Auxetic materials have been made by a variety of methods, including etching, printing, die cutting, and laser cutting. Examples of various patent publications that describe auxetic articles and their methods of production include U.S. Pat. No. 6,878,320B1 to Alderson et al., U.S. 2005/0142331A1 to Anderson et al., U.S. 2005/0159066A1 to Alderson et al., U.S. 2005/0287371A1 to Chaudhari et al., U.S. 2006/0129227A1 to Hengelmolen, U.S. 2006/0180505A1 to Alderson et al., U.S. 2006/0202492A1 to Barvosa-Carter et al., U.S. 2007/0031667A1 to Hook et al. EP1,165,865B1 to Alderson, WO91/01210 to Evans et al., WO91/01186 to Ernest et al., WO99/22838 to Alderson et al., WO99/25530 to Lakes et al., WO00/53830 to Alderson et al., WO2004/012785A1 to Hengelmolen, WO2004/088015A1 to Hook et al., WO2005/065929A1 to Anderson et al., WO2005/072649A1 to Hengelmolen, WO2006/021763A1 to Hook, WO2006/099975A1 to Wittner, and in M. A. Nkansah et al, Modelling the Effects of Negative Poisson's Ratios in Continuous-Fibre Composites, J
The present invention provides an article that comprises an auxetic mesh that has been molded into an intended shape.
The present invention also provides a method of making a molded article, which method comprises: (a) providing an auxetic mesh; and (b) molding the auxetic mesh into a desired shape.
The inventor discovered that auxetic meshes can be beneficial in that they can be placed into a desired molded shape or configuration with less distortion than non-auxetic meshes. The openings within the mesh, for example, do not vary as much when compared to molded non-auxetic meshes. The different sized openings in conventional molded meshes may be considered unsightly, and portions of the mesh may sometimes overlap and distort during the molding operation. The present invention alleviates such issues and accordingly provides a molded mesh that may be considered to have an improved appearance. There accordingly can be less opportunity for waste when molding an auxetic mesh according to the present invention—as there may be less products that are discarded due to manufacturing defects. Molded auxetic meshes may be suitable for use in filtering face-piece respirators and in a variety of other products where molded meshes are used. Molded auxetic meshes also may find new applications where the auxetic properties play a beneficial role.
The terms set forth below will have the meanings as defined:
“auxetic” means exhibiting a negative Poisson's ratio;
“comprises (or comprising)” means its definition as is standard in patent terminology, being an open-ended term that is generally synonymous with “includes”, “having”, or “containing”. Although “comprises”, “includes”, “having”, and “containing” and variations thereof are commonly-used, open-ended terms, this invention also may be suitably described using narrower terms such as “consists essentially of”, which is semi open-ended term in that it excludes only those things or elements that would have a deleterious effect on the performance of the inventive subject matter;
“mesh” means a structure that has a network of open spaces and that is substantially larger in first and second dimensions than in a third;
“molded” or “molding” means forming into a desired shape using heat and pressure;
“multitude” means 100 or more;
“polymer” means a material that contains repeating chemical units, regularly or irregularly arranged;
“polymeric” and “plastic” each mean a material that mainly includes one or more polymers and that may contain other ingredients as well;
“plurality” means two or more;
“respirator” means an air filtration device that is worn by a person to provide the wearer with clean air to breathe; and
“support structure” means a construction that is designed to have sufficient structural integrity to retain its desired shape and to help retain the intended shape of the filtering structure that is supported by it.
a is an enlarged area of the outer surface of the casting roll 58;
In practicing the present invention, an auxetic mesh can be molded into a desired three-dimensional configuration. The inventor discovered that the a molded auxetic mesh can be formed into a desired 3-D shape while preserving the size of the various open spaces in the mesh. As the auxetic mesh attains its three-dimensional shape during molding, the mesh deforms in a fractal manner, substantially retaining the initial mesh appearance, unlike the distortions observed after conventional meshes are formed over bi-curved surfaces. Before being molded, the auxetic mesh may be provided in an initial flat two-dimensional form, which is simple to handle and store. Converting the initial flat auxetic mesh into a three-dimensional shape may provide a more efficient manufacturing pathway when compared to batch processes that would normally required to fabricate a similar netting substantially free of defects. That is, if a non-auxetic mesh is used to produce a three-dimensional product, without the distortions mentioned above, a batch-type casting or injection molding process typically would be used for that purpose.
Examples of thermoplastic polymers that can be used to form auxetic meshes include: polyolefins, such as polyethylenes, polypropylenes, polybutylenes, blends of two or more of such polyolefins, and copolymers of ethylene and/or propylene with one another and/or with small amounts of copolymerizable, higher, alpha olefins, such as pentene, methylpentene, hexene, or octene; halogenated polyolefins, such as chlorinated polyethylene, poly(vinylidene fluoride), poly(vinylidene chloride), and plasticized poly(vinyl chloride); copolyester-ether elastomers of cyclohexane dimethanol, tetramethylene glycol, and terephthalic acid; copolyester elastomers such as block copolymers of polybutylene terephthalate and long chain polyester glycols; polyethers, such as polyphenyleneoxide; polyamides, such as poly(hexamethylene adipamide), e.g., nylon 6 and nylon 6,6; nylon elastomers; such as nylon 11, nylon 12, nylon 6,10 and polyether block polyamides; polyurethanes; copolymers of ethylene, or ethylene and propylene, with (meth)acrylic acid or with esters of lower alkanols and ethylenically-unsaturated carboxylic acids, such as copolymers of ethylene with (meth)acrylic acid, vinyl acetate, methyl acrylate, or ethyl acrylate; ionomers, such as ethylene-methacrylic acid copolymer stabilized with zinc, lithium, or sodium counterions; acrylonitrile polymers, such as acrylonitrile-butadiene-styrene copolymers; acrylic copolymers; chemically-modified polyolefins, such as maleic anhydride- or acrylic acid-grafted homo- or co-polymers of olefins and blends of two or more of such polymers, such as blends of polyethylene and poly(methyl acrylate), blends of ethylene-vinyl acetate copolymer and ethylene-methyl acrylate; blends of polyethylene and/or polypropylene with poly(vinyl acetate); and thermoplastic elastomer block copolymers of styrene of the A-B or A-B-A type, where A represents a thermoplastic polystyrene block and B represents a rubbery block of polyisoprene, polybutadiene, or poly(ethylene/butylene), examples include linear, radial, star and tapered styrene-isoprene block copolymers, linear styrene-(ethylene-butylene) block copolymers, and linear, radial, and star styrene-butadiene block copolymers. The foregoing polymers are normally solid, generally high molecular weight, and melt-extrudable such that they can be heated to form molten viscous liquids which can be pumped as streams to the extrusion die assembly and readily extruded therefrom under pressure.
Examples of suitable commercially-available polymers include: those sold as “ELVAX” ethylene-vinyl acetate copolymers, such as ELVAX 40W, 4320, 250, and 350; those sold as “EMAC” ethylene-methyl acrylate copolymers, such as EMAC DS-1274, DS-1176, DS-1278-70, SP 2220 and SP-2260; those sold as “VISTA FLEX” thermoplastic elastomers, such as VISTA FLEX 641 and 671; those sold as “PRIMACOR” ethylene-acrylic acid copolymers, such as PRIMACOR 3330, 3440, 3460, and 5980; those sold as “FUSABOND” maleic anhydride-polyolefin copolymers, such as FUSABOND MB-110D and MZ-203D; those sold as “HIMONT” ethylene-propylene copolymers, such as HIMONT KS-057, KS-075, and KS-051P; those sold as “FINA” polypropylenes, such as FINA 3860X; those sold as “ESCORENE” polypropylenes, such as ESCORENE 3445; the polymer sold as “VESTOPLAST 750” ethylene-propylene-butene copolymer; those sold as “SURLYN” ionomers, such as SURLYN 9970 and 1702; those sold as “ULTRAMID” polyamides, such as ULTRAMID B3 nylon 6 and ULTRAMID A3 nylon 6,6; those sold as “ZYTEL” polyamides, such as ZYTEL FE3677 nylon 6,6; those sold as “RILSAN” polyamide elastomers, such as BMNO P40, BESNO P40 and BESNO P20 nylon 11; those sold as “PEBAX” polyether block polyamide elastomers, such as PEBAX 2533, 3533, 4033, 5562 and 7033; those sold as “HYTREL” polyester elastomers, such as HYTREL 3078, 4056 and 5526; those sold as “KRATON” and “EUROPRENE SOL TE” styrene block copolymers, such as KRATON D1107P, G1657, G1750X, and D1118X and EUROPRENE SOL TE 9110, and 6205.
As mentioned above, blends of two or more materials also may be used in the manufacture of auxetic meshes. Examples of such blends include: a blend of 85 to 15 wt % poly(ethylene-vinyl acetate), such as “ELVAX” copolymer, with 15 to 85 wt % poly(ethylene-acrylic acid), such as “PRIMACOR” polymer, the poly(ethylene-vinyl acetate) component of the blend generally will have a weight average molecular weight, Mw, of 50,000 to 220,000 and will have 5 to 45 mol % of its interpolymerized units derived from the vinyl acetate comonomer and the balance of units from ethylene, the poly(ethylene-acrylic acid) component of the blend generally will have a Mw of 50,000 to 400,000 and have 1 to 10 mol % of its interpolymerized units derived from acrylic acid and the balance from ethylene; a blend of 20 to 70 wt % poly(ethylene-propylene-butene) terpolymer having Mw of 40,000 to 150,000 and derived from equally large amounts of butene and propylene and a small amount of ethylene, such as “VESTOPLAST 750” polymer, with 80 to 30 wt % isotactic polypropylene; a blend that contains from 15 to 85 wt % poly(ethylene-vinyl acetate) and 85 to 15 wt % poly(ethylene-methyl acrylate), such as “EMAC” polymer, the poly(ethylene-vinyl acetate) component of this blend can have a molecular weight and composition like that described above, the poly(methyl acrylate) component can have a Mw of 50,000 to 200,000 and 4 to 40 mole % of its interpolymerized units derived from the methyl acrylate comonomer.
Polypropylene may be preferred for use in a molded auxetic mesh that is used on a respirator to enable proper welding of the support structure to the filtering structure (filtering layers often comprise polypropylene as well). The polymeric materials used to make an auxetic mesh typically have a Young's modulus of about 0.3 to 1900 Mega Pascals (MPa), more typically 2 to 250 MPa. As shown in
When molding an auxetic mesh in accordance with the present invention, the auxetic mesh may be molded by itself or it may be molded in conjunction with other layers. For example, when making a filtering face-piece respirator, the auxetic mesh may be first molded, and the other layers, such as the filtering structure, may be subsequently joined to the molded mesh. Alternatively, the various layers may be stacked together and molded into the desired configuration. Further, the auxetic mesh may be cold-molded or hot-molded. When the auxetic mesh is cold-molded, the mesh is first heated before being placed between unheated molding members (see, for example, U.S. Pat. No. 7,131,422B1 to Kronzer et al.). The unheated molding members then conform the heated auxetic mesh to its desired configuration. Alternatively, the molding members may be heated, and that heat may be transferred to the auxetic mesh during the molding operation. Thus, in a cold-molding operation, the heat and pressure are not necessarily applied to the auxetic mesh contemporaneously, whereas in a hot-molding operation the heat and pressure tend to be applied at the same time. In hot molding, the various layers may become bonded to each other at one or more desired locations when the heat and pressure is applied. Alternatively, the various layers may be joined together at one or more desired locations through other operations such as welding (for example, ultrasonic welding) or adhesive bonding. The additional layers may be on one or both sides of the auxetic mesh. When making a filtering face-piece respirator, the mask body may be molded into a variety of different shapes and configurations. Many of these various shapes and configurations are described in the patent literature and accordingly will not be discussed further here.
Cell Size Determination
Auxetic mesh cell size was determined using defined diameter rods that were mounted in a fixture to facilitate measurement of the open spaces or cells. The probe rods ranged in diameter from 0.0254 cm (centimeter) to 0.5334 cm, in 0.0254 cm increments. The cell size was measured by selecting the maximum size probe that fit into the cell without causing distortion of the cell shape prior to placement of the probe. This size was recorded, and the next cell size was measured and recorded until all cells contained within the molded mesh were measured and the cells tallied at each probe size.
Auxetic Mesh Formation Apparatus and Process
An auxetic web was produced using a system 50 that resembles the apparatus shown in
During processing, the doctor blade 56 was forced against the rotating casting roll 58 at a pressure of 0.656 kN/cm (kilo-Newtons per lineal cm)—a pressure that forced molten polymer 60 to fill the channels or cavities 62 of the casting roll 58. The doctor blade 56 was maintained at a temperature of 246° C. The polymer bank 60 assured that sufficient polymer was present across the transverse length of the casting roll 58 to fill the channels 62 of the casting roll.
As shown in
As shown in
As shown in
Auxetic Mesh Characterization Test Method
Auxetic mesh produced as described in the Auxetic Mesh Formation Apparatus and Process were evaluated for their auxetic properties through a tensile testing procedure. In this procedure, a 10.2 cm by 1.0 cm section of mesh was cut such that the long axes of the mesh cells were oriented in line with the transverse axis of the tensile testing apparatus. The crosshead speed of the tensile testing apparatus was maintained at 50.8 centimeters per minute until the sample was elongated to 50 and 100 percent of its original length. As is indicative of an auxetic structure, when placed under tension, the sample section increased in width in response to axial loading. The sample increased to a width of 105 percent of its original width at both elongations.
Three-Dimensional Molding of an Auxetic Mesh
Auxetic mesh produced as described in the Auxetic Mesh Formation Apparatus and Process section was molded into a three-dimensional cup shape. The auxetic mesh was molded into the cup shape of a respirator by draping a 21.5 cm by 25.5 cm section of mesh over an aluminum male mold. The mold had a generally hemispherical shape with an elliptical base with a major axis of 13.3 cm, and a minor axis of 10.5 cm, and a dome height of 4.4 cm. The hemispherical-shape mold was fixed to a rectangular aluminum plate that extended approximately 3.4 cm beyond the base of the mold. The section of auxetic mesh was draped over the mold so that it's edges extended beyond the outer perimeter of the base plate. A perimeter aluminum frame, with an interior cutout that mirrored the perimeter of the mold, was placed over the auxetic mesh and mold so that the mesh could be drawn over the mold without significant mesh distortion. The perimeter frame was then fixed to the base plate to hold the mesh in position against the mold. The mold, mesh, and securing plate assembly was placed in a preheated, air circulating oven for 20 minutes at a temperature of 105 C. After heating in the oven for the specified duration, the assembly was removed from the oven and was allowed to cool to room temperature. When the assembly reached room temperature, the perimeter frame was uncoupled from the base plate, and the resultant molded auxetic mesh removed from the mold. It was observed that the molded auxetic mesh retained its general auxetic structure, and it was shape-retaining even after compression in the mold. It was also noted that the auxetic mesh was able to easily adapt to the male mold shape without significant distortions to the mesh, such as folds or creases.
Respirator Cell Size Comparison
A respirator shell mesh was produced as described above in the Three-Dimensional Molding of Auxetic Mesh section was evaluated for cell size uniformity by surveying the size of the cells over the entirety of the mold structure. The cell size uniformity of the auxetic mesh was compared to the uniformity of shell meshes that were removed from commercially available filtering face-piece respiratory masks. Detailed measurements of the cell opening size and size distribution for each of several shell meshes were determined Respirator shell mesh was evaluated from a JSP 822 mask, manufactured by JSP Ltd, Oxfordshire, UK; a Venus 190 mask, produced by Nani Mumbai-MN, India; a 2200 mask inner shell, a 2200 mask outer shell, and a 2600 outer shell, all manufactured by Moldex-Metric, Culver City, Calif. The meshes were removed from the filter media to enable cell size measurement, the exception being the 3M auxetic mesh which was free standing. Each cell opening size was measured and recorded for the entire mesh using gauging probes as described above in Cell Size Determination.
The resulting measurements were compiled to provide the number of cells contained within the mesh of a given size, see Table 2. From this data the cell size distribution and standard deviation determined were determined and are given in Table 2.
The data shown in Table 2 reveals that the molded auxetic mesh has the narrowest distribution of cell size compared to known non-auxetic molded meshes. Analysis of the data for standard deviation shows that the inventive auxetic mesh has the smallest standard deviation of all six meshes measured. The reduction of cell size distribution in the auxetic mesh is a result of the deformation characteristics of an auxetic structure, which allows it to more readily conform to highly contoured shapes without gross deformation of the mesh, such as folding or drawing.
This application claims the benefit of U.S. Provisional Patent Application No. 61/291,057, filed Dec. 30, 2009. The present invention pertains to a molded auxetic mesh and to a method of making such a mesh.
Number | Date | Country | |
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61291057 | Dec 2009 | US |