WO2018208355A2 - Dispositif et procédés de détection - Google Patents

Dispositif et procédés de détection Download PDF

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Publication number
WO2018208355A2
WO2018208355A2 PCT/US2018/019021 US2018019021W WO2018208355A2 WO 2018208355 A2 WO2018208355 A2 WO 2018208355A2 US 2018019021 W US2018019021 W US 2018019021W WO 2018208355 A2 WO2018208355 A2 WO 2018208355A2
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WIPO (PCT)
Prior art keywords
sensor
hazardous
sensing film
conductive polymer
polymer
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PCT/US2018/019021
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English (en)
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WO2018208355A3 (fr
Inventor
Hootan FARHART
Kateri Paul
Mitch Zakin
Shekar SHETTY
Phil GRAF
Piercen OLIVER
Joe MCLELLAN
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Nano Terra Inc.
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Publication of WO2018208355A2 publication Critical patent/WO2018208355A2/fr
Publication of WO2018208355A3 publication Critical patent/WO2018208355A3/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/082—Investigating permeability by forcing a fluid through a sample
    • G01N15/0826—Investigating permeability by forcing a fluid through a sample and measuring fluid flow rate, i.e. permeation rate or pressure change
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • G01N27/07—Construction of measuring vessels; Electrodes therefor

Definitions

  • U.S. Patent No. 6,783,989 describes polymers, including conductive polymers, for use sensors for the detecting extremely hazardous substances, such as chemical warfare agents.
  • U.S. Patent No. 9,086,351 describes a device and method for detecting and quantifying permeation of a chemical through a glove. The contents of that patent are also hereby incorporated by reference in their entirety. Other descriptions of prior art devices and methods can be found in the following references: "Development of a Contact Permeation Fixture and Method" ECBC-TR-1 141, Edgewood Chemical Biological Center, U.S. Army Research, Development and Engineering Command; and U.S. Patent No. U.S. 9,021,865, each incorporated herein by reference in their entirety.
  • one embodiment of the present invention provides a device for detecting permeation of a hazardous material through a test material.
  • the device comprises a test cell having a first chamber configured to receive the hazardous material.
  • the hazardous material may have a vapor pressure of less than 0.5 mmHg at standard temperature and pressure (i.e. , 25 ° C and 1 atm).
  • the device also comprises a removable sensor module configured to hold the test material therein, and also configured to hold a removable sensor module.
  • the removable sensor module comprises a sensor for detecting permeation of the hazardous material from the first chamber, wherein the sensor is comprised of a conductive polymer, a semi-conductive polymer or an electroactive polymer, the sensor being chemically reactive with the hazardous material to generate a change in electrical resistance in the sensor.
  • the device further comprises one or more conductive electrodes attached to the sensor configured to detect a change in resistance in the sensor.
  • the device comprises a resistance measuring device electronically connected to the one or more electrodes, the resistance measuring device configured to receive data from the one or more electrodes and generate an output based on the data corresponding to an amount of hazardous material detected by the sensing film.
  • Another embodiment of the present invention provides a method for detecting a hazardous analyte permeating through a test material in a test cell device having a first chamber and a second chamber.
  • the hazardous analyte may have a vapor pressure of less than 0.5 mml lg at standard temperature and pressure (i.e., 25 "C and 1 atm).
  • the method comprises receiving a removable sensor module between the first chamber and the second chamber, the removable sensor module comprising a sensing film comprising a conductive polymer, a semi-conductive polymer or an electroactive polymer that is chemically reactive with the hazardous analytc to generate a change in electrical resistance in the sensing film.
  • the method also comprises a system to continuously collect, using one or more conductive electrodes attached to the sensing film, data corresponding to changes in electrical resistance in the sensing film.
  • the method further comprises analyzing the electrical resistance data of the sensing film to generate, using an appropriate calibration or transfer function, an output corresponding to real-time concentrations of the hazardous analyte permeated from the first chamber to the second chamber.
  • a sensor for detecting presence of a hazardous material in an environment comprises a sensing film for detecting the presence of the hazardous material in the environment, wherein the sensing film is comprised of a conductive polymer, a semi-conductive polymer or an electroactive polymer, the sensing film being chemically reactive with the hazardous material to generate a change in electrical resistance in the sensing film.
  • the hazardous material may have a vapor pressure of less than 0.5 mml lg at standard temperature and pressure (i. e. , 25 " C and 1 atm).
  • the sensor also comprises a substrate comprising a non-conductive polymer, the substrate being configured to be in contact with or proximate to the sensing film such that a surface of the sensing film is exposed to the environment.
  • the sensor further comprises one or more conductive electrodes attached to the sensing film configured to detect a change in resistance in the sensing film.
  • the sensor comprises a resistance measuring device electronically connected to the one or more electrodes, the resistance measuring device configured to receive data from the one or more electrodes and generate an output based on the data corresponding to an amount of hazardous material detected by the sensing film in real-time. 100071
  • a method for real-time detection of a hazardous analyte in a remote location is provided.
  • the hazardous analyte may have a vapor pressure of less than 0.5 mmHg at standard temperature and pressure (i.e. , 25 " C and 1 atm).
  • the method comprises directing a remote-controlled device to enter the remote location, the device comprising a sensor comprising a sensing film for detecting the presence of the hazardous analyte, wherein the sensing film comprises a conductive polymer, a semi-conductive polymer or an electroactive polymer, the sensing film being chemically reactive with the hazardous analyte to generate a change in electrical resistance in the sensing film.
  • the method also includes s system to continuously collect, using one or more conductive electrodes attached to the sensing film, data corresponding to changes in electrical resistance in the sensing film.
  • the method further includes analyzing the electrical resistance data of the sensing film to generate, using an appropriate calibration or transfer function, an output corresponding to real-time concentrations of the hazardous analyte at the remote location.
  • FIG. 1A illustrates a schematic diagram of a modified AVLAG test cell of the present invention in a sealed configuration
  • FIGS. 1B 1 , 1 B2, and 1B3 illustrate schematic diagram of a component of the modified AVLAG test cell of the present invention in a unassembled configuration
  • FIGS. 1 C 1 , 1C2, and 1 C3 illustrate schematic diagram of a component of the modified AVLAG test cell of the present invention in a unassembled configuration
  • FIGS. 1 D 1 and 1D2 illustrate schematic diagram of a cross-sectional view of component of the modified AVLAG test cell of the present invention
  • FIG 2. shows experimental data for Example I demonstrating breakthrough of dibenylamine through a 10 mm .1 at ext. swatch;
  • FIGS 3 A and 3B show experimental data for the water proof sensors of Example 11 demonstrating sensitivity of sensor after total water immersion;
  • FIGS. 4 A and 4B show experimental data for Example III demonstrating breakthrough of 2-diethylaminoethanethiol through skin;
  • FIG. 5 shows experimental data for Example IV demonstrating breakthrough of nicotine through nitrile
  • FIG. 6 shows experimental data for Example V demonstrating breakthrough of nicotine through cloth; and [0018] FIGS. 7 A, 7B and 7C shows experimental data for Example VI demonstrating detection of Methyl salicylate (MeS).
  • MeS Methyl salicylate
  • This invention relates to a sensor for detecting and measuring the presence of a hazardous substance in real-time.
  • the invention further relates to a sensor for detecting and measuring the penetration of hazardous substances through a barrier in real-time.
  • this invention relates to a device, system and method for detecting and measuring the presence of a hazardous substance, and more particularly to a device, system and method for detecting and measuring the present of a chemical warfare agent (CWA) or a toxic industrial chemical (TIC).
  • CWA chemical warfare agent
  • TIC toxic industrial chemical
  • the devices, sensors and methods described herein provides real-time detection of amounts and/or concentrations of a hazardous analyte permeating through a test material (e.g., from a first chamber to a second chamber in a test cell device), which may be useful in providing improved monitoring of breakthrough of hazardous substances across protective materials, or in providing improved monitoring of unknown evironments, such as a combat zone.
  • This monitoring may be performed for predetermined times or continuously over a period of time.
  • the changes in concentration of hazardous analyte may be outputted in real-time, which can be used to provide life-saving alerts and/or prompt further action upon detection of hazardous materials, such as CWAs. simulants of CWAs and/or strong reducing agents above predetermined thresholds.
  • the devices, sensors and methods described herein provides may be utilized to provide a continuous monitoring and detection of amounts and/or concentrations of a hazardous analyte.
  • the sensors may detect changes in electrical insistence in the sensor continuously and provide a continuous output indictating real-time amounts and/or concentrations of the hazardous analyte detected over a period of time.
  • One aspect of the present invention is a sensor for detecting the presence of a hazardous substance in real time.
  • the sensor may be in contact or proximate to the substrate.
  • the sensor preferably has a substrate capable of containing, holding o supporting a sensing material which is capable of detecting the hazardous material.
  • the detection event can then be read or converted into a form of information, like a signal, that can be read or transmitted in real time.
  • the substrate can be made of a material of any kind, but is preferably a polymer. Further, the substrate may be conductive or made from a non-conductive material such as glass, a ceramic, or a non-conductive polymer. The substrate can be rigid or flexible, and any size, shape or thickness. For some applications, the material is preferably a thin, flexible polymer. Optionally, the substrate may be surface modified by any suitable means, such as for example, a thin layer of imprinted metal, metal ions and/or complexes, e.g. , zinc, gold copper, silver.
  • the sensing material can be any material capable of detecting the presence of hazardous materials.
  • the sensing material is chosen for its ability to detect the hazardous material or materials of interest and also the method of reading or transmitting the detection event. Factors such as the solubility and volatility of the hazardous material should be taken into account when choosing the sensing material. Other factors to consider include environment in which the sensing is to occur (e.g. , temperature, humidity, etc. ). and the phase of the hazardous material (e.g. , solid, liquid, vapor, gas, aerosol).
  • the sensing material can be formed into a film, array, or pattern.
  • the sensor may include any suitable materials capable f chemically reacting with the hazardous substance to be detected, and providing a detectable change, such as, for example, a change in electrical resistance in the sensing material.
  • the sensor may be in contact with or proximate to (e.g., separated by a protective material) the hazardous substance to be measured.
  • the sensor may include a thin-film, such as a polymeric film, capable of chemically reacting with the targetted hazardous substance to generate a detectable change in the polymeric film.
  • the thin-film may have any suitable thickness that is capable of reacting with the desired hazardous analyte.
  • the thin-film may have a thickness from about 50 nm to about 200 nm, preferably about 100 nm.
  • the detectable change may be in the form of a change in electrical resistance in the polymer.
  • the sensor may comprise, for example, a conductive polymer, a semi-conductive polymer, an electroactive polymer, and/or a non-conductive polymer.
  • conductive polymers are polymers whose backbones or pendant groups are responsible for the generation and propagation of charge carriers. These polymers typically exhibit dramatic changes in resistivity on exposure to certain chemical species. Many species have no effect on polymer resistivity. Typically, the resistivity of the virgin or doped conductive polymers decreases dramatically and irreversibly with exposure to dopant species.
  • electroactive polymers are polymeric materials that conduct electricity.
  • Chemical vapors interact with the polymer backbone, or a chemically reactive additive incorporated into the polymer, to produce a change (increase or decrease) in the electrical resistance of the polymer, which enables the polymer to function as a chemical sensor.
  • a measurement in the change in polymer resistance provides an accurate quantification of the dose or concentration of a particular CWA, simulant of CWA, or strong reducing agent.
  • a particular CWA, simulant of CWA, or strong reducing agent for example, U.S. Patent Nos. 5,310,507, 5,145,645, and 6,783,989, refer to several exemplary sensing materials such as conductive polymers.
  • Suitable polymer for use as a sensor for detecting strong reducing agents and/or CWAs or simulants thereof include, but is not limited to, polyani lines, polyacetylenes.
  • the strong reducing agents, CWAs and simulants of CWAs that may be detected by the sensor described herein include, for example, amines, sulfur and its derivatives, diols, and other strongly basic agents.
  • the detector may include regioregular poly(3-hexylthiophene (rrp3HT).
  • the rrp3HT may be in the form of a coating or a film onto a substrate, and may be suitable for reacting with and detecting a number of different types of strong reducing agents, CWAs or simulants of CWAs. e.g., diben/.ylamine. nicotine, 2-diethylaminoethanethiol, methyl salicylate, sulfur mustard, etc.
  • the senor may include any suitable materials capable of chemically reacting with a hazardous substance having low-volatility to detect, and provide a detectable change, such as, for example, a change in electrical resistance in the sensing material.
  • vapor pressure refers to vapor pressure of a substance unders standard temperature and pressure (i.e. , at 25 ° C and 1 atm).
  • a low-volatility hazardous material may refer to any reducing agents and/or CWAs or simulants thereof having a vapor pressure of about 0.5 mml lg or less.
  • such low-volatility hazardous materials may include:
  • the hazardous materials may include chemical warfare agents such as HD, VX, and GA.
  • the hazardous materials may include methyl salicylate, dimethyl methyl phosphonate (DMMP), paraoxon, and others.
  • the senor may be formed from a mixture of a conductive polymer and a non-conductive polymer (e.g. , polystyrene) further doped with a metal and/or metal oxide.
  • a conductive polymer e.g. , polystyrene
  • Such sensors may be capable of reacting with hazardous materilas having low- volatility and/or low redox properties, e.g. , a weak base and/or low volatility, as discussed above.
  • the substrate is made from a non- conductive polymer and the sensing material is a conductive polymer, such as one of the conductive polymers listed in U.S. Patent No. 5,310,507, 5,145,645, or 6,783,989; or from a semiconductive, or eletroactive polymer.
  • the choice of conductive polymer is chosen to optimize detection of the specific analyte(s) of interest.
  • the substrate with conductive polymer is coupled to one or more conductive electrodes which are then electrically connected to a resistance measuring device. The connection can be made through a wired connection, mobile or wireless connection, or any other means of communication or transmission.
  • this sensor may be modified to adjust for sensitivity, responsiveness, or environmental or other conditions.
  • the conductive electrodes are coated so as to have a tuned reduction oxidation potential. This coating would provide an advantage over prior art methods by reducing the need for incorporating additives or dopants to increase specificity.
  • the sensor surface may be doped with a material selected to modify the electrical resistance of the sensing film.
  • the dopant may be suitable for providing a redox reaction with the desired hazardous analyte, such as. for example, NOPF 6 .
  • the dopant may change the electrical resistance of the sensing film to any suitable range, such as for example, from about from about 500 to about 1000 ohm.
  • the senor is enhanced to perform better in humid environments, through the use of one or more of the following methods:
  • hydrophobic conductive polymers to reduce degradation in humid environments (e.g., use longer side-chain polythiophcnes - octyl as opposed to hexyl).
  • microporous membranes for example those mentioned in U.S. Patent No.
  • Coating sensor with absorbent layer e.g., MOF or carbon.
  • the senor may be further coated with a silcone polymer, such as for example, a polysiloxane. to provide a separation of the sensor material from the environment, in particular a humid or moist environment.
  • a silcone polymer such as for example, a polysiloxane.
  • the silicone coating may impart improved water resistance or water proofness to the sensor.
  • Hydrophobicity e.g. hydrophobic si lane treatment
  • ⁇ Reactivivity e.g. carboxylate, amine, oxime, zinc, epoxide
  • Bioactivity e.g. enzyme, antibody
  • a porous layer e.g. silica, metal oxide. MOF, carbon, porous polymer layer, cyclodextrin
  • Oxime derivatives pyridine aldoxime, pralidoxime, 4-dimethy 1 am inopyri d i ne o Metal, metal ions, complexes, e.g. zinc, gold, copper, silver,
  • Amphiphlic polymers e.g. Irgsurf, alkylamine, alkyl oxime, block copolymer
  • V arious functional groups can be attached to the conductive polymer backbone, e.g. the functional group on the 3-position of the polythiophene including PEG, carboxylic acid, sulfonic acid, amine, hydroxy 1, oxime, imidazolium, and siloxane o
  • the functional group on the 3-position of the polythiophene including PEG, carboxylic acid, sulfonic acid, amine, hydroxy 1, oxime, imidazolium, and siloxane o
  • Each section can have different detection capabilities due to differences in wetting, adsorption, chemical interaction and reactions
  • a sensor that can be delivered and retrieved remotely, without the need to directly expose a human to the site at which the sensing or detection is to occur.
  • Another aspect of the present invention is sensing or detection through the use of a sensor delivery device such as robot, drone, remote controlled mobile vehicle. Unmanned Ground Vehicle (UGV), Unmanned Aerial Vehicle (UAV) or any other means of delivering the sensor to and retrieving the sensor from the sensing/detection site.
  • UAV Unmanned Ground Vehicle
  • UAV Unmanned Aerial Vehicle
  • the sensor described above can be attached to, mounted on, or incorporated within the sensor delivery device.
  • Such device or vehicle can be delivered to and retrieved from the site of sensing or detection using human control or through programmed control, machine learning-derived control, artificial intelligence-derived control or otherwise.
  • the sensor delivery device such as robot, drone, remote controlled mobile vehicle, Unmanned Ground Vehicle (UGV), Unmanned Aerial Vehicle (UAV) or any other means of delivering the sensor in combination with one or more of the senors can provide unmanned, remote controled, real-time analysis of a sensing/detection site, which the sensor delivery device is still located at the site.
  • the sensor may chemically react with a hazardous analyte at the sensing/detection site, and the resistance measuring device may detect a change in electrical resistance in the sensor and wirelessly transmit data corresponding to the change in electrical resistance to a remotely located computational device.
  • the computational device may be located with a user within a known safe region, while the sensor delivery device is remotely controlled by the user to explore unknown sites.
  • the sensor delivery device can be a part of or used in connection with UAV's serving other purposes such as the following:
  • sampling means including but not limited to robotic hands, scoopers, swabbers, and adhesive contact pads can be used to grab or otherwise collect a sample.
  • the sampling means can be attached or connected to, mounted on, or incorporated within the sensor or sensor delivery devices described above.
  • the following reference describes method and device for remote sampling of hazardous materials: "Remote chemical biological and explosive agent detection using a robot- based Raman detector", Proc. SPIE 6962, Unmanned Systems Technology X, 69620T (April 16, 2008); doi: 10.1 1 17/12.781692. The contents of that reference are incorporated by reference herein in their entirety.
  • One aspect of the present invention is a sensor and sensor system for detecting and measuring such breakthrough.
  • One dev ice of the present invention for measuring breakthrough is a multi-chambered cell designed to hold a piece of material as an interface between at least two chambers; wherein a chemical is placed on the material in one chamber and a sensor capable of sensing the chemical is placed on the opposite side of the material in a second chamber and can detect when a chemical has traversed through the material from one side to the other.
  • the sensor can be of the type described above.
  • a preferred sensor is made of a non-conductive polymer coated with a conductive polymer.
  • the substrate is made of mylar and the sensor material is a conductive polymer. This flexible configuration can be used to measure penetration through flexible barrier materials, such as fabric, and can be incorporated between layers of barrier materials.
  • the device may be configured to measure breakthrough of one or more layers of test materials, said test material may comprise barrier materials and/or protective materials against hazardous agents (e.g. , CWAs, simulants of CWAs, and other strong reducing agents as discussed above).
  • the device may include a plurality of sensors and/or senor modules interspersed between multiple layers of test materials, e.g., barrier materials and/or protective materials.
  • the sensors and layers of test materials may be interdigitating articles having a plurality of layer. At least one sensor may be placed to one side of the interdigitating article.
  • a plurality of sensors may be interspersed between multiple layers o test materials such that breakthrough may be measured for each intermediary and/or additional layer.
  • the one or more layers of test materials may be in any suitable configuration and/or geometry in two-dimensional or three- dimensional space.
  • the layers of test materials may be in the form of stacked layers of sheets.
  • the layers of test materials may be in the form of nested three- dimensional shapes, e.g. , nesting spheres, cylinders, or other three dimensional regular or irregular shapes.
  • One aspect of the present invention is an improved testing device, as shown in FIGS. 1A through ID.
  • the present invention may encompasee any suitable testing device and is not limited to AVLAG cells. It is contemplated any suitable testing device or cell may be use, such as for example, any suitable device that is either open or closed that can hold a sensor below a swatch (in contact, or offset) with any type of agent challenge at the top (aerosol, liquid, vapor, or solid). In some embodiments, the testing device may not may not include a weight. In certain embodiments, ther may or may not also be different controls that allow for the ability to change temperature, pressure, and/or humidity within or surrounding the testing device or cell.
  • the testing cell may be an AVLAG cell having top plate, lower plate, connector and connector plate.
  • the connector is capable of receiving and holding one or more sensors.
  • the testing device of the present invention is constructed such that the connector and sensors are removable. (For example, by a removable sensor chip that can slide in and out of a slot in the AVLAG cell).
  • test cell of the present invention does not require the use of vacuum, application of weights to compress the testing material and the sensor together, or other modifications to apply a pressure between the sensor and the test material. Rather, the sensor may be placed in contact with or proximate to the test materials.
  • changes to the sensor may be measured while the removable sensor module remains in the test cell and provide analytical data in real-time, and does not require a separate step of removing the sensor module from the test cell and transporting it to a separate analytical device for a subsequent and delayed analysis.
  • a removal and transport of the sensor further exposes the sensor to environmental factors, e.g., humidity or contaminants, that may reduce accurracy or reliability of the sensor.
  • the present invention provides a single device (e.g., unitary device) that is configured to expose the sensor to a hazardous analyte, and detect the amount of hazardous analyte that permeates through the test material or layers of test materials.
  • the improved testing device may include a removable sensor module that modularly provides a sensor that reacts specifically to a desired analyte.
  • the removable sensor may be easily removed and replaced with a different sensor module to allow for detection of different types of CWAs depending on they sensor module used.
  • the sensor module may include a sensor as described above having a polymer that is chemically reactive with the desired hazardous analyte to generate a change in electrical resistance in the sensor.
  • the removable sensor module may be configured to hold a swatch of the test material therein, as well as a sensing material for detection of the desired hazardous analyte.
  • the amount of hazardous analyte permeating through the test materal may be measured using the test device in real-time, without delay from removal and separate testing of the sensor, after it has been exposed to the hazardous analyste. Instead, the removable sensor module may remain in the testing device while simultaneously providing data to a resistance measuring device to generate an output based on the data corresponding to real-time changes in amount or concentration of the hazardous analyte detected.
  • a swatch of material is positioned on top of the sensor or in standoff from the sensor. The hazardous agent to be tested is then placed in the testing cell in a manner similar to that employed in using current AVLAG testing cells, which includes liquid, vapor, aerosol, or even solid chemicals.
  • a sensor for detecting a hazardous material, particularly a hazardous mated la having low-volatility, or for measuring real-time breakthrough of low- volatility compounds (i.e., vapor pressure less than 0.5 mmHg at a temperature of 25 °C and a pressure of 1 atm) through a test article may be provided.
  • the sensor may be in contact with the test article.
  • the senosr may be positioned stand off from the test article.
  • the sensor may be placed in an environment where there is a no-flow condition of air.
  • sensor maybe positioned in the path of flow across the back of the test article so as to pick up the vapors of such a hazardous material.
  • sensor may be positioned in the path of flow across the back of the test article so as to pick up the vapors of low and/or high-volatility compound (i.e., above and below vapor pressures of 0.5 mmHg at 25 °C and 1 atm).
  • the sensor may be configured to detect low-volatility hazardous material in a no-flow condition of air.
  • the sensor may be suitable for detecting both high and low-volatility materials (i.e., above and below vapor pressures of 0.5 mmHg at 25 °C and 1 atm).
  • the sensors may be configured to detect both high and low-volatility compounds (i.e., above and below vapor pressures of 0.5 mmHg at 25 °C and 1 atm) in a no-flow condition of air.
  • the hazardous materials may include chemical warfare agents such as HD, VX, and GA.
  • the hazardous materials may include methyl salicylate, dimethyl methyl phosphonate (DMMP), paraoxon, and others.
  • the sensor may be configured to detect mixtures of compounds or compounds in solvents.
  • the sensor may be of a flexible material such that it can be placed into, onto, or behind any article while under any type of mechanical stress or strain (i.e., bending, warping, twisting, pressure, etc.).
  • the sensor response may be dosimetric (i.e., the sensor response does not revert back to the baseline response after the compound challenge is removed). In other embodiments, the sensor response may be reversible (i.e., the sensor response reverts back to the baseline response after the compound challenge is removed). Furthermore, the sensor may comprise a region comprising a sufficiently thin film (less than 1 mm thick) and is flexible so that it is capable of being inserted between layers of a material, into materials, and into, onto, or behind complex materials that are not necessarily planar or smooth.
  • the sensor may be rapidly responsive in detecting presence of a hazardous material.
  • the sensor may have an on/off response time of less than 1 second.
  • the sensor may have multiple (>2) independently-querable sensing regions on the same substrate.
  • the multiple sensing regions may be sufficiently close to each other (within 10 millimeters) that the lateral or spatial spread of a compound can be gathered (such as by analyzing the data and forming a "heat-map").
  • These sensor regions and/or substrate may be made into any suitable geomtry to accommodate testing of a variety of articles, such as for example, the sensor regions and/or substrates may conform to the shape of the article being tested.
  • the sensor region may comprise of any suitable conductive polymer, such as those discussed above.
  • the polymer may be dope, or not doped ,with a material selected to modify the electrical resistance of the sensing film, such as, for example, ferric chloride.
  • the sensing region may comprise of any sensor type that has a sufficiently low profile ( ⁇ 1 mm thick).
  • the sensor may further comprise one or more overcoats that are applied to decrease the sensor's susceptibility to humidity.
  • the sensor of the present invention is a (device) having a surface made with or having a surface coated, in whole or in part, with an indicator material which indicates a conductivity change in the presence of certain hazardous chemical compounds.
  • This indicator material may be any material capable of indicating a conductivity change visually, electrocheniically. or otherwise, such materials including but not limited to those described in U.S. Patent No. 6,783,989, the contents of which are hereby incorporated herein in their entirety.
  • the sensor is made of a polymer coated in part by a conductive polymer.
  • Example 1 Latex Breakthrough Testing
  • a device for detection of breakthrough or permeation of a hazardous material may be provided.
  • the test material in Example is a 10 mil latex swatch and breakthough of a hazardous analyte, i.e., dibenzylamine over time is determined using a test cell device.
  • FIG, 2 shows a plot of resistance (relative to the initial resistance, R/R 0 ) versus time for the breakthrough of dibenzylamine through a 10 mil latex swatch. The latex swatch was placed on top of the thin-film sensor and one microliter of dibenzylamine was added to the swatch.
  • Example II Waterproofed sensors 1 0581
  • a substantially waterproof sensor for detection of a hazardous material may be provided.
  • a thin regiorcgular poly(3 hexyl thiophene) (rrP3HT) film over interdigitated electrodes was coated with tluorinatcd si lane by vapor deposition for 1 hour.
  • This film was doped with NOPF 6 in acetonitrile to a resistance of between 500 and 1000 ohms.
  • This film showed enhanced resistance to dedoping when placed into water versus the film not containing the tluorinatcd si lane coating (see FIG. 3 A).
  • the film confers resistance to moisture, it does not completely block the film and still response to nicotine vapor with only a 2- fold decrease in response rate (see FIG. 3B).
  • Electrode Geometry 8.65 mm 2 area of 20 ⁇ width and 20 ⁇ spaced interdigitated electrodes
  • Post-treatment vapor treatment of (heptadecafluoro- 1.1 .2.2- tetrahy drodecy 1 )tri c h 1 oro si 1 ane for 1 hour at room temperature under vacuum o
  • Doping with NOPF 6 in acetonitrile to a resistance between 500 and 1000 ohm
  • FIG. 3A Sensor response to total water immersion without (solid line) and with (dashed line) peril uorosi lane treatment.
  • FIG. 3B Average sensor responses to -100 ppm of nicotine vapor without (solid line) and with (dashed line) treatment with the silane. There is a moderate decrease of roughly a factor of two in sensitivity after treatment. Curves are averages of several sensors run at the same time (shaded areas indicate one standard deviation from the mean).
  • Example III Breakthrough of an amine with skiN
  • Electrode Geometry 8.65 mm 2 area of 20 ⁇ width and 20 ⁇ spaced interdigitated electrodes
  • Post-treatment vapor treatment of (heptadecafluoro- 1 , 1 ,2,2- tetrahydrodecyljtrichlorosilane for 1 hour at room temperature under vacuum o
  • Doping with NOPF 6 in acetonitrile to a resistance between 500 and 1000 ohm o
  • Subsequent layer 7-mil silicone sheet
  • FIG. 3 A Effect of various coatings on rrP3HT on the baseline response when placed under chicken skin.
  • FIG. 3B The sensor with the fluorinated coating and silicone sheet was used in a breakthrough experiment using droplets of 2-diethylaminoethanethiol on chicken skin. An upturn in the response at 1 1 -12 minutes indicates break. Curves are averages of several sensors run at the same time (shaded areas indicate one standard deviation from the mean).
  • Breakthrough curves for a variety of simulants can be obtained.
  • a break curve for nicotine through glove material the palm area from a 4-mil nitrile glove.
  • Electrode Geometry 8.65 mm 2 area of 20 pm width and 20 ⁇ spaced interdigitated electrodes
  • FIG. 5 Break curve (calibrated) of nicotine through 4-mil glove Nitrile. Challenge is 1 microliter drop over each sensor surface. Each curve is from a single sensor face (four in total).
  • BreakthiOUgh curves for a variety of simulants can be obtained.
  • a break curve for nicotine through fabric a 50/50 nylon cotton blend of fabric.
  • the nicotine in this case is applied by a nicotine patch (NicoDerm CQ).
  • NicoDerm CQ a nicotine patch
  • Electrode Geometry 8.65 mm 2 area of 20 ⁇ width and 20 ⁇ spaced interdigitated electrodes
  • FIG. 6 Break curve (calibrated) of nicotine patch through 50/50 nylon cotton. Curve is average of six sensor faces. Shaded area indicates one standard deviation from the mean.
  • Methyl salicylate is a common CWA simulant for sulfur mustard (HD) due to its relatively low toxicity and similar chemical properties.
  • MeS is difficult to detect with conductive polymers because it does not have strong redox properties and is a very weak base.
  • a thin sensor film having a composition of 95% polystyrene and 5% rrP3HT was immersed in a concentrated sodium hydroxide solution and doped with ferric chloride to between 1000 and 2000 ohms. This sensor was tested against MeS vapor (saturated atmosphere, 45 ppm) and shows a strong dosimetric response to MeS vapor (Figure 5).
  • This sensor takes advantage of binding of ferric chloride to its hydrolysis product, salicylic acid, which dissociates the binding of iron (II or III) from the polymer backbone and dedopes the sensor.
  • the sensor is dosimetric due to the high content (95%) of polystyrene, which we believe has a strong affinity for methyl salicylate.
  • the infusion of NaOH into the polymer increases the rate of MeS hydrolysis and subsequent reaction with ferric chloride.
  • Electrode Geometry 8.65 mm 2 area of 20 ⁇ width and 20 ⁇ spaced interdigitated electrodes
  • FIGS 7A, 7B and 7C Effect of methyl salicylate (MeS) vapor detection (-45 ppm) on three sensor formulations.
  • the same base conductive polymer (rrP3HT) doped with ferric chloride is used as the transducer for each sensor. Sensitivity and reversibility are augmented with the integration of a polymer admixture and an active chemistry.
  • FIG. 7A shows that the formula containing only conductive polymer and dopant shows a reversible response to MeS.
  • FIG. 7B shows that the formula from FIG. 7A is diluted with 95% of polystyrene and shows a dosimetric response.
  • FIG. 7C shows that the formula from FIG. 7B is infused with NaOH by immersion into a sodium hydroxide solution, which increases the hydrolysis rate of MeS and the subsequent reaction with ferric chloride.
  • Each curve is from a separate sensor face.

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Abstract

L'invention concerne un dispositif et un procédé permettant de détecter la présence d'une matière dangereuse dans un environnement ou à travers un matériau d'essai, par exemple, un matériau de protection. Le dispositif peut comprendre un capteur destiné à détecter la présence de la matière dangereuse. En particulier, la matière dangereuse peut avoir une pression de vapeur inférieure à 0,5 mmHg. Le capteur contient un polymère conducteur, un polymère semi-conducteur ou un polymère électroactif, le capteur étant chimiquement réactif avec la matière dangereuse pour générer un changement de résistance électrique dans le capteur. Le dispositif peut comprendre une ou plusieurs électrodes conductrices fixées au capteur, conçues pour détecter un changement de résistance dans le capteur, et un dispositif de mesure de résistance connecté électroniquement à la ou aux électrodes pour recevoir des données provenant des électrodes et pour générer une sortie sur la base des données correspondant à une quantité de matière dangereuse détectée par le capteur en temps réel.
PCT/US2018/019021 2017-02-21 2018-02-21 Dispositif et procédés de détection WO2018208355A2 (fr)

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US11328582B1 (en) 2021-07-07 2022-05-10 T-Mobile Usa, Inc. Enhanced hazard detection device configured with security and communications capabilities
CN114813862A (zh) * 2021-11-12 2022-07-29 重庆大学 一种电化学生物传感器及其应用

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US4652396A (en) * 1983-05-06 1987-03-24 Akzona Incorporated Electrically conductive porous synthetic polymeric compositions, method for making same, and use thereof in an electrodialysis process
EP1117991A4 (fr) * 1998-10-02 2005-04-27 California Inst Of Techn Capteurs organiques conducteurs, mosaique de capteurs et procedes d'emploi
CA2445587A1 (fr) * 2001-04-26 2002-11-07 Boston Biomedica, Inc. Dispositif a chambres multiples et utilisations correspondantes dans le traitement d'echantillons biologiques
US6902701B1 (en) * 2001-10-09 2005-06-07 Sandia Corporation Apparatus for sensing volatile organic chemicals in fluids
US20090036327A1 (en) * 2003-07-08 2009-02-05 Trex Enterprises Corp. Method for chemical treatment of porous silicon surface
US8192685B2 (en) * 2008-11-04 2012-06-05 Advanced Concepts And Technologies International, L.L.C. Molecular separators, concentrators, and detectors preparatory to sensor operation, and methods of minimizing false positives in sensor operations

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US11328582B1 (en) 2021-07-07 2022-05-10 T-Mobile Usa, Inc. Enhanced hazard detection device configured with security and communications capabilities
CN114813862A (zh) * 2021-11-12 2022-07-29 重庆大学 一种电化学生物传感器及其应用
CN114813862B (zh) * 2021-11-12 2024-03-26 重庆大学 一种电化学生物传感器及其应用

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