WO2016171768A1 - Techniques et types d'échantillonneur d'analyte - Google Patents
Techniques et types d'échantillonneur d'analyte Download PDFInfo
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- WO2016171768A1 WO2016171768A1 PCT/US2016/000037 US2016000037W WO2016171768A1 WO 2016171768 A1 WO2016171768 A1 WO 2016171768A1 US 2016000037 W US2016000037 W US 2016000037W WO 2016171768 A1 WO2016171768 A1 WO 2016171768A1
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- Prior art keywords
- sampler
- polymer
- core
- ptfe
- glass
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5029—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures using swabs
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
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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
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/06—Fluid handling related problems
- B01L2200/0684—Venting, avoiding backpressure, avoid gas bubbles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/14—Process control and prevention of errors
- B01L2200/143—Quality control, feedback systems
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N2001/022—Devices for withdrawing samples sampling for security purposes, e.g. contraband, warfare agents
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N2001/028—Sampling from a surface, swabbing, vaporising
Definitions
- the present application relates generally to unique techniques, systems, methods, and devices for the collection, release, extraction and/or detection of analytes; and more particularly, but not exclusively, relates to the composition, and other features of anaiyte sampling devices; methods of designing, making, and using anaiyte samplers; anaiyte sampler kitting; and related systems.
- sampling device When used for transportation security screening, the sampling device should accommodate articles common to travel, which exhibit wide variation in terms of internal and external surface compositions and shapes desired to be sampled— posing significant challenges particularly to swipe sampler designers.
- IMS Ion Mobility Spectrometer/Spectroscopy
- Muslin cotton swipe material is often used to obtain samples for evaluation by a number of analytical instruments, such as Mass Spectroscopy (MS), thermal desorption Gas Chromatography (TD-GC), X-Ray Fluorescence (XRF), Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and extracted uranium detection techniques.
- MS Mass Spectroscopy
- TD-GC thermal desorption Gas Chromatography
- XRF X-Ray Fluorescence
- ICP-MS Inductively Coupled Plasma Mass Spectrometry
- extracted uranium detection techniques such as Mass Spectroscopy (MS), thermal desorption Gas Chromatography (TD-GC), X-Ray Fluorescence (XRF), Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and extracted uranium detection techniques.
- IMS Inductively Coupled Plasma Mass Spectrometry
- recovery of the analyte from cotton/muslin sampling media can be accomplished by rinsing with solvents; however,
- unprocessed cotton sampling swabs contain non-cellulosic compounds found in the native fibers (i.e. waxes, natural oils and starches) as well as sizing agents and lubricants added for textile processing.
- processes used to remove these impurities in industry include mechanical scouring, chemical scouring agents, and enzymatic methods that can weaken the cellulosic fibers and make them unsuitable for repetitious use.
- natural sampling materials can have variable backgrounds and variable chemical reactivity because of differences in natural growing processes and material sourcing from different geographic areas.
- synthetic sampling materials like certain polymeric coatings, can be produced under controlled conditions— minimizing background influence and variation from other sources using process control techniques.
- Various coatings can also improve uniformity.
- the decomposition of unstable swab material can release contaminants into a detection instrument and therefore interfere with the sample analysis and negatively impact the detection process.
- high specific heat > 1.3 J/g °C
- low thermal conductivity -0.24 W/m-K
- surface chemical heterogeneity of cellulosic fiber materials can adversely impact the release of analytes from the surface— concomitantly limiting detection performance.
- trap composition is stainless steel— apparently without any coating or other surface treatment. While Stainless steel was selected because of good analyte collection properties it was thought to be too abrasive for contact/swipe type applications (See the '513 Patent col. 3, lines 48-63; and col. 5, line 46 - col.6, line 2).
- the '513 Patent also specifies a polyamide fiber felt—apparently without any type of coating or other surface treatment.
- the '513 Patent also specifies a trap having an open weave glass fiber coated by PolyTetraFluoroEthylene (PTFE).
- PTFE PolyTetraFluoroEthylene
- the coating is systematically roughened with an abrasive to cut through it and break/expose glass fibers.
- a scrubbing material results from the broken fibers that acts in substantially the same manner as a brush— believed to be better for analyte collection (See the '513 Patent Fig. 2 and accompanying text).
- coating is sparsely applied so that open spaces remain in the glass fiber web as defined by the open weave. See, for example, the '513 Patent FIGs. 2 and 3 and accompanying text; and col. 2, lines 37-58.
- the '513 Patent fails to specify or consider various salient characteristics of samplers, leaving to the imagination many aspects significant to performance.
- the '513 Patent proposes to improve collection by exposing glass fibers and leaving unclosed holes in the glass fiber web— potentially exposing bordering glass fibers.
- untreated glass fibers have been found to hamper the desired release of certain analyte(s) because they bind too strongly as empirically established in the description set forth hereinafter.
- the '513 Patent is also silent as to desired thermal properties regarding analyte release by thermal desorption, glass type, and the like.
- sampling swipes including more rigid types, are relatively expensive and have poor thermal conductivity— typically having a relatively thick polymer (like PTFE) coating. Such configurations can impede analyte release by thermal desorption or otherwise diminish desired signal level.
- Current sampling techniques also fail to readily accommodate testing for certain nonstandard analytes of interest such as those associated with monitoring nuclear compliance programs and/or verifying compliance with heavy metal safety exposure standards applicable to mining and other industries.
- the sampling material needs to be digested and its chemical signature excluded from the analysis for the target analyte(s)— costing precious time and limiting the ability to obtain consistent results.
- Nanoparticle means any particle having a maximum dimension in the range of about 1 nanometer through about 1 000 nanometers (nm).
- Fabric broadly refers to both nonwoven and woven types.
- Nonwoven types include, but are not limited to: felts, knitting, braiding, plaiting, Chopped Strand Mat (CSM), velour, combinations of these, and any other nonwoven fabric type known to those skilled in the art at the time of the present application filing.
- CSM Chopped Strand Mat
- Woven fabric types encompass both closed weave and open weave varieties and include, but are not limited to: plain weaves, satin weaves (including, but not limited to Harness Satin (HS) weaves and crow(s)foot weave), twilled weaves, heddle weaves, herringbone weaves, houndstooth weaves, Dutch plain weaves, Dutch twilled weaves, reverse Dutch weaves, basket weaves, Leno weaves, mock Leno weaves, gauze weaves, cross weaves, tablet weaves, DURAWEAVEs, hybrid weaves, weft-faced weaves, warp-faced weaves (backstrap weaves), gauze weaves, oxford weaves, pinpoint weaves, poplin weaves, pile weaves, knotted weaves, real weight weaves, combinations of these various weaves, and other weaves as are known to those skilled in the art.
- plain weaves satin weaves (including, but not limited to Harness Satin (HS) weaves and crow(s)foot weave
- warp and weft refer to relative position of the fibers used to create the weave pattern.
- warp fibers refer to lengthwise fibers held in a loom while the weft fibers interlace at right angles with warp fibers.
- the weft fibers typically are carried with a shuttle during loom operation.
- the weft also may be referred to as filling, woof, and pick.
- “Closed weave” means any weave other than an "open weave” including that referenced in the '513 Patent; and/or means a weave that lacks a pre-defined pattern of one or more openings through the fabric, where each such opening is wider than any fiber element bordering the same and the weave is arranged so two adjacent fiber elements are held apart from each other to provide opening formation under nominal conditions.
- fiber glass or “fiberglass” sometimes refers to Glass-Reinforced Plastic (GRP), which often includes a pultrusion of roves or other configuration of a glass in combination with an amount of organic polymer, binder, and/or resin effective to prepare a corresponding composite combination thereof.
- GRP Glass-Reinforced Plastic
- fiber glass/fiberglass is also sometimes used to refer to glass fibers without organic
- glass fiber is more commonly accepted to refer to fibers of glass absent/before combination with organic polymer/binder/resin constituent(s) (if ever to be so combined); and such terminology shall be used to mean the same. If the term "fiber glass” or “fiberglass” is used herein, it shall have the same meaning as “glass fiber” set forth above. Any reference to an organic polymer, binder, and/or resin in combination with “glass fiber” and/or “fiberglass/fiber glass” is expressly stated herein and/or by utilizing the "glass-reinforced plastic" (GRP) terminology.
- GRP glass-reinforced plastic
- High Strength Glass means any non-crystalline solid composition (equivalently designated “glass” or “amorphous” composition) conforming to the following “HSG formula”: 50%wt to 100%wt of any combination of aluminosilicate, aluminum silicate, and/or alumina/silica constituents (such as, for example, A1 2 0 3 »Si0 2 ,), 0%wt to 25%wt of any combination of calcium oxide (CaO) and/or magnesium oxide (MgO), and 0%wt to 5%wt Boron oxide (such as, for example, B 2 0 3 ), with any balance consisting of other constituents and/or any minor impurities.
- HSG High Strength Glass
- This definition includes any glass complying with the HSG formula before or after any processing, including, but not limited to: furnace heating, floating on molten material to form sheet glass, ion implantation, molten salt bath exposure, annealing, coating, or the like.
- This definition also means any R-glass and/or S-glass as these terms are commonly understood by those of ordinary skill in the art at the time of filing of the present application-even if not conforming to the HSG formula.
- “Flexural modulus” is a measure of stiffness/rigidity/resistance to bending, and is defined as the result (in units of pressure) from testing in accordance with American Society for Testing and Materials (ASTM) Standard D790 of any released version in effect on or before the filing of the present application.
- the flexural modulus is sometimes called the "bending modulus” or the “elastic modulus;” however, these last two terms tend to be applied
- Flexural modulus corresponds to an intrinsic material property subject to certain constraints/limitations—being the ratio of stress to strain in flexural deformation as obtained by a three-point test per ASTM D790.
- This test applies force to a beam of the material under test as it rests on two supports. The test force is applied on the opposite side from the support contacts and at is positioned therebetween.
- the test beam has a specified span (length) to depth ratio and is believed to reduce or eliminate the influence of extrinsic factors (such as shapes that might impart different degrees of stiffness) during otherwise uniform the test results.
- the beam shall be prepared so that such direction coincides with the beam span— applying the test force approximately perpendicular to and across these fibers.
- the fibers extend approximately the same distance in multiple directions (as with a generally planar fabric), any of these directions may be oriented to coincide with the beam span for testing purposes.
- Flexural modulus is similar to Young's modulus in some respects and the two sometimes have values that are well within an order of magnitude or for the same material (both in units of pressure); however, flexural modulus has become a common industry alternative to Young's modulus for synthetic organic polymers and composites because these types of materials tend to have certain properties for which Young's modulus may not prove as readily obtainable, informative, or applicable.
- Metal means any elemental metal, with or without any minor impurities therein, and any metal alloy (defined below).
- Metalloid refers to any of the following elements: aluminum, antimony, arsenic, astatine, boron, carbon (as further defined hereinafter), germanium, polonium, selenium, silicon, tellurium, or combination thereof, with or without minor impurities therein.
- a carbon metalloid includes any allotrope of carbon, but excludes any carbon atom to the extent it is an atomic constituent in an organic compound recognized as such in any International Union of Pure and Applied Chemistry (IUPAC) reference to organic nomenclature in effect on or before the filing of the present application. To dispel any doubt, aluminum is considered both a metal and a metalloid for the purposes of the present application.
- Metal alloy means a compound comprised of a combination of two or more different metals, a combination of at least one metal and at least one metalloid, or any combination thereof, either with or without minor impurities.
- Inorganic metallic material means: (1) any inorganic substance with at least a majority of the following properties: malleability; ductility; electrical conductivity; thermal conductivity; ability to melt and/or fuse two or more portions of such substance together; shiny appearance/metallic luster to the extent not covered with a coating, compound, oxide, or other constituent altering visual appearance of the same; and/or (2) any inorganic substance with one or more metals and/or metalloids alone or as an atomic constituent of a salt, compound, molecule, complex, adduct, composite, anion, cation, or other combination with a nonmetal and/or a non-metalloid atomic constituent.
- inorganic metallic material includes, but is not limited to: any metal, metalloid, or metal oxide, and any glass, ceramic, or glass- ceramic having a metal or metalloid atomic constituent. To dispel any doubt, inorganic metallic material does not include any organometallic substance.
- Heavy metal means certain metals and metalloids that have the potential to seriously impact the environment (including flora and fauna, among other things) and/or the safety of humans including: arsenic, cadmium, mercury, lead, chromium, copper, zinc, nickel, selenium, silver, antimony, thallium, beryllium, and cobalt in any elemental form with or without minor impurities; and/or any combination or metal alloy thereof.
- Contraband or undesirable substance means any potential nefarious, illegal, dangerous, or threat agent listed in the '910 Patent (in its text and/or accompanying figures), and/or any substance that belongs in one or more of the following categories: (a) explosives; (b) illegally trafficked drugs; (c) chemical or biological warfare agents; (d) nerve agents; (e) pesticides; (f) pharmaceutical process contaminants; (g) environmental toxins; (h) heavy metals; (i) actinides; (j) radioisotopes of any element with the potential to seriously impact the environment (including flora and fauna, among other things) and/or human safety; and/or (k) a salt, compound, molecule, complex, metal alloy, combination, analogue, homologue, isomer, equivalent, adduct, derivative, hydrate, composite, and/or simulant of any substance listed in the '910 Patent (in accompanying text and/or figures), and/or belonging to any of categories (a)-(j).
- Ammonium broadly means any substance that includes: (a) an ammonium cation (referring to the general structure H4 + , for example); (b) like-charged amine including any such amine with primary, secondary, tertiary, or quaternary substituents; and/or (c) any salt, combination, compound, molecule, complex, equivalent, analogue, homologue, adduct, and/or, composite of any of the substances of the foregoing listings (a) and (b).
- any reference to the chemical formula NH 4 + for the cation alone or as part of another formula, such as (NH 4 ) 2 C0 3 shall be limited to the meaning of such formula and equivalents thereto as understood by those of ordinary skill in the art at the time of filing of the present application.
- Onium broadly means any substance comprising: (a) ammonium; (b) a cation formed by protonation (hydron addition) of a mononuclear parent hydride of: the nitrogen family (periodic table group 15), the oxygen family (periodic table group 16), or the halogen family (periodic table group 17); (c) derivatives formed by substitution of any cation of the above-listed parent substances of (a) & (b) by univalent groups, (the number of substituted hydrogen may be indicated by the adjectives primary, secondary, tertiary or quaternary); (d) derivatives formed by substitution of any cation of the above-listed parent substances of (a)-(c) by groups having at least two free valencies on the same atom; (e) independent of the meanings conveyed under the foregoing listings (a)-(d), onium cations shall also encompass any meaning conveyed by the onium nomenclature that follows in this listing, where such nomenclature has the meaning
- nitrenium refers to NH 2 + or more generally R 2 N + , for example
- nitronium refer to N0 2 + formed by protonation of nitric acid or removal of an electron from the nitrogen dioxide molecule, for example)
- nitrosonium refers to NO + and organic derivatives thereof, for example
- iminium refers to a protonated or substituted im
- Carbonate broadly means: (a) any salt or ester of carbonic acid or carbamic acid; (b) a carbonate anion (C03 2 ⁇ ), bicarbonate anion (HC0 3 ⁇ ), polyvalent percarbonate anion species including both a carbonate anion moiety and an oxide anion moiety, divalent
- peroxocarbonate anion CO4 2-
- divalent peroxodicarbonate anion C2O6 2-
- monovalent hydrogenperoxocarbonate anion H-0-0-C0 2 ⁇
- carbamate anion CH 2 N0 2 ⁇
- any reference to the chemical formula C0 3 2_ for the anion alone or as part of another formula, such as (NH 4 ) 2 C0 3 shall be limited to the meaning of such formula and equivalents thereto as understood by those of ordinary skill in the art at the time of filing of the present application.
- Thickness refers to the smallest dimension of an object unless expressly indicated to the contrary herein.
- thickness refers to the distance between opposing sides of a generally planar sampler, where such opposing sides have a length and width much greater than such distance (thickness). To the extent thickness is quantitatively specified herein, it is determined as the average of ten (10) measurements taken at ten (10) different locations along the object using a measurement device having a rated accuracy of +/- 0.01 millimeter (mm) or better.
- 'thin means at least a portion of an object under measurement has a thickness of less than or equal to 0.3mm determined in accordance with such measurements.
- calcine generally refers to heating a subject material in an enclosure at a selected temperature to remove a volatile fraction, desiccate, reduce, oxidize, and/or otherwise selectively change the subject material, and may be performed with or without control of air, oxygen, or other gas content in the enclosure in its broader form.
- heating temperature may be selected above the melting point of a polymer constituent (but not exceeding its decomposition temperature) while remaining below the melting point of a glass fiber fabric constituent to which the polymer is applied.
- the selected temperature completely or partially melts the polymer constituent, changing its morphology to promote the formation of longer polymeric molecules or "chains" and/or interconnection between the same under certain circumstances, while the glass fabric is only negligibly impacted if at all (but note polymer coverage of the fabric and the polymer-glass interface may be subject to change by in this calcination example).
- calcining may at least partially remove any volatile fraction present after certain liquid-based application of the polymer to the fabric (even with pre- calcination evaporation), and/or desiccate all of the constituents as a function of constituent composition, heating temperature selected, and/or heating duration.
- roasting is generally performed at a considerably higher temperature than calcination for a given material-where roasting typically heats an ore to promote one or more gas-solid reactions that improve metal component purity of/from the ore.
- sampler stiffness/rigidity can be controlled within certain limits through the manner of application, concentration, and composition of polymer(s) applied to a sampler fiber core and the thermal treatment of the polymer(s) after initial deposition on the sampler fiber core. Additionally or alternatively, in other unique embodiments certain thermal characteristics/properties of a sampler are provided that are conducive to thermal release of sampler-collected analyte(s) for analysis with existing instrumentation and/or facilitate at least partial thermal cleaning of such sampler with the same.
- a sampler with low surface energy /hydrophobic properties enables more effective release of certain sampler-collected analyte(s). Yet other unique embodiments have been discovered conducive to extraction of heavy metals and actinides (especially uranium).
- a fabric sampler core is utilized with controlled thermal sintering, particulate addition, minimal polymer concentration, and/or chemical core treatment to enhance particle collection efficiency, polymer
- sampler thermal conductivity deposition/application, sampler thermal conductivity, and/or the release of sampler analyte(s).
- a sampler in another embodiment, includes a fabric core comprised of one or more of: HSG, polymeric thermoplastic, polymeric thermoset, metal, metalloid, inorganic oxide, ceramic, and/or glass-ceramic; and a polymer applied to the fabric core that includes at least one of the group of: polymeric organofluorine, polyamide, polyimide, PolyBenzImidazole (PBI), PolyDiMethylSiloxane (PDMS), sulfonated tetrafluoroethylene (PFSA), and Poly(2,6-diPhenyl- p-Phenylene Oxide) (PPPO).
- HSG polymeric thermoplastic
- polymeric thermoset metal, metalloid, inorganic oxide, ceramic, and/or glass-ceramic
- a polymer applied to the fabric core that includes at least one of the group of: polymeric organofluorine, polyamide, polyimide, PolyBenzImidazole (PBI), PolyDiMethylSiloxane (
- the fabric core is comprised of one or more of: HSG, metal, metalloid, metal oxide, ceramic, and glass-ceramic.
- the fabric core is comprised of one or more of: HSG, carbon, metal, metal oxide, ceramic, and glass-ceramic.
- the fabric core includes a metal oxide coated glass (such glass may be HSG, but is not limited to such type) and/or metal oxide coated metal as further described elsewhere herein.
- the fabric core is comprised of HSG.
- the fabric core is comprised of S-glass in an even more particular form.
- the composition of the polymer applied to any of the previously described fabric core forms may be selected from any of the successively more specific listings (a)-(e) as follows: (a) perfluorocarbon, peril uoroether, Ethylene-TetraFluoroEthylene copolymer (ETFE), Ethylene ChloroTriFluoroEthylene copolymer (ECTFE),
- TSV poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) copolymer
- PVdF PolyVinylidene diFluoride
- FEP Fluorinated Ethylene-propylene
- PCTFE PolyChloroTriFluoroEthylene
- PVF Polyvinyl Fluoride
- PTRFE PolyTRiFluoroEthylene
- poly(vinylidene-tetrafluoroethylene) copolymer poly(vinylidene-trifluroethylene) copolymer, PPBI, PDMS, and PPPO
- PFA PerFluoroAlkoxy
- ETFE PerFluoroAlkoxy
- PVdF PerFluoroAlkoxy
- pefluoroether is inclusive of PFA
- Yet another embodiment is directed to a method of making a contraband or undesirable substance sampler, comprising: preparing the sampler with a fabric core formed of fibers including one or more of: glass, metalloid, metal, inorganic oxide, ceramic, and glass- ceramic; heating the fabric core to a first predefined temperature for a first predefined duration; applying a polymer to the fabric core to further prepare the sampler, the polymer being one or more of: polymeric organofluorine, polyamide, polyimide, PBI, PFSA, PDMS, and PPPO; controlling stiffness of the contraband or undesirable substance sampler by: selecting a predefined amount of the polymer for application to the fabric core, and regulating a heat treatment of the sampler at a second predefined temperature for a second predefined duration; and after the heat treatment, providing the sampler for application with detection
- Certain more specific forms include: applying the polymer by depositing it on the fabric core from a liquid particulate dispersion of such polymer, at least partially filling the fabric core with nanoparticles selected to provide a desired thermal performance before applying the polymer, functionalizing at least a portion of the surface of the fabric core with silane ligands before applying the polymer, and/or applying a further polymer layer on the polymer applied to the fabric core, where the further polymer layer has a different composition than the polymer applied to the fabric core in at least one particular embodiment.
- the fabric core composition may be selected from any of the successively more specific listings (a)- (c): (a) HSG, metal, metalloid, inorganic oxide, ceramic, and glass-ceramic; (b) HSG, metalloid, metal, and metal oxide; and (c) HSG, carbon, metal, and metal oxide.
- the fabric core includes a metal oxide coated glass (such glass may be HSG or a non-HSG type) and/or metal oxide coated metal.
- the fabric core is comprised of HSG.
- the fabric core is comprised of S-glass.
- the nanoparticle composition may be selected from any of the successively more specific listings (a)-(e): (a) inorganic metallic material; (b) one or more of metal, metal oxide, carbon, ceramic, and glass-ceramic; (c) one or more of metal, metal oxide, and carbon; (d) one or both of a nanotube or graphene allotrope of carbon; and (e) alumina.
- Still a further embodiment detects a contraband or undesirable substance, comprising: collecting the contraband or undesirable substance with a sampler, including a woven fabric with a closed weave and a first polymer layer deposited thereon to at least partially cover the fabric, the fabric having a thickness of less than or equal to about 0.3mm and being comprised of one or more of: glass, metalloid, metal, inorganic oxide, ceramic, and glass- ceramic, and the first polymer layer being comprised of one or more of: polymeric
- Other forms include, preparing the sampler by at least partially filling the fabric with nanoparticles selected to provide desired thermal performance; applying a second polymer layer on the first polymer layer, which has a different composition than the first polymer layer in certain forms; and/or functionalizing at least a portion of the surface of the fabric by silanizing at least a portion of the fabric and the nanoparticles (if nanoparticles are present).
- samplers have a thickness of less than or equal to 0.5 mm inclusive of all polymer layers applied to the fabric, and/or the sampler has a flexural modulus selected from among the following ranges (a)-(c): (a) from about 0.75 GPa through about 10 GPa, (b) from about 1 GPa through about 8 GPa, or (c) from about 2 GPa through about 6 GPa.
- Another embodiment is directed to a kit to test for presence of one or more contraband or undesirable substances, comprising: several samplers each structured to collect the one or more contraband or undesirable substances and release the one or more contraband or undesirable substances for analysis, the samplers each including a woven fabric and a polymer applied thereto, the fabric having a thickness of less than or equal to about 0.3mm and being comprised of one or more of: HSG, carbon, metal, ceramic, glass-ceramic, and metal oxide, and the polymer being comprised of one or more of: polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, and PPPO; and a container with at least one or more of the samplers enclosed therein.
- a further embodiment is directed to substance detection that includes: collecting the substance with a three-dimensional collection framework, the framework including a support structure, the support structure comprising one or more of: polymeric thermoplastic, polymeric thermoset, metal, metalloid, inorganic oxide, ceramic, and glass-ceramic; the framework including several recesses each defining an external opening facing away from the framework, a polymer applied to at least partially coat the support structure, the polymer being comprised of one or more of: polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, and PPPO; transferring the substance from the collection framework to detection instrumentation; and detecting the substance with the instrumentation.
- FIG. 1 depicts a partially diagrammatic view showing a sampler-based analyte processing system of one embodiment of the present application.
- FIG. 2 depicts a partially diagrammatic view illustrating a sampler kit that can be used with the system of FIG. 1.
- FIG. 3 depicts a partially diagrammatic view showing a handheld wand to receive and operate with a sampler of the type shown in FIG. 1 or FIG. 2.
- FIG. 4 is a flowchart representing one process for making a sampler according to the present application.
- FIGs. 5 & 5A-5D schematically represent a comparison of different weave patterns with FIGs. 5A-5D in partial view form.
- FIG. 5 schematically depicts all the partial views of FIGs. 5A-5D to indicate relative orientation among them.
- FIG. 5 A provides a partial, schematic view of a plain weave in the upper right corner and three different Harness Satin (HS) weaves: 4 HS weave (or “crowfoot” weave) in the upper left corner, a 5 HS weave in the lower right corner, and an 8 HS weave in the lower left corner;
- FIG. 5B provides a partial, schematic view of Five-Heddle (FHD) weave (upper), Herringbone weave (middle), and 3/3 twilled weave (lower);
- FHD Five-Heddle
- FIG. 5C provides a partial, schematic view of 2/2 twilled weave (upper), Dutch plain weave (middle), and Dutch twilled weave (lower); and FIG. 5D provides a partial, schematic view of Leno weave (upper) (more specifically a form of gauze weave), mock Leno weave (middle), and basket (panama) weave (lower).
- the weaves are depicted in FIGs. 5A-5D with disproportionate, exaggerated spacing between warp/weft constituents to enhance clarity.
- the partial views of FIGs. 5 A, 5B, and 5D each depict a planar weave swatch and at least one representation of a sectional/edge perpendicular to the swatch plane.
- FIG. 5C is a view of weave patterns in perspective that conveys the same information as the swatch and sectional/edge representations of FIGs. 5 A, 5B, and 5D.
- FIG. 6 is a partially diagrammatic, cross-sectional view of the sampler of FIG. 1 that corresponds to the section line 6— 6 of FIG. 1, it further includes a partial cutaway that stairsteps down from the top toward the left side.
- FIG. 7 is a schematic, perspective view of an alternative sampler depicting phenyl terminal groups in a functionalization sub-layer of the block-represented core fabric that is covered by multiple polymer layers.
- FIG. 8 is a flowchart representing one process for using a sampler according to the present application.
- FIG. 9 is a comparative graph of magnitude versus time of three differently- sourced samplers each in response to a 10 nanogram (ng) TNT sample.
- the "X" data point plot represents the response of a sampler embodiment of the present application— it has the highest peak
- the "hollow triangle” ( ⁇ ) data point plot represents the response of a SAFRAN MORPHO brand of sampler with an intermediate peak
- the "filled diamond” ( ⁇ ) data point plot represents the response of a DSA DETECTION brand of sampler with the lowest peak.
- FIG. 10 is a comparative graph of magnitude versus time responses of four PTFE- coated samplers with different cores each to a lOng TNT sample.
- the "filled diamond” ( ⁇ ) data point plot represents the response of a stainless steel core with the highest peak
- the "filled circle” ( ⁇ ) data point plot represents the response of a thin S-glass core with the second highest peak
- the "filled square” ( ⁇ ) data point plot represents the response of a thick S-glass core with the third highest peak
- the "filled triangle” ( A) data point plot represents the response of thick E-glass-it is the least responsive.
- FIG. 1 1 is a comparative graph of magnitude versus time responses of two samplers with different fabric core weaves to a lOng TNT sample.
- the "X" data point plot represents the response of a 4 HS weave pattern of thin E-glass with the highest peak
- the "hollow triangle” ( ⁇ ) data point plot represents the response of an 8 HS weave pattern of S-glass, which peaks at a slightly lower value.
- FIG. 1 1 includes inset computer-generated images of the 4 HS and 8 HS fabric weaves with like labeling.
- FIG. 12 is a comparative graph illustrating magnitude versus time responses of four samplers with different heat treatments each to a 1 Ong TNT sample.
- the "hollow triangle” ( ⁇ ) data point plot represents the response to about a 450 °C heat treatment, with the second highest peak
- the "X” data point plot represents the response to about a 400 °C heat treatment, with the highest peak
- the "filled triangle” ( A) data point plot represents the response to about a 325 °C heat treatment, with the third highest peak
- the symbol of an "X" with a vertical line intersecting the "X" cross-point provides a data point plot of the response to about a 150 °C heat treatment, with the lowest peak.
- FIG. 13 is a computer-generated Scanning Electron Microscope (SEM) image of a
- FIG. 14 is a computer-generated SEM image of a PTFE-coated silicon wafer after heat treatment at about 150 °C for comparison to FIG. 13.
- FIG. 15 is a computer-generated SEM image of a PTFE-coated fabric sampler with an S-type fiberglass core after heat treatment at about 325 °C.
- FIG. 16 is a computer- generated SEM image of a PTFE-coated silicon wafer after heat treatment at about 325 °C for comparison to FIG. 15.
- FIG. 17 is a computer-generated SEM image of a PTFE-coated fabric sampler with an S-type fiberglass core after heat treatment at about 400 °C.
- FIG. 18 is a computer- generated SEM image of a PTFE-coated silicon wafer after heat treatment at about 400 °C for comparison to FIG. 17.
- FIG. 19 is a computer-generated SEM image of a PTFE-coated fabric sampler with an S-type fiberglass core after heat treatment at about 450 °C.
- FIG. 20 is a computer- generated SEM image of a PTFE-coated silicon wafer after heat treatment at about 450 °C for comparison to FIG. 19.
- FIG. 21 is a comparative graph of magnitude versus time responses of each of three different PTFE-coated, S-type fiberglass core samplers, with and without phenyl surface functional ization, to a lOng TNT sample.
- the "X" data point plot represents the response of a Phenyl-PTFE sampler heat-treated at about 150 °C— it has the highest peak
- the "hollow triangle" ( ⁇ ) data point plot represents the response of a Phenyl-PTFE sampler heat-treated at about 400 °C— it has an intermediate peak
- the "hollow diamond” (0) data point plot represents the response of a PTFE sampler (no phenyl or other functional ization type) heat-treated at about 400 °C— it has the lowest peak.
- FIG. 22 is a diagrammatic, perspective view of a framework structure outlining the shape of a truncated octahedron and corresponding to an introductory, conceptual constituent of a substance collection framework of a 3-D (three-dimensional) sampler further shown in FIGs. 24 & 25.
- FIG. 23 is a diagrammatic, perspective view of a solid geometry representation of a bitruncated cubic honeycomb form of tessellation.
- FIG. 23 serves as a conceptual bridge from the framework structure of FIG. 22 to the collection framework of FIGs. 24 & 25.
- the bitruncated cubic honeycomb of FIG. 23 may be described as an arrangement of a number of coincident, solid truncated octahedral blocks. Each of these blocks correspond to the truncated octahedral shape outlined by the framework structure shown in FIG. 22.
- truncated octahedral blocks are geometrically coincident and arranged so they merge along coincident pairs of edges and vertices where brought together to correspond to the honeycomb.
- this figure is provided with grayscale shading to enhance clarity of three- dimensional aspects thereof.
- FIG. 24 is a diagrammatic, perspective view of an openwork, 3-D, lattice/cagelike substance collection sampler with a collection framework that corresponds to an open form of a bitruncated cubic honeycomb arrangement conceptually introduced in FIGs. 22 & 23.
- This FIG. 24 arrangement is of the same general type shown in FIG. 23; however, the number of coincident truncated octahedral-shaped constituents and the overall shape differ. As is common in the art, this figure is provided with grayscale shading to enhance clarity of three-dimensional aspects thereof.
- FIG. 25 is a diagrammatic, perspective view of a cross-sectioned portion of the three-dimensional sampler framework shown in FIG. 2— the cross-section being taken along a sectional plane approximately parallel to the view plane of FIG. 24. As is common in the art, this figure is provided with grayscale shading to enhance clarity of three-dimensional aspects thereof.
- FIG. 26 is a comparative graph of percent (%) extraction efficiency versus time for three different uranium compounds: uranium oxide ( ⁇ 3 0 8 ), uranyl fluoride (U0 2 F 2 ), and uranyl nitrate (U0 2 (N0 3 ) 2 )-each of these compounds being extracted from a respective PTFE- coated sampler with 6.0 molar (M) nitric acid aqueous solution.
- uranium oxide ⁇ 3 0 8
- U0 2 F 2 uranyl fluoride
- U0 2 (N0 3 ) 2 uranyl nitrate
- the uniform dashed/hidden line style " " represents a trend line plot for the response of U 3 0 8
- the phantom/cutting plane line style " " represents a trend line plot for the response of U0 2 F 2
- the chain/center line style " " represents a trend line plot for the response of U0 2 (N0 3 ) 2 .
- FIG. 27 is a comparative graph of percent (%) extraction efficiency versus time for the three different uranium compounds of FIG. 26-each of these compounds being extracted from a respective PTFE-coated sampler with a 1.0 M sodium carbonate aqueous solution. The same legend applies as described for FIG. 26.
- FIG. 28 is a comparative graph of percent (%) extraction efficiency versus time for the three different uranium compounds of FIG. 26-each of these compounds being extracted from a respective PTFE-coated sampler with a mixture of 1 .0 M ammonium carbonate and 1.0 M hydrogen peroxide in aqueous solution. The same legend applies as described for FIG. 26. DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS
- samplers include a fabric substrate with a selected thickness to which a polymer is applied to provide a selected degree of stiffness/rigidity.
- the sampler stiffness can be expressed in terms of flexural modulus, among other things, which can be controlled through the amount of polymer applied to the fabric substrate and heat treatment thereof.
- a sampler core support structure is comprised of one or more of:
- a sampler embodiment with a woven fiber core has a closed weave, thermally conductive particles added to the core; multiple polymer layers formed on the core, and/or at least one layer of the polymer applied is comprised of one or more of: polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, and PPPO.
- FIG. 1 depicts another embodiment of the present application in the form of analyte processing system 20.
- System 20 is of a type that may be used in an airport, train station, shipping port, or the like to perform security screening for contraband or undesirable substances.
- System 20 includes analyte trace detection instrumentation 30, test article 50, and analyte collection sampler 100.
- Sampler 100 is of a thin, planar configuration.
- Instrumentation 30 includes a form of thermal desorption Ion Mobility Spectroscopy/Spectrometer (IMS) detector 32, and the test article 50 is further designated as being of a suitcase 52 form.
- Test article 50 includes outer surface 54 that may be smooth or rough to either extent as might be expected for a standard suitcase 52. However, in other embodiments, a different type of test article 50 may include one or more different surface qualities.
- IMS thermal desorption Ion Mobility Spectroscopy/Spectrometer
- IMS detector 32 includes: operator display 34 to display relevant information regarding its operation; operator input control 36 in the form of a keyboard, touchscreen, mouselike pointers, voice-activation interface, touch keys, membrane switches, press buttons, sliders, toggle/rotary switches, dials, a combination of these, or the like; and integral printer 38 with a print-out sheet 39 generated thereby.
- print-outs 39 from printer 38 can be used to inform the operator of results of analysis performed with instrumentation 30; and instrumentation 30 may further be supplemented by an aural-output device to provide warnings, instructions, and the like.
- Print-out 39 further provides a written record of the testing performed with system 20.
- IMS detector 32 further includes sampler slot 40, in which sampler 100 can be inserted for the release and transfer of collected analyte(s) by thermal desorption into IMS detector 32 for analysis as further described hereinafter.
- IMS detector 32 embodiments are of any type suitable to sufficiency process samples, including, for example: those suitable models of IMS-based equipment from SARFAN MORPHO, SMITHS DETECTION, or another supplier; and instrumentation combinations of IMS with other detector types, such as High-Performance Liquid
- sampler 100 is utilized with non-IMS detection equipment with appropriate alterations (if any) to provide for proper analyte transfer/release and processing.
- IMS include: Thermal Desorption Gas Chromatographs (TD-GCs) and other GC types; liquid chromatography (LC) instrumentation; X- Ray Fluorescence (XRF); Inductively Coupled Plasma Mass Spectrometry (ICP-MS); gamma, beta, and alpha spectrometers and counting devices; Mass Spectrometry (MS) instrumentation; and combinations of these various instruments including, e.g., Thermal Desorption Gas Chromatographs (TD-GCs) and other GC types; liquid chromatography (LC) instrumentation; X- Ray Fluorescence (XRF); Inductively Coupled Plasma Mass Spectrometry (ICP-MS); gamma, beta, and alpha spectrometers and counting devices; Mass Spectrometry (MS) instrumentation; and combinations of these various instruments including, e.g., Thermal Desorption Gas Chr
- instrumentation 30 may employ IMS or other equipment that receives sampler-released analyte(s) in a manner other than thermal desorption—such as, analyte(s) released by sampler rinsing and/or other application of one or more agents from which a detector sample is prepared.
- Any sample preparing rinse(s) and/or agent(s) can be of any type suitable for the sampler type, substance(s) being detected, and sample composition requirements of the instrumentation used to detect such substance(s).
- an aqueous solution is used to rinse the sampler and prepare the sample, and may be acidic or basic to a degree desired to facilitate sample preparation.
- a mixture of an oxidizer (like hydrogen peroxide) and one or both of: onium and carbonate (like ammonium carbonate) in aqueous solution is utilized.
- an oxidizer like hydrogen peroxide
- onium and carbonate like ammonium carbonate
- one or more organic solvents may be used to prepare the sample.
- some form of agitation may be employed to facilitate analyte
- a Barringer lONSCAN 400A IMS (SMITHS DETECTION) was utilized in the following experimental examples 1 -10, and is among the embodiments of IMS detector 32.
- Sampler 100 is shown in a wiping/swiping position as applied to surface 54 of suitcase 52 with an arrow indicating direction of the wipe/swipe motion to the right.
- the width W of sampler 100 along its longitude is indicated by double-headed arrow 102 and the length L of sampler 100 is indicated by double-headed arrow 104.
- FIG. 1 includes section line 6— 6 through sampler 100, with a corresponding cross-sectional view of sampler 100 set forth in FIG. 6 to be discussed further hereinafter.
- FIG. 2 illustrates kit 200 for use with system 20; where like reference numerals refer to like features previously described. Kit 200 includes consumable materials that may be desired to perform testing with detector 32.
- kit 200 includes an outer container and/or packaging 201 that encloses various kit items 202.
- kit 200 instructions/directions may be provided on a surface of packaging 201 or on an inner surface, or separate sheet or card provided with kit 200 that may be self-contained and/or may refer to an online, computer network accessible website as an additional or alternative source for some or all of any remaining instruction, direction, and/or any update thereto.
- kit 200 includes multiple samplers 100 packaged together in container/package 101 that standing alone is also a form of kit.
- Container/package 101 includes related reference, instruction, and/or direction 204 regarding use, warnings, or the like printed on its surface.
- Samplers 100 may further include identifying marking, reference, instruction, and/or direction description directly thereon. Alternatively or additionally, some or the remainder of such information may be separately sourced from a sheet/card, packaging/container surface, website, or the like as previously described in connection with kit 200 and packaging 201.
- Package 1 1 1 includes multiple calibration strips 1 10 with approximately the same form factor as samplers 100.
- Package 1 1 1 includes related reference, marking, and/or directions 1 12 specific to calibrations strips 1 10 regarding use, warnings, or the like.
- Strips 110 include a predefined type/quantity of substance to calibrate detector 32.
- Package 121 also includes multiple verification strips 120 with approximately the same form factor as samplers 100.
- Package 121 includes related reference, marking, and directions 122 specific to verification strips 120 regarding use, warnings, or the like printed on its surface.
- Strips 120 include a predefined type/quantity of substance to verify proper calibration of detector 32 and can include identifying marking and direction description pertinent to the same.
- Samplers 100, strips 1 10, and/or strips 120 packaged in corresponding containers 101 , 1 1 1, 121 comprise a subset of detector 32 interface consumables, and each constitutes a kit individually, as do two or more provided collectively.
- Strips 1 10, 120 and/or package/container 1 1 1, 121 may additionally or alternatively provide separate sourcing of some or the remainder of instruction/direction information as previously described in connection with kit 200, samplers 100 and corresponding package and/or container.
- Kit 200 also includes a subset of IMS consumables 220 directed to replacement chemicals and hardware for detector 32.
- IMS consumables 220 include dopant 222 with directions 223 regarding identity, use, warnings, or the like. In other embodiments, multiple types of dopant may be included or obtained by kit or otherwise.
- IMS consumables 220 further include IMS membranes 224 with directions 225 regarding identity, use, warnings, or the like; and IMS filters 226 with directions 227 regarding identity, use, warnings, or the like.
- IMS consumables 220 may include specialized tools, O-rings, spare parts kits, a packet of sample collection envelopes,
- Kit 200 further includes operator gloves 232 contained in packaging 233.
- Packaging 233 includes related directions 260 regarding identity, use, warnings, or the like. Gloves 232 are worn by operators to reduce the chance of
- Kit 200 also includes a package 235 of finger cots 234 that may be used as an alternative to gloves 232.
- Package 235 includes related directions 270 regarding identity, use, warnings, or the like.
- Kit 200 also includes cleaning devices 236 in the form of a roll or other arrangement of multiple alcohol-soaked wipes to remove dirt, debris, and other detritus from equipment and desired /surfaces likely to contaminate the sampling process. In other embodiments, different cleaning items may be alternatively or additionally included, such as cleaning swabs, separately packaged wipes, cleaning cloths, and/or containers of cleaning solvent.
- Kit 200 also includes a can of pressurized air 238 to assist with keeping various surfaces clean. Another embodiment includes a powered air delivery device.
- gloves 232 or finger cots 234 may be configured to incorporate some or all of the materials of sampler 100 (as described hereinafter). Accordingly, in a further embodiment, it is envisioned that gloves 232 and/or finger cots 234 (or a portion of either) each constitute a form of sampler (including some or all of sampler 100 features), that can be wiped on the test article 50 to collect one or more analytes directly and then release the collected analyte(s) for transfer to detector 32— it being appreciated that detector 32 of system 20 likewise would be configured to accommodate glove 232 and/or finger cots 234 functioning as samplers.
- gloves 232 or cots 234 may include detachable/re-attachable sample-configured pieces (i.e. VELCO, reusable adhesives, or the like).
- the sampler 100 features incorporable with gloves 232 or cots 234 may include one or more of those previously or subsequently described herein.
- kit 200 may be changed to match the particular consumables, tools, and the like associated with the same.
- FIG. 3 depicts mobile sampling wand 300; where like reference numerals refer to like features previously described.
- Wand 300 may be provided in a kit, as an accessory for detector 32, an option, or separately— to name just a few examples.
- Wand 300 includes body 301 that is largely hollow.
- Body 301 is defined by shell 302 that includes surface 303.
- Body 301 includes proximal end portion 301a opposite distal end portion 301b.
- Proximal end portion 301b includes operator handle 310, and distal end portion 301b defines vacuum intake opening 304.
- Within shell 302 is a suction-producing device 320.
- Device 320 can be powered by an electrochemical cell, a battery of such cells, or a fuel cell— to name a few examples.
- wand 300 includes a power cable of suitable length for mobile wand 300 operation—such cable receives electricity from a utility-sourced power outlet to power wand 300.
- Device 320 is operatively connected to operator control 330.
- Operator control 330 turns suction device 320 off and on, and optionally adjusts suction speed, reverses air flow direction, and the like.
- Sampler 100 is mounted in sample chamber 340 defined by body 301 that is in fluid communication with opening 304, fluid pathways 350, and vents 306.
- the suction device 320 is turned on via control 330 to generate suction through opening 304 to move particles, volatiles, and/or other forms of analyte(s) of interest entrained in the resulting airflow for collection by sampler 100 in chamber 340. Airflow continues from opening
- sampler 100 is configured as an air filtration device for such purposes.
- Analyte(s) collected with sampler 100 may be transferred to detector 32 by removing sampler 100 from wand 300 and inserting sampler 100 in slot 40 for analyte release.
- collected analyte(s) may be transferred by reversing the airflow through wand 300 so that pressurized air is directed through and/or over sampler 100 in chamber 240 and out of opening 304— carrying the collected analyte(s).
- opening 304 is connected/interfaced to detector 32 to receive the sample by adaptive housing, hosing, or a similar mechanism.
- the speed of the air may be increased to assist with release from sampler 100.
- wand 300 includes a heating device (not shown) subject to control 330 to assist with the release of analyte(s) during reversed air flow.
- FIG. 4 is a flowchart describing one nonlimiting process 400 for making sampler
- Process 400 begins with sampler 100 formation starting stage 402. From stage 402, process 400 continues with operation 404.
- a sampler core/substrate material is selected and provided.
- the sampler substrate may take the form of one or more pieces comprised of a synthetic and/or natural substance.
- sampler ease of use, relative cost, and material safety any sampler constraints imposed by detection instrumentation requirements; sampler and core affinity for target analyte collection and retention, and ease of release/transfer of the same to detection instrumentation; existence of any core filling, functionalization, and/or polymer coating, and to the extent in existence, the composition and manner of application of the same; desired sampler and core surface homogeneity, smoothness, shape, or the like; sampler definition of any external openings, recesses, passages, or the like; sampler thermal conductivity, specific heat, thermal mass (or thermal capacitance) or the like; sampler gas permeability; and sampler wear resistance, durability, cleaning, and the like relating to sampler reuse suitability-to name just a few.
- Certain embodiments include a fibrous sampler core structure of a nonfabric or fabric variety, while others include a nonfabric without fibers.
- Such nonfibrous cores may be comprised of one or more nonfibrous solid pieces or the like.
- the core is comprised of a fibrous portion and nonfibrous portion.
- the fibers may be in the form of filaments, strands, yarn, threading, cord, roves, nanotubes, pultrusions, tows or the like; and may be categorized as being a: nonfabric, nonwoven fabric, and/or woven fabric.
- Nonfabric fibrous configurations include conglomerations of fibers that may be randomly oriented in terms of direction or in an unbound unidirectional configuration, and any other fiber arrangement that does not qualify as a fabric.
- Nonwoven fabric types include: spunlaced or any other arrangement of fibers bound together through entanglement without weaving, Chopped Strand Mat (CSM), felts, knitting, braiding, plaiting, velour, leather, and/or by binding fibers together through application of pressure, thermal, chemical, adhesive, resin, organic polymer and/or solvent treatment (either with or without a reinforcement backing), or any combination of these.
- CSM Chopped Strand Mat
- sampler core/substrate fibers of a fabric form have certain benefits.
- Woven types of fabric include any type of fibers interlaced in accordance with a weave pattern.
- weave patterns include: plain weaves, satin weaves (including harness satin weaves and crow(s)foot weave), twill weaves, heddle weaves, herringbone weaves, houndstooth weaves, Dutch plain weaves, Dutch twilled weaves, reverse Dutch weaves, Basket weaves, Leno weaves, mock Leno weaves, gauze weaves, cross weaves, tablet weaves, DURAWEAVEs, hybrid weaves, weft-faced weaves, warp-faced weaves (backstrap weaves), oxford weaves, pinpoint weaves, poplin weaves, pile weaves, real weight weaves, combinations of these various weaves, and other known weaves.
- FIG. 5 schematically illustrates the partial views of FIGs. 5A-5D together and designates the contents as weave comparison 500— showing the orientation of the FIG. 5A-5D partial views relative to one another.
- fibers 501 are interlaced to provide fabric 502 generically designated by reference numeral 502, which is also generically designated as substrate 503.
- reference numeral 502 which is also generically designated as substrate 503.
- FIGs. 5A-5D only a few of fibers 501 are specifically designated by reference numeral to preserve clarity.
- the collection, retention, and release of analyte(s) plus other aspects can vary with weave in terms of effective thickness, surface irregularity/roughness, fabric flexibility/stiffness, gas permeation, thermal desorption, solvent extraction, strength, composition, and durability. Further factors bearing on performance include: fiber thickness; filament configuration/size; number of filaments per strand; strand weight/count; number of strands (un)twisted and/or number of strand plies in a yarn, thread, or cord; and yarn/thread/cord texture/size— to name only a few examples.
- FIG. 5A depicts four different weave patterns of comparison 500. Plain weave
- 520 in the upper right corner schematically depicts the warp and weft fibers 501 of a plain weave pattern 526 to generically provide fabric 502.
- Plain weave 520 is shown from two perspectives: Warp/weft representation 522 and swatch 523.
- Representation 522 corresponds to a cross- section taken along section line 525. Due to the symmetry of pattern 526, another representation is not shown to preserve clarity.
- Representation 522 is turned 90 degrees (to line-up with the thickness projecting perpendicular to the view plane) relative to the depiction of swatch 523 parallel to the view plane to enhance understanding of weave pattern 526 by showing an edge- on/thickness view of the arrangement of fibers 501 among other things.
- plain weave 520 is relatively tight— being a type of closed weave that readily allows adjacent fibers to come together in contact along at least a substantial portion of the fiber length— and likewise being inhospitable to the formation of any pattern-defined openings as is typical of an open weave.
- FIG. 5A further schematically depicts three different types of harness satin weaves 505 of fibers 501 to provide corresponding substrates 503.
- 4 Harness Satin (HS) weave 510 schematically depicts the warp and weft of a 4 HS weave pattern 516 (also known as "crow(s)foot” weave).
- Weave pattern 516 is also represented schematically in FIG. 6 and designated as a type of fabric 502.
- 4 HS weave 510 is shown from three perspectives: swatch 513 parallel to the view plane, representation 512, and representation 514.
- the representations 512 and 514 correspond to the perpendicular weft/warp interlacing pattern 516 of fibers 501, and are turned 90 degrees relative to swatch 513 along the corresponding swatch edges as previously described for weave 520. Representations 512 and 514 enhance understanding of pattern 516 relative to swatch 513 by showing an edge-on/thickness view of pattern 516 and 4 HS weave 510 among other things. 4 HS weave 510 is typically a closed weave.
- 8 HS weave 530 schematically depicts the warp and weft of an 8 HS weave pattern 536 of fibers 501 to provide fabric 502 of substrate 503.
- 8 HS weave 530 is shown from three perspectives: swatch 533 parallel to the view plane, representation 532, and representation 534.
- the representations 532 and 534 correspond to sections through weft/warp arrangement of pattern 536, and are turned 90 degrees relative to swatch 533.
- Each representation 532, 534 is arranged parallel to its section line/swatch edge and perpendicular to one another.
- Representations 532 and 534 enhance understanding of pattern 536 relative to swatch 533 by showing an edge-on/thickness view of the arrangement of fibers
- 8 HS weave 530 is typically a closed weave.
- 5 HS weave 540 schematically depicts the warp and weft of a 5 HS weave pattern 546 of fibers 501 to provide fabric 502.
- 5 HS weave 540 is shown from three perspectives: swatch 543 along the view plane, representation 542, and
- representation 544 which correspond to sections through the weft/warp arrangement of pattern 546, are turned 90 degrees relative to swatch 54, are aligned parallel to the respective sections and corresponding edges of swatch 543, and are perpendicular to each other.
- Representations 542 and 544 enhance understanding of pattern 546 relative to swatch 543 by showing an edge- on/thickness view of the warp/weft arrangement of fibers 501, among other things.
- 5 HS weave 540 is a closed weave.
- FIG. 5B depicts three more weaves of comparison 500. The upper part of FIG.
- 5B schematically depicts 5 Heddle (HFD) weave 550 comprised of fibers 501 to provide fabric
- Weave 550 schematically depicts the warp and weft of HFD weave pattern 556.
- the HFD weave 550 is shown from three perspectives: swatch 553 in parallel to the view plane, representation 552, and representation 554.
- the representations 552 and 554 correspond to sections through the weft/warp arrangement of pattern 556, and are turned 90 degrees relative to swatch 553.
- Representations 552 and 554 are parallel to the respective sections/edges of swatch 553, and perpendicular to each other. Representations 552 and 554 enhance
- pattern 556 relative to swatch 553 by showing an edge-on/thickness view of the warp/ weft arrangement, among other things.
- herringbone weave 560 is depicted schematically— being comprised of fibers 501 to form fabric 502 of substrate 503.
- Weave 560 has the warp/weft arrangement of a herringbone weave pattern 566.
- Herringbone weave 560 is shown from three perspectives: swatch 563 parallel to the view plane, representation 562, and representation 564.
- the representations 562 and 564 correspond to sections through the weft/warp arrangement of fibers 501 at right angles, and are turned 90 degrees relative to swatch 563.
- Representations 562 and 564 are parallel to corresponding edges of swatch 563 and perpendicular to one another.
- Representations 562 and 564 enhance understanding of pattern 566 relative to swatch 563 by showing an edge-on/thickness view of the warp/weft arrangement among other things.
- herringbone weave 560 is of the closed weave type.
- FIG. 5B schematically depicts 3/3 twilled weave 570 which is one of a group of depicted twills 571 formed from fibers 501 each to provide a corresponding fabric 502 of substrate 503.
- Weave 570 schematically depicts the warp and weft of a 3/3 twilled weave pattern 576 from three perspectives: swatch 573 parallel to the view plane, representation 572, and representation 574.
- the representations 572 and 574 correspond to warp/weft sections through pattern 576, and are turned 90 degrees relative to swatch 573 perpendicular to the view plane.
- Representations 572 and 574 are aligned parallel with the corresponding edges/sections of swatch 573, and perpendicular to one another. Representations 572 and 574 lend understanding of pattern 576 relative to swatch 573 by showing an edge-on/thickness view of the warp/weft arrangement, among other things.
- the 3/3 twilled weave 570 is of a closed type.
- FIG. 5C shows three perspective visualizations of different weaves.
- the perspective view of these weaves renders separate edge/sectional representations largely redundant.
- the upper part of FIG. 5C depicts another of the twills 571 , namely 2/2 twilled weave 576a, which is formed from fibers 501 to provide fabric 502 of substrate 503.
- 2/2 twilled weave 576a includes swatch 576b, edge 576c, and edge 576d, that collectively show weave pattern 576e.
- Edges 576c and 576d provide an edge-on/thickness view of swatch 576b. It should be observed that pattern 576e is similar to pattern 576 (FIG.
- weave 577a is of a closed type.
- Dutch plain weave 577a is shown that is formed of fibers 501 to provide fabric 502 of substrate 503.
- Weave 577a includes swatch 577b, edge 577c, and edge 577d, that collectively show weave pattern 577e. Edges 577c and 577d correspond to the edge-on/thickness view of swatch 577b.
- weave 577a is a closed weave type. In the lower part of FIG.
- Dutch twilled weave 578a is illustrated, which is formed from fibers 501 to provide fabric 502 of substrate 503.
- Weave 578a includes swatch 578b, edge 578c, and edge 578d, that collectively show weave pattern 578e. Edges 578c and 578d correspond to edge- on/thickness views of swatch 578b.
- weave 578a is a closed type.
- FIG. 5D displays three more weave types of comparison 500 each comprised of fibers 501 to provide fabric 502 and corresponding substrate 503.
- the upper part of FIG. 5D depicts Leno weave 580 (a form of gauze weave) shown from two perspectives: swatch 581 in a plan view and representation 582 turned 90 degrees and aligned parallel with the corresponding edge of swatch 581.
- Swatch 581 and representation 582 illustrate weft/warp constituents of pattern 580a.
- Representation 582 shows an edge-on/thickness view of the warp/weft arrangement of pattern 580a, among other things.
- Leno weave 580 is of the open weave type.
- FIG. 5D depicts Mock Leno weave 584 shown from three perspectives: swatch 585 with length/width parallel to the view plane, representation 586, and representation 588 perpendicular to representation 586.
- the representations 586 and 588 correspond to sections through the weft/warp arrangement of weave pattern 584a, are each turned 90 degrees relative to swatch 585, and are each aligned parallel to the respective section/corresponding edge of swatch 585.
- Sectional representations 586 and 588 enhance understanding of pattern 584a by showing an edge-on/thickness view of the warp/weft arrangement, among other things.
- FIG. 5D depicts basket (panama) weave 590 shown from three perspectives: swatch 591 parallel to the view plane, representation 592, and representation 594.
- the representations 592 and 594 correspond to sections/edges parallel to respective weft/warp aspects of pattern 590a, are turned 90 degrees relative to swatch 591 , and are perpendicular relative to one another.
- Representations 592 and 594 enhance understanding of pattern 590a relative to swatch 591 by showing an edge-on/thickness view of the warp/weft arrangement among other things.
- certain embodiments include a fabric of a woven type.
- the weave is one or more of: plain weave, satin weave, twilled weave, heddle weave, arid herringbone weave.
- the sampler incorporates a closed weave fabric core.
- a closed weave fabric core includes one or both of a satin weave and a twilled weave.
- Still another even more particular form includes a closed harness satin weave.
- Yet a further particular form employs a closed weave of the 4 HS type.
- FIG. 6 a partially diagrammatic cross-sectional view of sampler
- FIG. 6 illustrates structural fabric core 606 of sampler 100; where like reference numerals refer to like features previously described.
- Core 606 includes two opposing functional ized sublayers 604 each covered by a corresponding polymer layer 602. Certain additional description of sublayers 604 and polymer layers 602 is deferred until corresponding
- Thickness Tl of sampler 100 corresponds to double-headed arrow 106 inclusive of core 606 and layers 602 and thickness T2 of sampler core 606 corresponds to double-headed arrow 108 inclusive of core 606 without layers 602.
- shape and volume of the sampler 100 inclusive of layers 602, and core 606 can impact thermal behavior, sampler flexibility/rigidity, viability of analyte collection (like sufficiency of collection surface area), and the like. Further, sampler dimensions may be constrained by other factors, such as instrumentation, durability and/or handling requirements.
- the dominant surface area (LxW- the "major surface area ”) is along the side with the Length L and Width W dimensions, where Tl and T2 are much less than L or W (Tl « L, Tl« W, T2 « L, T2« W).
- decreasing thicknesses Tl , T2 decreases thermal mass for a given composition and fiber 501 arrangement of core 606, such as its weave 516 for woven fabric 502 form of the core 606 (a specific type of substrate 503), which can enhance thermal desorption performance.
- Tl generally presents a tradeoff-decreasing the degree of polymer 602 coverage of core 606, and correspondingly reducing sampler 100 stiffness and/or increasing analyte affinity absent functionalization suitable to effective analyte release/transfer; while a decrease in T2 presents a trade-off in terms of mechanical sufficiency potentially impacting wear, durability, and stiffness.
- the core 606 has a thickness less than or equal to 0.5mm (T2 ⁇ 0.5mm); in a more specific form, T2 is less than or equal to 0.3mm (T2 ⁇ 0.3mm); in an even more specific form, T2 is less than or equal to 0.12mm (T2 ⁇ _0.12mm); and in an even more particular form, T2 is less than or equal to 0.1 mm (T2 ⁇ _0.1 mm).
- Tl is less than or equal to 1mm (Tl ⁇ 1 mm) in one form; in a more specific form, Tl is less than or equal to 0.8mm (Tl ⁇ 0.8mm); in an even more specific form, Tl is less than or equal to 0.5mm (Tl ⁇ 0.5mm); and in an even more particular form, Tl is less than or equal to 0.3mm (Tl ⁇ 0.3mm).
- natural fibrous materials include: wool, cashmere, alpaca, leather, cotton, silk, flax, hemp, tencel, jute, or the like; synthetic organic material includes: one or more synthetic organic thermoplastic or thermoset polymers, including polymeric nanotubes and nanofibers; inorganic material includes: glass, metal, metalloid, inorganic oxide, metal oxide coated fibers, ceramic, glass-ceramic, or a combination of these.
- fibers may be composed of pure silica (e.g., ASTROQUARTZ, JPS Composites Materials, Anderson, SC, USA), or predominantly silica with inorganic constituents to provide selected properties.
- such silica-based glass fibers may be selected from: HSG as previously defined herein, A-type glasses (e.g. alkali-lime glass with little or no boron oxide); E- type glasses (52%-56% silicon dioxide, 16%-25% Calcium Oxide, 12%-16% Aluminum Oxide, 5%-10% Boron Oxide, 0%-2% Sodium Oxide & Potassium Oxide, 0%-5% Magnesium Oxide, 0.05%-0.4% Iron Oxide, 0%-0.8% Titanium Oxide, and 0%-1.0% Fluorides); E-CR-type glasses (e.g., alumino-lime silicate with less than l %wt alkali oxides with high acid resistance); C-type glasses (e.g., alkali-lime glass with high boron oxide content); D-glass (borosilicate glass with high dielectric constant); R-glass (alumino silicate glass with no MgO or CaO); S-type glasses (64%-66% Silicon Dioxid
- metal fibers include, but are not limited to, e.g., iron (Fe), aluminum (Al), copper (Cu), nickel (Ni), silver (Ag), and including metal alloys thereof.
- metal fibers may be treated with acid or base to clean and activate the surface of the fibers prior to use or subsequent processing (such as operation 414).
- metal fibers may include a native oxide coating on the surface of the metal fibers. Fibers may be composed of or include, metal oxides, oxide-coated metals, or metals that include a metal oxide coating of the same or different metal provided that refractory properties of the metal oxide coating are compatible with the underlying metal.
- Inorganic oxides encompass both metal oxides and non-metal oxides for fibers, including, but are not limited to: Ag 2 0, AI2O3, As 2 0 3 , As 4 0 6 , BaO, B2O3, BeO, Bi 2 0 3 , CO, CaO, CdO, Ce0 2 , CoO, Cr0 3 , Cr 2 0 3 , CuO, Cu 2 0, Dy 2 0 3 , Er 2 0 3 , Eu 2 0 3 , FeO, Fe 2 0 3 , Ga 2 0 3 , Gd0 3 , Ge0 2 , Ho 2 0 3 , Hf0 2 , ln 2 0 3 , Ir0 2 , K 2 0, KNaO, La 2 0 3 , Li 2 0, Lu 2 0 3 , MgO, MnO, Mn0 2 , Mn 2 0 3 , Mo0 3 , N2O5, Na 2 0, Nb 2 0 3 , Nb 2 0 5 ,
- the sampler core whether fibrous or otherwise, includes one or more of: glass, metal, metalloid, inorganic oxide, polymeric thermoplastic, polymeric thermoset, ceramic, glass-ceramic, and/or metal or glass coated with metal oxide as described further herein.
- the core/substrate includes one or more of: glass, metal, metalloid, inorganic oxide, ceramic, and glass-ceramic.
- the core/substrate includes one or more of: HSG, metal, metalloid, metal oxide, ceramic, and glass-ceramic.
- the core is comprised of at least one of: HSG, metal, metalloid, and metal oxide.
- the core is comprised of one or more of: HSG, metal, carbon, and metal oxide.
- the core is comprised of HSG.
- the core is comprised of S-glass.
- the core is comprised of one or more glasses or metals coated with one or more compatible metal oxides. While S-glass is favored for some embodiments, it is surmised other materials, such as those of the progressively more specific groups/types listed above will perform similarly or even better in certain other embodiments.
- a fiber core has a thermal conductivity greater than about 0.2 W/m-K. In further embodiments, the thermal conductivity is greater than about 0.4 W/m-K. In still other embodiments, the thermal conductivity is greater than about 0.6 W/m-K. Alternatively or additionally, other embodiments have a specific heat of the fiber below about 1.3 J/g °C.
- the core fiber specific heat is in a range from about 1 J/g °C through about 1.3 J/g °C; yet in other embodiments, this specific heat is in a range from about 0.5 J/g °C through about 1.2 J/g °C; and still other embodiments have a fiber specific heat in a range from about 0.1 J/g °C through about 0.5 J/g °C.
- sampler 100 includes an analyte sampling surface 612 on each opposing side of sampler 100, as defined by respective opposing polymer layers 602.
- Layer 602 is disposed on fiber core 606 to collect, retain, transfer, and release trace particles and/or other forms of targeted contraband or undesirable substance(s) for detection. In some embodiments, such detection may be performed with instrumentation 30 through thermal desorption or in a different manner.
- Polymer layer 602 may completely coat fiber core 606, or only partially cover/coat core 606.
- the major surface area (LxW) on opposing sides of sampler 100 are completely or partially configured with sampling surface 612. In other embodiments, just a single side is completely or partially configured with a sampling surface 612.
- a glove 232 or finger cot 234 implementation of the sampler may only have a sampling surface on its outer side, and/or may be confined to a selected region or regions thereof.
- core 606 shown in FIG. 6 is comprised of a fabric
- fibers 501/fabric 502 is made of S-glass.
- the mechanical and/or compositional aspects of the core/substrate may vary— it being specific in this case just for the sake of example.
- the FIG. 6 representation is shown with level, horizontal surfaces in block form to preserve clarity of various features that may be readily obscured or confused otherwise.
- core 606 comprised of fabric 502/fibers 501 with 4 HS weave 516 would likely exhibit an undulating core surface 605 in a corresponding weave surface pattern— with greater complexity and unevenness (not shown).
- polymer layer 602 would tend to be uneven, too, depending somewhat on relative thickness and degree of coverage (not shown).
- some fiber surfaces can be tailored with a specified surface chemistry that may be useful to facilitate better polymer layer 602 coverage and/or provide a surface more compatible with selected analyte(s), and/or collection, retention, release, and transfer to the extent fiber core 606 is uncovered by layer 602.
- the enhanced surface chemistry may provide better surface homogeneity and more suitable analyte affinity— directed to better analyte recovery when compared with less homogeneous surface chemistry of other arrangements.
- enhanced surface chemistry can enhance polymer coverage and/or the collection, release, transfer, and detection (i.e., signal intensity) of released analyte(s) with it.
- an S-glass/4 HS weave 516 form of sampler 100 shall serve as the sampler core/substrate selected during operation 404 of process 400 (FIG. 4) for nonlimiting illustrative purposes.
- process 400 continues with conditional 405.
- Conditional 405 tests whether the selected core/substrate material would benefit from a pre-treatment. If the test of conditional 405 is affirmative (Yes), process 400 proceeds to operation 406. If this test is negative (No), process 400 proceeds to conditional 408, bypassing operation 406.
- an effective pretreatment procedure is available so process 400 continues with operation 406. Typically pretreatment in operation 406 removes contaminants, alters the material in some other fashion, or otherwise prepares the material for subsequent operations.
- pretreatment may involve application of a chemical, thermal, and/or mechanical procedure.
- a chemical, thermal, and/or mechanical procedure For the stated example, high levels of nitrates are sometimes present in S-glass and potentially some other glass types, which is an unwanted contaminant.
- a heat treatment is applied. It has been found exposure of the material to 500 °C for 4 hours or more is sufficient to reduce nitrates to an acceptable level.
- untreated glass and/or silica fibers can include many unavailable reactive surface sites because these surface sites are physically obstructed by a surface coating or undesirable contaminants, or are chemically unavailable because of a previous reaction between adjacent silanols (e.g., metal hydroxyl groups) that form, e.g., bridging oxo groups. Further pretreatment information is deferred until operation 414 is reached by process 400.
- silanols e.g., metal hydroxyl groups
- process 400 advances to conditional 408, which tests whether a fill procedure should be performed. If the test is negative (No), process 400 continues with conditional 412, bypassing operation 410. If the test is affirmative (Yes), process 400 advances to operation 410. In operation 410, a particulate material is applied to core
- operation 410 is performed to at least partially fill the core 606 with alumina (A1 2 0 3 ) nanoparticles to increase thermal performance because A1 2 0 3 has a thermal conductivity several times greater than S-glass.
- alumina A1 2 0 3
- These nanoparticles are represented by small circles in sublayers 604 of core 606 with only a few being designated by reference numeral 620 to preserve clarity.
- nanoparticles 620 are shown closer to surface 605 in sublayers 604; however, they may become more deeply embedded and uniformly dispersed than shown.
- the mean diameter of nanoparticles 620 is about 50 nanometers (nm); but, in other embodiments a differently sized nanoparticle, a larger particle, other than a nanoparticle, or nonparticle may be used.
- one or more carbon-based allotropes can be used as a nano-sized or other filling material that are selected for a desired level of thermal conductivity/performance; such allotropes including: carbon nanotubes, graphene, amorphous carbon, carbyne (linear acetylenic carbon), carbon nanofoam, fullerenes, glassy carbon, graphite, or the like.
- nanoparticles 620 also represent nano-sized carbon allotrope forms to the extent otherwise designated.
- the fill material is one or more of particles of: metal oxide, metalloid, metal, ceramic, and glass-ceramic.
- the fill material is comprised of particles of: metal oxide, carbon, ceramic, and glass-ceramic.
- the fill material is comprised of nanoparticles of metal, metal oxide and/or carbon.
- nanoparticles of a nanotube and/or graphene allotrope provide the fill material.
- a different and/or multiple types of fill material may be used to coat, partially fill or generally completely fill the core/substrate.
- fill material is selected to improve an aspect of the core 606 for which improvement is desired, such as a thermal characteristic.
- particles of at least one of metal and metal oxide is used at least some of which may be nanoparticles.
- the particles are alumina and are of nanoparticle size.
- operation 410 is not performed at all— such that no fill material is used, being bypassed by conditional 408.
- process 400 encounters conditional 412, which tests whether to
- surface 605 of core 606 functionalize surface 605 of core 606 to provide sub-layers 604. If the test is negative (No), procedure 400 continues with operation 416, bypassing operation 414. If the test is affirmative (Yes), process 400 moves to operation 414. In operation 414, surface sub-layers 604 of core 606 are formed to improve the desired collection and release of target analyte(s) with surface 605/sub-layer 604, improve subsequent application of polymer layer 602, and/or provide other desired features through installation of desired surface chemistry. In one form, functionalization may be performed according to the '910 Patent, which provides exhaustive description thereof.
- a glass form of core 606 generally tends to bind with certain analytes to such an extent that release/transfer by thermal desorption can be hampered, resulting in a reduced detection signal.
- glass surfaces tend to be polar which can affect the uniformity of polymer coverage in subsequent operations (such as polymer application in operation 416).
- Such nonuniformity also indirectly can impact analyte collection and/or release because polymer 602 covers surface 605 to a lesser/incomplete extent.
- polymer coating 602 may not be uniform over surface 605 of core 606 due to 4 HS weave shape or the like, so that functionalization facilitates a more robust, uniform analyte detection response.
- Fill particles (such as alumina nanoparticles 620), can also tightly bind to analyte(s) and/or may also benefit from functionalization.
- R is appended to core 606 by a line representative of bonding to core 606.
- the resulting interfacial sub-layer 604 is representative of organo-silanes provided according to the '910 Patent or other chemistry resulting from a different procedure.
- the relative size of sub-layers 604 is not to scale in FIG. 6, and may in fact only have a thickness of no more than about a molecule or so in some applications.
- the '910 Patent provides further details regarding various functionalization operations/options, and is generally compatible/adaptable with those of the present application. To accommodate functionalization, process 400 may include pre- and post- treatments per the '910 Patent to perform/enhance the formation of sublayers 604 and further improve compatibility with subsequent stages.
- Some pretreatments may already have been described for operation 406 but are repeated here in connection with functionalization, namely: (a) to remove commercial coatings or surface contaminants (See '910 Patent FIG. 2a and accompanying text), an exemplary pretreatment process to prepare for functionalization of the core surface 605 is further discussed, which may be used as an addition or alternative to that previously described for operation 406; where such functionalization preparation pretreatment can activate and increase density of reactive groups such as silanols on the surfaces of fibers 501 and/or correct unfavorable surface chemistry— by way of example, fibers 501 treated with, e.g., bases or acids can increase the density of silanols on the surfaces in the absence of added water— while in others, hydrotreating the surface with an aqueous medium can increase the density of silanols or reactive (-OH containing) groups on surface 605; (b) silanizing fibers 501 by chemically attaching silanes (e.g., phenyl silanes) on surfaces 605 of fiber
- FIG. 2b of the '910 Patent shows an exemplary condensation reaction for direct attachment of silane ligands or terminally functionalized silane ligands to activated anchor sites (e.g., silanols) on the surfaces of fabric fibers that may be performed in operation 414.
- Surfaces 605 including glass, metal oxide, and/or oxide coated glass or metal fibers are amenable to surface functionalization using a wide range of functional groups through Si-O-Si bonds [or metal (M)-O-Si bonds in the case of metal oxide and oxide-coated metal fibers] that form in concert with Anchor groups (Z) attached to a silicon (Si) atom at the terminal attaching end of a Linking group (Y).
- Another terminal end of the Linking group (Y) may include other terminal groups (X), e.g., as shown in chemical expression [1] of the '910 Patent.
- the silanization procedure of operation 414 may involve chemically attaching silanes to reactive Si-OH groups on the surface 605 of fibers 501 in sublayers 604.
- Si-OH reactive sites on the surface 605 of the fibers 501 may attach to selected silane ligands via an Anchor group (Z) positioned at the attaching end of the silane ligand.
- the reaction may form a Si-O-Si bond, e.g., via a condensation reaction.
- silanes can attach directly to reactive Si-OH (Anchor) groups (Z) in the absence of a Linking group (Y).
- FIG. 3 and accompanying text of the '910 Patent provides further information.
- Silane ligands suitable for selective collection of target analyte(s) include, but are not limited to, e.g., phenyl silanes; organosilanes; alkoxysilanes; alkyl silanes; siloxanes; phenyl- trimethoxysilanes; silanols; combinations of these various silanes; and/or hydrocarbyl derivatives thereof.
- phenyl silanes include, but are not limited to, e.g., phenyl silanes; organosilanes; alkoxysilanes; alkyl silanes; siloxanes; phenyl- trimethoxysilanes; silanols; combinations of these various silanes; and/or hydrocarbyl derivatives thereof.
- functionalization/passivation of any residual reaction sites can yield further improvements in surface chemistry results and/or
- Phenyl silanes represent an exemplary surface chemistry for modification and functionalization of glass, silica, metal oxide, and/or oxide-coated glass or metal fibers 501 within the sampling fabric 502 of core 606 for collection of a wide variety of organics. Phenyl silanes provide a thermally robust and thermally stable surface chemistry at temperatures in excess of 400 °C. In addition, phenyl silanes can provide a lipophilic surface with a general affinity for various organic materials, and additionally, greater chemical selectivity for TNT and other nitroaromatics, as detailed further in the '910 Patent.
- silanization is complete in operation 414, sampling surface 605 may be further treated to ensure that silanes are completely bound to the surface and to remove unwanted reactants and side products.
- This stabilization process prepares the functional ized surface for collection of target analytes.
- a surface chemistry functionalization based on something other than silanization may be used.
- operation 414 includes appropriate stabilization treatment, as applicable.
- FIG. 7 depicts a portion of alternative sampler 800 in perspective.
- Various features of sampler 800 are not shown relative to scale to highlight certain aspects and does not include complete crosshatching to avoid obscuring certain features.
- Phenyl terminal functional group P of sampler 800 is a specific implementation of operation 414, with only some being specifically designated by the reference characters to preserve clarity.
- phenyl groups P are a specific form of the generic silanization terminal groups R shown in FIG. 6.
- Double polymer layering 602, 802 is applied over phenyl groups P.
- Outer/upper surface 802 defines sampling surface 802.
- Sampler 800 does not specify any particular weave unlike weave 516 of sampler 100.
- polymer layer 602 is formed on core 606 that defines sampling surface 612.
- Polymer layer 602 may be applied to core 606 by various means, including without limitation: an aqueous or other liquid-based dispersion of polymer particles in the form of a painted or brushed-on coating, a spray, dipping in the liquid, or the like; a powder of polymer particles deposited on the core; molding a polymer film, sheet, or lamination onto the core, or such other application as known to those of ordinary skill in the art.
- the amount of polymer applied is typically in a range of about 2%wt through about 50%wt depending on various target properties of sampler 100 such as stiffness, analyte collection/release, the degree of core coverage by the polymer, sampler thickness/thermal mass, and the like— as discussed further hereinafter. Indeed, in some embodiments, only partial core coverage by the polymer may be desired.
- one preferred embodiment of the polymer layer 602, 802 is comprised of one or more of: polymeric organofluorine, polyamide, polyimide,
- PPPO Poly(2,6-diPhenyl-p-Phenylene Oxide)
- PBI PolyBenzImidazole
- PDMS PolyDiMethylSiloxane
- PFSA sulfonated tetrafluoroethylene
- PPPO Poly(2,6-diPhenyl-p-Phenylene Oxide)
- PPPO is also known by the trademark TENAX TA, and a PPPO/graphitized carbon combination (also known by the trademark TENAX GR) is included in the group because PPPO is a constituent of both the above group listing and the graphitized carbon combination.
- composition of the polymer applied to any of the previously described cores may be a member of any of the following successively more specific listings (a)-(e): (a) peril uorocarbon, perfluoroether, Ethylene-TetraFluoroEthylene copolymer (ETFE), Ethylene
- ChloroTriFluoroEthylene copolymer ECTFE
- poly(tetrafluoroethylene-hexafluoropropylene- vinylidene fluoride) (THV) copolymer tetrafluoroethylene-hexafluoropropylene- vinylidene fluoride) copolymer
- PVdF PolyVinylidene diFluoride
- FFP Ethylene-propylene
- PCTFE PolyChloroTriFluoroEthylene
- PVF Polyvinyl Fluoride
- PTRFE PolyTRiFluoroEthylene
- poly(vinylidene-tetrafluoroethylene) copolymer
- poly(vinylidene-trifluroethylene) copolymer PPBI, PDMS, and PPPO
- perfluorocarbon perfluoroether, ETFE, FEP, THV copolymer, PVdF, and PPPO
- perfluorocarbon perfluorocarbon
- PFA PerFluoroAlkoxy
- ETFE PerFluoroAlkoxy
- PVdF PerFluoroAlkoxy
- FEP PerFluoroether
- PTFE While PTFE is favored for certain embodiments, it is surmised that analog polymers and others like PTFE will perform similarly. Also, to the extent thermal desorption is used with the sampler 100, 800 it is a preference that polymer 602, 802 have a thermal decomposition temperature above the temperature applied to perform thermal desorption with detection instrumentation 30.
- sampler 100 applies PTFE to the exemplary
- PTFE is applied to S-glass fibers by depositing a coating on the core of an aqueous dispersion of PTFE polymer particles. This deposition may include brushing the dispersion on the core, dipping the core in the dispersion, or the like. In further embodiments, a different polymer may be applied and/or a different manner of application used. Additionally or alternatively, in other embodiments the core differs in composition and/or arrangement of core fibers.
- Such arrangement can differ among various embodiments as to type: non-fibrous nonfabric, nonwoven fabric, and/or woven fabric; and if the core includes a woven fabric, the weave type of such fabric can include or vary from the 4 HS type, and may have a closed or open weave for different embodiments.
- process 400 moves from operation 416 to operation 418. In operation
- the polymer application is cured/heat-treated as needed for the core/polymer materials utilized to prepare sampler 100, 800 for use with detection instrumentation.
- heat treatment is performed for the aqueous dispersion form of PTFE applied to an S-glass/4 HS woven fabric sampler core. It has been discovered that heat treatment in the range between the polymer melting point and the thermal decomposition temperature tends to yield a better detection response compared to heat treatment temperatures outside of this range, and further has been surprisingly found to be a factor in controlling sampler stiffness.
- operation 418 heats a glass core with a PTFE polymer core application to a temperature of about 400 °C for 30 minutes; where the PTFE melting point is about 327 °C and the thermal decomposition temperature is about 448 °C.
- the applied temperature is about 425 °C for 30 minutes.
- the heat treatment temperature is between about 390 °C and about 435 °C and applied for at least 30 minutes.
- a different cure/heat treatment may be applied after polymer application that may further include control of applied pressure/vacuum.
- a different core and/or polymer application is used with an appropriate heat treatment, if any.
- the calcined amount of the polymer applied is broadly in the range from about 2%wt through about 50%wt.
- the calcined polymer amount after curing is less than or equal to about 40%wt.
- the calcined polymer amount after curing is less than or equal to about 20%wt.
- the calcined polymer amount after curing is in a range from about 20%wt through about 40%wt.
- Still a different form has a calcined polymer amount in a range of about 24%wt through about 36%wt.
- thickness Tl of sampler 100 is established, which can have a bearing on thermal behavior and accordingly the release of analyte(s) through thermal desorption with instrumentation 30— much like thickness T2 of core 606.
- One preferred embodiment based on a nominal core thickness T2 of about 0.3mm has an overall sampler thickness Tl of less than or equal to about 0.8mm depending on polymer amount applied.
- the T2 thickness is less than or equal to about 0.5mm.
- sampler thickness T2 is less than or equal to about 0.12mm.
- process 400 continues with conditional 420.
- Conditional 420
- process 400 tests whether to apply a further coat of polymer. Such polymer may be the same or different from that applied previously. If the test is negative (No), process 400 continues with conditional 422. If the test is affirmative (Yes), process 400 loops back to operation 416 to apply further polymer of the same type or a different type. It should be understood, that with multiple applications of polymer(s), operation 418 may be performed for each layer separately or may be deferred until some or all of the polymer/polymers is/are applied depending on the nature of the polymer(s), the application regime in operation 416, and curing technique(s) in operation 418.
- sampler 800 includes two distinct polymer layers 602 and 802 that may be of the same or different compositions depending on amount and relative coverage.
- the outer polymer layer 802 defines sampling surface 812 that operates in a manner analogous to sampling surface 612, which is shown covered by polymer layer 802 in FIG. 7.
- Polymer layer 602 serves as an inner, base layer relative to outer layer 802.
- additional polymer applications may take place as practically limited by performance requirements or the like; while in other embodiments, no more than the first polymer layer 602 application takes place.
- Flexure of the sampler or conversely "stiffness" may be empirically evaluated by determining flexural modulus of the sampler as defined herein.
- the flexural modulus is similar in some respects to the more familiar Young's modulus, both are often similar in value for a given material with common units of measure (units of pressure) but each is determined differently. Flexural modulus is commonly used with synthetic organic polymers and composites thereof.
- a sampler has a flexural modulus greater than or equal to about 0.75 GigaPascal (GPa). In still further embodiments, the flexural modulus of the sampler is greater than or equal to about 1.0 GPa.
- the flexural modulus of the sampler is less than or equal to about 2.0 GPa. In still other embodiments, the flexural modulus of the sampler is less than or equal to about 3.0 GPa. In still further embodiments, the flexural modulus is less than or equal to about 4.0 GPa.
- the sampler flexural modulus is in a range of about 0.75 GPa through about 10 GPa. In some more preferred embodiments, the sampler flexural modulus is in a range from about 1 GPa through about 8 GPa. In some even more preferred embodiments, the flexural modulus is in a range from about 2 GPa through about 6 GPa.
- conditional 420 When conditional 420 is negative, whether following just one polymer application or multiple polymer applications, conditional 422 is encountered. Conditional 422 tests whether more sampler material is to be made. If the answer to this test is affirmative, process 400 loops back to operation 404 to perform the previously described conditionals and operations to the extent applicable— eventually returning to conditional 422 to test for continuation again. If the answer to the test of conditional 422 is negative (No), then process 400 halts.
- the sampler material resulting from process 400 is shaped as desired using stamping, etching, trimming, cutting, or another procedure to provide sampler 100 with the desired shape.
- sampler 100 has a sampling surface with a shape/perimeter selected from: a circle, an oval, an ellipsis, a rectangle, a square, a triangle, a regular polygon, an irregular polygon, a polyline, or combinations thereof.
- shaping may take place before provision in operation 404 or elsewhere during process 400 before conditional 422 is encountered.
- sampler 100 may be cleaned and dressed after process 400 and optionally packaged prior to use.
- the sampling surface takes the form of a finger cot 234, glove 232, or a portion thereof; or the sampler may be selectively attachable to the finger cot 234 or glove 232 (See kit 200 of FIG. 2).
- FIG. 8 is a flowchart describing process 700 directed to the use of sampler 100 or
- Process 700 begins in stage 702 to start sampler 100, 800 application. From stage 702, process 700 advances to conditional 704 to test if the application is for trace analyte detection or another application. If the test is negative (No), process 700 bypasses several stages to next encounter conditional 716 as described further hereinafter. If the test is affirmative (Yes) for conditional 704, operation 706 is encountered in which the test article 50 is identified or otherwise predefined or known in advance, and sampler 100, 800 is applied to collect analyte(s) from surface 54 of test article 50 in accordance with any of the approaches described in connection with FIGs.
- sampler 100, 800 to collect one or more target analytes by swiping, wiping, suction, with a wand, or the like, and/or through an analyte-entrained airflow-as could be employed with pass-through portals (See the '513 Patent) to name a few examples.
- Test article 50 may be in any of a number of different forms, such as cargo/freight, associated packaging, shipping canisters or containers, tanks, crates, boxes, luggage, barrels, packing cases, child car seats, strollers, wheelchairs, purses, briefcases, travel cases, books and other documents, backpacks, electronic equipment (like laptops, tablets, headphones/ear buds, Personal Digital Assistants (PDA), and/or cellular phones), clothing/apparel/accoutrements, skin surfaces, vehicles, countertops, floors, walls, ceilings, and/or other surfaces as may occur to an operator.
- cargo/freight associated packaging
- shipping canisters or containers tanks, crates, boxes, luggage, barrels, packing cases, child car seats, strollers, wheelchairs, purses, briefcases, travel cases, books and other documents
- backpacks electronic equipment (like laptops, tablets, headphones/ear buds, Personal Digital Assistants (PDA), and/or cellular phones), clothing/apparel/accoutrements, skin surfaces, vehicles, countertops, floors, walls
- Such release may be performed chemically using appropriate agents/solutions and or agitation (such as stirring, churning, rocking, shaking, swaying, teetering, quavering, rolling, wobbling, oscillating, vibration, mixing, scrubbing, scouring, or other physical disturbance) with subsequent transfer to instrumentation 30, or through thermal desorption to release analyte(s) for processing by detector 32 while sampler 100, 800 is at least partially inserted in slot 40— to name a few examples.
- appropriate agents/solutions and or agitation such as stirring, churning, rocking, shaking, swaying, teetering, quavering, rolling, wobbling, oscillating, vibration, mixing, scrubbing, scouring, or other physical disturbance
- application of more than one liquid may be used to clean/extract analyte(s) from sampler 100, 800; utilization of an acid (such nitric acid), a base (such as sodium hydroxide), water, or one or more organic solvents; and/or a mixture of a oxidizer (like a peroxide such as hydrogen peroxide) with a source of one or both of onium and carbonate.
- an acid such nitric acid
- a base such as sodium hydroxide
- water such as sodium hydroxide
- organic solvents such as sodium hydroxide
- a oxidizer like a peroxide such as hydrogen peroxide
- the surface of the swipe sampler fabric retains the analyte(s) until thermally released into instrumentation 30 at a release temperature greater than the collection temperature that may involve certain detection instrumentation gas flow(s) of controlled flow rate(s), composition(s), and temperature(s).
- the release includes thermally desorbing the analyte(s) at a temperature between about 100 °C and about 500 °C.
- the analyte release temperature is less than any thermal decomposition temperature associated with sampler 100, 800.
- a thermal desorption temperature equal to or less than 450 °C has been found suitable for PTFE-coated S-glass samplers to provide just one nonlimiting example.
- sampler 100, 800 is prepared for re-use.
- the analyte release/transfer to instrumentation 30 may self-clean/prepare sampler 100, 800 for reuse.
- the desorption temperature may be sufficient to self-clean/prepare sampler 100, 800 for reuse, or may be capable to subjecting sampler 100, 800 to an elevated temperature/time period sufficient to prepare for reuse.
- the release of analyte(s) includes mechanically and/or chemically cleaning the surface of the sampler 100, 800 to prepare for reuse or collection of other analyte(s) from a selected surface.
- conditional 714 tests whether to perform another trace detection, and may include reuse of sampler 100 after preparation in operation 710. If the test is affirmative (Yes), process 700 loops back to repeat operations 706, 708, 710, and conditional 714. If the test is negative (No), process 700 falls through to conditional 716, which is also reached directly from a negative result of the test of conditional 704.
- Conditional 716 tests whether sampler 100 is of a type suitable for detection of an actinide series member, such as uranium, and whether to test for the same.
- samplers suitable for use in earlier operations to detect non-nuclear analyte(s) may or may not be preferred for nuclear material detection. If the test result is negative (No), process 700 moves forward to conditional 720, and if the test result is affirmative (Yes), process 700 moves to operation 718.
- IAEA International Atomic Energy Authority
- NPT Non-Proliferation of Nuclear Weapons Treaty
- a principal technique employed by the International Atomic Energy Authority (IAEA) for the enforcement of the Non-Proliferation of Nuclear Weapons Treaty (NPT) involves the use of environmental sampling to detect nuclear signatures that might reveal improper activities at otherwise declared facilities. Nuclear processing activities can leave trace signatures on surroundings that may be sampled by collecting dust. Uranium is often found in the form ot U 3 8 or U0 2 , which are crystalline compounds with relatively low solubility in water.
- U 3 0 8 is one of the most stable forms of uranium, it is commonly found in nature.
- U0 2 is typically the uranium chemical form of choice in the final stages of nuclear fuel fabrication.
- Uranium Ore Concentrate (UOC) or "yellow cake,” as it is commonly known, is characteristically a commercial product of a uranium mill, usually containing a high concentration (at least 90%) of uranium oxide U 3 0 8 .
- Uranyl fluoride (U0 2 F 2 ) is a
- Uranyl nitrate U0 2 (N0 3 ) 2
- Uranyl nitrate is a compound sometimes encountered in the reprocessing of spent fuel.
- U0 2 (HP04)*4H 2 0 uranyl orthophosphate
- Standard sampling procedures normally smear highly clean pieces of cotton fabric across surfaces of interest to collect a dust sample that is later subjected to in-depth analysis.
- drawbacks of the existing scheme is the need for complete chemical digestion of the cotton/dust sample matrix, which is often time consuming/labor intensive, limiting laboratory throughput, elevating costs, and adding to background contamination from the sampling fabric, which ultimately limit test sensitivity.
- Extraction may or may not involve digestion of some or all of the PTFE-coated sampler because release of certain uranium compound(s) from PTFE can be accomplished without complete digestion depending on the applicable conditions—such as the extraction liquid composition, length of exposure to the extraction liquid, and the particular uranium compound(s) being sought for release. It is surmised that PTFE analogues/homologues and other similar polymers other than PTFE will perform suitably or even better than PTFE for certain core compositions, analytes, coating combinations, sampler applications, or the like.
- the degree of extraction depends on the uranium compound(s) being sought for removal, the relative amount of such compound(s) captured with the sampler, and the strength of one or more active agents of the extraction liquid.
- the extraction liquid includes an organic solvent.
- Certain embodiments include an acid in the extraction liquid; some more specific embodiments include the acid as a mineral acid type in aqueous solution; and even more specific embodiments include the acid as nitric acid (HN0 3 ) in aqueous solution.
- the extraction liquid include a base
- some specific embodiments include the base as an alkaline agent in aqueous solution
- even more specific embodiments of the extraction liquid include sodium carbonate (Na 2 C0 3 ) as the base in aqueous solution.
- Still other embodiments of the extraction liquid include a mixture of an oxidizer and one or both of onium and carbonate, while in still more specific embodiments the mixture includes an oxidizer in the form of a peroxide and includes one or more of onium and carbonate, and an even more specific embodiment includes the oxidizer in the form of a hydrogen peroxide, and ammonium carbonate. See Experimental Examples Eleven and Twelve for more details regarding uranium detection and related analysis.
- PTFE analogues/homologues and other similar polymers other than PTFE will perform suitably or even better than PTFE for certain core compositions, analytes, coating combinations, sampler applications, or the like.
- One embodiment for preparing the sampler includes depositing PTFE nanoparticles from a colloidal suspension on a glass fiber core by dipping in or painting on the suspension liquid.
- Another embodiment for preparing the sampler includes placing the PTFE- coated sampler in a liquid agent to reduce uranium content of the PTFE and/or reduce impurities.
- Yet another embodiment for preparing the sampler includes applying an acid form of the liquid agent in aqueous solution to the PTFE-coated sampler to reduce background uranium content of the PTFE and/or reduce impurities.
- An even more specific embodiment for preparing the sampler to reduce uranium content of the PTFE and/or reduce impurities includes applying an oxidizer and one or both of onium and carbonate; and a still more specific embodiment includes peroxide in this oxidizer; and yet an even more specific embodiment includes hydrogen peroxide in the oxidizer and ammonium carbonate.
- the uranium background is less than or equal to 10 ng/g (10 nanograms (ng) of uranium per sampler gram (g)).
- the uranium background of the sampler is less than or equal to 1.0 ng/g. In even more specific embodiments, the uranium background of the sampler is less than or equal to 0.1 ng/g. In still even more specific embodiments, the uranium background of the sampler is less than or equal to 0.010 ng/g. See Experimental Example Thirteen for more details regarding background uranium reduction and related analysis.
- process 700 continues with conditional 720.
- Conditional 720
- process 700 tests whether to apply a sampler to test for heavy metals in certain industrial settings. If the test result is negative (No), process 700 falls through to conditional 724. If the test result is affirmative (Yes), process 700 advances to operation 722. In operation 722, a PTFE-coated core sampler or similar arrangement will be swiped on selective surfaces to pick up dust in an industrial setting such as a mine or metal processing plant, where metal-based content will potentially be collected. Next, under operation 722, digestion and complimentary chemical testing will be performed to determine the degree to which a worker will be exposed to certain heavy metals. From operation 722, process 700 moves to conditional 724. Conditional 724 tests if sampler application(s) should be continued.
- process 700 If the test result is affirmative (Yes), process 700 returns to conditional 704 to repeat it and potentially any of operations/conditionals in the range from 706-722 as appropriate. If the test result is negative (No), process 700 halts in stage 726, stopping further sampler applications.
- contraband or undesirable substances previously defined
- any contraband or undesirable substance not listed therein may be a target of sampler 100 and instrumentation 30.
- any non-contraband substance and/or a desired substance may be a target for detection with sampler 100 and instrumentation 30.
- the substance targeted for detection may be one or more of contraband, non-contraband, undesirable, desirable, or a still different substance of interest.
- Samplers (such as sampler 100) have been described in terms of several different innovative mechanical, structural, thermal, and/or compositional/material features, elements, characteristics, properties, and parameters; however, dimensioning, relative or absolute- especially three-dimensional (3-D) qualities has not been a major focus-given that sampler 100 has largely been portrayed as a flat-type with L and W much larger than thickness (L, W » Tl, T2) thus far.
- sampler shape has been depicted as being a planar pad, swipe, or strip type such as that shown in FIGs. 1-3.
- the samplers appear as two-dimensional planar rectangles with little or effectively no third dimension; however, as a solid object it should be generally understood a working sampler implementation also has a third dimension, although it may be somewhat negligible compared to its other dimensions.
- planar samplers is one with qualitative stiffness/bending resistance in a range from that of polymer-coated 20 lb. weight print paper through polymer-coated cardstock, or that of a polymer-coated fabric; and to have comparable elastic resilience to "spring-back" or otherwise return to its original planar for-or at least substantially.
- different dimensional, stiffness, and/or elasticity properties are provided in other sampler embodiments, and it should be appreciated that the various sampler embodiments are not limited to the depictions and accompanying exemplary descriptions provided herein in connection with FIGs. 1-3 or otherwise.
- Widely used lineal dimension descriptors include length, width, depth, breadth, height, and thickness, but are sometimes used ambiguously, can vary in preferred use from one field to the next, and may be especially context sensitive.
- three lineal/axial dimensions that are orthogonal to one another (rectangular) are designated for the purpose of describing three-dimensional (3-D) aspects of samplers: length (L) as the largest dimension, height (H) as the smallest dimension, and width (W) as the intermediate dimension. Height H was selected in lieu of thickness to avoid confusion with previously described thicknesses Tl and T2— understanding they all correspond to the smallest dimension.
- L and W may be approximately equal to each other (L ⁇ W), W and H may be approximately equal to each other (W ⁇ H), and L, W, and H may be approximately equal to each other (L ⁇ W ⁇ H)-thus the general case is described by the inequality expression: L > W > H. Indeed, in the case of an ideal right cylindrical embodiment, two of the three dimensions would be equal to each other. Accordingly, as used herein, L, W, and H are oriented in such a manner that as each axis extends along the object being measured the inequality expression L > W > H is obeyed.
- the absolute longest dimension need not be designated by L as long as L along the object is longer than W, W along the object is longer than H along the object, and L, W, and H are orthogonal. This corresponds to the usual way a rectangular parallelepiped (rectangular solid) would be measured along its outer edges rather than using the absolute longest length, which is the diagonal.
- the height dimension H may be considerably less than a tenth (1/10th) of the width dimension W-such that width W varies from height H by one order of magnitude or more.
- samplers so dimensioned H «W by at least an order of magnitude
- sampler 1000 it has also been discovered a generally nonplanar form of sampler may be desirable under certain circumstances that has height H generally closer to width W than for the planar type, and either or both of height H and width W are comparable to length L.
- This dimensioning corresponds to a three-dimensional (3-D) sampler type that is more naval than generally flat, planar samplers with H « W.
- collector 1002 one type of three-dimensional substance sampler 1000 (alternatively designated collector 1002) is illustrated in the form of substance collection framework 1010.
- Length L of framework 1010 is represented by the vertical juxtaposed line segment (axis) designated by reference numeral 1012 and the width W of framework 1010 is represented by the horizontal juxtaposed line segment (axis) designated by reference numeral 1014, which are perpendicular to each other and parallel to or coplanar with the view plane of FIG. 24.
- the height H extends along an axis perpendicular to the view plane of FIG. 24 and is represented by the concentrically arranged circle and cross hairs designated by reference numeral 1006.
- L, W, and H of three-dimensional sampler 1000 are all dimensionally within the same order of magnitude.
- H is one-eighth (1/8) or more of W and W is at least five-eighths (5/8) of L.
- H is three-fourths (3/4) or more of W and/or W is at least three-fourths (3/4) of L.
- H is one- half (1/2) or more of W and W is at least seven-eighths (7/8) of L.
- none of L, W, and H are more than 1.5 greater than another.
- none of L, W, and H are more than 1.25 greater than another.
- FIG. 22 provides a description of the fundamental mechanical/structural constituent 1005 that corresponds to a geometrically pattern repeated in a coincident fashion to build honeycomb 1030 of FIG. 23. The edges and adjoining vertices of this honeycomb corresponds to the framework 1010 of FIG. 24.
- FIG. 22 provides a description of the fundamental mechanical/structural constituent 1005 that corresponds to a geometrically pattern repeated in a coincident fashion to build honeycomb 1030 of FIG. 23. The edges and adjoining vertices of this honeycomb corresponds to the framework 1010 of FIG. 24.
- solid coincident blocks 1034 each are diagrammatically representative of the shape outlined by mechanical/structural constituent 1005, fit together to provide a solid geometry honeycomb 1030 structure used to better explain and visualize the role of its features in the subject sampler 1000 of FIGs. 24 and 25. From the description of the FIG. 23 honeycomb 1030, it transitions to the more complex cage/reticular/lattice-like embodiment of collection framework 1010 of FIG. 24 and further assists in explaining various attendant embodiments. From there, the cross-sectioned framework portion 1080 of FIG. 25 is described to further explain and visualize sampler 1000. FIGs. 24 & 25 conclude by describing various sampler 1000 representative applications and alternative embodiments thereof.
- FIG. 22 a diagrammatic perspective view of a convex polyhedron in the form of a dodecahedral, truncated octahedron 1008 represented by schematic wireframe structural pattern 1013 is illustrated, with mechanical/structural constituent 1005 corresponding to the illustrated shape; where like reference numerals refer to like features previously described.
- Truncated octahedron 1008 defines thirty-six (36) edges 1013a joined together by twenty-four (24) vertices 1013b (a truncated octahedron is equivalently a bitruncated cube).
- Structural constituent 1005 is provided in the form of a schematically illustrated truncated octahedron framework 1015.
- Framework 1015 is based on wireframe pattern 1013, which corresponds to edges 1013a and vertices 1013b of the truncated octahedron 1008.
- pattern 1013 the arrangement of edges 1013a and vertices 1013b define twelve (12) open faces 1017 that correspondingly have twelve (12) facial openings/apertures 1018 that open external to framework 1015 and constituent 1005.
- Six (6) open faces 1017 are approximately regular, geometrically coincident hexagons 1020, and the remaining six (6) open faces 1017 are approximate, geometrically coincident rectangles 1022 (approximately squares).
- framework 1015 internally defines a like-shaped chamber 1019.
- Chamber 1019 intersects the twelve (12) open faces 1017 and corresponding facial openings 1018. Only a few of edges 1013a, vertices 1013b, faces 1017, openings 1018, hexagons 1020, and rectangles 1022 are designated by reference numerals to preserve clarity.
- truncated octahedron framework 1015 is comprised of link/bar members 1024 each corresponding to a different edge 1013a.
- Bar members 1024 are each elongate, and generally straight with one bar end 1026 positioned opposite another bar end 1026.
- Three bar ends 1026 come together at a corresponding node/vertex 1013b to form a nodal joint 1028.
- the three joined bar members 1024 extend away from joint 1028 in correspondence to the respective edges 1013a.
- thirty-six (36) bar members 1024 and twenty-four (24) joints 1028 define framework 1015, which is also a form of truncated octahedral cage 1021.
- Bar members 1024 and joints 1028 may be integral to one another, consisting of a single piece of material. Such construction can be performed by mechanical or laser machining, etching, or the like of a unitary piece of material, such as a metal, ceramic, or metalloid. Alternatively, bar members 1024 may be fastened together with mechanical fasteners, by welding, brazing or soldering, by chemical medium/media such as adhesive(s), a 3-D printing technique, or the like. In still other embodiments, a combination of these approaches may be utilized. Only a few of bar members 1024, bar ends 1026, and joints 1028 are designated by reference numeral to preserve clarity. It should further be noted that members 1024 may be coated with a polymer such as that previously described in connection with sampler 100.
- FIG. 23 a diagrammatic, perspective view of a 3-D bitruncated cubic honeycomb 1030 is illustrated that is comprised of geometrically coincident truncated octahedra 1008; where like reference numerals refer to like features previously described.
- Honeycomb 1030 is also called a truncated octahedrille and is more generally a form of tessellation 1032.
- Honeycomb 1030 is of a solid geometric form to function as a visualization aide to conceptually bridge understanding from constituent 1005/framework 1015 (FIG. 22) and truncated octahedron 1008 (FIGs. 22 & 23), to framework 1010 (FIGs. 24 & 25).
- solid truncated octahedral "blocks" 1034 are geometrically solid polyhedrons shown with appropriate shading to illustrate the nature/shape of the honeycomb 1030. It should be appreciated that the shaping and sizing of blocks 1034 renders them approximately coincident relative to one another. As a result, blocks 1034 approximately, if not exactly, occupy the same space if overlapping one another. Blocks 1034 fit together congruently, arranged and shaped in a complementary orientation such that edges 1013a and vertices 1013b of octahedra 1008 abutting one another can be merged or united because of the respective coincidence.
- Truncated octahedral framework 1010 is a form of tessellation 1032 similar to honeycomb 1030. Analogous to the arrangement of honeycomb 1030, framework 1010 may be conceptualized as the merger/union or congruent interconnection of pairs of coinciding bar members 1024 and pairs of coinciding joints 1028 that come together as adjacent truncated octahedral frameworks 1015 are fit together. In other words, in effect, a single bar member 1024 and joint 1028 is substituted for each of the respective coincident pairs.
- framework 1010 corresponds to a form of wireframe 1011 outlining a bitruncated cubic honeycomb shape. Also, the arrangement of bar members 1024 and joints 1028 of framework 1010 collectively define a form of cage 1044. In further description, framework 1010 is generally a form of openwork 1052, defines a reticular/reticulated structure 1054, and is a type of lattice 1056.
- the alignment of open faces 1017 of hexagons 1020 and rectangles 1022 form recesses in the form of internal passages 1040 that intersect one another in several different directions to form a passage network 1042.
- Passage network 1042 defines chamber 1046 bounded by the outermost bar members 1024 and outermost joints 1028.
- Chamber 1046 is comprised of adjacent truncated octahedral-shaped chambers 1019 each corresponding to a different truncated octahedral framework 1015 (see also FIG. 22).
- interspatial intersections between adjacent chambers 1019 result through open faces 1017/facial openings 1018 that are defined by corresponding bar members 1024 and vertex joints 1028. Furthermore, outermost facial openings 1018 correspond to external apertures 1048 that open externally-such that chamber 1046 opens/intersects external space through apertures 1048. Only a few of edges 1013a, vertices 1013b, truncated octahedral frameworks 1015, open faces 1017, facial openings 1018, chambers 1019, hexagons 1020, rectangles 1022, bar members 1024, joints 1028, passages 1040, and apertures 1048 are designated by reference numerals to preserve clarity.
- framework 1010 is comprised of a like-shaped support structure core 1062 coated with a polymer 1070. Accordingly, in some embodiments, it is desirable to form support structure core 1062 before any polymer 1070 is applied so the manufacturing techniques are generally described in terms of support structure core 1062 rather than framework 1010 given the possible absence of polymer 1070 coating. Nonetheless, in some other embodiments, support structure core 1062 may be partially or completely coated by polymer 1070 before or during manufacture.
- framework 1010 may or may not actually be made from multiple frameworks 1015 depending on the selected manufacturing procedure; however, framework 1010, framework 1015, and support structure core 1062 all still appropriately use the same bar members 1024 and joints 1028 in view of the framework 1015 relationship to framework 1010 and support structure core 1062.
- support structure core 1062 is formed from a single, unitary piece of material— with portions of support structure core 1062 corresponding to bar members 1024 and vertices 1028 being integrally shaped.
- support structure core 1062 may be used to make support structure core 1062.
- a standard "3-D printing" technique is utilized, such as those shaping a series of layers that are stacked and joined together to provide the desired article.
- one or more of these techniques are utilized to make support structure core 1062 from relatively few parts (such as two halves, four quarter parts, or the like) that may be connected together using other suitable mechanical, thermal, and/or chemical joining techniques, some of which are described further below.
- support structure core 1062 may be partially or completely assembled by mechanical fasteners, by welding, brazing, or soldering, by chemical agency, such as bonding parts together with adhesive(s), or the like.
- framework 1010 is comprised of multiple frameworks 1015 joined together.
- each pair of coincident bar members 1024 and joints 1028 may be complementarily shaped and/or sized to approximate merger/union of each pair into a single bar member 1024 and a single joint 1028.
- Coincident joints 1028 complementally unite/merge in correspondence with the effective substitution of each pair of bar members 1024 by a single bar member 1024.
- single bar members 1024 and vortex joints 1028 are substituted for each corresponding coincident pair.
- Further embodiments combine some or all of these techniques to provide support structure core 1062 and/or may be partially or completely coated by polymer 1070 before or during manufacture where appropriate.
- FIG. 25 a diagrammatic, planar cross-sectional view of the three-dimensional sampler 1000 is depicted; where like reference numerals refer to like features.
- the cross-section is taken along a plane approximately parallel to the view plane of FIG. 24 and illustrates sectioned portions 1050 with cross-hatching.
- the sectioned sampler 1000 further illustrates framework 1010 in part, more specifically designated as cross-sectioned framework portion 1080. While briefly introduced already, compositional configuration 1060 of framework portion 1080 is more specifically described attendant to the depiction in the vicinity of the sectioned portions 1050. This depiction contrasts support structure core 1062 composition (cross-hatched) from adjacent portions to which polymer 1070 have been applied.
- framework 1010 may be rigid, semi-rigid, or somewhat flexible.
- thermal performance compatible with thermal desorption of a collected sample and/or thermal cleaning of sampler 1000 would be desirable, while in other embodiments different thermal performance is desired.
- the composition of support structure core 1062 in one form is comprised of one or more of: glass, polymeric thermoplastic, polymeric thermoset, glass, metal, metalloid, inorganic oxide, ceramic, and glass-ceramic.
- the composition of support structure core 1062 includes metal, metalloid, metal oxide, ceramic, or glass-ceramic. Still a more specific embodiment is comprised of metal, carbon, metal oxide, ceramic, or glass-ceramic.
- the composition of support structure core 1062 includes carbon.
- the carbon composition is anisotropic in terms of strength and/or thermal performance.
- the support structure core 1062 includes one or more carbon allotropes as previously described.
- the composition of support structure core 1062 includes ceramic material. Only a few of sectioned portions 1050 are designated by reference numerals to preserve clarity.
- Compositional configuration 1060 further comprises polymer 1070 applied to the support structure core 1062 to at least partially coat or cover all surfaces thereof.
- polymer 1070 provides an approximately complete covering of support structure core 1062. Internally, the polymer at least partially lines internal passages, chambers, and the like. In an even more favored form, internal surfaces of core 1062 are generally completely lined.
- Polymer composition may be the same as any of the embodiments previously described in connection with sampler 100.
- sampler 1000 may be directed to any of the various sampling targets previously described in connection with sampler 100.
- Internal passages 1040 of network 1042/chamber 1046 that are externally open through intersection with apertures 1048 operate during the sampling activity to intake various substance(s) of interest (if present in trace amount(s)) and temporarily trap the same within chamber 1046 or on interstitial bar members 1024 internal to sampler 1000 either physically, mechanically, and/or chemically.
- Such mechanisms may correspond to those described previously in connection with sampler 100 where the influential parameters are of like type.
- Instrumentation 30 or other detection equipment like that previously listed is adapted to receive 3-D sampler 1000 directly for thermal desorption processing and/or receives the sample by rinsing and/or treatment of sampler 1000 with one or more agents to release/prepare the sample. Once prepared, the sample is processed in the previously described manner, as applicable.
- sampler 1000 is of particular applicability to the collection of uranium, plutonium, and heavy metals that typically are released from sampler 1000 through liquid treatment/rinsing/processing/preparation with appropriate agents as described previously and further described in connection with Experimental Examples 1 1 -13.
- sampler 1000 is of particular applicability to the collection of uranium, plutonium, and heavy metals that typically are released from sampler 1000 through liquid treatment/rinsing/processing/preparation with appropriate agents as described previously and further described in connection with Experimental Examples 1 1 -13.
- radioisotope nuclear material sampling like uranium and plutonium
- radioactive decay detection equipment appropriate to the expected decay
- type(s)/substance isotopes may be used (alpha particle, beta particle, and/or gamma ray detectors).
- a method of the present application comprises: providing a sampler including an inorganic fiber core and a polymer applied thereon with background uranium of less than or equal to 10 ng/g; selecting a surface with dust thereon; collecting at least a portion of the dust with the sampler; chemically processing the sampler to analyze the dust for uranium content.
- the inorganic fiber core is comprised of at least one of glass, metal, metalloid, inorganic oxide, ceramic, and glass-ceramic and the polymer includes PTFE with background uranium of less than or equal to 1 ng/g.
- the core material is comprised of one or more of: HSG, metal, metalloid, metal oxide, ceramic, glass-ceramic and the polymer is comprised of PTFE with background uranium of less than or equal to 0.1 ng/g.
- the core is comprised of one or more of: HSG, metal, carbon, and metal oxide and the polymer is comprised of PTFE with a background uranium level of less than or equal to 0.01 ng/g.
- the inorganic fiber core is made of carbon and/or S-glass and the polymer is made of PTFE with a background uranium level of less than or equal to 0.01 ng/g.
- a method comprising: providing a sampler including an inorganic fiber core and a polymer applied thereon; selecting a surface with dust potentially containing one or more heavy metals (previously defined); collecting at least a portion of the dust with the sampler; chemically processing the sampler to analyze the dust for heavy metal content.
- the inorganic fiber core is comprised of at least one of glass, metal, metalloid, ceramic, glass-ceramic, and inorganic oxide
- the polymer includes at least one of polymeric organofluorine, polyamide, polyimide, PDMS, PBI, PFSA, and PPPO.
- the core material is comprised of one or more of: HSG, metal, metalloid, metal oxide, ceramic, glass-ceramic and the polymer is comprised of one or more of: perfluorocarbon, perfluoroether, ETFE, FEP, THV, PVdF, and PPPO.
- the core is comprised of one or more of: HSG, metal, carbon, and metal oxide; and the polymer is comprised of PTFE.
- the inorganic fiber core is made of carbon and/or S-glass and the polymer is made of PTFE.
- sampler to collect and release one or more contraband or undesirable substances
- the sampler includes: a woven fabric of S-glass fibers, the fabric having a closed weave of satin and/or twilled weave type; a polymer applied to the fabric, the polymer being comprised of polytetrafluoroethylene; and the sampler having a thickness less than or equal to 0.3 mm and a flexural modulus equal to or less than 3 GPa.
- a further example is directed to a detection system comprising: a sampler including a fabric core with a polymer applied thereto, the fabric core being comprised of S- glass; and a thermal desorption IMS detector structured to receive the sampler.
- the sampler has at least one of: a flexural modulus of greater than or equal to 1 GPa, the fabric core with a thickness of about 0.3mm or less, and a calcined polymer content in a range of about 20%wt through about 40%wt.
- a different example is directed to a method of detecting a contraband or undesirable substance, comprising: collecting the contraband or undesirable substance on a sampler, the sampler including a fabric with a first polymer layer applied thereto and a second polymer layer applied on the first layer, the fabric being comprised of one or more of: HSG, metal, metalloid, inorganic oxide, ceramic, and glass-ceramic, the first polymer layer and the second polymer layer each being comprised of one or more of: polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, and PPPO; transferring the contraband or undesirable substance from the sampler to detection instrumentation; and detecting the contraband or undesirable substance with the instrumentation.
- the inorganic fiber core is comprised of at least one of HSG, metal, metalloid, metal oxide, ceramic, and glass-ceramic.
- the core material is comprised of one or more of: HSG, metal, carbon, metal oxide, ceramic, glass-ceramic and the polymer is comprised of one or more of: perfluorocarbon, perfluoroether, ETFE, FEP, THV, PVdF, and PPPO.
- the core is comprised of one or more of: HSG, metal, carbon, and metal oxide; and the polymer is comprised of PTFE.
- the inorganic fiber core is made of carbon and/or S-glass and the polymer is made of PTFE.
- a further example is directed to a method of making a sampler, comprising: providing a fabric core; applying at least a partial particle fill to the fabric core to alter thermal conductivity of the sampler, the particle fill being comprised of one or more types of inorganic metallic material; applying polymer to the fabric core; heating the fabric core and the polymer after application to the fabric core to provide the sampler.
- One refinement includes heating the fabric core before the applying of the polymer.
- Another refinement includes functionalizing the core/substrate before polymer application.
- Still a further refinement includes the polymer comprising a first polymer layer and further applying a second polymer layer on the first polymer layer that may be the same composition or a different composition.
- the particle fill material is comprised of one or more nanoparticles of: metal, metalloid, and metal oxide
- the polymer includes at least one of: polymeric organofluorine, polyamide, polyimide, PDMS, PBI, PFSA, and PPPO.
- the particle fill material are nanoparticles comprised of one or more of: carbon and metal oxide; and the polymer is comprised of one or more of: perfluorocarbon, perfluoroether, ETFE, FEP, THV polymer, PVdF, and PPPO.
- the particle fill comprises nanoparticles including one or more of: alumina, nanotubes of carbon, and/or graphene; and the polymer is made of PTFE.
- Yet another example is directed to a method of making an sampler for one or more contraband or undesired substances, comprising: providing an inorganic fabric core defining a surface; performing a silane functionalization of the surface to provide an affinity to the one or more analytes and improved polymer application to the core; applying a first polymer to the fabric core; heating the fabric core and the polymer after application to the fabric core to provide the sampler.
- One refinement includes heating the fabric core before the applying of the polymer.
- Still a further refinement includes applying a second polymer layer on the first polymer layer.
- another refinement includes applying at least a partial particle fill to the fabric core to alter thermal conductivity of the sampler before the performing of the silane functionalization, the particle fill being comprised of one or more of: metal, carbon, and a metal oxide.
- a device comprises: a sampler to collect and release one or more contraband or undesirable substances, the sampler including: a woven fabric of S- glass fibers, the fabric having a 4 HS weave; and a polymer applied to the fabric, the polymer being comprised of polytetrafluoroethylene.
- the sampler fabric has a thickness less than 0.3 mm and a flexural modulus of at least 3 GPa; which includes means for thermally cleaning the sample and thermally releasing the one or more contraband or undesirable substances from the sampler; and/or which includes means for analyzing the one or more contraband or undesirable substances released to detect the same.
- coincident cube-shaped constituents are provided by structural bar linkages extending in three different approximately orthogonal directions and intersecting one another to define adjoining nodes of four linkages, and corresponding to the shape of a cubic honeycomb and further define external passage openings in different directions (approximately orthogonal to one another); where the core is at least partially coated by one or more polymer types previously described.
- a 3-D sampler collection framework includes a cage-type structural core comprised of: ceramic, metal, metal oxide, glass, glass-ceramic and/or metalloid, which has structural linkage members and nodal joints corresponding to the edges and vertices of a convex polyhedron that defines several passages opening externally, and with one or more polymers of any of the types previously described applied thereto, at least partially coating the same.
- the convex polyhedron is one or more of: a geometric convex uniform honeycomb, a convex space-filling polyhedron, and an archimedean solid.
- a 3-D sampler collection framework includes a cage-type structural core comprised of: ceramic, metal, glass, glass-ceramic, metal oxide, and/or metalloid; at least a portion of which corresponds to approximately a
- a structural core comprised of one or more of: metal, ceramic, glass, metal oxide, glass-ceramic, and/or metalloid includes a number of passages that are formed by approximately helical coils joined together; where each coil externally opens to collect and trap a substance that is a sampling target and to which a previously described polymer may be applied to provide at least a partial coating.
- 3-D sampler embodiments differ from those previously described by lacking any generally discernable solid geometry classification, and may include a random or pseudorandom arrangement of structural members; where such members defined a 3-D openwork, cage, lattice, reticular, and/or other backbone structure providing: recesses that define external openings thereto and/or may recede inward sufficiently to provide a passage into the structure that may intersect another passage or chamber, or may extend therethrough; and/or passages defining external openings.
- Such recesses/passages with external openings receive and trap substance(s) targeted for sampling and may be at least partly coated by one or more polymers previously described.
- FIG. 1 Further alternative embodiments are directed to a 3-D sampler provided in the form of a pad including a structural core comprised of one or more of: glass, metal, ceramic, metalloid, and glass-ceramic, that defines a number of passageways each externally opening along at least one face of the pad; where the core is coated by a polymer previously described.
- Other alternative embodiments include one or more of the treatments, options, enhancements, and/or processes previously described in connection FIGs.
- l -2l including, but not limited to: (a) surface activation by silanizaLion or other functionalization procedure; (b) specifically processing to provide a surface phenol functional group; (c) at least partly filling with particles (such as nanoparticles) of a metal oxide (including without limitation alumina), a metal, one or more allotropes of carbon, and/or a different element or compound; (d) providing two or more applications of polymer-such applications each being the same or different compositions; (e) providing a polymer thickness in accordance with any of the previously disclosed ranges or other limits; (f) applying polymer in any of the alternative %wt listings previously described; and/or any others as previously described with any of FIGs. 1-21 herein.
- a method to detect as substance includes: collecting the substance with a sampler including a structural core, the structural core being comprised of one or more of: ceramic, metal, and metalloid; a polymer applied to at least partially coat the core, the polymer being comprised of one or more of: polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, and PPPO; the sampler defining several recesses therein that externally open to receive the substance; transferring the substance from the sampler to detection instrumentation; and detecting the substance with the instrumentation.
- at least some of the recesses may be defined by external openings with passages receding into the core.
- Still another embodiment is directed to a system, comprising: means for collecting a substance, the collecting means including a structural core, the structural core being comprised of one or more of: glass, polymeric thermoplastic, polymeric thermoset, ceramic, metal, metal oxide, metalloid, and glass-ceramic; means for at least partially coating the structural core; the structural core including means for defining several recesses and/or passages extending into the structural core that externally open to receive the substance; means for transferring the substance from the collecting means to detection instrumentation, the detection instrumentation including means for analyzing the substance.
- Yet another embodiment is directed to a method to detect a substance including uranium, comprising: collecting the substance with a sampler at least partially coated with a polymer; performing liquid extraction of the substance from the sampler after the collecting of the substance with the sampler; and detecting the uranium in the substance from the liquid extraction.
- the polymer includes PTFE.
- the polymer comprises any of those previously described in connection with polymer application to a core.
- a further embodiment is directed to an apparatus to detect a substance including uranium, comprising: means for collecting the substance, the collecting means being at least partially coated with a polymer including PTFE; means for performing liquid extraction of the substance from the collecting means; and means for detecting the uranium in the substance from the liquid extraction.
- the polymer comprises any of those previously described in connection with polymer application to a core.
- This first experiment was performed with a sampler prepared in accordance with process 400 at Pacific Northwest National Laboratory (PNNL), a facility managed by the Assignee of the present application.
- This PNNL sampler was made from S-glass/4 HS woven fabric with PTFE polymer applied thereto. The fabric thickness was less than or equal to about 0.3 mm and PTFE application was less than or equal to 35% by weight.
- the PTFE coating was created by painting a colloidal slurry of suspended particles on the core fabric surface followed by evaporation of the solvent. The slurry was prepared using DUPONT TEFLON PTFE TE- 3859 aqueous dispersion. It contained negatively charged, 0.05 to 0.5 micrometer ( ⁇ ) PTFE resin particles suspended in water, and about 6% (by weight of PTFE) of a nonionic wetting agent and stabilizer.
- the PNNL sampler was compared to sampling swipes sourced from: (a) SARFRAN MORPHO (MORPHO) and (b) DSA DETECTION (DSA).
- MORPHO SARFRAN MORPHO
- DSA DETECTION DSA DETECTION
- MORPHO sampling swipes used for the comparison were commercially available materials. Data was taken with a BARRINGER IONSCAN 400A ion mobility spectrometer (SMITHS DETECTION) via thermal desorption. This instrument was operated in negative ion mode at a thermal desorption temperature of 180 °C and a collection time of 10 s. The drift and inlet temperatures were set at 1 14 °C and 240 °C, respectively. The sample gas was set at 239 mL/min and the drift gas at 351 mL/min, as per standard instrument settings.
- FIG. 9 is a comparative graph illustrating magnitude versus time responses of samplers from the three different sources to a 10 nanogram (ng) sample of TNT (hand spiked) as detected with the indicated IMS detector. Describing the data plots in top to bottom order of the inset legend: (1) the "X" data point plot represents the response of the PNNL sampler embodiment of the present application— it has the highest peak and quickest peak response, (2) the "hollow triangle" (A) data point plot represents the response of the MORPHO brand of sampler that is intermediate in terms of peak magnitude and speed, and (3) the "filled diamond” ( ⁇ ) data point plot represents the response of the DSA brand of sampler with the slowest and lowest peak response.
- ng nanogram
- the relatively higher response of the PNNL sampler illustrates its superior performance under like conditions. It is theorized that the use of a relatively thin S- glass for the fabric core and/or a relatively modest amount of PTFE polymer resulted in higher thermal conductivity, higher gas permeability, and reduced thermal mass to provide a better TNT signal response of the PNNL sampler.
- Table I data was taken with a BARRINGER IONSCAN 400A ion mobility spectrometer (SMITHS DETECTION) using conditions/parameters like those for Example One.
- the different sampler configurations correspond to the entries in the left hand column of Table I.
- the maximum TNT signal from the sampling material was averaged and reported in the right hand column of Table I.
- the first three entries of Table II resulted from samples taken with three different core/substrate material configurations without application of a polymer thereto, which in like order (top to bottom) are: thick E-glass core, thick S-glass core, and thin E-glass core.
- the fourth entry of Table I is for a sampler prepared from thin S-glass and functional ized per operation 414 of process 400 to provide phenyl terminal groupings (See FIG. 7), but still lacking any polymer application.
- the fifth and final entry of Table I is prepared in the same manner as the fourth sample, but also has PTFE polymer applied in accordance with operation 416 of process 400. It has been discovered through such experimentation that the application of a polymer like PTFE may controllably increase stiffness of the sampler as a function of the amount applied and other operations/treatments, such as heat applied to cure the PTFE.
- Table I relates to properties and parameters useful for the development of suitable samplers with varying stiffness, including: the composition of the substrate/core (in this case E- glass or S-glass), substrate/core thickness (whether “thick” or “thin”), surface chemistry (functionalization), and polymer application.
- the sampler stiffness can be controlled with the amount of polymer applied and/or heat treatment used to cure the polymer.
- a certain degree of stiffness/flexure is desired in some embodiments to provide for more suitable handling, detector equipment interfacing, and longevity, among other things.
- the fabric core sampler material of S-glass fibers provides higher IMS signals as compared to E-glass fibers even without functionalization (like that of operation 414) or polymer application (like that of operation 416), which is theorized to be due to its better thermal properties.
- the thinner sampler core appears to significantly improve the IMS signal, which may be because of improvement in mass transport of the analyte out of the sampling material during a thermal desorption analyte release/transfer.
- the phenyl silane surface functionalization of thin S-glass indicates performance improvement relative to TNT release.
- the PTFE polymer application to the core and functionalized thin S-glass core combination provides the stiffness and other properties desired for some robust applications; however, indicates a trade-off in terms of a slightly reduced IMS signals. This reduction is most likely due to the change of mass transfer and/or surface chemistry alteration because of the PTFE application.
- Experimental Example Three relates to the varying performance of different PTFE-coated core/substrates used for trace analyte detection (See FIG. 10). It should be appreciated that a thermal desorption sampler used with IMS, gas chromatography, or the like preferably has good thermal conductivity and low specific heat capacity to facilitate rapid desorption heating. A comparison of these properties for various candidate core/substrate materials at 25°C was determined as provided in Table II as follows: Thermal
- Metal oxides have similar limitations. Furthermore, these materials can scratch certain test article surfaces. Also, carbon surfaces can promote rapid oxidation of TNT through TNT methyl groups, and may chemically interact with other analytes in an unacceptable manner. Nonetheless, it has been found that a carbon core fully covered with PTFE exhibits excellent release of TNT for thermal desorption purposes. Nonetheless, all these metals, metal oxides, carbon, and the like can find application in certain embodiments— especially depending on target analyte(s) and particular treatments applied thereto. In FIG.
- results for other PTFE-coated core materials are graphically presented as comparative plots of magnitude versus time responses of samplers to a TNT lOng sample using thermal desorption IMS with setup/conditions comparable to Experimental Example One.
- 6- 10%wt PTFE coating was applied to each core and all samples were heated at 400°C in a furnace for 30 minutes prior to testing.
- the "filled diamond” ( ⁇ ) data point plot represents a PTFE-coated stainless steel core response— it has the highest peak
- the "filled circle” ( ⁇ ) data point plot represents a PTFE-coated thin S-glass core response— it has the second highest peak
- the "filled square” ( ⁇ ) data point plot represents a PTFE-coated thick S-glass core response— it has the third highest peak
- the "filled triangle” (A) data point plot represents a PTFE-coated thick E-glass core response— it has the lowest peak.
- PTFE-coated stainless steel had better TNT release performance than PTFE-coated glass fibers of the E- or S-type— theorized to be due to stainless steel's higher thermal conductivity and lower specific heat compared to glass fibers per Table II.
- FIG. 1 1 presents a graph that compared magnitude versus time responses of two samplers with different cores to a TNT lOng sample when tested by IMS under experimental setup/conditions comparable to those described for Experimental Example One.
- the "X" data point plot represents the response of a 4 HS weave pattern comprised of thin E-glass fibers with 225 yarn pattern— it has the highest peak
- the "hollow triangle" ( ⁇ ) data point plot represents the response of an 8 HS weave pattern comprised of thin S-glass fibers with 450 yarn pattern— it peaks at a slightly lower value.
- FIG. 11 indicated how the core weave pattern can impact particle pickup and analyte recovery.
- the enhanced desorption of the E-glass fabric results from the higher gas permeability of the 4 HS weave/225 yarn strand weight/count compared to the 8 HS weave/450 yarn strand weight/count of the S-glass fabric. From this experiment, it is theorized that higher gas permeability results in better analyte mass transport of the thin material. Data was taken on the same day and with the same instrument. Suitable weave/yarn pattern varies with the application and detection system used. Typically, different detection systems also may have different responses to released analytes. The weave and yarn pattern also significantly impacted the collection of materials from the surface. It is hypothesized that S-glass material should be a higher grade weave material for superior performance. Moreover, for installation of surface chemistry silanes per the '910 Patent, S-glass may be a better substrate as it generally contains a higher density of surface silanol sites for ligand loading than E-glass.
- Tables I & II, and FIGs. 10 & 1 1 show that thickness, type, and weave/yarn of glass fiber make significant contributions to the thermal desorption releasing ability of TNT from corresponding samplers.
- Glass fiber and many other inorganic materials have thermal properties acceptable for use as a sampling medium for thermal desorption analysis.
- a combination of inorganic oxide compounds form active surfaces for collection of analyte(s).
- these active surfaces bind more strongly than desired to target analytes, hampering release.
- coating and/or lamination of glass fibers with a suitable material, such as PTFE can provide an attractive alternative.
- Polymer composition and other characteristics can be varied to serve different purposes, such as to: cover overly active glass fiber surface sites, provide a desired degree of sampler stiffness/rigidity, increase target analyte collection ability, and enhance thermal desorption of target analyte(s).
- the PTFE polymer provided the highest signal for TNT thermal desorption release when compared to the other polymers (Table III). Surprisingly, there was no occurrence of TNT signal from PB1, which is known to have high thermal stability— suggesting that some polymer compositions demonstrate better adsorption ability than desorption for TNT.
- TENAX TA (PPPO) and TENAX GR (PPPO/graphite) demonstrate TNT desorption behavior of more interest than several of the other polymers. The release of TNT was pronounced when TENAX was coated after PTFE coating to provide a double coating layer of different polymer compositions (PPPO or PPPO/graphite on PTFE) of the type illustrated in FIG. 7.
- Both TENAX TA and TENAX GR polymers were obtained from dissolved beads of the same. The beads were dissolved in dichoromethane for a few days or until the beads were mostly dissolved.
- PTFE-coated thin fiber S-glass was chosen for further study and development because it provided the highest signal of TNT thermal desorption release in conjunction with high thermal stability (high thermal decomposition temperature in Table III).
- PTFE is relatively chemically inert, thermally stable, and highly hydrophobic, and the surface properties and structures of PTFE change as a function of cure temperature.
- PTFE stock is typically a white, fine powder; but its physical morphology/structure becomes the extended chain type by curing it at a temperature above its melting point and also becomes more transparent/translucent.
- cure temperature can influence sampler stiffness/rigidity (or conversely flexure) as quantified by flexural modulus determinations, and sampler surface property changes.
- the proper heat treatment of PTFE applied to glass fiber fabric can significantly contribute to the stability, stiffness, and surface properties of the corresponding sampler with a glass fiber core having PTFE applied thereto.
- FIG. 12 indicates a PTFE coating treatment temperature in the range from the
- FIG. 12 presents a comparative graph illustrating magnitude versus time response for each of four different samplers to a TNT lOng sample when tested with IMS with setup conditions comparable to those for Example One. Each of these different samplers were subjected to a different heat treatment as reflected by the FIG. 12 inset legend.
- the "hollow triangle” ( ⁇ ) data point plot represents the response to approximately a 450 °C heat treatment, which has the second highest peak; (2) the "X” data point plot represents the response to approximately a 400°C heat treatment, which is the highest peak; (3) the "filled triangle” (A) data point plot represents the response to approximately a 325 °C heat treatment, which is the third highest peak; and (4) the symbol (an "X" with a vertical line intersecting its cross-point) provides a data point plot representative of the response to approximately a 150 °C heat treatment, which has the lowest peak. Peak timing is comparable for all the plots.
- Each sampler was comprised of a 10%wt PTFE coating on thin fiber S-glass fabric, and did not have phenyl surface or other functionalization. All samplers were placed in a furnace at the indicated temperature for 30 minutes.
- PTFE coatings on thin S-glass fiber fabrics were heat-treated at different temperatures including, below its melting point (150 °C and 325 °C), above its melting point (400 °C), and near its thermal decomposition temperature point (450 °C).
- FIGS. 13-20 provide a sequence of computer-generated SEM images of PTFE-coated surfaces on both fabric and a silicon (Si) wafer heated at 150 °C, 325 °C, 400 °C, and 450 °C, respectively.
- the PTFE coating was created by painting a colloidal slurry of suspended PTFE particles on the sampler surface followed by evaporation of the solvent.
- the slurry was prepared using DUPONT TEFLON PTFE TE-3859 aqueous dispersion. This dispersion contains negatively charged, 0.05 to 0.5 ⁇ PTFE resin particles suspended in water, which also contains approximately 6% (by weight of PTFE) of a nonionic wetting agent and stabilizer.
- FIGs. 13 and 14 are computer-generated SEM images of the thin S-glass sampler fabric and Si wafer, respectively, with the coating dried at 150 °C which removes the
- FIG. 13 corresponds to a contact angle in the range of 0-10 degrees and FIG. 14 corresponds to a contact angle in the range of 50-90 degrees.
- FIGs. 15 and 16 are computer-generated SEM images of the sampler fabric and Si wafer, respectively, with the coating calcined at 325 °C and baked to remove the nonionic wetting agent (typically at 290 °C).
- FIG. 15 corresponds to a contact angle in the range of 45-65 degrees and FIG. 16 corresponds to a contact angle in the range of 70-95 degrees. From the SEM images, a granular form of PTFE is observed with sintering and voids in PTFE structure for the 325 °C heat treatment. Based on the contact angle values, samplers prepared at this temperature are in the range indicating hydrophilic surfaces.
- FIGs. 17 and 18 are computer-generated SEM images of the sampler fabric and Si wafer, respectively, with the coating calcined at 400 °C which is above the crystalline melting point of the PTFE resin particles (the PTFE melting point is approximately 327 °C).
- FIG. 17 corresponds to a contact angle in a range of 95-105 degrees
- FIG. 18 corresponds to a contact angle in a range of 90-100 degrees.
- the PTFE particles/granular forms change from white to mostly transparent material with this treatment temperature.
- the computer-generated SEM images reveal a completely different, transformed morphology, in which the extended chain structure/folded chain structure can be seen.
- FIGs. 19 and 20 are computer-generated SEM images of PTFE coating calcined at
- 450 °C which is approximately the decomposition temperature of PTFE (See Table III).
- a contact angle in a range of 80-95 degrees was determined and for FIG. 20 a contact angle in a range of 90-105 degrees was determined.
- the material demonstrated a similar morphology and contact angle as the PTFE-coated Si wafer obtained at 400 °C, but with longer polymer chains.
- a poorer coating and lower contact angle is observed, which may be due to the PTFE starting to decompose based on empirical observations.
- Shrinking of PTFE film can be observed, which results in a greater tendency for direct interaction between the glass fiber surface and analyte(s) as compared to the 400 °C heat treatment.
- PTFE melting point appear to still allow the spiked TNT analyte to directly contact and interact with the active surface of the glass fiber fabric because the PTFE morphology was relatively unaltered. As a consequence, a lower TNT desorption signal results.
- a similar outcome is observed for the PTFE-coated sampler subjected to the 450 °C heat treatment. While 450 °C was above the PTFE melting point, it is approximately the same as the empirically-determined PTFE thermal decomposition temperature (448 °C per Table III). The highest signal of TNT thermal desorption is obtained from the PTFE-coated sampler with the 400 °C heat treatment. This heat treatment resulted in a hydrophobic surface with a more uniform coating appearance, which is believed to reduce direct contact/interaction between the TNT analyte and the glass fiber surface.
- multiple coatings of the same type of polymer are applied to the fiber substrate/core, which may be a fiber fabric or a nonfabric fiber conglomeration; while in other applications, multiple coatings of different compositions/types of polymer are applied to the fiber substrate/core, which also may be a fiber fabric or a nonfabric fiber type.
- Example Seven As reflected in the Table IV entries, glass fiber samplers were coated with selected coating masses (given as %wt of entire swipe) and then heated to different temperatures of about 325 °C, 400 °C, and 425 °C, respectively, for approximately 30 minutes each. Higher rigidity/stiffhess/flexural modulus and hydrophobicity resulted from increased PTFE concentration. The samplers prepared at different temperatures demonstrate a similar response tendency along with increasing PTFE concentration (Table IV). The IMS signals of TNT release were more pronounced with increased concentrations of PTFE up to about 35%wt for the indicated experimental setup.
- the higher surface hydrophobicity generally resisted polar solvents and analytes entering and diffusing into/through PTFE, which resulted in less chance of TNT contacting undesired active sites on the core surface underneath the PTFE. After solvent evaporation, TNT typically stays on the hydrophobic surface of PTFE, therefore, a higher TNT thermal desorption release signal is obtained.
- Samplers prepared at approximately 325°C demonstrated a lower signal and less rigidity/stiffness— having little or no PTFE melting.
- higher signals and higher rigidity/stiffness were obtained from both higher temperature samples at approximately 400°C and 425°C. These high temperatures exceed the melting temperature of PTFE of about 330°C but remained below the thermal decomposition temperature of about 448°C, which facilitates transformation of the PTFE particles to extended chain morphology (See also, FIGs. 13-20 and accompanying text).
- These results tend to indicate that sampler rigidity/stiffness increases with polymer melting— such melting appearing to bind core fabric fibers together.
- Even with relatively thicker PTFE sampler coatings a thin S-glass fabric sampler core still provided better TNT release when compared with commercial swipes.
- the comparative plots of the graph presented in FIG. 21 illustrate the effect of surface chemistry on thin fiber S-glass for lOng TNT detection using IMS with experimental conditions and setup comparable to that for Experiment One. More specifically, the comparative graph of FIG. 21 depicts the lOng TNT response of each of three different forms of PTFE-coated samplers with an S-type fiberglass core, two with and one without phenyl surface treatment of the core. The graph presents magnitude versus time of the three sampler responses.
- the "X” data point plot represents the response of a phenyl-PTFE sampler configuration heat treated at approximately 150 °C— it has the highest peak
- the "hollow triangle” ( ⁇ ) data point plot represents the response of a phenyl-PTFE sampler configuration heat treated at approximately 400 °C— it has an intermediate peak
- the "hollow diamond” (0) data point plot represents the response of a PTFE sampler
- the samplers with and without phenyl functionalization were coated with ⁇ 30wt% PTFE solution and then cured at 325 °C or 400 °C to result in ⁇ 20wt% of PTFE after curing.
- Phenyl installation was achieved by phenyl silane functionalization; refluxing the sampler with 10% by volume phenyl silane in toluene for 18 hours, and preconditioning in a vacuum oven at 180 °C overnight.
- the maximum TNT signal from sampling material was averaged and reported; using IMS experimental setup/conditions comparable to Example One.
- FIG. 7 provides a conceptual perspective image of a polymer coated on phenyl functionalized glass core.
- the phenyl silane (shown as a tethered 6 sided rings P in FIG.7) provides a surface passivation layer to prevent analyte loss.
- the interfacial phenyl silane layer provides compatibility with the polymer layer and improves both adhesion and uniform distribution of the polymer coating.
- EXAMPLE TEN Many polymers are solvent-resistant and thermally stable; however, they often have thermal heat properties (i.e. low thermal conductivity and high specific heat as shown in Table II), which is believed to slow release of analytes from the surface when using thermal desorption techniques common to IMS and other detection instrumentation. It has been surprisingly discovered that for the samplers with PTFE coating, thermal conductivity could be enhanced by adding selected thermally conductive materials, such as Al 2 0 3 (alumina) nanoparticles into the substrate/core. The Al 2 0 3 nanoparticle has a thermal conductivity around 30 W/m-K, ⁇ 100x better than PTFE and 6x better than fiber S-glass.
- nanoparticles to add include metals, other metal oxides, certain carbon allotropes, ceramics, and glass-ceramics. More specifically, Cu, Al, Fe, and Ag are exemplary metals. Other metal oxides include Ce0 2 , and T1O2.
- Al 2 0 3 nanoparticles have a high surface area and chemical activity, strong retention of analytes can occur, reducing the signal from the detection instrumentation. As can be seen in Table VI, the higher the concentration of Al 2 0 3 used, the lower the release signal of TNT obtained. Therefore, before Al 2 0 3 nanoparticles are used for their enhanced thermal properties; they should be chemically passivated to avoid analyte binding, which can be accomplished by silanization or thin polymer coating. It is also posited that incorporation of the particles should not block mass transfer and air permeability through the sampler during desorption and detection.
- Al 2 0 3 -thin S-glass was then functionalized with phenyl silane or coated with 20%wt PTFE.
- the post-functionalizations significantly improve the performance of the samplers. It provides a much higher release signal for TNT than those that are not functionalized.
- the Al 2 0 3 -thin S-glass coating with 20%wt PTFE and treated at 400 °C also show the enhanced desorption of TNT, Accordingly, both post- phenyl functionalization and coating with 20%wt PTFE of Al 2 0 3 -filled thin S-glass provides the highest signal of TNT release.
- Table VI also shows the consistent
- a sampler material includes a phenyl coated S-glass fiber fabric core with phenyl-coated alumina particles and a thin PTFE coating.
- the surface functionalization of the PN L sampler has chemical selectivity for
- TNT and other nitroaromatics to provide better chemical uniformity. Selectivity and affinity further improve analytical performance.
- Thermal conductivity can be further enhanced by adding small amounts of highly thermal conductive materials, such as Al 2 0 3 nanoparticles, into the core substrate. It has thermal conductivity around 30 W/m-K.
- Table VII shows extraction percentage of selected uranium compounds obtained with a PTFE-coated sampler for each of several different extraction agents— most of these agents were applied at two or more different molar (M) concentrations of the same active constituent. Namely, three different nitric acid (HNO3) concentrations were tested (O.OOOIM, 0.01M, and 6M aqueous solutions), two different sodium carbonate (Na 2 C0 3 ) concentrations were tested (0.1M and 1.0M aqueous solutions), and two different concentrations of an equal molar mixture of ammonium carbonate and hydrogen peroxide ((NH4) 2 C0 3 /H 2 0 2 ) were tested (1.OM/1.0M and 2.0M/2.0M aqueous solutions).
- HNO3 nitric acid
- Na 2 C0 3 sodium carbonate
- 0.1M and 1.0M aqueous solutions two different concentrations of an equal molar mixture of ammonium carbonate and hydrogen peroxide
- Uranium oxide U 3 0 8 or U0 2 was tested, which are crystalline compounds with relatively low solubility in water.
- Uranium Ore Concentrate UOC was also tested, which is characteristically a uranium mill product containing a high
- Uranyl fluoride U0 2 F 2
- U0 2 (N0 3 )2 Uranyl nitrate
- uranium compounds each can have a different solubility with respect to the same solution.
- a relatively weak acid solution (0.01 M HN0 3 ) provided suitable extraction and solubility of U0 2 F 2 and U0 2 (N03) 2 , while a stronger solution (i.e. (NH 4 ) 2 C0 3 /H 2 0 2 (2 M)) more suitably provided for complete extraction of U 3 0 8 and UOC.
- the U 3 0 8 form of uranium (including typical yellow cake) exhibited the greatest chemical stability (and associated resistance to extraction) even with a 6M nitric acid concentration.
- Uranium/uranium compound sample preparation traditionally has involved acquisition with a cotton fabric swipe. Sample extraction from a cotton swipe has proven rather labor-intensive, extending a day or more in some cases.
- a range of different uranium extraction agents were tested comparatively with both a TEXWIPE 304 cotton swipe and a PTFE-coated glass core sampler of the type used in Experimental Example Eleven, which demonstrated various differences leading to the unexpected, surprise discovery of several advantages of the PTFE-coated sampler.
- the TEXWIPE 304 swipe is a double-sided twill- pattern cotton wiper purportedly woven in a cross section of 1 18x60 threads per square inch with long staple cotton yarn under clean room conditions, and reportedly has cellulose fibers with a relatively low level of naturally occurring uranium. Extraction and analysis of deposited uranium compound particles on PTFE samplers were achieved in hours, or up to a day for hard mineral compounds. In contrast, pre-existing cotton swipe schemes take many more chemical steps and more time (with corresponding labor cost increases) to analyze uranium particles with standard protocols.
- Table VIII presents basic extraction efficiency results that shows better recovery of analyte from the PTFE-coated sampler than the TEXWIPE 304 cotton swipe for most tested conditions.
- a PTFE-coated sampler may enable recovery of uranium analytes of interest (e.g., by acidic leaching) without requiring total digestion of the sampler material under certain c ircumstances.
- Acetone is a polar high-volatility organic solvent.
- the selection of acetone as an extraction agent was because of its relatively high volatility under standard temperature and pressure conditions, so that it provided concentrated uranium-bearing solids after its quick and relatively easy evaporation.
- the resulting solid uranium extract was a form more suitable for certain subsequent analytical techniques; however, it should be appreciated dissolution is still required typically to perform ICP-MS. While the data in Table VIII indicates that uranium extraction with acetone from the PTFE-coated sampler is slightly more effective than the cotton TEXWIPE 304 swipe, the extraction efficiency for acetone relative to the other extraction agents was consistently less:
- U0 2 (N0 3 )2 b 100 100 100 64
- DMSO Dimethyl Sulfoxide
- the extraction was performed by placing the spiked swipes in 5 mL of extractant and continually shaken for approximately 18 hours at room temperature.
- U 3 0 is a stable, common form of uranium oxide commonly found in nature; UOC is a commercial, uranium mill product high in U 3 0 8 ; U0 2 F 2 is a hydrolysis product of UF 6 that is water soluble and decomposes to U 3 0 8 at 300 °C; U0 2 (HP04)*4H 2 0 is a naturally occurring uranium complex corresponding to strong uranium immobilization properties of different phosphate minerals; and U0 2 (N0 3 ) 2 is prepared from uranium salts treated with nitric acid.
- PTFE gas-phase chemical reaction synthesized PTFE for submission to uranium background content testing. From such a source, it has been discovered that PTFE can have some of the lowest metal (e.g., uranium) backgrounds relative to commercial sampling materials. Experimentally, background levels of uranium for different PTFE-coated samplers was found highly dependent on the sampler source. A pretreatment acid wash of the PTFE-sampler materials was found to reduce background levels substantially, with some as low as
- Empirical investigation further included rinsing a batch of TEXWIPE 304 swipes five (5) successive time with ultrapure nitric acid (6.0 M) to leach uranium therefrom. After each rinse, ICP-MS instrumentation provided measurements of the remaining background uranium. These measurements of the TEXWIPE 304 swipe material with each successive acid rinse were: 0.55, 0.036, 0.028, ⁇ 0.010, ⁇ 0.010 nanogram per gram (ng/g) of sampler material, respectively. Table IX summarizes these test, results, comparing them to two different PTFE- coated sampling materials also submitted to successive rinsing with concentrated nitric acid (6.0 M) five (5) times and corresponding background uranium measurement.
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Abstract
La présente invention porte sur une composition d'échantillonneur de noyau de fibre unique, sur des systèmes associés et sur des techniques permettant de concevoir, de fabriquer et d'utiliser cette dernière. L'échantillonneur est utilisé de sorte à avoir une interface avec des équipements de mesure de champ existants, tels qu'un équipement de spectrométrie de mobilité ionique (IMS pour Ion Mobility Spectrometer). Les caractéristiques souhaitées de l'échantillonneur comprennent : sa rigidité/flexibilité; sa masse thermique et sa conductivité; sa chaleur spécifique; sa fiabilité, sa sensibilité et sa possibilité de répétition de collecte/libération de substance à l'état de trace; son épaisseur; sa réutilisabilité; sa durabilité; sa stabilité pour un nettoyage thermique; et analogue. Selon un aspect, l'échantillonneur comporte un noyau en fibres de verre ayant une épaisseur inférieure à 0,3 millimètre qui est recouvert d'un polymère comprenant : un polymère organofluoré et/ou un polyimide et/ou un polyamide et/ou un polybenzimidazole (PBI pour PolyBenzImidazole) et/ou le polydiméthylsiloxane (PDMS pour PolyDiMethylSiloxane) et/ou le tétrafluoroéthylène sulfoné (PFSA) et/ou l'oxyde de poly(2,6-diphényl-p-phénylène) (PPPO pour Poly(2,6-diphenyl-P-Phenylene Oxide). De multiples revêtements polymères ayant les mêmes types de polymère ou des types différents peuvent être inclus, une fonctionnalisation de surface de noyau/substrat peut être utilisée et/ou le noyau/substrat peut être partiellement rempli de particules thermoconductrices.
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US14/692,371 US10453664B2 (en) | 2015-04-21 | 2015-04-21 | Collection, release, and detection of analytes with polymer composite sampling materials |
US14/692,460 US10254248B2 (en) | 2015-04-21 | 2015-04-21 | Collection, release, and detection of analytes with polymer composite sampling materials |
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PCT/US2016/000037 WO2016171768A1 (fr) | 2015-04-21 | 2016-04-21 | Techniques et types d'échantillonneur d'analyte |
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US20100099192A1 (en) * | 2007-03-12 | 2010-04-22 | Bayer Healthcare, Llc | Test-sensor cartridge |
US20110092377A1 (en) * | 2007-12-19 | 2011-04-21 | Berylliant, Inc. | High throughput methods for analysis of contamination in environmental samples |
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WO2014165634A2 (fr) * | 2013-04-05 | 2014-10-09 | President And Fellows Of Harvard College | Réseaux tridimensionnels comprenant des éléments nanoélectroniques |
US20150330879A1 (en) * | 2014-05-16 | 2015-11-19 | Junyu Mai | Method and apparatus for biomolecule analysis |
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US4003257A (en) * | 1974-03-12 | 1977-01-18 | Nasa | Analysis of volatile organic compounds |
US5147967A (en) * | 1988-10-11 | 1992-09-15 | Amoco Corporation | High strength polymer of hydroquinone poly(iso-terephthalate) containing residues of p-hydroxybenzoic acid |
US5468842A (en) * | 1992-06-23 | 1995-11-21 | E. I. Du Pont De Nemours And Company | Annealed linear high density polyethylene and preparation thereof |
US7550189B1 (en) * | 2004-08-13 | 2009-06-23 | Hrl Laboratories, Llc | Variable stiffness structure |
US7222546B2 (en) * | 2004-10-26 | 2007-05-29 | Dakota Techologies, Inc. | Method and apparatus for sediment characterization |
US20070251822A1 (en) * | 2005-09-02 | 2007-11-01 | William Hoagland | Visual hydrogen sensors using nanoparticles |
WO2012071605A1 (fr) * | 2010-11-29 | 2012-06-07 | The University Of Melbourne | Procédé pour préparer des nanoparticules d'or |
US8943910B2 (en) * | 2012-04-18 | 2015-02-03 | Battelle Memorial Institute | Enhanced surface sampler and process for collection and release of analytes |
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US20100099192A1 (en) * | 2007-03-12 | 2010-04-22 | Bayer Healthcare, Llc | Test-sensor cartridge |
US20110092377A1 (en) * | 2007-12-19 | 2011-04-21 | Berylliant, Inc. | High throughput methods for analysis of contamination in environmental samples |
US20110186436A1 (en) * | 2009-07-13 | 2011-08-04 | Enertechnix, Inc | Particle Interrogation Devices and Methods |
WO2014165634A2 (fr) * | 2013-04-05 | 2014-10-09 | President And Fellows Of Harvard College | Réseaux tridimensionnels comprenant des éléments nanoélectroniques |
US20150330879A1 (en) * | 2014-05-16 | 2015-11-19 | Junyu Mai | Method and apparatus for biomolecule analysis |
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