US 20140334998A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0334998 A1 WOOd (43) Pub. Date: Nov. 13, 2014

(54) MATERIAL SUCH AS FILM, FIBER, WOVEN Publication Classification AND NONWOVEN FABRIC WITH ADSORBANCY (51) Int. Cl. BOI 20/26 (2006.01) (75) Inventor: Willard E. Wood, Arden Hills, MN (US) BOID 53/04 (2006.01) (52) U.S. Cl. (73) Assignee: Cellresin Technologies, LLC, CPC ...... B01J 20/262 (2013.01); helps Bloomington,oomington, MN (US)(US USPC ...... 423/210; 442/121; 128/206.12: 428/36.1 (21)21) Appl. NoNo.: 14/128,3249 (57) ABSTRACT (22) PCT Filed: Jul. 27, 2011 Compositions that can be used to adsorb low concentration, of unwanted or target Substances from a dynamic fluid stream (86). PCT No.: PCT/US2O11AO4S485 or from an enclosed static vapor phase. Such adsorbency can S371 (c)(1), be obtained with thermoplastic materials used in the form of (2), (4) Date: Apr. 23, 2014 bulk polymer or a film, fiber, web, woven fabric, non-woven fabric, sheet, packaging and other such structures including (30) Foreign Application Priority Data or Surrounding the enclosed Volume. The concentration should be reduced to non-offensive sensed limits or a limit Jun. 23, 2011 (CA) ...... 27.4478O that does not produce a biological response.

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MATERIAL SUCHAS FILM, FIBER, WOVEN When target Substances are in the very low pressure range, AND NONWOVEN FABRIC WITH adsorption takes place on the most active sites on the Surface ADSORBANCY or within very narrow pores. Adsorbency by a synthetic poly 0001. This application is being filed as a PCT International mer material Such as polyolefin, polyester, polystyrene and Patent application on Jul. 27, 2011, in the name of CELL other such materials in the functional form of fiber, film or RESIN TECHNOLOGIES, LLC, a U.S. national corpora fabric is one example of this substantial problem. tion, applicant for the designation of all countries except the 0006 We have also found, as the boiling point or partial U.S., and Willard E. Wood, a U.S. Citizen, applicant for the pressure of the undesired molecules or Substances decreases, designation of the U.S. only, and claims priority to Canadian adsorption of the gaseous Substance at a constant concentra Patent Application Serial Number , filed Jun. 23, tion become increasingly more difficult because there is no 2011; the contents of which are herein incorporated by refer energetic reason to promote adsorption and the gaseous Sub CCC. stances Substantially remain in the vapor phase of the mobile 0002 Compositions can be used in an article or structure, fluid or the enclosed volume. Low partial pressure does not including fiber, film and fabric that can adsorb or remove low cause adsorption. The molecular interactions between the concentration of an unwanted or target Substance from gas or gaseous Substance and interfacial layer are dependent on the vapor under Static and dynamic conditions. A fundamental particular Surface composition and/or the pore structure. As a problem exists in adsorbing low concentrations of a variety of molecule in a vapor phase approaches a Solid Surface, a bal unwanted or target Substances from a gaseous Volume or ance is established between the intermolecular attractive and vapor phase in a static or a dynamic condition. A static con repulsive forces. Further, many adsorbing materials, as bulk dition is characterized by minimal or no flow of gas or vapor. material or in a coating, can have a small residual charge Dynamic condition is characterized by a flow of at least 1 present on the Surface or displays a separation of charges, i.e., liters'min' (16.6 cm sec') through a layer or aperture. At a dipole, effect. Any such extant charge or dipole can inhibit minimal parts per million concentrations, adsorbing signifi the target Substance approach to a surface and prevent Sub cant quantities of a variety of unwanted or target Substances stantial adsorption on the Surface. For example, in many become a significant problem. Adsorption occurs when a containers a low, but objectionable, concentration of an Solid Surface is exposed to and accepts or bonds to one or unwanted or target Substance can accumulate and be main more unwanted or target Substance (undesired molecules) in tained in the container contents. A Substantial need arises to a fluid (gas or liquid droplets) in an area of the interface overcome these energetic and Surface effects and improve between the fluid and the solid. Low partial pressure of an adsorbency of malodors. unwanted or target Substance reduces the tendency to absorb. 0007. The compositions that can adsorb in static condition The term adsorption deals with the process in which the and obtain Surprising adsorption in dynamic conditions unwanted or target Substance (undesired molecules) accumu include a source of a ferric (Fe(III) iron) compound and a late in an interfacial layer between a fluid and a surface. The polyethylenimine (PEI). The PEI can be free of substituent adsorption (a Surface process) process is accompanied by groups on the nitrogen or carbon atoms of the molecule. The absorption, i.e. the penetration of the gas or liquid into the adsorbent composition can comprise a Fe(III) compound and Solid phase. The total uptake and removal (adsorption and a PEI compound or a Fe(III) compound and a PEI compound absorption) of gas or liquid by a solid material is sorption. in at least a monolayer coating. This composition can Suc 0003. At low concentrations in the enclosed volume or cessfully overcome the natural tendency of such materials to enclosed ambient vapor phase, there is very little physical prevent or avoid adsorption. The adsorbent materials can cause, on an energetic basis, for the undesired molecules to be remove, preferably, for example at concentrations less than adsorbed. 15 ppm, of unwanted or target Substances from a static or 0004 Adsorption theory is based mainly on the Langmuir dynamic gaseous or vapor phase. (concept of monolayer adsorption, formed on energetically 0008 Improved adsorbency in both dynamic and static homogeneous solid surfaces) and BET (multilayer isotherm mode is derived from an adsorbent comprising a combination equation proposed by Brunauer, Emmett and Teller) equa of materials that can adsorb unwanted or target Substances at tions, capillary condensation theory, Polanyi potential theory low concentration. A removal compound or structure (an (adsorption potential and the characteristic adsorption curve, adsorber) with reduced charge effects and high Surface area which are independent on the of adsorption temperature) and can obtain functional adsorbency for low Substance concen the DR equation (adsorption based on considerations of trations. The structural material can contain the adsorbent adsorption energies) related to the latter. The Langmuir and composition as a component or the adsorbency can be BET equations have distinct deviations from experimental obtained from a coating on a Substrate. The Substrate can be values particularly in the range of low and high relative pres made of a natural or synthetic material made with thermo SUCS. plastic materials that can be used in the form of bulk polymer 0005. A problem arises in the divergence between theory in a film, fiber, web, woven fabric, non-woven fabric, rigid and experimental. This suggests the existence of additional sheet, cellulosic packaging and other Such structures includ physical factor that influences adsorption processes; an effect ing or Surrounding the enclosed Volume. resulting from interactions in the interface area. The disparity is related to the energetic heterogeneity of most real Solid 0009. A first aspect comprises an adsorbent, adsorbant (polycrystalline and amorphous) adsorbent. Without wishing layer or coating comprising a Fe(III) compound and a PEI to be bound by any theory, it is believed that it has been compound. experimentally shown that the concept of Surface heteroge 0010. A second aspect comprises a polymer comprising a neity (besides defects on the solid surface) can be distur majorportion of a polymer mass and an effective amount of a bances in the structure. The presence of structural flaws can adsorbent, adsorbant layer or coating comprising a Fe(III) affect significantly the Surface properties of adsorbents. compound and a PEI compound. US 2014/0334998 A1 Nov. 13, 2014

0011. In a third aspect structure can comprise a film or 0.018 The term “dynamic stream” is a fluid (gaseous or fiber and a coating of an adsorbent comprising a Fe(III) com vapor) stream flowing a flow rate of at least 1 liters'min pound dispersed in a adherent promoting PEI compound. (16.6 cm sec') through a layer or aperture. "Gas" implies a 0012. In a fourth aspect, this adsorbent layer or coating can uniform phase or blend of gaseous components. "Vapor be made from a solution or Suspension of a major proportion implies a dispersion of Small particulate (often liquid drop of a solvent or liquid medium and an adsorbent comprising lets, Solid particles, and combinations of these) materials in a Fe(III) compound and a PEI compound. The solution or sus gas phase. pension can comprise a liquid aqueous medium and can also 0019. The term "enclosed volume or enclosed ambient comprise a mixed liquid aqueous/non-aqueous medium. vapor phase' means a static atmosphere containing a target 0013 Lastly, in a fifth, a non-woven article or a shaped substance is held in a volume with little or no flow. object or other common polymer form of product can have an 0020. The unwanted or target substances can exist in the effective amount of an adsorbent, adsorbent layer or coating enclosed Volume or enclosed ambient vapor phase as a gas, comprising a Fe(III) compound and a PEI compound. These vapor or dispersion of a liquid droplet or solid. These sub include a container, a woven or non-woven fabric article, a stances often are malodors, irritants, or offensive or inoffen Sachet or other product format. sive odor compounds. 0014. The adsorbency can be used in a woven or non 0021 “Dynamic removal an adsorption followed by woven or a container structure to reduce the concentration of absorption include a reduction in concentration of unwanted unwanted or target Substances. The adsorbent compositions substance by at least a flow of at least 1 liters'min' (16.6 can be a compound of the structure or can be at least a cm:sec') through a layer or aperture at a contact time of less monolayer coating. The adsorbent of the invention is typi than 1 Second. cally used in the context of a dynamic or moving fluid or in a 0022. A thermoplastic composition comprising a thermo static enclosed Volume, also known as an enclosed ambient plastic polymer material with an active adsorbent composite vapor phase that contains the adsorbent of the invention and can maintain a Substantially neutral balance of negative the unwanted or target Substances at a concentration that is charge and positive charge material and can enhance the not desirable. The concentration should be reduced to below adsorption of compositions onto or into the adsorbent mate detectable or human sensed limits. Often the lowest possible rial. The combination of Fe(III) species and PEI in these concentration is desired. Since the contact time in dynamic Surfaces obtains excellent adsorbency. The compositions can mode is shorter, obtaining adsorption in dynamic conditions also containmaterials that can enhance or increase the Surface is made more difficult than experienced in static conditions. area of the surface of the thermoplastic articles. An increased 0015 The thermoplastic material contains an active Surface area and favorable pore size can increase the adsorp adsorbing composition, or a coating thereof, having a certain tion of compounds into the adsorbing materials. The thermo defined minimum surface area. Minimum coated thermoplas plastic material of the invention can be used in a variety of end tic surface area is 0.1 migram' that uses about a 2 to 50 um uses including webbing layers or structures, protective barrier fiber diameter fiber. The minimum surface area associated fabrics or articles, filtration units, face masks, storage bags, with the Fe(OH) is about 0.5 m. See FIG. 2 for the relation garbage bags, deodorizing materials and other Such applica ship between fiber surface area and fiber diameter. A brief tions. One particularly useful application is a face mask hav inspection of FIG. 2 shows that as the fiber diameter of the ing one or more layers that can remove malodors from breath. nonwoven is reduced to less than 4L and in particular less than Such malodors arise from H2S and organo Sulfur compounds. 2u, the Surface area of the nonwoven increases rapidly. As the 0023 The term “fiber' is used in its conventional meaning. Surface area increases, the fiber coating process and coating The term “fabric' typically means both woven and nonwoven Solution solids change to achieve uniform Surface coating. webs including materials of various thicknesses, lengths, Accordingly while fibers in the range of 2 to 20LL can be widths and compositions. Products include fabrics made typi effectively coated and while fibers of the smaller diameter can cally from the thermoplastic fibers of the invention but can also be coated the fibers in the range of 1 to 50 L, 2 to 20LL are also be made of other fabrics such as cellulosics, linens, and most readily coated and used in manufacture. others. The applications for the materials of the invention can 0016. The material can have the adsorbent blended or dis be used in face masks, tissue, wipes, towels, clothing, furni persed into the bulk polymer extending to the Surface or in a ture, automotive and other transportation, filtration for indus Surface coating of one or more coated layers. The Surface of trial or consumer applications. The fibers used in yarn or other the polymer must expose a minimum amount of the Fe(III) nonwovens as described in the invention typically means and PEI compound to effectively adsorb. fibers having relatively small fiber diameters. Such a diameter 0017 Depending on context, virtually any, gas or vapor is generally ranging from about less than 1 micron to as much phase, chemical species or mixtures thereof can be an as 100 microns. Often such fibers have a diameter from about “unwanted or target Substance' existing in a dynamic flow or 1 to about 50 microns. Once assembled, a final product can in an enclosed Volume or enclosed ambient vaporphase. Such include one or more of the structures disclosed above. The Substances can be presentata concentration of at least 5 ppb. fiber can be combined in a thermoplastic layer, two or more about 15 to 0.01 ppm; 5 to 0.01 ppm, 1 to 0.01 ppm or less than thermoplastic layers can be combined, and a wovenfabric can 0.5 to 0.01 ppm (concentration based on the total volume) and be combined with a nonwoven fabric which can also be lami can be the subject of the adsorption characteristics of the nated onto a film or other such structure. There are a variety of invention to reduce the concentration to a undetectable limit, combinations or combinations of the structures of the inven a limit that is not offensive to humans or to a limit that does not tion that can be made without departing from the spirit and produce a biological response. As the concentration of these Scope of the invention. materials in the vapor is reduced, and as the dynamic contact 0024. The term “container” in the context of the invention time is reduced to less than 1 second, the difficulty of absor is used in its conventional meaning. The container can com bance increases. prise a structure Surrounding a Void or Volume and the con US 2014/0334998 A1 Nov. 13, 2014

tainer can contain the adsorbent materials or a coating -continued thereof. The container, for example, can Surround a volume containing a small piece of adsorbent material held within the First Second Third container. Such containers can include virtually any article Embodiment Embodiment Embodiment that can enclose the vapor phase or atmosphere of the inven Components (Wt.%) (Wt.%) (Wt.%) tion. The containers can be made from virtually any materials Optional Silicate O.1-10 O.S.-S including cellulosics, plastics, thermosets, metals and other Optional CD O.1-10 O.S.-S conventional packaging materials. The containers can obtain virtually any geometric shape or dimension. The internal 0031. The adsorptive compositions can be in the form of a Volume of the container can range from as Small as 10 milli layer or coating and can also contain a silica, a CD (cyclo meters to more than 100 liters, but typically ranges from about dextrin), a substituted cyclodextrin (substituted CD) or a 100 millimeters to 4 liters in size. The configuration of the polymer with pendent CD moiety. These materials with the container can be virtually any configuration, including con adsorbent and optional components can be coated and lami tainers made from flexible plastic, rigid and semi-rigid sheet, nated into a variety of useful films, sheets, fibers, nonwoven blow molded plastic bottles, folded and glued paperboard webs, monolithic structures, or other shapes using conven materials, plastic and cellulosic envelopes and other con tional processing technology. These useful forms can be tainer configurations. incorporated into a container configuration. 0025 FIG. 1 is a cross section of a test cell. 0032) Virtually any chemical species that can form a gas or 0026 FIG. 2 is a graph representing the change is surface vapor can be an unwanted or target Substances. The unwanted area of fiber as fiber diameter changes. or target Substances can exist in a mobile fluid, gaseous stream or liquid or in an enclosed Volume or enclosed ambient 0027. The adsorptive composition comprises a source of vapor phase as a gas, vapor or dispersion of a liquid or Solid. ferric iron including Fe(III)), a ferrate salt or Fe(OH), com These substances often are malodors, irritants, or offensive or bined with a polyalkylenimine (PEI) on a surface. A polymer inoffensive odor compounds. Such compound chemical composition can be modified by including an effective families include hydrocarbons C alcohols or acids, Sulfur amount of adsorbent onto the polymer mass. compositions, amines, and can include alkanes, alkenes, 0028. Adsorbent Compositions Solids Content on the alkynes, alkane thiols, alkyl sulfides, alcohols, aldehydes, Composition amines, carboxylic acids, ethers, and ketones. Non-limiting example compounds include HS, methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, 2-butanethiol, carbonyl Sul First Adsorbent Second Adsorbent Third Adsorbent fide, methyl allyl sulfide, methyl sulfide, dimethyl disulfide, Embodiment Embodiment Embodiment dimethyl trisulfide, ethyl sulfide, methyl propyl sulfide, allyl Components (Wt.%) (Wt.%) (Wt.%) mercaptan, formic acid, formaldehyde, acetaldehyde, Polyethylenimine 1.0-80 15-65 20-60 acrolein, diacetyl, dimethyl ether, diethyl ether, methylamine, Fe(III) 10-85 15-70 20-65 dimethylamine trimethylamine, ethylmethylamine, buty Compounds Optional Silica 1-3O lamine, cyclopropylamine, methane, ethane, propane, Optional CD 1-10 butane, ethylene, acetylene, propylene, 1-butene, 2-butene, allene, isobutene, 1,3-butadiene, 1-butyne, 2-methylpropene, 2-methyl-2-butene, cyclopropane, cyclobutane, methylcy 0029 Polymer Compositions on the Total Polymer Com clopropane and others. Many of these malodors are present in position breath associated with halitosis. 0033 Such substances can be presentata concentration of at least 5 ppb or about 15 to 0.010 ppm (10 ppb) and can be the First Polymer Second Polymer Third Polymer subject of the adsorption characteristics of the invention to Embodiment Embodiment Embodiment reduce the concentration that cannot be sensed by humans or Components (Wt.%) (Wt.%) (Wt.%) to a limit that does not produce a biological response. An Polymer 75-98 80-95 85-95 offensive limit refers to the limit which is objectionable or Polyethylenimine O.1-3S O.S-30 1-2O Fe(III) O.1-3S O.2-30 1-2O unpleasant to an individual to sense the unwanted or target Compounds Substances. A limit that can produce a biological response Optional O.1-10 O.S.-S refers to the amount that a pheromone or gaseous hormones Silica CD Such as ethylene can produce its desired result in a biological organism. 0034 Polyethylenimine, used as an adsorbent, is a 0030 Coating on Polymer Compositions on the Coated polyamine made by polymerizing the cyclic monomer ethyl Material ene imine. The typical polymer can contain primary terminal (—NH) groups, secondary ( NH-) amine groups within First Second Third the polymer and in a chain branch and tertiary amine groups Embodiment Embodiment Embodiment at a branch point. Linear polyethylenimines (PEIs) contain Components (Wt.%) (Wt.%) (Wt.%) primarily secondary amines with terminal primary amine groups. Branched PEIS contain primary, secondary and ter polymer 75-98 80-95 85-95 Polyethylenimine O.1-10 1-9 2-8 tiary amino groups. The linear PEIs are solids at room tem Fe(III) O.1-15 O.2-10 O3-9 perature where branched PEIs are liquids at all molecular Compounds weights. Linear polyethylenimines soluble in hot or cold water, at low pH, in methanol, ethanol, or chloroform and is US 2014/0334998 A1 Nov. 13, 2014

insoluble in benzene, ethyl ether, and acetone. Polyethylen precisely formulated as FeC(OH) known as ferric oxide imine (CAS REGISTRY NUMBER 09002-98-6) is repre hydroxide. sented by the following general formula: 0042. A number of species are dubbed iron(III) oxide H(NACHCH ), (NA2CH2CH2—),(— hydroxide. These chemicals are oxide-hydroxides of iron, NACH-CH NH), H: and may occur in anhydrous (FeC(OH)) or hydrated (FeC) (OH).nHO) forms. The monohydrate (Fe0(OH).HO) 0035 wherein each A1 is independently hydrogen, an might otherwise be described as iron(III) hydroxide (Fe(OH) alkoxy group or a linear or branched polyethylenimine ), and is also known as hydrated iron oxide. The active ferric group and wherein each X is independently from 5 to hydroxide is a highly porous (mesosphere with a micropore 20,000. volume approximately 0.0394+/-0.0056 cmg', mesopore 0036 Polyethylenimine has an average molecular weight volume approximately 0.0995+/-0.0096 cm.g') adsorbent from about 500 to about 1,000,000; preferably from about with a BET surface area of 235+/-8 m.g. 2,000 to about 800,000; more preferably from about 10,000 to 0043. Iron(III) oxide-hydroxide can be obtained by react about 750,000; and most preferably from about 50,000 to ing ferric chloride with sodium hydroxide, potassium about 750,000. Non-limiting examples of additional materi hydroxide or Sodium bicarbonate in typically aqueous solu als include: epichlorohydrin modified PEI, ethoxylated poly tion: ethyleneimine, polypropylenimine diamine dendrimers, poly (1,2-dihydro-2,2,4-trimethylduinoline), and poly (dimethylamine-co-epichlorohydrin-co-ethylenediamine). 0037. The preferred Fe(III) compound useful in the con struction comprises a ferrate salt or ferric hydroxide Fe(OH) also known as the ferric oxyhydroxide as a result of unique Some amount of Na', K", or NaCl salt remains in the coating iron stoichiometry. Typically the Fe(III) compound is com as a result of these synthesis charateristics. bined with a polymerand is coated into an adsorbent layer and 0044 Alternatively, redox reactions of potassium ferrate after coating and final assembly, the Fe(III), is typically con (KFe0) produce rust-like iron oxides which are environ verted into ferric hydroxide. A variety of sources of iron III mentally innocuous and have been described as a green (Fe(III)) compounds can be used to form the active adsorbent oxidant. KFe0 is reactive as indicated by the fact that it materials. decomposes in contact with water evolving oxygen and form ing ferric hydroxide: 0038. The source of Fe(III) can be any iron-providing material, which can include carbonyl iron, iron salts, chelated iron, encapsulated iron, iron complexes, and mixtures 0045 Optionally, the construction can contain a CD com thereof. Illustrative sources of Fe(III) contemplated by this pound or one or more of three forms of amorphous silica invention include any of the ferric halides such as Fe(Cls, silica gel, precipitated silica and fumed silica. ferric citrate, ferric nitrilotriacetic acid (Fe(III)-NTA). 0046. The particle size of the preferred materials range Fe(OH), ferric ammonium citrate, Fe(NO), Fe(SO), fer from about 0.001 to 10 or 0.050 to 700 microns and the ric oxide hydrate, ferric ammonium sulfate, ferric sodium preferred materials have a surface area that ranges from about citrate, ferric sodium edetate, ferric acetate, ferric phosphate, 60 to 750 mgm or 200 to 1,000 mgm. The composi ferric pyrophosphate, ferric fumarate, etc. Ferrous salts can tions of the invention are often prepared by dispersing the be used if oxidized to Fe(III) before or after coating including Fe(III) compound and polyethylenimine materials into a ferric succinate, ferrous hydroxide, ferrous nitrate, ferrous polymer or into a coating liquid. In one embodiment, the carbonate, ferric sodium pyrophosphate, ferric tartrate, ferric adsorber can be used with a CD or with a silica materials for potassium tartrate, and organo-ferric compounds. the purpose of introducing a relatively high Surface to the 0039. Preferred sources of Fe(III) is selected from the Fe(III) polyethylenimine material surface. group consisting of ferric hydroxide, alkali metal ferrate, 0047 Silica particles can be used to enhance the surface ferric chloride, ferric citrate, ferric nitrate, ferric nitrilotriace area of the materials of the invention. In particular, silica gel tic acid, powered ferric oxyhydroxide, other similariron salts, particles that are preferred for use in the invention are rela and mixtures thereof. tively small particle size materials having large Surface areas per gram. Synthetic amorphous silica (CAS #7631-86-9), a 0040. A number of iron compounds in the ferric form, can form of silicon dioxide (SiO) is manufactured, thus differ remove malodors such as Volatile Sulfur compounds in an entiating it from naturally occurring amorphous silica, e.g. active infinely divided form on a substrate. Testing has shown diatomaceous earth. As a manmade product, it is greater than that a source of Fe(OH) in combination with PEI provides a 95% pure amorphous silica whereas naturally occurring degree of dynamic removal not achieved in the past chemis amorphous silica also contains crystalline forms of silica. tries. Removal directly related to the nature of the surface Amorphous silica can be further divided into two forms that including particle size, morphology and Surface area. The are characterized by their distinct manufacturing processes— surface of Fe(OH) combined with PEI has a better removal wet process silica (CAS #112926-00-8) which includes pre character than comparable combinations of FeO and PEI. cipitated silica and silica gel, and thermal process silica (CAS 0041. In industrial applications, iron (III) chloride is used #112945-52-5) which includes fumed or pyrogenic silica. in sewage treatment and drinking water purification. In these Fumed silica is essentially non-porous whereas precipitated applications, FeCls in slightly basic water reacts with the silica contains some micropores (>0.3 um) and silica gel is hydroxide ion to form a floc of iron (III) hydroxide, or more highly porous and contains macro-, meso-, and micro-pores US 2014/0334998 A1 Nov. 13, 2014 offering a pore size range from 0.0001 to 1 Lum. Pore size is Additionally, there can be modified terpolymers of, for defined as the pore width measured as the diameter of the example, ethylene-acrylate (ethyl or butyl)-maleic anhy cylindrical pore or distance between opposite walls of the slit. dride, ethylene-methyl acrylate-glycidyl methacrylate, and Fumed silica is commercially manufactured by Degussa Cor like polymers. In embodiments, any packaging grade of a poration (Areosil) and Cabot Corporation (Cab-O-Sil). Silica vinyl polymer can be used. The modified polymers of the gel is manufactured by W.R. Grace (Davisil) and Merck invention can be derived in Some embodiments from a poly Chemicals. mer having a melt index of about 0.7 to 1,800 g 10 min'. In 0048 Cyclodextrin can be used as an unmodified material, other embodiments, the modified polymers of the invention as a Substituted material or as a CD grafted polymer material. can be derived from a polymer having a melt index of about 1 CD is a cyclic oligomer of C-D-glucose formed by the action to about 1,200 g 10 min'. of certain enzymes Such as CD glycotransferase (CGTase). 0051 Functionalized polyolefins can be used with the Three CDs (alpha, beta, and gamma) are commercially avail coatings of the invention or blended with the CD pendant able consisting of six, seven, and eight C.-1.4-linked glucose polymers. Functionalized polyolefins, have extensive indus monomers, respectively. The most stable three-dimensional trial applications such as extrusion or coextrusion tie resins in molecular configuration for these oligosaccharides is a toroid multi-layer films and bottles for the food industry, compati with the Smaller and larger opening of the toroid presenting bilizers for engineering polymers and plastic fuel tank tie primary and secondary hydroxyl groups. The specific cou resins for the automotive industry, flexibilization and com pling of the glucose monomers gives the CD a rigid, truncated patibilization of halogen free polymers for cables, for filler conical molecular structure with a hollow interior of a specific materials used in roofing construction, and like applications. volume. The CD can be used as a substituted CD or a polymer Functionalized polyolefins useful in the present disclosure with pendent CD moiety. CD molecules have available for include, for example, maleated polyethylene and polypropy reaction a primary hydroxyl at the six position of the glucose lene (OREVAC and LOTRYL from AtofinaChemicals Inc. of moiety, and at the secondary hydroxyl in the two and three Philadelphia, Pa., PLEXAR and INTEGRATE resins from positions. Because of the geometry of the CD molecule, and Equistar Chemicals L.P of Houston, Tex., FUSABOND res the chemistry of the ring Substituents, all hydroxyl groups are ins from DuPont Co. of Wilmington, Del. OPTM resins from not equal in reactivity. However, with care and effective reac Manas of Ankara, Turkey, ADMER resins from Mitsui tion conditions, substantially dry CD molecules can be Chemicals of Rye Brook, N.Y., and EXXELOR from Exxon/ reacted to obtain a substituted or grafted CD. A CD with Mobil Corp. of Irving, Tex.), maleic anhydridefunctionalized selected Substituents, i.e., Substituted only on the primary ethylene vinyl acetate copolymers (EVA-MA, such as Orevac hydroxyl or selectively substituted only at one or both the EVA-MA from Atofina or Fusabond C series EVA-MA from secondary hydroxyl groups can also be grafted if desired. DuPont); EPDM (such as ethylene-propylene-butadiene or Directed synthesis of a derivatized molecule with two differ ethylene-propylene-1,4-hexadiene polymers) ethylene? 1 ent substituents or three different substituents is also possible. butene copolymers, ethylene? 1-hexene copolymers, ethyl These substituents can be placed at random or directed to a ene? 1-octene copolymers, ethylene-n butyl acrylate-maleic specific hydroxyl. These substituents may be chosen such that anhydride copolymers, ethylene-ethylacrylate-maleic anhy they the site of the grafting reaction. For example, alcohol dride terpolymers, or copolymers of ethylene and glycidyl derivatives (e.g., hydroxyethyl and hydroxypropyl) and methacrylate. Other polymers, that are not olefinic, can also amino derivatives of CD can be reacted with a substituent on be employed in embodiments of the invention. For example, a polymer backbone to make a grafted CD. styrene-maleic anhydride (SMA) copolymers are a particu 0049. A preferred preparatory scheme for producing a larly useful group of reactive copolymers. SMA copolymers substituted CD material involves reactions at the primary or are available as, for example, Hiloy SMA copolymers from A. secondary hydroxyls of the CD molecule. It is meant that a Schulman Inc. of Akron, Ohio, Prevex, SMA from General hydroxyl functionality of the CD reacts with a substituent Electric Co. of Fairfield, Conn. and Dylark SMA from NOVA forming reactant. The formation of an ester or ether bond on Chemicals of Calgary, Alberta Moon Township, Pa. Ethyl either the primary or secondary ring hydroxyls of the CD ene-propylene-1,4-hexadiene polymer can be represented as: molecule involve well-known reactions. For the purpose of wherein X, y and Z can be selected to obtain, for example, this patent disclosure, the term “degree of substitution (D.S.) about 70 to 90 wt % ethylene, about 10 to 30 wt % propylene for the CD means the statistical average number of substitu and up to about 5 wt % 1,4-hexadiene R and R may be ents on each glucose moiety of the CD ring. similar groups, H, or end groups. 0050. The invention can also include a polymer with pen 0.052 The copolymerization of styrene with maleic anhy dent CD moiety. Commercial polymer functionalization can dride to form SMA copolymer provides a material with a be achieved, for example, using solution, melt and Solid State higher glass transition temperature than polystyrene and is routes known in the art. The process covalently bonds mono chemically reactive as it provides maleic anhydride function mers onto polymers generally. Polyolefin polymers can be ality. SMA copolymers are often used in blends or composites used including, for example, copolymers of olefins with other where interaction or reaction of the maleic anhydride pro monomers, such as vinyl monomers, which predominately vides for desirable interfacial effects. SMA is utilized in the constitute the olefin portion. Polyolefins useful in this disclo automotive industry for the injection molding and thermo Sure include, for example, poly(ethylene) or PE, poly(propy forming of interior parts. The superiority of SMA over poly lene) or PP poly(ethylene-co-propylene) or PEP, ethylene/ styrene is due to its higher heat deflection temperature, which methyl acrylate copolymer, ethylene/ethyl acrylate is required for automotive use. SMA copolymers have also copolymer, ethylene-C.-octene copolymer, ethylene-butene been extensively used as binder polymers due to the reactive copolymers, and like polymers and copolymers. The polyole maleic anhydride moieties, which can easily be functional fins can be functionally modified with unsaturated com ized with a group or groups to provide tailorable Surface pounds such as unsaturated anhydrides and carboxylic acids. energy and chemical compatibility. For example, Keil et al., US 2014/0334998 A1 Nov. 13, 2014

U.S. Pat. Nos. 5,576,145, 5,698,370, and 5,773,518 disclose woven) sheet, rigid or semi rigid layer or other article. The an SMA based binder polymer in which the maleic anhydride construction can use a single or multilayered assembly hav residues are mono-esterified to between about 50 and about ing an adsorbent as a compound of the construction or as a 65 mole percent of an alkyl, aryl, cycloalkyl, alkaryl, or removal layer. A removal layer with an active chemistry arylalkyl alcohol having a molecular weight greater than 100 capable of removing malodorous Substances from a dynamic as a means of providing interlayer adhesion between two stream passing past or through the construction can improve incompatible polymers. adsorption. 0053 Another useful polymer that can be grafted with CD 0057 The removal layer can be made by either blending to form a CD grafted polymer of the invention is polypropy the adsorbent with the substrate material or by coating a lene. Commercially, maleic anhydride bonded to polypropy structure or substrate with a solution of the Fe(III) compound lene is available, for example, from Honeywell Performance and the polyethylenimine. The Substrate can be any material Products of Heverlee, Belgium or the Sigma Aldrich Com in the form of film, fiber, sheet, semi-rigid or rigid sheet, pany of St. Louis, Mo. However, maleic anhydride is also containers, non-woven or woven fabrics, etc. The Substrate easily added to polypropylene, e.g. in an extrusion reaction by can be a natural or synthetic polymer. adding maleic anhydride to a molten extrusion stream of 0.058 Examples of useful substrate materials are natural polypropylene. In Such reaction schemes, CD can advanta materials or synthetics such as non-woven polyesters; syn geously be added further down in the extrusion path, where it thetic nonwoven polypropylene and natural woven cotton can react with the maleic anhydride groups on the modified interlock materials. Substrate materials can be selected from polypropylene. The general reaction scheme of incorporating the group consisting of polyolefins (e.g., polyethylene, maleic anhydride into polypropylene using a radical Source polypropylene), polylactic acid, polyesters (PET, CPET & Such as hydrogen peroxide is shown below. rPET), nylons, acetates, nylon, polyethylene, polyesters, 0054 Polymer with pendent CD compositions of this dis polypropylene, polystyrene, ethylene vinyl acetate copoly closure may be prepared using, for example, reactive extru mers, polyurethanes, poly-C-olefins such as polybutadiene sion by feeding a dry CD, or derivative thereof, (<0.10% and poly C-octene, and polyamides such as nylon-6 and moisture), a functionalized polyolefin and optionally a sec nylon-6.6, polyureas, polycarbonates, polyethers, polyke ond polyolefin, into an extruder attemperatures such that the tones, poly(vinyl chloride), fluoropolymers, and silicone CD reacts with the functionalized polyolefin as the molten polymers are commonly used polymers in forming useful polymer and CD are transported through the extruder to form articles. Similarly, many commercially useful copolymers, a reaction product containing. One class of useful polymers is terpolymers, and the like can be used. For example, polyes polyolefins, including polyethylene, polypropylene and ters, PLA polymers and copolymers, acrylonitrile-butadiene related copolymers and terpolymers. In some embodiments, a styrene (ABS), poly(ethylene oxide)-co-(propylene oxide), mixture of a cyclodextrin (CD), a substituted CD or a polymer ethylene-Vinyl acetate copolymers, poly(ether-ether-ketone) with pendent CD moiety can be used or blended with an and the like are useful copolymers and terpolymers for vari unmodified polyolefin resin. In these embodiments, the ous end use applications. Any other polymer and copolymer unmodified thermoplastic resin can have a melt index of capable of being formed into film or fibers can be used. about 0.5 to 1800 g 10 min', and the modified polymer can Natural fibers comprising cotton or cellulose capable of being be derived from a polymer having a melt index of about 0.7 to formed into a sheet or woven and combinations thereof. 1,500 g 10 min', or about 1 to 1,200 g 10 min'. Another 0059 Polyesters are a generally useful class of polymers class of useful polymers is polyesters. from which many containers, nonwoven fabrics, and various 0055 Airflow rate past a layer or through a composite can other articles are made. Uses of polyesters include applica be in the range of 1 to 50 liters'min', 5 to 20 liters'min' tions set forth in co-pending U.S. patent application Ser. No. (16.6 to 833.3 cm.sec.' or 83 to 333 cm.sec.) depending 10/163,817. One useful polyester material that can be incor on application. In a face mask the Volume is an inspiration/ porated into a blend with, or topically coated with the inven expiration volume (the lung Volume of men versus that of tion is polylactic acid, or polylactide (PLA). PLA is a biode women) and normal breathing or rapid breathing results in a gradable, thermoplastic, aliphatic polyester derived from contact time on the fiber of about 0.1 to less than 0.01 sec. and renewable resources and having a general repeat unit of CH about 0.05 to 0.01 seconds. Normal static or dynamic HS (R)—C(O)—O—. It is most commonly formed from starting scrubbing processes require several minute contact times. materials such as corn starch or Sugarcane. Bacterial fermen Some PEI coatings on silica-monoliths have contact times in tation is used to produce lactic acid, which is oligomerized the range of 0.1 to 0.2 sec based onlinear flow. The adsorbent/ and then catalytically dimerized to make a lactide monomer adsorbent structures disclosed can be effective with for ring-opening polymerization. It can be easily produced in extremely low HS to Fe(OH)/PEI/fiber surface contact a high molecular weight form through ring-opening polymer time. Using a static test instead of a dynamic test, most coat ization using most commonly a stannous octoate or tin (II) ings will provide some removal depending on Surface area/ chloride ring opening catalyst. PLA can be processed like geometry and concentration of malodor, Fe(III) and PEI. In a most thermoplastics into fiber (for example using conven dynamic test, a ferrate compound with a cation and a ferrate tional melt spinning processes) and film. NatureWorks LLC, anion (Fe0) such as sodium Na(Fe0) or potassium fer a wholly owned subsidiary of Cargill Corporation, produces rate K(FeC) or Fe(OH) in combination with PEI obtains PLA under the trade name NatureWorks polymer. Other com enhanced removal. Ferrate compounds are converted into panies from which PLA can be obtained include Toyota (Ja Fe(OH), in the mask layers. pan), Hycail (The Netherlands), and Galactic (Belgium). 0056. A useful construction can contain a substrate with Because it is biodegradable, PLA can be employed in the an active concentration of the Fe(III) and PEI in the substrate preparation of bioplastic for Such articles as food packaging, or the substrate can contain a coating of the Fe(III) and PEI. loose fill packaging, and disposable containers. PLA can also Such a substrate can be a fiber, film, fabric (woven or non be made into fibers. US 2014/0334998 A1 Nov. 13, 2014

0060. In addition to the adsorbent, the substrate can permeable, porous or non-porous materials. The container include, in various embodiments, a mixture of natural and can take any form including but not limited to an envelope, a synthetic fibers; reactive fibers; scavenging fibers (e.g., Zeo sheet, a non-woven or woven format. The containers can be lite, activated charcoal, and like Scavengers); biodegradable closed using any closure technology including adhesive clo polymer materials such as polylactic acid; a reduced basis Sure, heat seal technology or sewing. The porous materials are weight; or combinations thereof. The containers of the dis porous to the target adsorbent of the invention. The sachets of closure may have a range of properties imparted to them, Such as breathability; stretchability: shape or body-conforming our invention are fabricated from permeable or porous mate capability; cloth-like aesthetics and feel; rigidity; high rials that can be formed into enclosures. The fabric, non strength; transparency or opacity; a Smooth or patterned Sur woven or sachets can be made of natural fibers or from syn face; and the like. thetic thermoplastics in the form of woven fabric, non-woven 0061 The compositions are directed to reducing the con or film. The adsorbent article can also be fabricated from centration of unwanted or target Substances within an non-porous materials if the walls have discrete openings so enclosed atmosphere or vapor phase. Such an atmosphere or that adsorbent may pass there through as they arise. vapor phase is often held within and substantially surrounded 0066. In certain embodiments, the present disclosure pro by a container. The important characteristic of the container vides a container article comprising a film of the present of the invention is that it encloses the atmosphere or vapor invention containing the adsorbent or having an adsorbent phase of the invention and can be made from or combined coating. Such a film preferably has a thickness of 500 um or with the compositions of the invention for the purpose of less and more preferably 0.5 to 400 um. In certain thin-film reducing the concentration of the unwanted or target compo applications and/or handling, the thickness of the film is sitions of the invention from the enclosed atmosphere or preferably 5 to 200um and more preferably 10 to 100 um. The vapor phase. In this regard, in the manufacture of the contain film can comprise athermoplastic polymer composition com ers of the invention, the compositions of the inventions can be prising a blend of a polyolefin resin and a chemically-modi incorporated into the materials from which the containers are made. For example, a PET beverage container can be made fied polyolefin resin or a blend of thermoplastic resins (e.g., from a thermoplastic polyester that contains the Fe(III) and PE, PP, PET and polylactic acid (PLA)) and can be made PEI compounds and the other materials of the invention that using conventional methods. Flexible films are typically melt can reduce the concentration of undesirable or target Sub extruded through a straight or circular die and can have thick stances that can form within the vapor phase held within the ness of for example, from about 4 micrometers (Lm) to about PET plastic container. Alternatively, such a container can be 200um. The films may be extruded at much greater thickness, made by coating the interior of the container with the adsor and then stretched in one or two directions to a thin, uniform bent composition. film. Post-extrusion stretching, uniaxial or biaxial, can also 0062 Alternatively, an insert can be used by placing it into provide orientation of the molecular structure that can further the interior of the container. The insert material can be made enhance strength and barrier properties of the film. Processes from the composition of the invention or coated by the com for extrusion and laminating thermoplastic materials are positions of the invention and as long as the insert can adsorb described in U.S. Pat. Nos. 3,400,190, 3,440,686: 3,477,099: and is held within the internal structures of the invention, the 3,479,425; 3,476,627; 3,524,795; 3,557,265; 3,583,032; and compositions of the invention can reduce the concentrations 3.365,750. Many coextruded structures are made up of poly of the unwanted or target composition. The insert comprising olefins such as polyethylene and polypropylene. These poly the compositions of the invention oramaterial coated with the olefins are useful for compositions of the invention. Low compositions of the invention can take a variety of embodi density polyethylene (LDPE) and linear low density polyeth ments. For example, a flexible food wrapper can be coated ylene (LLDPE) resins have been used extensively in coex with the compositions of the invention. Such a wrapper can be truded structures for their toughness and sealability. High made from thermoplastic materials or from cellulosic or density polyethylene (HDPE) resins are selected for their paper derived compositions. Such wrappers can be used as a moisture barrier, stiffness and machineability characteristics. primary wrapping structure or can comprise an internal enve Polypropylene (PP) is chosen for its ability, through orienta lope containing a food product, for example, as used in an tion, to provide clear machineable films with high impact and internal envelope for breakfast cereal. The thermoplastic stiffness properties. Polyolefins can be combined with other compositions in the invention can beformed into virtually any resins to achieve multilayer functionality. Copolymers of eth shape or configuration useful in packaging food and the coat ylene-vinyl acetate (EVA), ethylene-C crylic acid (EAA), and ing compositions of the invention can be coated on virtually ethylene-methacrylic acid (EMA) are regularly used as skin any container Surface useful in packaging technologies. layers for their low-temperature sealing characteristics. 0063 Another embodiment of the invention is a porous 0067 Semi-Rigid Films are produced by straight die melt nonwoven (spunbond or meltblown) or woven fabric com extrusion or calendaring. Multilayer structures can be, for prising the adsorbent composition. Such a fabric can be used example, a co-extrusion or an adhesive lamination. Typical to continuously reduce unwanted or target Substances from a thermoforming grade films can have thickness of for dynamic stream or from the closed atmosphere of a package. example, from about 200 microns to about 1 millimeter. The 0064. The compositions of the invention can be used in the coextruded sheet structures may be high-barrier packages. form of sachets. The Sachets can contain the compositions of Polystyrene, polyester, polypropylene, and polyethylene are the invention in the form of particulate film or fiber. the predominant structural materials used in co-extrusions for 0065. Alternatively, the sachets can be made of fiber or semi-rigid packaging applications. Known co-extrusion film made from the compositions of the invention and can be structures for semi-rigid packaging is described in U.S. Pat. formed to contain the materials of the invention. The sachets Nos. 3,479,425 and 3,557,265. Structural resin selection is of our invention comprise hollow container fabricated from dependent on use requirements, co-extrusion processability, US 2014/0334998 A1 Nov. 13, 2014 and container-forming considerations. Such films can be heat enclosed ambient vapor phase. The fabric comprising a softened and vacuum formed into tubs, pots, blisters, trays woven or nonwoven web, the web comprising a fiber com and punnets. prising a thermoplastic polymer composition comprising a 0068 Rigid films can be made by, for example, extrusion, blend of a polyolefin resin and a chemically-modified poly co-extrusion, profile extrusion, injection molding, compres olefin resin or a blend of thermoplastic resins (e.g., PE, PP, sion molding, reaction injection molding, injection blow PET and polylactic acid (PLA)). The article comprises a molding, or any other thermal processes known in the art. nonwoven web comprising a spunbond fabric, a meltblown Rigid structures typically have thicknesses greater than 1 fabric, an electrospun fabric, and combinations thereof. millimeter, and may have thickness of up to 2.0 cm or even Examples of spunbond fabric and meltblown fabric are greater thicknesses. Many of these containers are of a mono known in the art, and may be spun-bond-meltblown-spun layer structure as the large wall thickness provides for an bond (SMS), spunbond-meltblown-meltblown-spunbond adequate barrier. Where a high barrier is required, multilayer structure techniques can be used. One such rigid structure is a (SMMS), and like permutations or combinations. Other storage unit. Such as for storing food, clothing, Soiled items, articles, such as a litterbox, shoe box, food storage box orbin, household wastes, and the like. Such structures can be, for laundry basket, or clothing box or bag may advantageously example, a diaper pail, a vegetable bin for a refrigerator, a incorporate liners having compositions of the invention reusable food container, a general storage bin, or a garbage incorporated therein. Further, the polyolefin used in dispos container. able plastic garbage bags, garment bags, diaperbags, Vacuum 0069 Composite Materials typically multilayer plastic cleaner bags, and the like can also be made using polymer structures can be further extended with the inclusion of one or with an effective amount of polyolefin having covalently more plastic or non-plastic materials. Materials that can be bonded CD. In embodiments, any of the abovementioned combined with plastics to form composites can be, for articles or components can be prepared or processed with any example, thermoset resin, aluminum, paper, felt, paperboard, of the abovementioned processes or any of the following melt nonwovens and like materials. The combination of paper, based processes to form a desired article or component struc paperboard, foil, and thermoplastic polymers, can provide, ture, and combinations thereof, including: spunbond, melt for example, a sealable high-barrier structure. Multilayer blown, nanofiber, porous film, or co-form. In embodiments, packaging structures are described in U.S. Pat. Nos. 3,274, any of the abovementioned articles or components can also be 905; 4,720,039; 5,829,669 and 6.244.500. Combining ther prepared or processed with any of the following staple-based moplastics with paperboard can provide hermetic, rigid com or natural fiber based processes or structures, and combina posite structures, such as round, canister and shaped tions thereof, including: hydroentanglement, bonded-carded, composite paperboard cans, paperboard pails, fiber car needle punched, airlaid, wetlaid, and like processes and struc tridges. Common uses of Such structures are, for example, tures, or combinations thereof. powdered beverages and infant formulas, cereal, coffee, 0072 Fiber in this disclosure refers to generally continu Snacks, nuts, cookies and crackers, confectionery, spices/ ous lengths of materials having a diameter of about 0.1 seasonings, nutritional Supplements, and pet foods. In Such micron to 200 microns and about 2 to 50 microns. Such fiber applications, the compositions of the invention provide new can be used as fluff, as a web, a woven or non-woven fabric or packaging performance attributes for high barrier packages, as a composite material. The webs and fabrics fashioned there particularly when used for foods that are susceptible to unde from can also comprise bicomponent fibers. Bicomponent sirable food decomposition flavor and odor within the pack fiber technology enables manufacturers to, for example: age. reduce cost; improve strength and softness; produce ultra-fine 0070 Multifunctional packaging resins can be combined fibers; provide improved loft, crimp, or both; and like process into one manufacturing step using, for example, co-extrusion and product improvements. One type of bicomponent fiber is technology. Multilayer structures are distinct coextruded lay a known material in which the fiber contains an amount of ers of different polymers formed by a simultaneous extrusion polymer having a relatively high melting point and a second of the polymers through a single die. Multilayer films pro amount of a polymer having a relatively low melting point. In duced by lamination or co-extrusion can offer an enhance the formation of a web or layer of a web, the fiber is heated to ment of many or all performance properties compared to a temperature Such that the low melting point polymer can monolayer films. Typically, a multilayer plastic film can melt, fuse and bind the layer or web into a mechanically incorporate compositions of the invention into one or more stable, unitary mass. The relatively high melting point poly layers, typically a layer exposed to the enclosed atmosphere mercomponent can provide mechanical strength and stability depending on the desired functionality. to the layer or web. Bicomponent fibers can thus allow the Coextruded multilayer structures can be divided into three fabrication of thermally bonded webs, thus providing addi categories: single-resin, unbalanced, and balanced. There can tional strength, cohesiveness, and robustness of nonwoven be, for example, multilayer films using only one polymer webs made from them. Where such properties are desired, use (AAA), unbalanced coextruded films with combinations of of bicomponent fiber is often sufficient to impart these prop two or more polymers (ABC), and balanced multilayer struc erties and no further binders or procedures are required to tures with combinations of two or more polymers (A/B/C/B/ provide the web with additional cohesiveness, strength, etc. A). Unbalanced structures typically combine a functional Some embodiments of the invention may also comprise layer with a heat-seal resin. Balanced structures generally nanofiber. Nanofiber can be formed, for example, by electro have the same heat-sealable resin on both the outside and spinning, where fibers are spun with diameters of from about inside surface of the film. 10 nm to several hundred nm. The resulting fiber properties 0071. In certain embodiments, the present disclosure pro can depend on, for example, field uniformity, polymer vis vides a containerarticle comprising a fabric. Sucha fabric can cosity, electric field strength, the distance between nozzle and be a portion of the structure with the enclosed volume or collector, and like considerations. US 2014/0334998 A1 Nov. 13, 2014

0073 Web production methods useful for fiber and fabric Solvent Coating Compositions preparation can include any other suitable method, such as extrusion. Co-extrusion, spunlace, porous film, co-form, 0078 bonded-carded, needle punch, airlaid, wetlaid, and like meth ods, or combinations thereof. Spunlace processing, also First Second Third known as hydroentangling, involves mechanically wrapping Embodiment Embodiment Embodiment and knotting fibers in a web through the use of high velocity Components (Wt.%) (Wt.%) (Wt.%) jets of water. Spunlaced nonwovens work well for wipes Solvent 40-99 70-95 75-90 because they are soft, strong, easy to handle, and provide Co-Solvent O.1-20 1-15 2-10 good absorption. In embodiments, methods useful for fiber Polyethylenimine O.O1-15 O.O2-10 O.03-9 and fabric preparation can additionally include any other Fe(III) O.O1-15 O.O2-10 O.03-9 Suitable processing methods, for example, thermo-bonding, Compounds chemical or resin bonding, and like methods. In some embodiments, fibers, fabrics and absorbent materials of the invention can include other suitable functional or perfor Aqueous Coating Compositions mance additives or treatments, for example, an antimicrobial, an anti-static agent, a flame retardant, a fluorochemical, a 0079 wetting agent, an ultraviolet stabilizer, a laminate, a binder or an adhesive, a hot melt adhesive, a filler, a silane coupling First Second Third agent, and like additives or treatments, or combinations Embodiment Embodiment Embodiment thereof. In embodiments, depending upon its disposition and Components (Wt.%) (Wt.%) (Wt.%) purpose in the fiber or final article, an additive can be Water 40-99 70-95 75-90 included, for example, in a masterbatch, added directly to an Co-Solvent 1-30 2-25 extruder, applied topically to a fiber or web surface, and like Polyethylenimine O.O1-15 O.O2-10 O.03-9 inclusion methods, or combinations thereof. In embodiments, Fe(III) O.O1-15 O.O2-10 O.03-9 a binder or an adhesive can include, for example, an acrylic, Compounds a hot melt, a latex, a polyvinyl chloride, a pressure sensitive adhesive, a styrenated acrylic, styrene butadiene, vinyl 0080. The coatings can be continuous or partial coatings. acetate, ethylene vinyl acetate, vinyl acrylic, a melt-fusible The coatings can be made on film, fiber, fabric (non-woven or fiber, a partially meltable bicomponent fiber (e.g., PE/PP. woven), container, sheet or other polymer format. The coat PE/PET, specially formulated PET/PET), and like materials, ings can have a thickness of about 0.5 to 25 microns, 1 to 20 or combinations thereof. microns or 5 to 10 microns. The add-on amounts to non 0074 The coatings can be made by contacting a surface woven can be about 30 to 800 micrograms cm, about 50 to Such as a thermoplastic film, fiber, nonwoven etc., with a 600 micrograms cm’ or about 100 to 400 micrograms cm’. solution of both the Fe(III) compound and the PEI. The add-on amounts to fiber can be about 15 to 300 milli 0075. The thermoplastic materials can be coated with grams-gm', about 25 to 225 milligrams-gm' or about 50 to aqueous or co-solvent based coating. Preferred co-solvents 175 milligrams'gm'. The add-on amounts to container, film are benign liquid media Such as lower alcohols, glycol, glycol or sheet can be about 30 to 800 micrograms-cm', about 50 to ethers, glycol esters or aqueous media. Coatings are typically 600 micrograms cm or about 100 to 400 micrograms cm. made by blending the coating components into the liquids to I0081. The adsorbent compositions illustrated above are form a coating solution. The Solution can contain the active normally dispersed in Solvent, in aqueous medium, Solvent Fe(III) material and PEI with conventional additives, co and water or water with useful co-solvents. The aqueous Solvents, dyes, etc. The coating Solution can then be coated compositions are then applied to a Substrate to reduce using conventional coatings technology including knife coat unwanted or target Substances from an enclosed Volume ing, roll coating, slot coating, saturation coating, flooded nip which the substrate is exposed. The amount of the composi coating, rod coating, curtain coating, spray coating, gravure tion used in or applied to may vary depending on the nature of coating, etc. the substrate (i.e., fiber or film) and the intended application. 007.6 Fe(III) or PEI compounds, or both, can be uniformly In most embodiments, the odor control composition consti Surface coated onto a particulate to increase surface area Such tutes from about 2.5 to about 50 wt.% of the substrate, in as on a silica particle or onto CD particles prior to grafting CD some embodiments from about 5 to about 30 wt.% of the onto functionalized polyolefin by reactive extrusion. The substrate, and in some embodiments, from about 10 to about Fe(III)/PEI coating and drying of the particulate are carried 20 wt.% of the substrate. The adsorbent composition may be out concurrently in a dryer providing heating in a controlled applied to a substrate using any of a variety of well-known atmosphere. A stainless steel tumble dryer, jacketed with application techniques. For instance, the composition may be circulating oil heating walls, and equipped with a liquid spray incorporated within the matrix of the substrate and/or applied bar running along the center of horizontal rotation of the dryer to the Surface thereof. Suitable techniques for applying an can be used to spray the aqueous PEI coating Solution onto the aqueous composition to a substrate include spraying, dipping, particulate in constant motion. The vacuum lowers the boiling aqueous coating, printing, and so forth. Techniques for apply point of the water, while particle contact with the vessel walls ing non-aqueous compositions include various melt extrusion provides fast heat input for uniform drying. This coating techniques previously described. process prevents lumping, segregation and allows uniform I0082. The compositions can be incorporated into a variety PEI coating of the CD particles. of articles including film, non-wovens, Sachets, inserts, fil 0077. The compositions can be made with amounts of the ters, couplings, vents, caps, closures, trays, lids, laminated components as shown in the following tables. foils, sheets, etc. US 2014/0334998 A1 Nov. 13, 2014

0083. A food package article or food package component hols, diethylamine and other compounds known to cause of the disclosure can be, for example, a package component offensive or malodorous breath and achieves Surprising Such as a tray, a packing liner, a barrier layer, a scavenger dynamic activity. layer, and like components, or combinations thereof. Long I0087 Disposable face masks have been manufactured for established food packaging concepts are limited in their abil many years. Face masks include a plurality of layers of ity to extend the shelf-life of food products. Innovative food selected fibrous materials. This invention relates to dispos packaging concepts of the disclosure can, for example, inter able face mask materials having a relatively low pressure drop act with the environment inside the package and respond by to permit easy breathing, while preventing odorous vapors changing their properties to maintain, adjust or improve the from passing through the mask structure. The inventive face specific package headspace atmosphere or minimize food mask materials comprise different types of fibrous non-wo flavor loss to the package by “scalping” (i.e., uptake of Vola ven (e.g., spunbond, meltblown and spunbond/meltblown) or tile components by the polymeric package material from the cellulosic filter material having a range of basis weights. The food) thereby adding to product quality and extending shelf selection of these materials provide for the desired degree of life. The most notable group of technologies in use today for filtering or barrier to germs while at the same time having the controlling package headspace oxygen is oxygen scavengers. desired properties to mitigate unpleasant odor in air passing 0084. The present disclosure relates to the use of the pack through the mask to the wearer or through the mask from the aged food contact polymer layer to selectively remove unde exhaled breath of the mask wearer. Materials used in a face sirable off-flavors from the packaged foods. A food package masks are meant to help block large-particle droplets, contact layer can be constructed to remove offensive odors/ Splashes, sprays or splatter that may contain germs (viruses aromas from the interior of food packages produced by, for and bacteria) from reaching the wearer's mouth and nose. example, lipid oxidation, lipid hydrolysis, protein/amino acid Face masks may also help reduce exposure of the wearer's breakdown, and like changes or reactions of the packaged saliva and respiratory secretions to others. The mask has food. These active packaging polymer improvements of the significant technical advantages in that the face mask mate disclosure are significant compared to conventional polyole rials provide for germ barrier properties and, in addition, fins and can considerably improve food taste over the shelf prevents the passage of odorous vapors (e.g., hydrogen Sul life term of the product. fide HS, methanethiol CHSH, dimethylsulfide— CHSCH). Desirable barrier materials are engineered to 0085. A film or a multilayer film can be used as a food freely pass airin either direction, while restricting the passage packaging film, wherein at least one layer has a composition of odorous vapor components. It will be appreciated that that can adsorb off odors or plant hormones such as ethylene more than one non-woven or cellulosic barrier material may in static condition and obtain Surprising adsorption in be used to accomplish specific performance requirements. dynamic conditions. Principal manufacturing processes used in producing packaging materials include, for example, cast I0088 Breathed air treatment is achieved by air flow film extrusion, blown-film extrusion (tubular), extrusion through most of the area of the face mask. One or more layers coating, extrusion lamination, adhesive laminations, oriented offibrous filter material in the mask are surface treated with a extruded films, blow molding, injection molding, and com composition to remove noxious vapors including non-con pression molding. For packaging purposes, thermoplastics densable gasses from the air passing either direction through can usually be processed into one of the following structural the mask. Surface treatment compositions do not change the categories: flexible films, rigid sheets, bottles and tubs. The modulus in nonwoven face mask materials. Typical dispos film can contain a source of ferric Fe(III) iron and a polyeth able face masks comprise three layers—an outer layer, an ylenimine (PEI) or a coating thereof. The adsorbent compo inside layer and interior mask layer. Any layer or combina sition can comprise a coating comprising a Fe(III) compound tions can be coated. The outermost face mask layer serves as and a PEI compound in at least a monolayer coating. In yet a partial barrier to droplets, Splashes, sprays or splatter. Face another embodiment of the invention, CD grafted polymers of masks are held to minimum requirements in Bacterial Filtra the invention can be provided as a Fe(III) or PEI coated web tion Differential, Pressure Efficiency (BFE), Sodium Chlo of film or as nonwoven fibers, wherein a piece of web is ride Aerosol Challenge NIOSH, Viral Filtration Efficiency simply added to a package that is then filled with fresh fruits, (VFE) and Synthetic Blood Penetration-Splash Resistance. Vegetables, or flowers. In Such an embodiment, the packaging I0089. The Bacterial Filtration Efficiency (BFE) test is per material used can be any Suitable material and is not limited in formed on filtration materials and devices Such as face masks, any way. Commonly used packaging materials such as poly Surgical gowns, caps, and air filters, which are designed to ethylene, PLA or polyester, and the like can be used without provide protection against biological aerosols. The test deter any limitation, as the composition of the invention is simply mines the filtration efficiency of these materials when chal added to the finished packaging along with the fresh produce lenged with a biological aerosol of Staphylococcus aureus. to be packaged. Since the composition is present in a separate The BFE test procedure is based on Military Specification material, it can be added to any package where undesirable 36954C and can evaluate filtration efficiencies up to 99.9%. vapor phase Substances are desirably scavenged. This test is required by the ASTM F2100 and EN 14683, as I0086. The compositions may be formed into a face mask. well as used for 510K submissions to the FDA. The test is A face mask can use the materials to reduce halitosis. The performed in compliance with Military Specification adsorbent uses at a minimum a combination of a polyethyl 36954C, ASTM F2101, and ASTM F2100. eneimine (PEI) and an Fe(III) compound sufficient to achieve 0090. The Differential Pressure test determines the air at least 20% reduction in HS. The combination of the poly exchange differential of porous materials such as Surgical meric amine compound and the iron compound provides face masks and other filtration devices. This test was designed enhanced removal of malodorous compounds such as hydro after the Military Specification 36954C and is commonly gen Sulfide, alkyl sulfide, Small molecule C acids or alco requested for samples submitted for Bacterial Filtration Effi US 2014/0334998 A1 Nov. 13, 2014

ciency (BFE) testing. The test is required by ASTM F2100, of moisture vapor contained within the mask. Removal of EN 14863, and is used for 51OK Submissions to the FDA. odorous vapors is not affected as moisture accumulates on the 0091. The Sodium Chloride Aerosol Challenge (NaCl)– surface of the fiber during use. NIOSH Respirator Pre-qualification test uses a widely 0098. We have shown a substantial improvement in accepted method for evaluating particle penetration and air adsorption as tested by a dynamic hydrogen sulfide (H2S). flow resistance properties of a variety of filtration materials. Dynamic H2S test method involves analytical techniques This test is able to determine filtration efficiency measure designed to measure the odor attenuation performance of a ments up to 99.999%. Respirators must be pre-qualified nonwoven face mask structure using a dynamic olfactometer before submitting to NIOSH for certification; other materials, presentation gradient of HS. The test olfactometer simulates Such as breathing system filters and face masks, are tested to a dynamic hydrogen Sulfide concentration based on the dis determine filtration efficiency for marketing. Testing is per tance of 12 inches (30.5 cm) from source using a flow rate of formed in compliance with 42 CFR Part 84 and NIOSH 7 liters per minute. For example, a hydrogen Sulfide concen Procedure No. RC-APR-STP-0057, 0.058, and 0059. tration of 200 ppb measured in the oral cavity will have a 0092. The Viral Filtration Efficiency test determines the concentration of 20 ppb at the typical distance of 12 inches at filtration effectiveness of various filtration materials such as a 10 liter/minute breathing rate. Oral cavity hydrogen sulfide masks and filter material. This test is necessary for making can range from less than 20 ppb (vol/vol) to more than 1,000 marketing claims as to the viral filtration efficiency of the ppb (vol/vol). Sulfur gases such as hydrogen Sulfide and mask or other filter material. This test has been adapted from methylmercaptain (methanethiol) (CHSH) together are often the ASTM F2101 implicated for halitosis malodors. “Socially accepted oral 0093. The Synthetic Blood Penetration Splash Resistant cavity hydrogen sulfide is less than 250 ppb (vol/vol). The test is one of two different synthetic blood resistance tests method measures the attenuation of H2S across the face mask offered by Nelson Labs to determine a product’s ability to act structure. This procedure allows for the determination of the as a barrier to blood-borne pathogens. The Splash Resistant following compound: test method challenges medical face masks with a fixed Vol ume of synthetic blood directed at high velocity at the center of the mask. This test is required by ASTM F2100 and is Malodor and Concentration tested in compliance with ASTM Method F1862, ASTM Test Compound ppb (nl/L) F2100, and EN 14683. 0094. The mask has an outer layer, an interior comfort Hydrogen sulfide (H2S) S to SOO layer adjacent to the skin and one or more inside adsorbent layers placed there between. These layers are made of spun 0099. In this test method, three steps are involved. They bond. meltblown or cellulosic materials typical in this manu are (a) the instrument sensitivity calibration, (b) dynamic face facture. Such materials include a spunbond with a basis mask testing to measure HS attenuation, and (c) the quality weight about 20 to 30gm; a meltblown with a basis weigh control of the test. of about 17 to 26 gm; a combined meltblown/spunbond 0.100 Face mask structure is tested in a 13 cm diameter with a basis weight of about 30 to 40 gm’: a cellulose glass permeation cell (FIG. 1) mounted on an olfactometer. comfort layer can be used with a basis weight of about 17 to FIG. 1 shows a glass test a device for testing mask structure 21 gm’. under dynamic flow of hydrogen sulfide. In FIG. 1 the glass 0095. The outer mask layer can be constructed from non test device 10 includes a first enclosure 12 a and a second wovens Such as spun bond polypropylene, a cellulosic tissue enclosure 12 b. The volume is defined by enclosures 12 AM or spun bond polyester. Spun bond fiber may also be made of 12 be a separated by the test nonwoven 11 positioned there bicomponent fiber with, for example, polyethylene. The outer between. The inflow 13 is provided continuously at a defined layer typically has preferably a basis weight range of 15 to 35 rate by an olfactometer device (not shown). The outflow 14 is g-mi (0.45 ozyd’ to 1.0 ozyd'). measured for hydrogen Sulfide using an appropriate measur 0096 Interior comfort mask layer is preferably composed ing device. Aluminum clamp rings, fitted on either side of the of nonwovens. These layers may also be constructed from glass flask flanges, are tightened using six screws to hermeti polyester and/or polyolefin(polyethylene or polypropylene) cally sealing the face mask structure between the two flasks material or cellulosic tissue. Inner layers typically have a glass flanges. Dynamic flow from the olfactometer (St. Croix basis weight range of 13 to 30gm (0.4 ozyd to 0.85 Sensory ACSCENTR. Olfactometer) is delivered into the ozyd), preferably about 13-25gm in basis weights. The inflow end of the permeation cell at 7 liters per minute for a 15 interior layers can be effectively coated. consecutive minute test period for a total flow volume of 105 0097. The inside adsorbent mask layer can be a meltblown liters. A Jerome 631-X hydrogen sulfide test meter is used to polyolefin woven or non-woven with a basis weight of 15 to measure the HS concentration as a function of time; inflow 30gm and an adsorbent coating. One embodiment is typi and outflow HS concentrations are measured. Before start cally constructed from a meltblown polypropylene, but may ing the test, nonwoven webs mounted in the permeation cell be constructed from meltblown polyolefin, polyester or ure are humidified by breathing across the fibers with seven lung thane. The layer(s) may include one two or multiple coated or volumes of air. The permeation cell is then mounted over the uncoated interior layers. The interior layer material has good olfactometer flow port. Three hydrogen sulfide measure gas permeability characteristics and permits air to pass ments are taken at 1, 5 and 15 minutes in duplicate. The values through the filter body in both directions. The interior layer is are average over the 15 minute test period and reported in ppb a nonwoven with the adsorbent compositions preferably in a (vol/vol). fiber coating. Covering the nose and mouth with the face 0101 Hydrogen sulfide is a common test malodor and can mask results in warm, moist air exhaled by the wearer. The be used to predict the activity of other sulfur compound exhaled air has a tendency to result in the high concentration malodors. The attenuation rate (percent reduction) of HS is US 2014/0334998 A1 Nov. 13, 2014

calculated from average HS concentrations of control and polypropylene; the coated MB fiber contained 2 wt % alpha coated Samples. An HS reduction greater than 20% is accept CD grafted onto maleic anhydride grafted polypropylene. able as an indication that malodor control can be achieved. I0106 Two basis weight cellulosic papers (15 g/m and 65 The performance of the coated nonwoven fiber face mask g/m) are tested. structure is determined from the HS Vapor mass taken up by 0.107 An accurate volume of solution is transferred to the the coated fiber compared to the control mask structure over sheet using a Mohr pipette. Since the coating solution is the fifteen minute test time (control fiber structure-coated hydrophilic relative the hydrophobic polypropylene fiber, the fiber structure)--control fiber structurex 100% HS Reduc coating solution is dispersed into the fiber sheet uniformly tion. using a rubber ink roller. 0102 The hydrogen sulfide sorptions of compositions 0.108 Cellulosic paper sheets are starch sized requiring a illustrated below are applied to a fiber substrate to mitigate rubber ink roller to uniformly disperse the coating solution unwanted or target Substances passing through fibrous layers into the fiber. The sheet is turned over and the coating process of a face mask. The amount of the composition used or is repeated. applied to the fiber Surface may vary depending on the non 0109 Coated sample sheets are place on a porous drying woven (e.g., spunbond, meltblown and spunbond/meltblown) screen and allowed to air dry overnight in a 20°C./50% RH or cellulosic filter material as well as the material basis weight room. Coated sheets are re-weighed and coating weight cal and the intended application. In most embodiments, the odor culated (coated sheet wt.-uncoated sheet wt.)/uncoated sheet control composition constitutes from about 1.5 to about 30 wt.x100%-coating wt %. Coating formulation C is prepared wt.% of the substrate, in some embodiments from about 3 to from aborate/phosphate buffer. A 0.001 molar sodium borate about 20 wt.% of the substrate, and in some embodiments, solution (1 mM NaOH, pH -8.2) is prepared by adding 0.040 from about 5 to about 10 wt.% of the substrate. The compo gNaOH (50% Solution), to 500 ml distilled water, then 0.118 sition may be applied to a Substrate using any of a variety of g boric acid. Final solution is filtered by 0.2 micron filter well-known application techniques. For instance, the aque membrane. The 0.005 molar phosphate/0.001 molar borate ous compositions can be applied to the Surface using Suitable buffer (pH-9) is prepared by adding 0.670g NaHPO.7HO techniques including spraying, dipping, aqueous coating, etc. to 500 mL borate solution. The potassium ferrate, ethanol, The compositions can be made with amounts of the compo glycerin and polyethylenimine are added as previously nents as shown in the following table. described. Coated sheets are prepared and coating weights determined as expressed above. 0110 Hydrogen sulfide sorption is determined by the Fiber Coating Compositions dynamic hydrogen Sulfide test method for control (uncoated) First Second Third MB nonwoven and cellulosic paper sheets and identical Embodiment Embodiment Embodiment sample sheets coated with coating formulations A, B and C. A (Wt 9% on (Wt 9% on (Wt 9% on plurality of layers of selected fibrous materials—MB Components polymer) polymer) polymer) polypropylene and cellulosic paper is tested using the pre Fiber substrate 98 90 70 viously described hydrogen sulfide sorption method. Control Polyethylenimine 1.5 6 10 sheets were found to Sorb no hydrogen Sulfide by comparing Ferric Hydroxide O.S 4 2O upstream hydrogen Sulfide measurements before the sample test sheets and down stream hydrogen sulfide measurements Optimum Coating Formula after passing through the sample test sheets. Materials Wt.-% on solution Wt.-% on solids

PEIEPOMIN O.65 19 A. B C FeCl 1.25 37 Material Wt-9/o Wt.-90 Wt.-90 KOH 1.5 44 Deionized Water (pH 12.5) 96.6 Polyethylenimine OSO O.SO OSO Ethanol S.O S.O S.O Totals 100 100 Glycerin OSO O.SO O.25 Potassium Ferrate O.04 O.09 O.04 0.001Mborate? O.005M 94.2 0103) In the examples section below, material composi phosphate buffer tions and detailed sample preparation information for each D.I. Water 94.0 94.O coated fibrous material is provided. Total 1OOO 1OO.O 100 pH 12.0 12.O 8.0 EXAMPLE1 0104 Aqueous coating solutions are prepared in 100gram and 50 grams batches for hand coating fiber substrates. With coating formulations A and B, the order of addition is water Number Surface Ave. and potassium ferrate. The solution is mechanically stirred Layers Basis Coating Coating H2S Conc. % HS until a reddish ferric hydroxide floc forms, then ethanol and Meltblown Wt. g/m ID Wt.-% ppb (volivol) Reduction glycerin are added. Lastly, Polyethylenimine (Aldrich 2 27 Ctrl 23.4 181978) is added as a 10 wt.-% solution (water accounted for 1 27 A. 2.5 19.8 16 2 27 Ctrl 21.0 in overall formulation). 3 27 B 2.7 19.8 6 0105 Meltblown (MB) nonwoven polypropylene fiber 1 27 B 2.7 16.0 24 and cellulosic paper samples (stored in a 20° C./50% RH 1 27 B 2.7 16.8 2O room) are cut into 16.5 cmx16.5 cm hand sheets and accu 2 27 Ctrl 22.8 rately weighed to 0.1 milligrams. MB fiber control is 27 g/m US 2014/0334998 A1 Nov. 13, 2014

-continued Surements before the sample test sheets and down stream hydrogen Sulfide measurements after passing through the Number Surface Ave. sample test sheets. Layers Basis Coating Coating H2S Conc. % HS Meltblown Wt.g/m ID Wt.-% ppb (vol/vol) Reduction 2 27 C 2.5 21.4 6 Material Wt.-90 2 27 C 2.5 2O2 11 2 27 Ctrl 25.3 Polyethylenimine 1.O 2 27 B 30 15.8 38 Ethanol 1O.O Potassium Ferrate O.35

Number Number Surface Ave. Layers Basis Layers Basis Coating Coating H2S Conc. % HS Cellulose Wt.g/m Cellulose Wt.g/m ID Wt.-% ppb (volivol) Reductin 3 15 24.5 3 15 B 27 19.5 2O 1 65 1 27 32 1 65 1 27 B 15.30 18.3 43

EXAMPLE 2 -continued 0111. The aqueous coating solution is prepared in 100 0. gram and 50 grams batches for hand coating fiber Substrates. Material Wt.-90 The order of addition is water and potassium ferrate. The D.I. Water 88.65 solution is stirred until a reddish ferric hydroxide floc forms, then ethanol is added. Lastly, Polyethylenimine (Aldrich Total 1OOO 181978) is added as a 10 wt.-% solution (water accounted for pH 12.2 in overall formulation). A plurality of layers of nonwoven materials—meltblown (MB) and spunbond (SB) polypropy

Number Number Number Surface Ave. Layers Basis Layers Basis Layers Basis Coating Coating H2S Conc. % HS MB Wt.g/m SB Wt.g/m Cellulose Wt. g/m ID Wt.-% ppb (volivol) Reduction 1 21 1 27 1 19 Ctrl 29.5 1 21 1 27 1 19 Ex2 22, 12.6 21.1 28 1 21 2 27 Ex2 10, 11.5 18.6 37 lene (stored in a 20° C./50% RH room) are cut into 16.5 EXAMPLE 3 cmx16.5 cm hand sheets and accurately weighed to 0.1 mil ligrams. Polypropylene MB and SB fiber controls are 21 g/m 0113 Aqueous coating Solutions are prepared in 100gram and 27 g/m webs, respectively; the coated spunbond fiber and 50 grams batches for hand coating fiber substrates. With samples contained 2 wt % alpha CD grafted to maleic anhy coating formulations D, E and F, the order of addition is water dride grafted polypropylene while the meltblown doesn’t and potassium ferrate. The solution is mechanically stirred contain CD. Cellulosic paper webs are 19 g/m. An accurate until a reddish ferric hydroxide floc forms. Lastly, Polyethyl volume of solution is transferred to the sheet using a Mohr enimine (Aldrich 181978) is added as a 10% solution (water pipette. Since the coating solution is hydrophilic relative the accounted for in overall formulation). A plurality of layers of hydrophobic polypropylene fiber, the coating Solution is dis nonwoven materials—spunbond/meltblown (S/M) and spun persed into the fiber sheet uniformly using a rubber ink roller. bond (SB)-(stored in a 20° C./50% RH room) are cut into Cellulosic paper sheets are starch sized requiring a rubberink 16.5 cm x 16.5 cm hand sheets and accurately weighed to 0.1 roller to uniformly disperse the coating solution into the fiber. milligrams. The polypropylene S/M and SB fiber control are The sheet is turned over and the coating process is repeated. 30 g/m and 27 g/m, respectively. The coated SB fiber Coated Sample sheets are place on a porous drying screen and samples contained 2 wt % alpha CD grafted onto maleic allowed to airdry overnightina 20°C./50% RH room. Coated anhydride grafted polypropylene. Coated S/M fiber is not CD sheets are re-weighed and coating weight calculated. Coating modified. An accurate volume of solution is transferred to the formulation C is prepared from aborate/phosphate buffer. sheet using a Mohr pipette. Since the coating solution is 0112 Hydrogen sulfide sorption is determined by the hydrophilic relative the hydrophobic polypropylene fiber, the dynamic hydrogen Sulfide test method for control (uncoated) coating solution is dispersed into the fiber sheet uniformly MB nonwoven and cellulosic paper sheets and identical using a rubber ink roller. The sheet is turned over and the sample sheets coated with coating formulation. A plurality of coating process is repeated. Coated Sample sheets are place layers of selected fibrous materials—MB, SB and cellulosic on a porous drying screen and allowed to air dry overnight in paper is tested. Control sheets were found to sorb no hydro a 20° C./50% RH room. Sample sheets are weighed and gen Sulfide by comparing upstream hydrogen sulfide mea coating weights calculated. US 2014/0334998 A1 Nov. 13, 2014

0114 Hydrogen sulfide sorption is determined by the coating solution is dispersed into the fiber sheet uniformly dynamic hydrogen Sulfide test method for control (uncoated) using a rubber ink roller. The sheet is turned over and the meltblown nonwoven and cellulosic paper sheets and sample coating process is repeated. Cellulosic paper sheets are starch sheets coated with coating formulations D, E and F. A plural sized requiring a rubber ink roller to uniformly disperse the ity of layers of selected fibrous materials—S/M, MB and coating Solution into the fiber. Coated sample sheets are place cellulosic paper is tested. Control sheets were found to sorb on a porous drying screen and allowed to air dry overnight in no hydrogen Sulfide by comparing upstream hydrogen Sulfide a 20° C./50% RH room. Sample sheets are weighed and measurements before the sample test sheets and downstream coating weights calculated. hydrogen sulfide measurements after passing through the sample test sheets. At the end of the 15 minute sorption test, 0116. Hydrogen sulfide sorption is determined by the coated nonwoven fibers mounted in the permeation cell are dynamic hydrogen Sulfide test method for control (uncoated) re-humidified by breathing across the fibers with seven lung MB nonwoven and cellulosic paper sheets and sample sheets volumes of air. The permeation cell is then re-mounted over coated with coating formulation. A plurality of layers of the olfactometer flow port. Two hydrogen sulfide measure selected fibrous materials—MB polypropylene and cellulo ments are taken at 17 minutes. The re-humidified 17 minute sic paper is tested. Control sheets were found to Sorb no average values are about 4 ppb (vol/vol) lower then the 15 hydrogen Sulfide by comparing upstream hydrogen Sulfide minute reading. Re-humidified uncoated control nonwoven measurements before the sample test sheets and down stream fiber showed about one ppb (vol/vol) lower the 15 minute hydrogen Sulfide measurements after passing through the reading. sample test sheets.

D E F Material Wt.-90 Material Wt.-90 Wt.-90 Wt.-90 Polyethylenimine 1.2 O.65 O.30 Polyethylenimine O.77 Potassium Ferrate 1.O 1.O 1.O Potassium Ferrate 3.80 D.I. Water 97.8 98.3 98.7 D.I. Water 95.43

Total 1OOO 100 1OO.O Total 1OOO pH 12.5 12.2 12.O pH 12.2

Number Number Surface Ave. Layers Basis Layers Basis Coating Coating H2S Conc. % HS S/M Wt. g/m SB Wt. g/m ID Wt.-% ppb (vol/vol) Reductin 2 27 Ctrl 27.4 2 27 D 24 19.8 28 2 27 E 12 18.6 32 2 27 F 13 2O.O 27 2 30 E 13 17.3 37 2 30 1 27 Ctrl 30.1 2 30 1 27 E 1721 37 37 2 30 1 27 E 1721 41 41 2 27 Ctrl 29 2 27 E 13 19.6 32 2 27 E 13 20.9 28 2 27 E 3 17.1 41

EXAMPLE 4 Number Surface Ave. 0115 The aqueous coating solution is prepared in 100 Layers Basis Coating Coating H2S Conc. % HS gram and 50 grams batches for hand coating fiber Substrates. Meltblown Wt. g/m ID Wt.-% ppb (volivol) Reductin The order of addition is water and potassium ferrate. The solution is mechanically stirred until a reddish ferric hydrox 2 27 32.9 ide floc forms. Then polyethylenimine (Aldrich 181978) is 2 27 Ex 4 19 29.8 10 added as a 10 wt.-% solution (water accounted for in overall 2 27 Ex 4 17 29.0 12 formulation). Meltblown (MB) nonwoven polypropylene fiber and cellulosic paper samples (stored in a 20°C./50% RH room) are cut into 16.5 cmx16.5 cm hand sheets and accu rately weighed to 0.1 milligrams. MB fiber control is 27 g/m Number Surface Ave. polypropylene; the coated MB fiber contained 2 wt % alpha Layers Basis Coating Coating H2S Conc. % HS CD grafted onto maleic anhydride grafted polypropylene. Cellulose Wit. g/m ID Wt.-% ppb (volivol) Reductin The cellulosic paper—control and coated samples—is 55 1 55 23.1 g/m. An accurate volume of solution is transferred to the 1 55 Ex 4 2 15.6 32 sheet using a Mohr pipette. Since the coating Solution is hydrophilic relative the hydrophobic polypropylene fiber, the US 2014/0334998 A1 Nov. 13, 2014

EXAMPLE 5 Number Surface Ave. 0117 Aqueous coating solutions are prepared in 100gram Layers Basis Coating Coating H2S Conc. % HS and 50 grams batches for hand coating fiber substrates. With Spunbond Wt. g/m· ID Wt.-% ppb (volivol) Reduction coating formulations G and H, the order of addition is water 2 27 22.1 2 27 G 13 19.3 13 and ferric chloride. The solution is mechanically stirred to 2 27 G 7 18.4 17 dissolve the ferric chloride. Next, the ferric chloride solution 2 27 H 7 18.8 15 is neutralized with 10 wt.-% potassium hydroxide (water 2 27 H 1.6 21 5 accounted for in overall formulation) producing a ferric hydroxide floc. Then polyethylenimine (Aldrich 181978 or EPOMIN P1000) is added as a 10 wt.-% solution (water accounted for in overall formulation). Final coating Solution EXAMPLE 6 pH is adjusted with 10% potassium hydroxide to pH 12.5. 0119 The aqueous coating solution is prepared in 100 Spunbond (SB) nonwoven polypropylene fiber samples gram and 50 grams batches for hand coating fiber Substrates. (stored in a 20° C./50% RH room) are cut into 16.5 cmx 16.5 The order of addition is water and potassium ferrate. The cmhand sheets and accurately weighed to 0.1 milligrams. SB solution is mechanically stirred until a reddish ferric hydrox fiber control is 27 g/m polypropylene; the coated SB fiber ide floc forms. Then polyethylenimine (Aldrich 181978) is contained 2 wt % alpha CD grafted onto maleic anhydride added as a 10 wt.-% solution (water accounted for in overall grafted polypropylene. An accurate Volume of Solution is formulation). Lastly, fumed silica is mechanically dispersed transferred to the sheet using a Mohr pipette. Since the coat into the solution. Meltblown (MB) nonwoven polypropylene ing solution is hydrophilic relative the hydrophobic polypro fiber samples (stored in a 20°C./50% RH room) are cut into pylene fiber, the coating solution is dispersed into the fiber 16.5 cm x 16.5 cm hand sheets and accurately weighed to 0.1 sheet uniformly using a rubber ink roller. The sheet is turned milligrams. MB fiber control is 27 g/m polypropylene; the over and the coating process is repeated. Coated sample coated MB fiber contained 2 wt % alpha CD grafted onto sheets are place on a porous drying screen and allowed to air maleic anhydride grafted polypropylene. An accurate Volume dry overnight in a 20° C./50% RH room. Sample sheets are of solution is transferred to the sheet using a Mohr pipette. weighed and coating weights calculated. Since the coating solution is hydrophilic relative the hydro phobic polypropylene fiber, the coating solution is dispersed 0118 Hydrogen sulfide sorption is determined by the into the fiber sheet uniformly using a rubber ink roller. The dynamic hydrogen Sulfide test method for control (uncoated) sheet is turned over and the coating process is repeated. spunbond non-woven and 2 wt % alpha CD grafted onto Coated Sample sheets are place on a porous drying screen and maleic anhydride grafted polypropylene SB sample sheets allowed to air dry overnight in a 20° C./50% RH room. coated with coating formulation. A plurality of layers of SB Sample sheets are weighed and coating weights calculated. fiber is tested. Control sheets were found to sorb no hydrogen I0120 Hydrogen sulfide sorption is determined by the Sulfide by comparing upstream hydrogen Sulfide measure dynamic hydrogen Sulfide test method for control (uncoated) ments before the sample test sheets and down stream hydro MB nonwoven and 2 wt % alpha CD grafted onto maleic gen Sulfide measurements after passing through the sample anhydride grafted polypropylene MB sample sheets coated test sheets. At the end of the 15 minute sorption test, coated with the coating formulation. A plurality of layers of MB SB fibers mounted in the permeation cell are re-humidified by polypropylene fiber is tested. Control sheets were found to breathing across the fibers with seven lung volumes of air. The Sorb no hydrogen Sulfide by comparing upstream hydrogen permeation cell is then re-mounted over the olfactometer flow sulfide measurements before the sample test sheets and down port. Two hydrogen Sulfide measurements are taken at 17 stream hydrogen sulfide measurements after passing through minutes. The re-humidified 17 minute average values are the sample test sheets. about 3 ppb (vol/vol) lower the 15 minute reading. Re-hu midified uncoated control nonwoven fiber showed about one ppb (vol/vol) lower the 15 minute reading. Material Wt.-90 Polyethylenimine O.65 Potassium Ferrate O.70 G H Fumed silica OSO Material Wt-9/o Wt.-90 D.I. Water 98.15 Total 1OOO Polyethylenimine O.65 pH 12.0 (Aldrich 181978) Polyethylenimine O.65 (EPOMIN P1000) Ferric Chloride 1.35 1.25 Number Surface Ave. Potassium hydroxide 1.12 1.12 Layers Basis Coating Coating H2S Conc. % HS D.I. Water 96.88 96.98 Meltblown Wt. g/m ID Wt.-% ppb (volivol) Reduction 2 27 22.1 Total 1OOO 1OO.O 2 27 Ex 6 7 18.8 15 pH 12.5 12.5 2 27 Ex 6 1.6 21 5 US 2014/0334998 A1 Nov. 13, 2014

0121 The foregoing discloses embodiments of the inven 9. The adsorbent of claim 1, wherein there is about 1 to 85 tion. In the Specification and claims, “about modifying, for wt % of the Fe(III) compound and 0.1 to 80 wt % of polyeth example, the quantity of an ingredient in a composition, con ylenimine based on Solids content. centration, Volume, process temperature, process time, yield, 10. The adsorbent article of claim 1, the adsorbent article flow rate, pressure, and like values, and ranges thereof, comprising a nonwoven Substrate having Surface area. employed in describing the embodiments of the disclosure, 11. The article of claim 1 wherein the source of Fe(III) refers to variation in the numerical quantity that can occur, for compound is a ferric sulfate. FeCls, Fe(NO) or mixtures example, through typical measuring and handling procedures thereof. used for making compounds, compositions, concentrates or 12-13. (canceled) use formulations; through inadvertent error in these proce 14. The article of claim 10 wherein the substrate has a dures; through differences in the manufacture, Source, or surface area of at least 0.1 mgm. purity of starting materials or ingredients used to carry out the 15. The article of claim 10, wherein the polyethylenimine methods, and like proximate considerations. The term has a molecular weight (M) of 800 to 1,000,000 and the "about also encompasses amounts that differ due to aging of article is free of a solid Support Such as silica. a formulation with a particular initial concentration or mix 16-18. (canceled) ture, and amounts that differ due to mixing or processing a 19. The article of claim 10, wherein there is about 0.1 to 35 formulation with a particularinitial concentration or mixture. wt % of the Fe(III) compound and 0.1 to 35 wt % of polyeth Where modified by the term “about the claims appended ylenimine based on the article. hereto include equivalents to these quantities. “Optional or 20. The article of claim 10 wherein the nonwoven substrate “optionally’ means that the subsequently described event or comprises Substrate comprising a polyolefin or a polyester. circumstance may but need not occur, and that the description 21-23. (canceled) includes instances where the event or circumstance occurs 24. The article of claim 10, wherein the substrate comprises and instances in which it does not. For example, "A optionally a web having a thickness B” means that B may but need not be present, and the descrip of about 0.01 to 1 mm. tion includes situations where A includes B and situations 25. The article of claim 10, wherein the substrate comprises where A does not include B. “Includes” or “including or like a polyester non-woven. terms means “includes but not limited to.” The present inven 26. The article of claim 10, wherein the substrate comprises tion may suitably comprise, consist of, or consist essentially a polyolefin non-woven. of any of the disclosed or recited elements. Thus, the inven 27. The article of claim 10 comprising a container com tion illustratively disclosed herein can be suitably practiced in prising athermoplastic polymer with an enclosed Volume, the the absence of any element which is not specifically disclosed Volume comprising a vapor phase comprising unwanted or herein. The use of the singular typically includes and at least target Substance. does not exclude the plural. 28-41. (canceled) 0122 The specification, figures, examples and data pro 42. The article of claim 10 comprising a face mask com vide a detailed explanation of the invention as it has been prising a fabric layer comprising a nonwoven fabric. developed to date. The invention, however, can take the form 43-54. (canceled) of nonwovens, fibers, films, sheets, bottles, caps, and other 55. A method of adsorbing unwanted or target substances embodiments without departing from the spirit or the from a dynamic gas or vapor phase with the adsorbent of intended scope of the invention. The invention therefore claim 1 comprising a nonwoven, the dynamic gas or vapor resides in the appended claims. phase having a concentration of unwanted or target Sub 1. An adsorbent for adsorbing unwanted or target Sub stances of less than 15 ppm, the method comprises: stances from a gas or vapor phase at a concentration of less i. positioning the adsorbent Such that the dynamic gas than 15 part per million, the adsorbent comprising a non vapor phase is in contact with the adsorbent at a contact woven fabric having a coating, the coating comprising: time of less than 1 Second; and a. an Fe compound selected from an alkali metal ferrate, a ii. causing the concentration of the unwanted or target ferric hydroxide or a reaction product of an hydroxide Substance be reduced in the dynamic gas or vapor phase. reactant and a source of an Fe(III) compound; and 56-63. (canceled) b. a polyethylenimine. 64. The method of claim 55, wherein in the coating there is 2. The adsorbent of claim 1 wherein the source of Fe(III) about 0.01 to 80 wt % of the Fe(III)) compound and 0.01 to 80 compound is a ferric sulfate. FeCls, Fe(NO) or mixtures wt % of polyethylenimine based on the solids content of the thereof. coating. 3-4. (canceled) 5. The adsorbent of claim 1, wherein the polyethylenimine 65-68. (canceled) has a molecular weight (M) of 800 to 1,000,000 and the 69. The method of claim 55, wherein the nonwoven com adsorbent is substantially free of solid Support such as silica. prises a web having a thickness of about 0.01 to 10 mm. 6. The adsorbent of claim 1, wherein the polyethylenimine 70. The method of claim 55, wherein the nonwoven com is free of substituents. prises a polyester non-woven. 7. The adsorbent of claim 1, wherein the polyethylenimine 71. The method of claim 56, wherein the nonwoven com comprises an ethoxylated polyethylenimine. prises a polyolefin non-woven. 8. (canceled) k k k k k