinal height of the gap,
(b) a primary biasing means longitudinally biasing the members away from one another,
(c) an elastic element positioned within the gap between the first and second orifices,
(d) a repositioning means for longitudinally repositioning the repositionable member towards the other member against the bias of the primary biasing means as between (i) a first position wherein the elastic element does not seal the gap so as to allow fluid flow from the first orifice to the second orifice through the gap, and (ii) a second position wherein the elastic element is compressed between the members and seals the gap so as to prevent fluid flow from the first orifice to the second orifice through the gap.

2. The valve system of claim 1 wherein the first orifice extends through the first member and the second orifice extends through the second member.

3. The valve system of claim 1 wherein the primary biasing means is a larger-diameter elastic O-ring positioned within the gap and encompassing both the first and second orifices.

4. The valve system of claim 3 wherein the elastic element is a smaller-diameter elastic O-ring surrounding only one of the first or second orifice.

5. The valve system of claim 4 wherein the longitudinal height of the larger-diameter elastic O-ring is greater than the longitudinal height of the smaller-diameter elastic O-ring.

6. The valve system of claim 1 wherein the repositioning means is an adjustable-strength biasing means for longitudinally biasing the repositionable member towards the other member against the bias of the primary biasing means between (i) a first biasing strength sufficient to achieve the first position, and (ii) a second biasing strength sufficient to achieve the second position.

7. The valve system of claim 6 wherein the adjustable-strength biasing means is a pneumatic piston.

8. The valve system of claim 6 wherein the adjustable-strength biasing means is a hydraulic piston.

9. A bidirectional valve system, comprising:
(a) first and second longitudinally facing members defining a gap therebetween in fluid communication with a first inlet and a first outlet orifice through one member and a second inlet and a second outlet orifice through the other member, wherein (i) the inlet orifices are transversely offset, (ii) the outlet orifices are transversely offset, and (iii) one of the members is longitudinally repositionable relative to the other member for adjusting the longitudinal height of the gap,
(b) an inlet larger-diameter elastic O-ring positioned within the gap and encompassing both the first and second inlet orifices,
(c) an inlet smaller-diameter elastic O-ring positioned within the gap and surrounding only one of the first or second inlet orifices,
(d) an outlet larger-diameter elastic O-ring positioned within the gap and encompassing both the first and second outlet orifices,
(e) an outlet smaller-diameter elastic O-ring positioned within the gap and surrounding only one of the first or second outlet orifices,
(f) a repositioning means for longitudinally repositioning the repositionable member towards the other member against the bias of the larger-diameter elastic O-rings as between (i) a first position wherein the larger-diameter O-rings are compressed between the members and seal the gap so as to prevent fluid flow through the gap from the inlet orifices to the outlet orifices without compressing the smaller-diameter O-rings between the members so as to allow fluid flow from the first inlet orifice to the second inlet orifice through the gap and from the first outlet orifice to the second outlet orifice through the gap, and (ii) a second position wherein both larger-diameter O-rings are compressed between the members and seal the gap so as to prevent fluid flow through the gap from the inlet orifices to the outlet orifices, the inlet smaller-diameter O-ring is compressed between the members so as to prevent fluid flow from the first inlet orifice to the second inlet orifice through the gap, and the inlet smaller-diameter O-ring is compressed between the members so as to prevent fluid flow from the first outlet orifice to the second outlet orifice through the gap.

10. The bidirectional valve system of claim 9 wherein the longitudinal height of the larger-diameter elastic O-rings is greater than the longitudinal height of the smaller-diameter elastic O-rings.

11. The bidirectional valve system of claim 9 wherein the repositioning means is an adjustable-strength biasing means for longitudinally biasing the repositionable member towards the other member against the bias of the larger-diameter elastic O-rings between (i) a first biasing strength sufficient to achieve the first position, and (ii) a second biasing strength sufficient to achieve the second position.

12. The valve system of claim 11 wherein the adjustable-strength biasing means is a pneumatic piston.

13. The valve system of claim 11 wherein the adjustable-strength biasing means is a hydraulic piston.