Composite building materials and methods of manufacture

Information

  • Patent Grant
  • 12172421
  • Patent Number
    12,172,421
  • Date Filed
    Monday, February 6, 2023
    a year ago
  • Date Issued
    Tuesday, December 24, 2024
    a day ago
Abstract
An example composite building material includes one or more layers of polymeric and/or glass fibers, binding agent, and optional fillers. At least one surface layer of resin-impregnated paper or a fiberglass film can be disposed above and/or below the one or more layers. The one or more layers can include a core layer (e.g., with longer polymeric fibers) and a top layer (e.g., with shorter polymeric fibers). An example method of manufacturing the composite building material includes forming the one or more layers, applying the at least one surface layer above and/or below the one or more layers, and heating and pressing the combined layers.
Description
FIELD OF THE INVENTION

In certain examples, the subject matter described herein relates to composite building materials and, more particularly, to composite building materials that include polymeric fiber and/or fiberglass.


BACKGROUND

Natural and manmade composites can be used in building construction, industrial applications, consumer goods, automotive products, and other industries requiring moisture or thermal resistance with various physical properties, such as low moisture absorbance and low thermal distortion. The ability to build composites of this nature, while controlling physical properties such as strength, stiffness, ductility, impact resistance, and hardness, opens a variety of application opportunities. Plastic composites (PCs), however, may be expensive to produce, due in part to the high cost of virgin thermoplastic materials used therein. While use of PCs may be desirable as an alternative to natural wood products to limit the depletion of timber resources, the high cost of PCs compared to wood products may limit their use. Moreover, manufacturing PCs requires the manufacturing of even more virgin plastics, thus presenting an additional environmental problem.


There exists growing pressure to re-utilize waste streams which are high in volume and low in degradability. In particular the manufacture, installation, use and (eventually) replacement of floor covering products, especially carpeting, produces a large amount of waste product. Carpet waste from new carpet production, post-consumer landfill or other used carpet applications, is a several billion pound-per-year waste problem. Often, carpet and glass waste is not recycled, but rather is disposed of by land-filling or burning, with the obvious attendant environmental and cost concerns.


What is needed, then, is a plastic composite that may still function acceptably in a variety of applications, while being inexpensive to manufacture, due to incorporation of readily available waste products.


SUMMARY

In general, the subject matter of this disclosure relates to composite building materials that include polymeric fibers and/or fiberglass (or other synthetic fibers) and a binding agent or matrix resin. In one example, a composite building material includes (i) one or more layers of polymeric fibers and/or polymeric filler mixed with a binding agent and (ii) top and/or bottom layers (e.g., on outer surfaces) of a resin-impregnated paper (e.g., phenolic paper) and/or a fiberglass film. The one or more layers of polymeric fibers and/or polymeric fillers and binding agent can include a core layer having long polymeric fibers (e.g., greater than 25 mm in length, on average) and top and bottom layers having shorter polymeric fibers (e.g., less than 25 mm in length, on average) disposed above and below the core layer, respectively. The polymeric fibers can be derived from carpet, automotive headliners, automotive sidewalls, fabric materials, insulation materials, other sources, or any combination thereof. The polymeric fillers can be or include, for example, biaxially oriented polypropylene, polymeric films, packaging films, barrier packaging films, recycled polymeric materials, or any combination thereof. The one or more layers of polymeric fibers and/or polymeric fillers and binding agent can include various additives and/or other fillers, such as, for example, natural fiber fillers, inorganic fillers, fire retardants, mold inhibitors, and/or other performance enhancing chemical additives.


Advantageously, use of the top and/or bottom layers of resin-impregnated paper (and/or a fiberglass film) can significantly improve various performance characteristics of the composite building materials including, for example, greater stiffness, greater resistance to mechanical damage, less moisture absorption, and greater resistance to dimensional changes caused by moisture or temperature variations. In one experiment, for example, the use of top and/or bottom layers of resin-impregnated paper was found to reduce the coefficient of thermal expansion (CTE) by as much as a factor of ten (e.g., CTE was reduced from 6.00E-05 to 6.00E-06). In another experiment, the use of top and/or bottom layers of resin-impregnated paper was found to reduce linear expansion caused by moisture absorption by a factor of about eight (e.g., linear expansion of a 6.1 meter board submerged in water for 144 hours was reduced from 2.5 cm to 0.33 cm). Additionally or alternatively, use of the top and/or bottom layers of resin-impregnated paper and/or the fiberglass film can provide a smoother exterior surface, which can improve an overall appearance of the final product and/or can achieve a more consistent or improved adhesion with surface coatings, such as paints or clear coats. Use of the top and/or bottom layers of resin-impregnated paper or fiberglass film can also make manufacturing processes more consistent and/or reliable, for example, by reducing the adhesion of carpet or binding agent materials to press components during heating and pressure cycles, as described herein.


Additionally or alternatively, use of multiple layers of polymeric fibers and binding agent can have various performance benefits. For example, using a core layer with long fibers can improve mechanical properties, such as stiffness and dimensional stability. The long fibers, however, can result in a core layer that is nonuniform or irregular in thickness (e.g., with large peaks and valleys). Advantageously, the top and bottom layers of shorter fibers can cover thickness irregularities in the core layer to achieve a combined thickness of the core layer, the top layer, and the bottom layer that is substantially uniform (e.g., with small or no peaks and valleys). This can facilitate the formation of composite materials that are uniform in thickness and/or have smooth external surfaces. Additionally or alternatively, the multiple layers of polymeric fibers and binding agent can allow fillers and/or additives to be included or concentrated in individual layers where the fillers and/or additives will have the greatest performance benefits.


In general, in one aspect, the subject matter of this disclosure relates to a composite building material. The composite building material includes: a core layer including a first type of polymeric fibers and a first binding agent, the first type of polymeric fibers having a first average fiber length; a top layer disposed above the core layer and including a second type of polymeric fibers and a second binding agent, the second type of polymeric fibers having a second average fiber length different than the first average fiber length; a bottom layer disposed below the core layer and including the second type of polymeric fibers and the second binding agent; and at least one surface layer of resin-impregnated paper and/or a fiberglass film disposed above the top layer or below the bottom layer.


In certain examples, the first type of polymeric fibers and/or the second type of polymeric fibers can be derived from carpet, automotive headliners, automotive sidewalls, automotive fabrics, insulation materials, or any combination thereof. The second average fiber length can be less than the first average fiber length. The first average fiber length can be greater than about 25 mm. The core layer can have a substantially nonuniform thickness, and/or the core layer, the top layer, and the bottom layer together can have a substantially uniform thickness. The substantially nonuniform thickness can include an irregular thickness with peaks and valleys. The substantially nonuniform thickness can include a minimum thickness and a maximum thickness, and the minimum thickness can be less than half of the maximum thickness. The substantially uniform thickness can include a minimum thickness and a maximum thickness, and the minimum thickness can be at least 90% of the maximum thickness. In certain implementations, the first type of polymeric fibers and the second type of polymeric fibers can include fibers having the same or similar chemical composition and/or fiber diameters.


In some implementations, the first binding agent and/or the second binding agent can include methylenediphenyldiisocyanate (MDI), polyurea, polyurethane (e.g., a foamed polyurethane), a polyol, a polyester resin, a phenol formaldehyde resin, or any combination thereof. The core layer, the top layer, and/or the bottom layer can include a polymeric filler having particles of biaxially oriented polypropylene, a polymeric film, a packaging film, a barrier packaging film, a MRF residual, or any combination thereof. The core layer, the top layer, and/or the bottom layer can include an inorganic filler, a natural fiber filler, and/or fiberglass. The core layer can include at least one filler or additive that is not present in the top layer or the bottom layer. At least one of the top layer or the bottom layer can include at least one filler or additive that is not present in the core layer. The at least one surface layer of resin-impregnated paper can be or include phenolic paper. The at least one surface layer of resin-impregnated paper and/or the fiberglass film can be bonded to the top layer and/or the bottom layer with a glue.


In another aspect, the subject matter of this disclosure relates to a method of manufacturing a composite building material. The method includes: forming a core layer having a first type of polymeric fibers and a first binding agent, the first type of polymeric fibers having a first average fiber length; forming a top layer having a second type of polymeric fibers and a second binding agent, the second type of polymeric fibers having a second average fiber length different than the first average fiber length; forming a bottom layer having the second type of polymeric fibers and the second binding agent; applying at least one surface layer of resin-impregnated paper and/or a fiberglass film above the top layer and/or below the bottom layer; and heating and pressing the core layer, between the top layer and the bottom layer, and the at least one surface layer to form the composite building material.


In some instances, the first type of polymeric fibers and/or the second type of polymeric fibers can include fibers derived from at least one of carpet, automotive headliners, automotive sidewalls, automotive fabrics, insulation materials, or any combination thereof. The second average fiber length can be less than the first average fiber length. Each of the first type of polymeric fibers and the second type of polymeric fibers can include granulated polymeric fibers. Forming the core layer can include mixing the first type of polymeric fibers with the first binding agent, and forming the top layer and the bottom layer can include mixing the second type of polymeric fibers with the second binding agent. The first binding agent and/or the second binding agent can include methylenediphenyldiisocyanate (MDI), polyurea, polyurethane (e.g., a foamed polyurethane), a polyol, a polyester, a phenol formaldehyde, or any combination thereof. Forming the core layer can include applying the core layer over the bottom layer, and forming the top layer can include applying the top layer over the core layer.


In various examples, applying the at least one surface layer can include applying a surface layer from the at least one surface layer over the top layer. Applying the at least one surface layer can include bonding the at least one surface layer to the top layer and/or the bottom layer with a glue. The at least one surface layer can include phenolic paper and/or a fiberglass film. The core layer can have a substantially nonuniform thickness, and the core layer, the top layer, and the bottom layer together can have a substantially uniform thickness. The method can include performing a heat treatment on an edge of the composite building material.


In another aspect, the subject matter of this disclosure relates to a composite building material. The composite building material includes: a core layer including a binding agent and at least one of polymeric fibers or polymeric film particles; and at least one surface layer of resin-impregnated paper and/or a fiberglass film disposed above or below the core layer.


In certain implementations, the core layer can include the polymeric fibers, and the polymeric fibers can include a mixture of long polymeric fibers (e.g., having an average length greater than 25 mm) and short polymeric fibers (e.g., having an average length less than 25 mm). The mixture of long polymeric fibers and short polymeric fibers can include a bimodal distribution of fiber lengths (e.g., with a first peak at a short fiber length and a second peak at a long fiber length). The polymeric fibers can be derived from carpet, automotive headliners, automotive sidewalls, automotive fabrics, insulation materials, or any combination thereof. The core layer can include the polymeric film particles, and the polymeric film particles can include biaxially oriented polypropylene, a packaging film, a barrier packaging film, or any combination thereof. The binding agent can be or include methylenediphenyldiisocyanate (MDI), polyurea, polyurethane (e.g., a foamed polyurethane), a polyol, or any combination thereof.


In another aspect, the subject matter of this disclosure relates to a method of manufacturing a composite building material. The method includes the steps of: forming a core layer having a binding agent and at least one of polymeric fibers or polymeric film particles; applying at least one surface layer of resin-impregnated paper and/or a fiberglass film above and/or below the core layer; and heating and pressing the core layer and the at least one surface layer to form the composite building material.


In certain examples, forming the core layer can include adding the polymeric fibers, and the polymeric fibers can include fibers derived from at least one of carpet, automotive headliners, automotive sidewalls, automotive fabrics, insulation materials, or any combination thereof. Forming the core layer can include adding the polymeric film particles, and the polymeric film particles can include biaxially oriented polypropylene, a packaging film, a barrier packaging film, or any combination thereof. The binding agent can be or include methylenediphenyldiisocyanate (MDI), polyurea, polyurethane (e.g., a foamed polyurethane), a polyol, or any combination thereof.


In one aspect, the invention relates to a composite adapted for use as a building material, the composite including processed carpet waste, between about 2% and about 10% binding agent by weight of the composite, and between about 20% and about 30% natural fibers by weight of the composite in intimate association with the recycled carpet waste and the binding agent. In an embodiment of the above aspect, the composite includes about 5% binding agent, by weight. In another embodiment, the composite has about 30% natural fibers, by weight. In certain embodiments of the above aspect, the processed carpet waste includes a material selected from the group consisting of wool, nylon, polyester, polypropylene, jute, sisal, and combinations thereof. In certain embodiments of the above aspect, the natural fibers are selected from the group consisting of wood chips, wood flour, wood flakes, sawdust, flax, jute, hemp, kenaf, rice hulls, abaca, and combinations thereof.


In yet another embodiment of the above aspect, the composite includes an additive selected from the group consisting of a colorant, a fire retardant, a fiberglass, a mold inhibitor, and combinations thereof. In certain embodiments, the processed carpet waste is at least one of post-industrial waste and post-consumer waste. In other embodiments of the above aspect, after submersion testing according to ASTM D1037-96A, the composite exhibits water absorption of not more than about 3%, by weight. Other embodiments of the composite include processed carpet waste having a melted polypropylene and an unmelted nylon. In certain embodiments, the processed carpet waste is at least one of a pelletized carpet waste and a fiber carpet waste.


In another aspect, the invention relates to a method of manufacturing a composite adapted for use as a building material, the method including the steps of applying heat and pressure to a processed carpet waste and a binding agent to form the composite material, and cooling the composite material while applying pressure to the composite material. This aspect may include the step of processing carpet waste, wherein the processing step is at least one of chopping, shredding, grinding, contaminant separating, palletizing, agglomerating, pulverizing, fine grinding, and fiberizing the carpet waste. In some embodiments of the above aspect, the step of applying heat and pressure occurs in a first cycle press, and wherein the step of cooling the composite while applying pressure occurs in a second cycle press. In other embodiments, the step of applying heat and pressure and the step of cooling the composite while applying pressure occur in a first cycle press. In still other embodiments of the above aspect, the step of applying pressure heats the composite material to a temperature of about 100° F. to about 600° F., to a temperature of about 200° F. to about 550° F., to a temperature of about 340° F. to about 420° F., or to a temperature of about 420° F. to about 500° F. In yet another embodiment, the step of cooling the composite material while applying pressure cools the composite material to a temperature of about 300° F. to about 32° F., or to a temperature of about 250° F. to about 180° F., or to a temperature of about 80° F.


In another embodiment of the above aspect, the pressure applied during the applying heat step and the cooling step is substantially constant. Certain embodiments may include the processed carpet waste as an unmelted carpet waste. Additional embodiments include the step of mixing the processed carpet waste and the binding agent. In some embodiments of the above aspect, the composite has about 90% to about 98% processed carpet waste, by weight, or about 95% processed carpet waste, by weight. In another aspect, the invention relates to a composite building material manufactured according to the processes described above.


In another aspect, the subject matter of this disclosure relates to a composite building material. The composite building material includes: a core layer including a first binding agent and fibers; and a top layer disposed above the core layer and including a second binding agent and fibers, wherein the fibers in the core layer and the fibers in the top layer include fibers derived from at least one of a scrap fiber source, a used fiber source, a recycled fiber source, or any combination thereof, wherein at least one of the fibers in the core layer or the fibers in the top layer include glass fibers, and the glass fibers are at least partially coated with an organofunctional silane, wherein the fibers in the top layer have an average length less than about 6 mm, and wherein the core layer and the top layer form a rigid board or a rigid sheet.


In certain examples, the fibers in the core layer and/or the fibers in the top layer can include fibers derived from at least one of carpet, automotive headliners, automotive sidewalls, automotive fabrics, insulation materials, or any combination thereof. The fibers in the core layer and/or the fibers in the top layer can include glass fibers derived from fiberglass insulation materials. At least one of the first binding agent or the second binding agent can include polyurea, polyurethane, epoxy, acrylic resin, unsaturated polyester resin, isocyanate, MDI, pMDI, phenol formaldehyde (PF), a product derived therefrom, a thermoset, or any combination thereof. The first binding agent and the second binding agent can be different or identical. The fibers in the core layer can have an average length less than about 6 mm. An average length of the fibers in the core layer can be greater than an average length of the fibers in the top layer. The first binding agent or the second binding agent can include a polyurea foam and/or a polyurethane foam.


In various instances, the core layer can have a substantially nonuniform thickness, and the core layer and the top layer together can have a substantially uniform thickness. At least one of the core layer or the top layer can include a polymeric filler including particles formed from at least one of biaxially oriented polypropylene, a polymeric film, a packaging film, a barrier packaging film, a MRF residual, or any combination thereof. The core layer and/or the top layer can include an inorganic filler and/or a natural fiber filler. The fibers in the core layer and the fibers in the top layer can be compressed. The rigid board or the rigid sheet can be configured for use in a building product, such as siding, trim, molding, panels, roofing, or decking. The composite building material can include a resin-impregnated paper disposed above the top layer. The composite building material can include a fiberglass film disposed above the top layer.


In another aspect, the subject matter of this disclosure relates to a method of manufacturing a composite building material. The method includes: forming a core layer including a first binding agent and fibers; forming a top layer including a second binding agent and fibers; and heating and pressing the core layer and the top layer to form the composite building material, wherein the fibers in the core layer and the fibers in the top layer include fibers derived from at least one of a scrap fiber source, a used fiber source, a recycled fiber source, or any combination thereof, wherein at least one of the fibers in the core layer or the fibers in the top layer include glass fibers, and the glass fibers are at least partially coated with an organofunctional silane, wherein the fibers in the top layer have an average length less than about 6 mm, and wherein the core layer and the top layer form a rigid board or a rigid sheet.


In some examples, forming the core layer can include mixing the first binding agent with fibers, and forming the top layer can include mixing the second binding agent with fibers. Forming the top layer and/or forming the bottom layer can include applying the organofunctional silane to the glass fibers. The method can include applying at least one surface layer above the top layer, and the at least one surface layer can be or include resin-impregnated paper or a fiberglass film.





BRIEF DESCRIPTION OF THE DRAWINGS

Other features and advantages of the present invention, as well as the invention itself, will be more fully understood from the following description of the various embodiments, when read together with the accompanying drawings, in which:



FIG. 1 is a perspective view of a plastic composite fabricated in accordance with one embodiment of the present invention;



FIG. 2 is a flow chart depicting the types of size reduction equipment and the variety of size reduction procedures depending on the final carpet waste material form desired for the process equipment;



FIG. 3 depicts steps for coating the processed carpet waste material a bonding agent and subsequent forming process to produce the plastic composite product;



FIG. 4 depicts steps for finishing the plastic composite product;



FIG. 5A is a schematic, perspective view of a composite having multiple layers of carpet fiber, binding agent, and optional fillers, in accordance with certain embodiments;



FIG. 5B is a schematic, perspective view of a composite having a single layer of carpet fiber, binding agent, and optional fillers, in accordance with certain embodiments;



FIG. 6 is a schematic, side view of three layers having polymeric fibers, in accordance with certain embodiments;



FIG. 7 is a schematic, side view of a composite material having three layers of polymeric fibers and top and bottom surface layers of a resin-impregnated paper (and/or a fiberglass film), in accordance with certain embodiments;



FIG. 8 is a schematic diagram of a manufacturing process for a composite material, in accordance with certain embodiments; and



FIG. 9 is a schematic diagram of a manufacturing process for a composite material, in accordance with certain embodiments.



FIG. 10 is a flowchart of a method of manufacturing a composite building material, in accordance with certain embodiments.



FIG. 11 is a flowchart of a method of manufacturing a composite building material, in accordance with certain embodiments.





DETAILED DESCRIPTION

It is contemplated that apparatus, systems, methods, and processes of the claimed invention encompass variations and adaptations developed using information from the embodiments described herein. Adaptation and/or modification of the apparatus, systems, methods, and processes described herein may be performed by those of ordinary skill in the relevant art and are considered to be within the scope of the disclosed invention.


It should be understood that the order of steps or order for performing certain actions is immaterial, so long as the invention remains operable. Moreover, two or more steps or actions may be conducted simultaneously.


In certain examples, a “binding agent” (alternatively referred to as a “matrix resin”) can be or include a material or blend of materials that binds or holds ingredients of a composite together. The binding agent can coat or surround the ingredients and/or form a continuous phase or mostly continuous phase within the composite. During composite manufacture, the binding agent (e.g., in liquid form) can be mixed with the ingredients and then dried or cured to form a rigid, adhesive material. In certain examples, the binding agent can include or be derived from an isocyanate (e.g., MDI or pMDI), urea formaldehyde (UF), melamine urea formaldehyde (MUF), phenol formaldehyde (PF), a polyurea, a polyurethane, one or more polyols, epoxy, acrylic resin, polyester (e.g., unsaturated polyester resin), an organofunctional silane, or any combination thereof. The binding agent can be a thermoset or a thermoplastic.


In certain examples, a “fiber” can be a thread or filament having a length that is longer than its diameter (e.g., by a factor of about 10, 30, 100, 300, 1000, 3000, 10000, or more). Diameters of carpet fibers, glass fibers, or other fibers described herein can be, for example, from about 10 microns to about 50 microns, or about 30 microns.


In certain examples, a “film” can be a thin, flexible sheet of material having a thickness that is smaller than its length and/or width (e.g., by a factor of about 10, 30, 100, 300, 1000, 3000, 10000, or more). Thicknesses of BOPP and other films described herein can be, for example, from about 10 microns to about 40 microns, or about 25 microns.


In various examples, a “filler” can be or include a material that is added to or present in the composite building materials described herein. Inclusion of a filler does not require that any other ingredients or components also be present in the composite building materials. For example, when a layer in a composite building material includes a filler, the layer may include only the filler and no other ingredients or components. Alternatively or additionally, in addition to the filler, the layer may include other ingredients or components, such as, for example, a binding agent and/or polymeric fibers.


In certain examples, the new systems and methods can be used to process and combine recycled carpet waste with a binding agent to form a PC with equivalent properties to those PCs made with virgin plastics at reduced cost.



FIG. 1 shows one embodiment of a sheet or board plastic composite 10 including recycled carpet waste formed in accordance with the present disclosure. The composite 10 is generally a dimensional composite body 12 formed from a mixture including recycled carpet waste and a binding agent. Length L, width W, and thickness t, of the composite 10 are dictated by the production machinery used. Functional performance parameters of the composite 10 may be defined in part by the amount of carpet waste, binding agent, natural fillers, and other optional additives. In general, however, the density of the composite 10 is directly related to the total amount of carpet waste used and the final thickness t of the board. The recycled carpet waste, which may be blended or dispersed with natural fillers within the fiber-polymer compound, can result in a composite having physical properties equivalent to PCs made with virgin thermoplastics. The recycled carpet waste may be processed into a fiber fluff, or other form, from post-industrial or post-consumer carpet waste. Depending on the composition of the carpet used, the recycled carpet waste can include wool, nylon, polyester, polypropylene, jute, sisal, like materials, and combinations thereof. Due at least in part to processing controls, described in greater detail in the following paragraphs, the recycled carpet waste is dispersed and distributed substantially uniformly throughout the composite 10. Various binding agents may be utilized as desired for a given application. Certain embodiments of a PC made in accordance with the present invention utilize methylenediphenyldiisocyanate (MDI) as a binding agent, a binding agent precursor, or a reactant used to form a binding agent. MDI can act as a binding agent for the fibers or agglomerated carpet waste materials to contribute to the structural integrity of the composite products. As an alternative to (or in addition to) MDI, binding can be accomplished using urea formaldehyde (UF), melamine urea formaldehyde (MUF), phenol formaldehyde (PF), one or more polyols, epoxy, acrylic resin, polyester resin, similar binding agents, and combinations of agents. The binding agent can be or include a thermoset or a thermoplastic.


In addition to the binding agent, the composite 10 may incorporate natural fibers to help provide the composite with the appearance and feel of a natural wood product. Types of natural fibers, such as wood fillers or the like, include wood chips, wood flour, wood flakes, wood shavings, sawdust, flax, jute, abaca, hemp, kenaf, rice hulls, like materials, and combinations thereof. The sizes of the various natural fibers is not critical and may range from that of sawdust and wood flour, up to and exceeding 1″ long wood chips, though fibers and chips less than about 0.5″ may be preferred. The composite may include additives such as colorants, lubricants, flame retardants, compatiblizers, coupling agents, other materials, and combinations thereof. The relative amounts of components (i.e., recycled carpet waste, filler, additives, etc.) may be modified as desired for a particular application. The various component amounts, ratios of components, and finished composite properties in certain embodiments, are described in more detail below.


Unless otherwise noted, the use of one material when describing a particular application, process, or embodiment does not limit the described application, process, or embodiment to the specific material identified. The materials may be used interchangeably, in accordance with the described teachings herein. Moreover, the terms “composite building materials,” “plastic composites” (or “PCs”), “composite sheets,” “composite materials,” and the like, are used interchangeably herein to describe composite boards or sheets made from recycled carpet waste, polymeric fiber, and/or fiberglass and optionally including one or more additives. In addition to PCs, other composite products may be manufactured utilizing, in whole or in part, recycled carpet waste. A non-limiting list of such composite products includes plastic piping, molded articles such as flower pots or seeding trays, building siding or roofing, trim boards, decking, fencing, furniture, or other types of extruded, injection molded, and/or compression molded products.



FIG. 2 shows the types of equipment and the variety of procedures for carpet waste size reduction, depending on the final form desired for the process equipment. The final form may also be dependent on the desired finished composite product and physical or visual appearance properties. In short, the carpet waste is processed as described below to reduce its size or generate small pieces, particles, and/or fibers of the carpet waste. The size-reduced carpet waste is then mixed or coated with a binder or binding agent to produce material that is subjected to temperature and/or pressure to yield the composite material. The size reduction process may take place at the same facility where the PCs are manufactured, or the carpet waste may be processed at a first facility and delivered to a second facility for incorporation into the PC products. Post-manufacture treatments for the composite material are also described below.


The carpet waste can include selvedge, post-industrial carpet waste, post-consumer carpet waste, and/or waste carpet reclaimed from landfills. Post-industrial carpet waste refers generally to waste material produced as a byproduct to the manufacturing process, such as trimmed carpet segments, as well as to carpet that fails to pass quality or other inspections, thus rendering it unsuitable for consumer use. Post-consumer carpet waste refers generally to carpet waste that is generated during installation at a consumer site or that is removed from a consumer site during demolition and/or replacement. Regardless, the terms selvedge, carpet waste, waste carpet, reclaimed waste, recycled waste, and similar terms are used herein interchangeably and may be used in the processes described herein interchangeably. These materials generally will be in baled form to begin the size reduction phase of the pre-processing. The bales vary in size but usually are about 1000 lb. to about 2000 lb. Some or all of the equipment described in the carpet reduction processes below may be supplied by PALLMANN MASCHINENFABRIK GMBH, DIEFFENBACHER GMBH, ROTOGRAN, VECOPLAN, WEIMA, or other manufacturers that produce similar equipment. Alternative manufacturers of specific equipment are identified below.


The first step in the size reduction phase includes reducing the waste to a manageable size for the remainder of the process. As depicted in FIG. 2, either a combination of a shredder/chopper and grinder (Process Option A), or a major capacity grinder (Process Option B) is used to process the materials to smaller sizes. Process Option A may be used to reduce carpet waste to pellets or granules that may be further processed into various PC products. The shredder/chopper first reduces the selvedge or carpet waste to chunks approximately three inches square (3″×3″), although other sizes are contemplated, depending on the equipment used. In addition to Pallmann Maschinenfabrik, the shredder/chopper may be manufactured by DIEFFENBACHER, ROTOGRAN, METSO, GMBH, VECOPLAN, LLC, OR WEIMA AMERICA, Inc. The shredded material then passes through a grinder which further reduces the chunks to a fiber fluff material with a diameter of the fibers similar to the diameter of the original carpet fibers and a length of about 0.25″ to about 1″. Other manufactures of comparable grinders include VECOPLAN, LLC, ROTOGRAN, CUMBERLAND ENGINEERING Corp., and REPUBLIC MACHINE, Inc.


The waste optionally can be run through a separator which acts as a hammer mill/cyclone to remove the dirt from the carpet waste. In this step, some of the carpet backing containing inorganic fillers may also be removed. Generally, however, it is unnecessary to deliberately separate the various carpet components prior to incorporating the recycled carpet waste into PCs. All of the components of carpet may be used, not only one component, such as the carpet fibers, as certain methods may disclose. Thus, manufacturing time is decreased, since the step of component separation may not be utilized. The slightly size reduced material, due to the hammer mill effect, is ready for the next step, the agglomeration process, while the dirt and carpet backing materials that may have been removed from the small chunks can be disposed. Carpet backing that is not removed, however, does not have any adverse effect when incorporated into a PC using recycled carpet waste. The fiber fluff, regardless of the use of the separator or not, also may be blended with other materials such as wood or natural fibers, synthetic fibers (e.g., fiberglass), inorganic fillers, or other reinforcing fillers. The fiber fluff material or the blended material can then be conveyed to the agglomeration step.


The agglomeration of the above materials occurs inside the agglomerator. The materials enter a horizontal drum containing a revolving rotor that is shaped so as to force the fiber fluff or blends against the drum wall. The drum wall is perforated so that, as the rotor forces the contained materials against the perforated wall, the material is forced through the perforations, thereby forming strands of a fixed diameter. On the outside of the drum are stationary knives which cut the strands into a fixed length. During this process, the material can be heated by friction to a temperature that remains below the melting point of the highest melting point material in the blend. The temperature is controlled by the speed of the rotor, the diameter of the perforations, and the thickness of the drum wall. As each component of the carpet waste (e.g., backing and carpet fibers) is pressed against the wall of the drum, the material can heat up due to friction, for example, until the material sufficiently softens and is pressed through the perforated drum by the rotor. The agglomerating machinery could be replaced by a pellet mill manufactured by Bliss Industries or California Pellet Mill Co.


The granules that are formed in the agglomeration step are generally cylindrical in shape and approximately 0.125″ in diameter and about 0.125″ to about 0.25″ long, though other shapes and sizes can be achieved. The diameter and length of the granules can be modified by changing the diameter of the holes in the drum wall and/or changing the speed of the rotation against the knives. Because the granules are hot when they are formed and cut to length, some of the granules may be stuck to one another. Therefore, for better size consistency, the granules next pass through a grinder which separates any stuck granules. This grinder step may also be used to reduce the size of the granules, and/or the granules may be further reduced in size by a pulverizer. For example, if the final desired dimension is less than 0.125″, the pulverizer may be used to reduce the particle size to 8-16 mesh. This is the equivalent of about 0.04″ to about 0.10″.


As an optional step, the granules or pulverized particles may be fiberized. The fiberizing process includes a mechanical roughing of the surface so that the surface takes on a fuzz-like characteristic that may be desirable for the composite product process described below. After processing to the desired condition, the material is then sent to the composite production process.


As an alternative to the above process, Process Option B may be used to reduce carpet waste to a fiberized mass. First, a major capacity grinder can reduce the carpet waste to fibers about 0.25″ to about 1.0″ in length (or other lengths, as described herein) and about 1/32″ to about 0.125″ in diameter may be utilized. These random-sized fibers are ready for the agglomeration process or for alternative processes not requiring agglomeration. Next, the material optionally may be passed through a separator, as described above. The fibers may then be passed through the agglomeration process as described above, or the fibers may pass directly to the fiberizer equipment. Again, the fiberizer changes the surface characteristics of the fibers, giving them a fuzz-like surface with greater surface area and a different bulk density. The fiberizing step is again optional, and may not be required for all end uses of the composite products. Next, the fibers pass through a blender where wood or natural fibers, synthetic fibers (e.g., fiberglass), inorganic fillers, or mineral fillers (if any) may be added. Once the blending of the fibers and added materials is complete, the blend is ready for the composite production process.


Significantly, it has been determined that it is not necessary to separate or classify the various materials contained in selvedge or carpet waste, even though most carpet surface materials are nylons, polyester, polypropylene, or wool and the backing material is usually polypropylene and/or highly filled synthetic latex. These materials exhibit considerably different physical properties and processing properties, but the entire waste product may be used in the composite sheet material, regardless of the differences in the components that comprise the carpet waste. The waste carpet, having been made into an agglomerate, a fiberized agglomerate, a pulverized agglomerate, a fiberized, pulverized agglomerate, a fiberized fluff, etc., becomes the base material for the composite product. Additionally, other waste fiber or fiberized waste fiber may also be used to manufacture a composite product. The whole range of materials in carpet waste may be part of the composition. Alternatively or additionally, the composite material may include only certain portions from the carpet waste, such as, for example, carpet face fiber and/or carpet backing fiber.


After the size reduction process(es), the carpet waste is ready to be formed into composite sheets, a process that is depicted in FIG. 3. The carpet waste materials may be loaded into a large rotating drum or a drum with rotating mixing blades and/or a resination blow line. This equipment is used to coat the carpet waste with a binding agent or precursors or reactants for the binding agent. Other materials such as natural fiber fillers, polymeric fillers, and/or inorganic fillers may be loaded with the carpet waste material. If the material is loaded into a drum, water and/or MDI (or other binding agent or binding agent reactants) can be sprayed out of the resination blow line to coat the materials, while the drum and/or blades spin to cause the material within to become evenly distributed. The addition of water may achieve a desired moisture content for the material and prepare the material for the binding agent. In some examples, the water and the MDI can react to form a binding agent that includes polyurea. For the resination blow line method, the material is blown through a tube that has water and MDI introduced into it. The blowing action causes the air to become turbulent which allows the water and MDI to evenly coat the material. In one embodiment, the binding agent is applied in this manner to the granules or fibers at a concentration of about 1% to about 20% of the total weight of the granules plus any other additives. Concentrations between about 2% to about 10% and about 5% to about 6% are also contemplated. Generally, higher concentrations of resin produce composite sheets with higher moduli of elasticity and rupture. This coated carpet waste dries rapidly under ambient conditions, allowing the granules or fibers to continue to flow without adhering to one another. Accordingly, once coated and dried, the resin coated particles need not be used immediately, and may be stored and/or transported for later use.


The MDI-coated carpet waste and other additives (if applicable) are conveyed to a mat forming station that includes conveyors, metering scales, spreader heads and a control management system. The spreading equipment distributes the material onto a forming belt such that the spread material becomes a mat which has a generally uniform thickness, width and initial density. Board properties may be determined by the shape of the carpet waste composite particles/fibers and by their position in the formed mat. Additionally, the forming station can distribute more than one type of material for a multi-layered board. For example, the spreader head in the forming station could spread a mat of fibers on the forming belt, then a second spreader head could spread a mat of pellets on top of the fibers, then a third spread head could spread a top layer of fibers onto the pellets. Many different combinations of materials can be spread onto the forming belt to make various types of boards. The number of layers per board also can be varied. For example, a board could be manufactured to have an outer layer of carpet waste with a fiberglass core, or an outer layer comprising carpet waste pellets, and carpet waste fiber underlayers with a carpet waste pellet core.


After the mat is spread formed, the forming belt then transports the mat into a pre-heater, a pre-press, or directly to a press machine. The pre-heater and pre-press may be utilized to reduce total processing time of the composite sheet. Due to the thermal inertia and thickness of the material, heat from the press platens or rolls may take longer to penetrate the total thickness of the mat, thereby extending process time and costs. Preheating brings the temperature of the entire mat up to a higher starting temperature. In some examples, the pre-heater can be located directly ahead of a press (e.g., a hydraulic press) and can be used to preheat the mat after the mat has been formed and/or pre-pressed, as described herein. The pre-press compresses the starting materials to a thickness that is more appropriate for introduction into the final presses and, additionally, the pre-heater and pre-press may be a single unit or separate units. In certain embodiments, the temperature of the mat can be elevated from about 65° F. to about 200° F. before entering the board forming process. This rapid heat transfer to the carpet waste may be accomplished by microwaves or by the injection of a steam/air mix (moist air) alternately from either surface into the mat. The steam can condense during this process, transferring the heat into the mat. The pre-heater may also pre-press or compress the material before it enters the board forming process. The heated mat is then transferred by an intermediate belt conveyor to the compression section of the infeed end of a continuous roll press or into a cycle press which is the beginning of the board-forming process.


In one embodiment, composite sheets are manufactured using a cycle press, which may have single or multi-daylight openings. Ranges of various process parameters for manufacturing various embodiments of PCs utilizing recycled carpet waste in a cycle press are presented in Table A-1, below. The composite material is transferred into the cycle press where it is subjected to temperature and pressure from a top and bottom platen that compresses the mat to a predetermined thickness or height. The elevated temperature and pressure activates the binding agent and, depending on the temperature, melts certain of the carpet components while leaving others unmelted, to produce in a finished board or sheet. During the cycle press process, steam may be injected into the mat to ensure thorough heating of the binding agent and bonding of the composite material. The cycle press may also use an active cooling cycle to reduce the temperature of the board before it exits the press. The platens may be engraved with a pattern to give the board outer surface a structured pattern.









TABLE A-1







Composite Sheet Processing Parameters (Cycle Press)










Range











High
Low















Total Time for heating material, during
360
60



press-cycle [sec]



Temperature of Heating Plates [° F.]
600
100



Pressure of Heating Press [psi]
600
150



Internal Temperature of Board [° F.]
500
340



Cure Time [sec]
400
30



Transition Time from Heating to Cooling
600
0



Press [sec]



Total Time for cooling material, during
360
60



press-cycle [sec]



Temperature of Cooling Plates [° F.]
300
32



Pressure of Cooling Press [psi]
600
150



Internal Temperature of Board [° F.]
300
70










Heat is generally delivered to the platens in the form of hot water, steam, electric coils, or circulating heated chemicals. In certain embodiments of the process, the platens may be heated from about 100° F. to about 600° F. Temperature ranges from about 200° F. to about 550° F., and about 340° F. to about 420° F. also may be desirable. Additionally, temperature ranges from about 420° F. to about 550° F. may be utilized. Final internal temperatures of the composite being compressed within the cycle press will be dependent at least in part on the temperature of the platens and compression time. If left in the cycle press for a sufficient period of time, the internal temperatures of the composite material will generally equal those of the platens, the ranges of which are given above. Final internal temperatures up to about 250° F., about 300° F., about 340° F., about 350° F., about 400° F., about 420° F., and about 480° F. have produced composite sheets displaying acceptable performance. Unlike known recycled carpet waste composite sheet material manufacturing processes, which heat the composite sheets to a temperature below the melting points of the carpet fibers and other carpet components, it has been discovered that heating the carpet waste to higher temperatures may be desirable. For example, temperatures of approximately 340° F. will melt polypropylene, a component in many modern carpet constructions, or other polymeric fillers (e.g., polyethylene or materials recovery facility (MRF) residuals containing a variety of polymers and/or other filler materials) without melting any nylon fibers (that melt at about 420° F.). The melted polypropylene, combined with binding agent resins of the types disclosed herein, form a sheet material having very desirable properties. The unmelted nylon provides additional structural strength to the finished composite and may increase flexural strength, though completely melting the carpet fibers can also produce a PC displaying acceptable performance properties. Pressures applied by the platens in the heating press may range from about 150 psi to about 6000 psi or greater, to obtain a desired thickness and density.


The cycle press may include channels within the platens that thereafter circulate water or chemical coolant(s) to reduce the temperature of the board. The water or coolants may be chilled and volumetric flow rates controlled to reduce the total cooling time for the board to achieve acceptable manufacturing cycle time. This cooling step may take place in the heating press or the board may be transferred from the heating press to a cooling press. If the board is transferred from the heating press to the cooling press, the transfer time should be minimized to avoid warping of the PC. It has been determined that transfer time of less than about 600 seconds are acceptable. The cooling platens may have a temperature range of about 300° F. to about 32° F. Cooling temperature ranges from about 390° F. to about 65° F. may also be desirable. Ranges from about 250° F. to about 180° F. may also be utilized. If left in the cycle press for a sufficient period of time, the internal temperatures of the composite material will generally equal those of the platens, the ranges of which are given above. Final internal temperature of as high as 300° F., however, may be desirable to minimize warping of the composite sheet. Additionally, final internal temperatures of about 100° F., about 80° F., and about 70° F. have produced composite sheets displaying acceptable performance. The board is rapidly cooled under pressure to maintain its flatness. Due to its high polymer content, the board will usually warp if allowed to cool unrestrained using ambient air. Pressures applied by the platens in the cooling press may range from about 150 psi to about 6000 psi or greater.


Table B presents the ranges of various components that may be utilized in composite formulations to produce acceptable PCs. Specifically, materials utilized may include colorants, wood filler, fire retardants, fiberglass, mold inhibitors, binders, and recycled carpet waste. The recycled carpet waste can be about 20% to about 98% of the total formula weight and still retain acceptable physical properties in the composite sheet. Certain embodiments may include carpet wastes in the amount of about 90% to about 98% total weight. Still other embodiments may include carpet wastes in the amount of about 94% to about 95% total weight. It has been found that composites that utilize approximately 95% carpet waste and about 5% binding agent produce a composite that exhibits satisfactory performance while being economically advantageous, due to the low cost associated with using recycled carpet waste versus virgin materials. In other embodiments, a 9:1 ratio of carpet waste to MDI, up to a 49:1 ratio of carpet waste to MDI may be utilized. Table B also presents percentages of additives, such as wood filler, color, fire retardant, fiberglass, and mold inhibitor that may be added to the binder/carpet waste mixture. The percentages of these additives may be up to those identified in Table B, relative to the carpet waste/MDI content. Additionally, there is no discernible difference in the performance of the composite when using recycled carpet waste obtained from post-industrial carpet waste or post-consumer carpet waste, as compared with using virgin materials.









TABLE B







Formulation Ranges for Composite Sheets










Range













Low
High



Material
%
%















Carpet Waste
10
98



Moisture Content
0
10



Additives:



Binders: MDI
2
20



UF
2
20



MUF
2
20



PF
2
20



Wood filler
0
65



Color
0
25



Fire Retardant
0
25



Fiberglass
0
50



Mold Inhibitor
0
25










Tables C-1 to C-4 present formulations and performance parameters for PCs made in accordance with the cycle press process described above. Tables C-1, C-2, and C-3 present this information for PCs made with different types of binding agents, but having the same total percentage of binding agents. The water absorption, thickness swell and moisture content testing was performed in accordance with the ASTM D1037-96A testing standard. The PC described in Table C-1 is made with MDI and has higher modulus of rupture (MOR) and modulus of elasticity (MOE) values, with lower moisture absorption properties.









TABLE C-1







Example 1 Formulations and Performance Properties










Material
%







Carpet Waste
90.2% 



Moisture Content
4.8%



Additives:



Binders: MDI
5.0%



UF
0.0%



MUF
0.0%



PF
0.0%



Wood filler
0.0%



Color
0.0%



Fire Retardant
0.0%



Fiberglass
0.0%



Mold Inhibitor
0.0%



total
100% 



Thickness (inch)
   0.250



Density (pcf)
  53.3



MOR (psi)
1,866  



MOE (psi)
80,331   



Tensile - Perpendicular [IB] (psi)
728 



Tensile - Parallel (psi)
14



Linear Expansion
0.10% 



Thickness Swell (inch)
   0.002



Thickness Swell (%)
0.00% 



Moisture Content (%)
0.27% 










Table C-2 presents information for a PC utilizing PF as the binding agent, that results in significantly lower, though still acceptable, MOR and MOE values.









TABLE C-2







Example 2 Formulations and Performance Properties










Material
%







Carpet Waste
90.2% 



Moisture Content
4.8%



Additives:



Binders: MDI
0.0%



UF
0.0%



MUF
0.0%



PF
5.0%



Wood filler
0.0%



Color
0.0%



Fire Retardant
0.0%



Fiberglass
0.0%



Mold Inhibitor
0.0%



total
100% 



Thickness (inch)
   0.250



Density (pcf)
  48.0



MOR (psi)
971 



MOE (psi)
49,600   



Tensile - Perpendicular [IB] (psi)
716 



Tensile - Parallel (psi)
58



Linear Expansion
0.54% 



Thickness Swell (inch)
   0.007



Thickness Swell (%)
2.97% 



Moisture Content (%)
4.12% 










Table C-3 presents information for a PC manufactured with a mixture of MDI and UF as binding agents. While this formulation displays performance characteristics higher than those listed for the Table C-2 sample, the performance values are not as high as the sample using MDI as the binding agent, presented in Table C-1.









TABLE C-3







Example 3 Formulations and Performance Properties










Material
%







Carpet Waste
90.2% 



Moisture Content
4.8%



Additives:



Binders: MDI
1.25% 



UF
3.75% 



MUF
0.0%



PF
0.0%



Wood filler
0.0%



Color
0.0%



Fire Retardant
0.0%



Fiberglass
0.0%



Mold Inhibitor
0.0%



total
100% 



Thickness (inch)
   0.250



Density (pcf)
  45.4



MOR (psi)
1,359  



MOE (psi)
66,716   



Tensile - Perpendicular [IB] (psi)
1002 



Tensile - Parallel (psi)
44



Linear Expansion
0.31% 



Thickness Swell (inch)
   0.007



Thickness Swell (%)
2.78% 



Moisture Content (%)
3.02% 










Table C-4 presents a composite sheet utilizing 25% wood filler, with double the amount of binding agent utilized in the Table C-1 through Table C-3 samples. Estimates of the performance properties of this sample utilizing wood filler are identified with an asterisk.









TABLE C-4







Example 4 Formulations and Performance Properties










Material
%







Carpet Waste
60.0% 



Moisture Content
5.0%



Additives:



Binders: MDI
10.00% 



UF
0.00% 



MUF
0.0%



PF
0.0%



Wood filler
25.0% 



Color
0.0%



Fire Retardant
0.0%



Fiberglass
0.0%



Mold Inhibitor
0.0%



total
100% 



Thickness (inch)
    1.000



Density (pcf)
  66.7



MOR (psi)
2,815  



MOE (psi)
236,000   



*Tensile - Perpendicular [IB] (psi)
1500 



*Tensile - Parallel (psi)
100



*Linear Expansion
0.40% 



*Thickness Swell (inch)
    0.010



*Thickness Swell (%)
3.00% 



*Moisture Content (%)
3.00% 










The differences in the performance properties of the above-identified examples indicate that the types and amounts of binders may be varied as desired to achieve acceptable results. Binder type and amount may be varied to adjust cost or other properties. Although particular embodiments have not yet been tested, additives such as fire retardants may be added to produce a composite sheet having a Class A fire rating.


According to an alternative embodiment, the PC may be manufactured using a continuous roll process. The continuous roll press can utilize a double-belted press capable of maintaining a range of temperatures and pressures on the mat to allow the binding agent reaction and/or melting of select components to take place. The continuous roll press belts may be steel or other material. Process parameters for a continuous roll press are depicted in Table A-2. Temperatures utilized are generally similar to those utilized in the cycle press process.









TABLE A-2







Composite Sheet Processing Parameters (Continuous Roll Press)










Range











High
Low















Temperature of Heating Rolls [° F.]
600
100



Pressure of Heating Rolls [psi]
6000
150



Internal Temperature of Board [° F.]
500
340



Temperature of Cooling Plates [° F.]
300
32



Pressure of Cooling Rolls [psi]
6000
150



Internal Temperature of Board [° F.]
300
70










For example, pressures from about 150 psi to about 6000 psi are used to squeeze the fiber mat to the desired thickness and density of the final product. The continuous roll press consists of a press structure that tensions the belts. In general, the press includes a number of frame units, depending on the length of the press and pressure that is required for a particular application. Cylinders arranged at the frame units in various combinations exert the desired pressure. The press includes top and bottom heated platens which roller rods and the belts travel over. The press has an infeed head to guide the roller rods, belts and mat to be pressed. The roller rods are located between the heated platens and the belts and support the mat as it is moved from one cylinder to the next. The belts are driven by two or more drums at generally opposite ends of the roll press. Drum scrapers may be used to keep the board from sticking to the belts. A release agent also may be sprayed onto the belts to keep the mat from sticking to the belts, allowing the composite to exit easily the press at the completion of forming. A control system regulates the operation of the press, such as the speed of the belts, temperature, pressure, thickness of the mat, etc.


The continuous roll press transfers heat to the binding agent-coated composite material. As the heat activates the coating, the cylinders press the mat together to achieve the desired thickness. Thus, while the mat material moves from the infeed section of the press, the mat's thickness is reduced while being heated to a temperature that ensures activation of the binding agent and melting of certain fibers. As the mat moves through the continuous roll press, the platens gradually reduce the thickness of the mat to a predetermined thickness. Depending on the amount of material introduced to the infeed section of the press, the density of the finished board can be directly related to its final thickness.


After the binding of the material and desired height dimension of the mat has been reached in a continuous roll press, a board is formed which is in the shape of a continuous ribbon or sheet. When the ribbon exits the press, it undergoes a continuous edge trimming operation to reach the desired width and then it is cross-cut to a pre-selected length. The ribbon is transported through the trimming and cross-cutting operations by a roller conveyor and pinch rollers. The cut boards are then transported to a cooling station. The cooling station can employ a variety of different machines such as a star cooler, with subsequent stacking, or a stacking roller conveyor. The star cooler is a large diameter wheel with multiple rows of spoked arms extending from the wheel. The arms lift each board from the conveyor and allow the boards to rotate with the wheel and be air cooled. If needed, the continuous roll press can have a cooling section with chilled rollers near the press outlet. This will cool the board (as described above) eliminating the need for further cooling. The board is then conveyed to a stacking operation and stored for future use. Alternatively the boards may be conveyed to a separate cooling press as described above. The boards are now ready to be shipped or they can go through a variety of decorating alternatives.



FIG. 4 shows the finishing and decorating steps that may be employed following cutting to final width. The composite product can now be processed further to change the cross-sectional profile to take on the shape required in the finished product. The processing can be done on a variety of cutting machines of different designs, the most common of which is a molder using rotating knives. This machine allows for the setting of the knife blades to adjust the cut to the desired profile (e.g., siding or molding having a non-rectangular profile). Another common device is the router which cuts a specific groove or grooves (routs) into the surface of the composite product. The router has the same effect as the molder in that it changes the initial profile out of the process into the desired profile required for the final product.


The profile may also be changed using thermoforming methods. In this case, the composite product is placed in a mold of the desired profile and with heat and pressure the product takes on the shape of the mold. This profile change offers an additional decorating capability in that the desired color and/or pattern may be on a transfer foil placed in the mold. With the application of the heat and pressure during the process, the color and/or pattern are transferred from the carrier foil to the composite product. Thus, at the end of the thermoforming process, the composite product has the desired profile and also the desired decoration.


The composite product may be embossed after manufacturing. The embossing is accomplished with an embossing plate or roll. The plate or roll has the pattern to be transferred to the product on the surface of the plate or roll. This surface is heated to a temperature that will soften the surface of the composite product. Then the plate or roll is pressed onto the surface of the product to give the desired pattern transfer. As the surface of the composite product cools, the embossed pattern becomes fixed on the surface of the composite product. The embossed composite product is now ready to be coated, or if no coating is required for the end-use product, it is ready for packaging.


Composite products that will be decorated may first pass through a sander. This smoothing of the surface prepares the product for coating, transfers, and laminating. The sanded or embossed composite product may be coated with primers, finish paints, or stains. The coating application employs various conventional spray techniques using exhaust systems to remove the excess spray and solvents. Either penetrating or film-forming coatings may also be applied, and the choice is dependent on the desired finished product appearance and application. The sanded composite product can also act as a core to which decorative and protective layer(s) may be hot stamped from a foil or film or laminated to achieve improved physical and visual enhancement. In this regard, U.S. patent application Ser. No. 11/054,258, filed Feb. 9, 2005, and published as U.S. Patent Application Publication No. 2006/0147693, and U.S. Provisional Patent Application Ser. No. 60/641,308, filed Jan. 4, 2005, describe exemplary processes and are incorporated by reference herein in their entireties.


The composite product also may be decorated using transfer foils. Once again the product is first sanded to smooth the surface, then an adhesive layer is applied to the profile using a conventional application technique. The transfer foil has the desired color and/or pattern on a polymeric substrate, and is brought into contact with the surface of the product using stamping equipment designed for the specific application. Using heat and pressure, the color and/or pattern is transferred from the foil to the product. The heat required for the transfer activates an adhesive layer on the surface of the profile ensuring bonding of the decoration to the profile. With the color and/or pattern now on the composite product, the spent foil is then collected for disposal, and the finished product has the desired decorated effect.


Another decorating method that may be employed is lamination. Several materials may be used as the laminate surface, such as wood veneers, synthetic veneers, foils, films, and polymeric sheets. The application of rigid laminates like wood veneers is done using conventional laminating equipment. Generally, an adhesive system (either a wet adhesive system or a hot-melt adhesive system) employing a primer and an adhesive is applied to the PC substrate. The rigid surface laminate is then applied to the substrate and heat and pressure are applied. After heating and pressing, the laminated product is then set for a fixed period of time to allow the adhesive system to cure. In the case of the composite product, the composite product is the substrate. The adhesive system, usually a hot-melt adhesive, is applied to the composite product. The rigid veneer is then placed on the adhesive layer forming a sandwich of composite product, adhesive, and rigid laminate. The sandwich is then pressed to secure the bond of the laminate to the composite product. After curing, the laminated product with the desired decorative appearance is ready for packaging.


Another laminating technique used with the composite product is foil laminating. This technique can be referred to as wrapping; wherein, the composite product profile is wrapped in the decorative foil. After the composite product profile has been sanded, the profile passes through a wrapping device that takes the foil wrap from a coil then applies the adhesive (and primer, if required) to the foil. In a continuous process, the foil wrap is then passed over the composite product profile. Using a series of rollers, the foil wrap is shaped to the composite product profile. The foil wrap may incorporate an integral topcoat material, such as polyurethane, acrylic, or other protective materials, for physical property enhancement. If, however, the foil wrap integrates only the decorative elements, then the wrapped composite product will require a separate topcoat for certain applications.


If the end-use product application requires significant surface property enhancements, such as abrasion resistance, a topcoat may be added to the decorating process. The topcoat can be polyurethane, acrylic, or other protective material that will impart better physical properties to the surface of the wrapped finished product. The topcoat may be spray applied or hot melt applied. If spray applied, the wrapped composite product will pass through a spray applicator and then may or may not pass through a curing device, such as an ultra-violet radiation station. If the topcoat is hot melt applied, then a layer of polyurethane is applied to flat surfaces of the decorated composite product. The cure process for this type of material is time dependent and could take several days depending on the hot melt topcoat chosen for a specific end-use application for the completed finished product.


Referring to FIG. 5A, in various examples, a composite material 50 includes a core layer 52, a top layer 54 disposed above the core layer 52, a bottom layer 56 disposed below the core layer 52, a top surface layer 58 disposed above the top layer 54, and a bottom surface layer 60 disposed below the bottom layer 56. The composite material 50 can be in the form of a sheet or board having a thickness T, a width W, and a length L. The thickness T can be, for example, from about 6 mm to about 40 mm, the length L can be from about 10 cm to about 5 m, and the width W can be from about 25 mm to about 1.2 m. In general, the thickness T, the length L, and/or the width W can depend on an intended use or application for the composite material 50. The composite material 50 can be used for interior or exterior building applications, including, for example, siding, trim, molding, panels, roofing, decking, or other building products. While a cross-section of the composite material 50 is depicted in FIG. 5A as being rectangular, other cross-sectional profiles can be used. For example, the thickness T can vary within the composite material 50 (e.g., along a dimension corresponding to the length L or the width W) to obtain a variety of profiles for siding (e.g., a tapered profile), molding (e.g., a curved profile), or other products.


Table D includes low, typical, and high values for the thicknesses (e.g., average thicknesses) of the composite material 50, the core layer 52, the top layer 54, the bottom layer 56, the top surface layer 58, and the bottom surface layer 60, in accordance with certain examples. The values for the core layer thickness T1, the top layer thickness T2, and the bottom layer thickness T3 are presented as percentages of the total thickness T. In some examples, when the total thickness T is high (e.g., about 40 mm), the values for the top layer thickness T2 and the bottom layer thickness T3 can be near the lower ends of the respective ranges of the table (e.g., near 5% of the total thickness T). Likewise, when the total thickness is low (e.g., about 6 mm), the values for the top layer thickness T2 and the bottom layer thickness T3 can be near the upper ends of the respective ranges in the table (e.g., near 40% of the total thickness T). Such values for the top layer thickness T2 and the bottom layer thickness T3 can be used to achieve desired performance characteristics for the composite material 50 (e.g., a desired stiffness) and/or may be used to achieve a substantially uniform combined thickness of the core layer 52, the top layer 54, and the bottom layer 56, as described below.









TABLE D







Average thickness values for composite material.










Average Thicknesses
Low
Typical
High













Total Composite Thickness T (mm)
6
25
40


Core Layer Thickness T1 (% of Thickness T)
20
65
90


Top Layer Thickness T2 (% of Thickness T)
5
25
40


Bottom Layer Thickness T3 (% of Thickness T)
5
10
40


Top Surface Layer Thickness T4 (mm)
0.1
0.3
1


Bottom Surface Layer Thickness T5 (mm)
0.1
0.3
1









In certain implementations, the core layer 52, the top layer 54, and the bottom layer 56 can each include fibers (e.g., polymeric fibers and/or glass fibers), a binding agent, and optionally one or more fillers and/or additives. The fibers can be or include polymeric fibers such as, for example, nylon fibers, polyester fibers, polypropylene fibers, bicomponent fibers, other types of fibers, or any combination thereof, and can be derived from carpet, carpet waste, automotive headliners, insulation materials, or other sources, as described herein. Polymeric fibers derived from carpet or carpet waste can be referred to herein as “carpet fiber.” Additionally or alternatively, polymeric fibers can be obtained from scrap, used, new, and/or recycled fiber sources, such as, for example, interior automotive surface materials (e.g., automotive headliners, sidewalls, floor mats, or automotive fabrics), thermal insulation materials, sound insulation materials, industrial or commercial fabrics (e.g., polyester woven fabric), cushions, pads, carpet tiles, product waste or recycling streams, or any combination thereof.


In some examples, the core layer 52, the top layer 54, and/or the bottom layer 56 can include any portion of carpet or carpet waste, including face fibers, backing, inorganic materials, contaminants (e.g., dirt or sand), and/or adhesives. Alternatively or additionally, the core layer 52, the top layer 54, and/or the bottom layer 56 may include only one or more portions of the carpet or carpet waste, such as face fibers.


In other examples, the core layer 52, the top layer 54, and/or the bottom layer 56 can include fiberglass fibers (alternatively referred to as glass fibers), instead of or in addition to polymeric fibers. In some instances, for example, the fibers in the core layer 52 may be or include a mixture of polymeric fibers and glass fibers, while the fibers in the top layer 54 and/or the bottom layer 56 may be or include glass fibers (with little or no polymeric fiber). Other combinations of fiber types are possible. In one example, the fibers in the core layer 52 can be about 67% polymeric fiber and about 33% glass fiber, and the fibers in the top layer 54 and/or the bottom layer 56 may be about 50% polymeric fiber and about 50% glass fiber, or may be glass fiber with little or no polymeric fiber (e.g., 100% glass fiber). The inclusion of glass fibers in the top layer 54 and/or the bottom layer 56 can improve a fire rating for the composite material 50. The glass fibers can be obtained from scrap, used, new, and/or recycled glass fiber sources, such as, for example, fiberglass insulation or glass wool. Other types of fibers (e.g., new or recycled carbon fibers, metallic fibers, etc.) can be included in the composite materials described herein.


In general, it is desirable to achieve good contact and a strong bond between the binding agent and other composite ingredients described herein. Organic resins (e.g., polyurethane, polyurea, polyester, and phenol formaldehyde) can have a natural affinity for and can readily bond with organic fibers, such as nylon fibers, polyester fibers, or polypropylene fibers. The organic resins, however, may not readily contact or bond with glass fibers. To improve bonding between the organic resins and glass fibers, one or more coupling agents such as an organofunctional silane can be added. The coupling agent can come in a variety of forms and can serve as a bridge between the glass fibers and the organic resin. In some examples, the coupling agent can be or include a molecule that has inorganic functionality (e.g., of an alkoxysilane) and reactive organic group functionality. Suitable organofunctional silane coupling agents include, for example, 3-aminopropolytrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl/alkoxy silane, amine-functional silane, phenyl silane, and/or mercapto-functional silane. Such materials can be applied to fiberglass before the fiberglass is exposed to the binding agent. This can involve (i) mixing the organofunctional silane with a solvent (e.g., ethanol, methanol, and/or water), (ii) applying the mixture to fiberglass, and (iii) evaporating the solvent (e.g., by applying heat, radiation, or other energy) to obtain organofunctional silane bonded to the fiberglass. The fiberglass with attached organofunctional silane (or other coupling agent) can then be mixed with binding agent as described herein.


In some examples, the glass fibers can be coated with a sizing agent, which can facilitate bonding between the glass fibers and the binding agent or matrix resin. For example, the sizing agent can provide a compatible interface between the glass fibers and the binding agent. In some examples, the sizing agent can include a film former, which can be chemically similar to the binding agent (e.g., MDI), and a coupling agent, which can be or include an organofunctional silane. The coupling agent can serve as a primer that allows the film former to bond to both the glass fibers and the binding agent. The sizing agent coating can be present when the glass fibers are first obtained (e.g., scrap glass fibers coated with silane), and/or the sizing agent can be added to the glass fibers during the composite manufacturing processes described herein.


Additionally or alternatively, fibers in the core layer 52, top layer 54, and/or bottom layer 56 (e.g., polymeric and/or glass fibers) can be pretreated to improve adhesion with the binding agent. For example, glass fibers obtained from fiberglass insulation or other sources can be cleaned or modified. This can involve, for example, baking the fibers in ovens or kilns for a prescribed time, washing the fibers in solvents or other cleaners, and/or subjecting the fibers to scrubbing, cutting, chopping, or other mechanical processes. The fibers can be treated with one or more adhesion promotors such as, for example, a coupling agent or a sizing agent. The coupling agent (e.g., organofunctional silane) can form bonds between inorganic surfaces (e.g., on glass fibers) and organic binding agents (e.g., polyurea). The sizing agent can modify fiber surface chemistry for improved bonding with binding agents. The adhesion promoters can be applied to the fibers using a variety of application methods, including, for example, spray coating, dip/flood coating, or roll coating. The adhesion promoters can be cured or dried (e.g., with ambient air, forced air, etc.) before the fibers are mixed with a binding agent or matrix resin.


In general, the process for blending a matrix resin with fibers can vary by fiber type. The blending process can involve a single step or multiple steps, and not all steps are required in each case. In one example, used or recycled fibers can be cleaned, adhesion promoters (e.g., coupling agents and/or sizing agents) can be applied to the fibers (and optionally cured or dried), and then the matrix resin can be applied to the fibers.


The binding agent or matrix resin can be or include, for example, a polyurea, a polyurethane, an isocyanate (e.g., MDI or pMDI), one or more polyols, epoxy, acrylic resin, polyester, unsaturated polyester resin (e.g., derived from phthalic and maleic anhydride), or other suitable binding agent materials or precursors, or any combination thereof. In some instances, for example, the binding agent can be or include a polyurea derived from a reaction between MDI and water. Additionally or alternatively, the binding agent can be or include a polyurethane derived from a reaction between MDI (or other isocyanate) and a polyol. The polyol can be or include, for example, a polyether polyol or a polyester polyol, such as polyethylene oxide, polyethylene glycol, or polypropylene glycol. The polyurethane can be or include a foam, such as a rigid polyurethane foam and/or a closed-cell polyurethane foam. The reaction to form the polyurethane foam can utilize or involve auxiliary materials, such as one or more catalysts, foaming agents, and/or stabilizers. Advantageously, use of foamed materials can significantly reduce a weight of the resulting composite materials. In some examples, the binding agent can include or be derived from MDI (methyl diphenyl diisocyanate), pMDI (polymeric methyl diphenyl diisocyanate), TDI (toluene diisocyanate), a different isocyanate, urea formaldehyde (UF), melamine urea formaldehyde (MUF), phenol formaldehyde (PF), one or more polyols, epoxy, acrylic resin, polyester resin, or any combination thereof. In various examples, the binding agent can be a thermoset or a thermoplastic. For example, the polyurea or polyurethane derived from MDI can be a thermoset. The binding agent or combination of binding agents used in the core layer 52, the top layer 54, and the bottom layer 56 can be the same or different (e.g., one layer can have a different binding agent compared to another layer).


In some examples, a polyurea foam can be produced through use of an accelerant. For example, the accelerant can increase a rate of the reaction used to produce polyurea (e.g., between MDI and water) and can cause bubbles of carbon dioxide or other blowing agent to form voids or cells in the polyurea. In one example, the accelerant can be a surfactant that promotes mixing between the reactants (e.g., MDI and water). In another example, the accelerant can be a catalyst such as a non-emissive amine or a strong metal catalyst that increases the reaction rate. The accelerant can be mixed with the binding agent reactants before or after the reactants have been applied to the fibers (e.g., by spray application).


The fillers for the core layer 52, the top layer 54, and the bottom layer 56 can be or include, for example, polymeric fillers, natural fiber fillers, inorganic fillers (e.g., mineral fillers), and/or fiberglass. The polymeric fillers can be or include various single layer films and/or multilayer films, which can be or include, for example, barrier packaging films. Such polymeric fillers can include, for example, single or multilayer films having biaxially oriented polypropylene (BOPP), nylon, polyvinylidene dichloride (PVDC), ethylene vinyl alcohol (EVOH), metallic or other impervious materials or layers, or any combination thereof. Such polymeric fillers can be obtained or derived from food packaging or other scrap or waste sources. BOPP and/or other films can be shredded and/or granulated (e.g., to form particles) prior to being used as a filler, as described herein. Additionally or alternatively, polymeric fillers can be or include recycled polymeric materials obtained from a recycling facility, such as a materials recovery facility (e.g., MRF residuals) or a commercial waste disposal operation. In some instances, the polymeric fillers can be or include fibers that are recycled or sourced from used, old, or waste fiber materials (e.g., manufacturing scrap), including clothing (e.g., jackets, shirts, and/or pants), paint rollers, and shoddy fiber (e.g., from cushions). Other suitable polymeric fillers can include, for example, granulated or shredded polyethylene, polypropylene, polyester, and/or nylon, in film or non-film form.


In some implementations, the composite building materials described herein can include polymeric filler (e.g., polymeric film particles) but little or no polymeric fibers. Such composite building materials can include, for example, binding agent and polymeric filler, and optionally one or more additional fillers and/or additives. It is presently discovered that such composite building materials having polymeric filler but little or no polymeric fibers can have certain performance benefits over composites that include polymeric fibers or greater amounts of polymeric fibers. The improved performance benefits can include, for example, less water absorption, which can result in composites that exhibit less swelling due to moisture exposure and/or fewer issues related to mold or mildew. For example, polymeric fillers such as BOPP or barrier packaging films can be generally impervious to water and/or can absorb little or no moisture. By comparison, polymeric fiber (e.g., carpet fiber) can have a more porous structure and/or can be more susceptible to moisture absorption. Additionally or alternatively, composites made with polymeric fibers (and little or no polymeric film materials) may exhibit more thermal expansion and/or contraction due to temperature changes, compared to composites made with polymeric film materials (and little or no polymeric fibers).


The natural fiber fillers can include, for example, wood chips, wood flour, wood fibers, wood flakes, wood shavings, sawdust, flax, jute, abaca, hemp, kenaf, rice hulls, like materials, other cellulosic fillers, or any combination thereof. The inorganic fillers can include, for example, talc, silica, calcium carbonate, fly ash, like materials, or any combination thereof. The additives can include, for example, one or more colorants, fire retardants, mold inhibitors, and/or compatibilizers.


In various examples, the polymeric fillers, natural fiber fillers, inorganic fillers (e.g., mineral fillers), and/or fiberglass can be used to achieve or adjust certain performance characteristics for the composite material 50. For example, polymeric fillers (e.g., BOPP or other single or multilayer films and/or MRF residuals) can decrease water absorption and/or avoid or minimize dimensional changes in length and thickness caused by water absorption. Natural fiber fillers (e.g., cellulose fillers) can increase modulus of elasticity (MOE), modulus of rupture (MOR), and/or coefficient of thermal expansion, which can be desirable; however, natural fiber fillers may also increase water absorption and dimensional changes caused by the water absorption, which can be detrimental. Inorganic fillers (e.g., fly ash or talc) can reduce water absorption and, in certain percentages, can increases MOE and MOR. Fiberglass can increase MOE and MOR while simultaneously reducing water absorption and associated dimensional changes. Fiberglass can be obtained from a variety of sources, including, for example, recycled wind turbine fan blades, boat hulls, machine components, insulation, construction materials, and the like.


In some examples, the use of polymeric fibers described herein can be replaced entirely or partially by use of fiberglass fibers. For example, the composite material 50 (or any layer thereof) may include fiberglass fibers but no polymeric fibers, or the composite material 50 (or any layer thereof) may include a mixture of fiberglass fibers and polymeric fibers.


To take advantage of the benefits of some of these fillers, a concentration of filler can be different in the core layer 52 than in the top layer 54 and/or the bottom layer 56. This can allow the amount of filler in the composite material 50 to be adjusted by changing the thickness of the core layer 52, relative to the thicknesses of the top layer 54 and the bottom layer 56. For example, if the core layer 52 contains a higher concentration of certain fillers (e.g., natural fiber filler), the amount of filler in the composite material 50 can be increased by increasing a thickness of the core layer 52. In this way, material properties of the composite material 50 can be adjusted by varying relative thicknesses of the core layer 52, the top layer 54, and the bottom layer 56.


Additionally or alternatively, the core layer 52, the top layer 54, or the bottom layer 56 can include one or more fillers or additives that are not present (or are present in lower concentrations) in one of the other layers. For example, the core layer 52 can include a filler (e.g., natural fiber filler) or an additive (e.g., a compatibilizer) that is not present in the top layer 54 and/or the bottom layer 56. Additionally or alternatively, the top layer 54 or the bottom layer 56 can include a filler or an additive that is not present in the core layer 52. This approach can allow fillers or additives to be used only in layers where they are needed or most helpful, or it can avoid using fillers or additives in layers where they are detrimental. For example, in some instances, it can be desirable to avoid using natural fiber fillers near an exterior surface of the composite material, because such use may increase moisture absorption and/or lead to mold or mildew problems.


Still referring to FIG. 5A, in various examples, the top surface layer 58 and/or the bottom surface layer 60 can be or include one or more layers of a resin-impregnated paper, which can include a cellulose-based paper and a resin. The resin can include or be derived from a phenolic resin (e.g., PF), MDI, MUF, UF, latex, acrylic resin, epoxy, polyester, any of the binding agents described herein, like materials, or any combination thereof. The resin-impregnated paper may be referred to herein as “phenolic paper,” regardless of the type of resin used.


Alternatively or additionally, in various examples, the top surface layer 58 and/or the bottom surface layer 60 can be or include a mat, web, or film of fiberglass fibers (referred to herein as a “fiberglass film”). The fiberglass fibers can be woven or non-woven to form the fiberglass film. The fiberglass film can be impregnated with or otherwise include a resin, such as a phenolic resin (e.g., PF), MDI, MUF, UF, latex, acrylic resin, epoxy, polyester, polyethylene, polypropylene, any of the binding agents described herein, like materials, or any combination thereof. The fiberglass film can have a thickness from about 0.001 inches (0.025 mm) to about 0.003 inches (0.076 mm). In some examples, the fiberglass film can have a thickness from about 0.005 inches (0.13 mm) to about 0.020 inches (0.51 mm). The fiberglass film can be or include, for example, ADVANTEX glass strand mat, UNIFILO filament mat, HYDROSTRAND, or SUSTAINA, available from OWENS CORNING. The fiberglass film can be or include a laminated film and/or a multi-layer film.


The top surface layer 58 and the bottom surface layer 60 can be bonded to the top layer 54 and the bottom layer 56, respectively, using an adhesive, such as melamine glue or one or more of the binding agents described herein. In some examples, a resin in the top surface layer 58 and the bottom surface layer 60 can be the same as the binding agent or resin used in the core layer 52, the top layer 54, and/or the bottom layer 56. Using the same resin may help promote adhesion between or among the layers. In certain implementations, the resin can be applied as a liquid that is saturated into paper (or the fiberglass film) when the phenolic paper (or the fiberglass film) is manufactured and/or used to form the composites described herein. Alternatively or additionally, the resin can be applied in powdered form and dispersed within the paper or fiberglass film. The resin can be activated or cured (e.g., polymerized) by heat and/or pressure during the composite manufacturing process described herein. In various implementations, a “surface layer” (e.g., of resin-impregnated paper or fiberglass film) can be covered with paint, coatings, or other materials and does not need to be positioned at an outermost surface of the composites described herein.


In other examples, the composite material 50 may not include the top layer 54 and/or the bottom layer 56. For example, referring to FIG. 5B, the composite material 50 may include the core layer 52 with the top surface layer 58 and/or the bottom surface layer 60 disposed above and below the core layer 52 (e.g., a single layer with binding agent and polymeric fibers and/or polymeric film particles), respectively. Additionally or alternatively, the composite material 50 may not include or may include only one of the top surface layer 58 and the bottom surface layer 60. Similarly, the composite material 50 may include only one of the top layer 54 and the bottom layer 56.


Table E lists various parameters relating to the composition and structure of the core layer 52, the top layer 54, the bottom layer 56, the top surface layer 58, and the bottom surface layer 60. The table includes low, typical, and high values for each parameter. Various embodiments include any parameter value (e.g., any integer or real number) within the cited ranges. For example, the polymeric fiber weight percentage (wt %) in the core layer 52 can be 0, 1, 2, . . . , 97, or 98. Likewise, the average or median length of polymeric fibers and/or glass fibers in the core layer 52 can be 2, 3, 4, . . . , 49, or 50 mm. Express support and written description of these parameter values for each parameter are hereby represented.









TABLE E







Parameter values for each layer in the composite material.










Layer Composition
Low
Typical
High













Core Layer





Polymeric and/or Glass Fiber (wt %)
0
45
98


Average/Median Length of
2
30
50


Fibers (mm)


Total Filler (wt %)
0
45
98


Natural Fiber Filler (wt %)
0
0
75


Polymeric Filler (e.g., BOPP) (wt %)
0
45
98


Inorganic Filler (wt %)
0
0
50


Fiberglass (wt %)
0
0
98


Total Additives (wt %)
0
4
25


Total Binding Agent (e.g., MDI +
2
6
10


water) (wt %)


Top and Bottom Layers


Polymeric and/or Glass Fiber (wt. %)
0
45
98


Average/Median Length of
1
6
25


Fibers (mm)


Total Filler (wt %)
0
45
98


Natural Fiber Filler (wt %)
0
0
75


Polymeric Filler (e.g., BOPP) (wt %)
0
45
98


Inorganic Filler (wt %)
0
0
50


Fiberglass (wt %)
0
0
98


Total Additives (wt %)
0
4
25


Total Binding Agent (wt %)
2
6
10


Top and Bottom Surface Layers


Paper Weight (without Resin) (lb)
90
215
280


Thickness of Single Paper Sheet (mm)
0.13
0.30
0.46


Number of Paper Sheets per Layer
1
1
3


Thickness of Fiberglass Film (mm)
0.025
0.1
0.51


Resin Content (wt %)
20
35
45









As indicated in Table E, the fibers (e.g., polymeric fiber and/or glass fiber) in the core layer 52 can be longer than the fibers in the top layer 54 and/or the bottom layer 56. In general, longer fibers in the core layer 52 can result in improved performance characteristics for the composite material 50, as described herein. For example, a composite having longer fibers can be stiffer than a composite having only shorter fibers, possibly due to greater entanglements among neighboring fibers. In such instances, it can be desirable to use relatively thick core layers with longer fibers, to achieve a higher overall amount or concentration of longer fibers in the composite material 50.


It is presently discovered, however, that longer fibers can be more difficult to form into uniform layers during the manufacturing processes described herein. For example, longer fibers can result in a core layer that is unevenly distributed within the composite material 50 and/or that has an irregular or nonuniform thickness or rough surface with large peaks and valleys. The longer fibers tend to form clumps or masses of fibers, possibly due to the greater fiber entanglements, when attempting to spread the fibers into a mat or sheet. By contrast, shorter fibers are generally easier to form into uniform layers.


For example, FIG. 6 illustrates an example in which three layers 64 of fiber mixtures have been spread onto a flat substrate 66. A bottom layer 68 includes short fibers (e.g., polymeric fibers and/or glass fibers) and a binding agent, a core layer 70 includes long fibers (e.g., polymeric fibers and/or glass fibers) and binding agent, and a top layer 72 includes short fibers (e.g., polymeric fibers and/or glass fibers) and a binding agent. As depicted, the short fibers in the bottom and top layers 68, 72 are able to form relatively uniform layers and/or fill in any peaks or valleys in the core layer 70, which can be irregular or nonuniform due to the long fibers. For example, the bottom layer 68 can be initially formed as a layer having a substantially uniform thickness on the flat substrate 66. When the core layer 70 is applied to the bottom layer 68, however, the long fibers in the core layer 70 can form clumps or balls of fiber that can disrupt the bottom layer 68 and/or result in a core layer that is substantially nonuniform in thickness. For example, as depicted in FIG. 6, the core layer 70 can have a minimum thickness T1min and a maximum thickness T1max, and a ratio of T1min to T1max can be less than or equal to about 0.1, 0.25, 0.5, or 0.75. Finally, the top layer 72 can be spread onto the core layer 70 and can be used to cover any peaks or valleys (or other bumps or recesses) in the core layer 70. A combined thickness of all three layers 64 can be substantially uniform. For example, the three layers 64 can have a minimum thickness T6min and a maximum thickness T6max, and a ratio of T6min to T6max can be greater than or equal to about 0.7, 0.8, 0.9, or 0.95.



FIG. 7 illustrates an example in which the three layers from FIG. 6 have been pressed and heated to form a composite material 76 having top and bottom surface layers of resin-impregnated paper 78 (e.g., phenolic paper) and/or fiberglass films. The thickness variations described above with respect to FIG. 6 can also be present in the composite material 76. For example, the core layer 70 can be substantially irregular or nonuniform in thickness, and the composite material 76 itself (or a combination of the bottom layer 68, the core layer 70, and the top layer 72) can be substantially uniform in thickness.


Referring again to FIG. 5B, in other examples, the composite materials described herein may include the core layer 52 and at least one surface layer of resin-impregnated paper and/or fiberglass film (e.g., the top surface layer 58 and/or the bottom surface layer 60), but may not include top and bottom layers of polymeric and/or glass fiber (e.g., the top layer 54 and/or the bottom layer 56). In such instances, a substantially uniform (e.g., less than 20%, 10%, or 5% thickness variation) core layer can be obtained by using shorter polymeric and/or glass fibers (e.g., 13 mm average length) than may be used when the top and bottom layers are included. Additionally or alternatively, a substantially uniform core layer can be obtained by using a mixture of shorter fibers and longer fibers. The mixture can include, for example, a distribution of polymeric and/or glass fibers having a variety of lengths that include the longer fibers and the shorter fibers (e.g., a substantially uniform distribution of fiber lengths). Such variations in fiber lengths can be achieved in some instances by shredding and/or granulating fibers, as described herein. Additionally or alternatively, in some examples, the mixture of fibers can include a bimodal distribution of fiber lengths. A histogram for the bimodal distribution can include, for example, a first peak corresponding to a shorter fiber length and a second peak corresponding to a longer fiber length, such that the bimodal distribution includes a relatively high concentration of shorter fibers, a relatively high concentration of longer fibers, and a relatively low concentration of medium-length fibers (e.g., having lengths between the shorter fibers and the longer fibers). The bimodal distribution can be achieved by mixing a supply of longer fibers with a supply of shorter fibers. In general, the longer polymeric and/or glass fibers can result in composite materials having higher stiffness or strength, and the shorter polymeric and/or glass fibers can be used to achieve smoother exterior surfaces and/or more uniform thicknesses for the core layer 52. For example, the shorter fibers can fill in voids, interstitial spaces, or valleys formed by the longer fibers. In some examples, the longer polymeric and/or glass fibers can have an average length greater than about 8 mm, greater than about 30 mm, or from about 8 mm to about 50 mm. The shorter polymeric and/or glass fibers can have an average length less than about 25 mm, less than about 13 mm, less than about 6 mm, or from about 1 mm to about 25 mm. The single core layer 52 can be formed using, for example, rotating brushes, pick rollers, air laying, and/or similar devices, which can adjust or rearrange a mat of fibers to make the mat more uniform or smooth, prior to heating or compression. Such techniques can avoid or reduce the need for using the top and/or bottom layers of fiber to achieve fiber mats that are substantially uniform in thickness.


In various implementations, the length of polymeric fibers, glass fibers, or other types of fibers can play an important role in the surface quality and rigidity of the composite materials described herein. Shorter fibers can have a lower tendency to form clumps or balls, as described herein, and therefore can produce smoother composites, while longer fibers tend to produce composites having higher stiffness or rigidity. In certain implementations, the fibers (e.g., polymeric and/or glass) in the top layer 72 and/or the bottom layer 68 can have an average length that is less than or equal to: about 10 mm, about 8 mm, about 6 mm, about 5 mm, about 4 mm, or about 2 mm. Such short fibers can help achieve smooth top and bottom surfaces and/or a uniform thickness for the composite material 76, as described herein. In one example, an average fiber length (e.g., for polymeric and/or glass fibers) less than or equal to about 6 mm (0.25 inches), about 5 mm, or about 4 mm in the top layer 72 and/or the bottom layer 68 can provide an optimal surface quality while still providing adequate rigidity.


A variety of fiber lengths can be used for the core layer 70. Relatively long fibers (e.g., having an average length of about 20 mm, about 25 mm, about 30 mm, or more) in the core layer 70 can make the composite material 76 more rigid; however, longer fibers can form clumps that adversely affect surface quality and/or result in thickness variations for the composite material 76. By comparison, relatively short fibers (e.g., having an average length that is less than or equal to about 12 mm, less than or equal to about 8 mm, or less than or equal to about 6 mm) in the core layer 70 can result in a composite that is less rigid but has smoother surfaces and/or a more uniform thickness. In one example, an average fiber length less than about 6 mm in the core layer 70 has been found to reduce or substantially eliminate the formation of clumps during the manufacturing process described herein. In another example, a desirable combination of rigidity and surface quality can be achieved using the following combination of average fiber lengths (e.g., for polymeric and/or glass fibers): less than or equal to about 6 mm in the core layer 70 and less than or equal to about 6 mm, about 5 mm, or about 4 mm in the top layer 72 and/or the bottom layer 68.



FIGS. 8 and 9 include schematic diagrams of a manufacturing process 80 for producing a composite material in accordance with certain embodiments. Referring to FIG. 8, materials containing carpet fiber, other polymeric fiber, and/or glass fiber can be added to a surface fiber shredder 82a and a core fiber shredder 82c, which can generate shredded fiber materials. The surface fiber shredder 82a and the core fiber shredder 82c can provide the shredded fiber materials to a surface fiber granulator 84a and a core fiber granulator 84c, respectively, which can generate granulated fiber materials. The granulated fiber materials can be or include, for example, individual polymeric and/or glass fibers that have been reduced in size or length, separated from one another, and/or not bonded together (e.g., with adhesive). The surface fiber granulator 84a and the core fiber granulator 84c can deliver the granulated fiber materials to a surface fiber storage 86a and a core fiber storage 86c.


In parallel, polymeric filler materials, such as BOPP (or other single or multilayer films, as described herein), and/or MRF residuals, can be provided to a filler shredder 82b, which can deliver shredded polymeric fillers to a filler granulator 84b, which can deliver granulated polymeric fillers to a filler storage 86b. The granulated polymeric fillers can include particles or chips of BOPP films (e.g., films of BOPP that have been reduced in size or converted to small pieces), other polymeric films (e.g., films that include or are formed from polymers or materials other than BOPP), packaging films, barrier packaging films, MRF residuals, or other suitable polymeric filler materials. Average or median particle sizes for the granulated polymeric filler materials can be, for example, from about 0.5 mm to about 10 mm, or about 5 mm in diameter, length, or width. An average or median thickness of the BOPP particles or other polymeric filler particles can be from about 8 microns to about 75 microns. In some implementations, the filler shredder 82b, the filler granulator 84b, and/or the filler storage 86b can be used to process and/or store other types of fillers, besides polymeric filler materials, such as natural fiber fillers, inorganic fillers (e.g., mineral fillers), and/or fiberglass fillers, as described herein. As described herein, to promote bonding between the fibers and the binding agent, the fibers can be pretreated with one or more coupling agents (e.g., an organofunctional silane) and/or sizing agents.


In general, the surface fiber granulator 84a, the core fiber granulator 84c, and/or the filler granulator 84b can granulate materials through fixed diameter screens, which can result in a range of fiber lengths and particle sizes, which can be normally distributed. For example, a screen size for the surface fiber granulator 84a can be about 4 mm, about 8 mm, or about 16 mm. A screen size for the core fiber granulator 84c can be about 6 mm, about 13 mm, about 25 mm, about 38 mm, or about 50 mm. A screen size for the filler granulator 84b can be about 3 mm, about 6 mm, or about 12 mm.


Next, binding agent components, such as MDI 86 and water 88 (and optionally a polyol and/or auxiliary materials for creating a polyurethane foam), can be added to the granulated fiber materials and the granulated polymeric filler. The granulated fiber materials from the surface fiber storage 86a and the granulated filler from the filler storage 86b can be mixed with MDI 86 and water 88 in a surface mixer 90. Likewise, the granulated fiber materials from the core fiber storage 86c and the granulated filler from the filler storage 86b can be mixed with MDI 86 and water 88 in a core mixer 92. A ratio of water to MDI can be, for example, from about 1:4 to about 1:1, or about 1:2, by weight. In general, it can be desirable to use enough water so that a reaction between MDI and water can proceed to completion (e.g., to form polyurea). Insufficient amounts of water may result in unreacted MDI adhering to and/or contaminating process equipment, such as a cycle press or a continuous roll press. A mold release can be sprayed onto the process equipment to avoid or reduce this issue; however, if enough water is utilized, there may be no need to use the mold release. Once formed, the mixtures can be delivered to a bottom layer former 94a, a core layer former 94b, and a top layer former 94c, as shown.


As described herein, other binding agents can be used in addition to or instead of MDI 86 and water 88. The binding agent can be, include, or be derived from, for example, a polyurea, a polyurethane, an isocyanate, one or more polyols, epoxy, acrylic resin, polyester resin, MDI, pMDI, TDI, a different isocyanate, urea formaldehyde (UF), melamine urea formaldehyde (MUF), phenol formaldehyde (PF), a thermoset, a thermoplastic, other suitable binding agent materials or precursors, or any combination thereof. Compared to MDI, pMDI can be less reactive and easier to work with. In some examples, the binding agent can be selected according to a type of fiber included in the granulated fiber materials from the surface fiber storage 86a or a type of filler included in the granulated filler from the filler storage 86b. For example, a polyurea or a polyurethane (e.g., derived from MDI) may be preferable for polymeric fibers and/or polymeric fillers, while an epoxy, acrylic resin, and/or phenol formaldehyde (PF) may be preferable for glass fibers and/or fiberglass.


Additionally or alternatively, multiple types of binding agents can be used. For example, polymeric fibers and/or polymeric fillers can be mixed with MDI 86 and water 88, and fiberglass (e.g., treated with organofunctional silane or sizing agent) can be mixed with epoxy, acrylic resin, phenol formaldehyde (PF), or any combination thereof. This can enable specific types of fibers and/or fillers to be coated at least initially by binding agents that are most compatible with the fibers and/or fillers. Once the initial mixtures are formed, the coated fibers and/or fillers can be combined for further mixing (e.g., using the surface mixer 90 and/or core mixer 92) and/or can be provided to the bottom layer former 94a, the core layer former 94b, and/or the top layer former 94c.


Referring to FIG. 9, the bottom layer former 94a, the core layer former 94b, and the top layer former 94c can be used to generate a bottom layer 96a, a core layer 96b, and a top layer 96c, respectively, from the respective mixtures of fiber, filler, MDI, and water. One or more dissolving rollers 98 can be used to form these layers. Alternatively or additionally, the bottom layer former 94a, the core layer former 94b, the top layer former 94c, and/or the dissolving rollers 98 can utilize or include rotating brushes, pick rollers, air laying, and/or similar devices. In the depicted example, the bottom layer 96a, the core layer 96b, and the top layer 96c are formed on a bottom sheet 100 or web of phenolic paper and/or fiberglass film traveling on a conveyor 102 in a process direction 104, preferably at a constant or near constant speed. One or more scales 106 can be used to measure a weight of the bottom layer 96a, the core layer 96b, and/or the top layer 96c. The bottom sheet 100 of phenolic paper and/or fiberglass film can be obtained from a roll 108 or other source.


In certain examples, when the binding agent includes a polyurethane (e.g., a polyurethane foam), the bottom layer 96a, the core layer 96b, and the top layer 96c can include polyurethane precursors, such as a polyol, MDI (or other isocyanate), water, and/or auxiliary materials (e.g., catalysts, foaming agents, and/or stabilizers). The polyurethane precursors can be combined with other ingredients in the surface mixer 90 and/or the core mixer 92, such that the bottom layer 96a, the core layer 96b, and/or the top layer 96c include the polyurethane precursors when initially formed (e.g., by the bottom layer former 94a, the core layer former 94b, and/or the top layer former 94c). Alternatively or additionally, one or more of the polyurethane precursors (e.g., the polyol) can be added or applied to the bottom layer 96a, the core layer 96b, and/or the top layer 96c after the bottom layer 96a, the core layer 96b, and/or the top layer 96c have been formed. For example, one or more of the polyurethane precursors can be sprayed or coated onto the bottom layer 96a, the core layer 96b, and/or the top layer 96c. A location in the manufacturing process 80 at which the polyurethane precursors are combined with one another and/or mixed with other materials can depend on polyurethane precursor stability. It can be desirable to choose polyurethane precursors that are relatively stable, so that the polyurethane precursors provide an adequate working time and/or do not react too quickly to form the polyurethane. For example, it can be desirable in some instances for the polyurethane reaction to be triggered by the application of heat (e.g., in a hydraulic press), as described herein.


Once formed, the bottom layer 96a, the core layer 96b, and the top layer 96c can be delivered along the conveyor 102 to a pre-press 110, which can apply heat and/or pressure to form a compressed mat 112 of the bottom sheet 100 and the three layers 96a, 96b, and 96c. The compressed mat 112 can have a substantially smooth top surface. A top sheet 114 of phenolic paper and/or a fiberglass mat can then be obtained from a roll 116 and applied (e.g., using adhesive) to the compressed mat 112, and the compressed mat 112 and the top sheet 114 can be conveyed to a hydraulic press 118, which can be a cycle press or a continuous roll press, as described herein. The hydraulic press 118 can apply additional heat and pressure to convert the compressed mat 112 with the top sheet 114 into panels or sheets of a composite material 120. The heat and pressure in the hydraulic press 118 can further compress the bottom layer 96a, the core layer 96b, and the top layer 96c until a desired final thickness is reached. The heat and pressure can cure the MDI (or other binding agent) and/or can cure the resin in the phenolic paper or fiberglass film. In some examples, a resin, binding agent, or glue can be applied to the bottom sheet 100 and/or the top sheet 114 (or other composite layers) using spray nozzles, a roller, a blade, or other coating techniques, for example, to achieve bonding between the bottom sheet 100 and/or the top sheet 114 and other composite layers.


In some instances, when the binding agent includes polyurethane precursors, the heat and pressure in the hydraulic press 118 can trigger a reaction between one or more polyurethane precursors to form a polyurethane. The polyurethane can include a polyurethane foam that expands to fill an entire space between platens in the hydraulic press 118. For example, the polyurethane foam can expand to fill any voids or interstitial spaces between fibers (e.g., polymeric fibers and/or glass fibers) and/or filler materials in the bottom layer 96a, the core layer 96b, and/or the top layer 96c. Additionally or alternatively, use of polyurethane foam as a binding agent can require less compression or pressing of fiber and/or filler materials. For example, a separation distance between the platens can be set to a predetermined value, and the polyurethane foam can expand to fill a gap or space between the platens. The polyurethane foam can act as a matrix that carries or holds the fibers and/or fillers, which can be distributed throughout the polyurethane foam.


Advantageously, when a polyurethane foam is formed and/or used in the composite materials described herein, the polyurethane foam can occupy a significant portion (e.g., greater than 25%, greater than 50%, or more) of a total volume of the resulting composite, such that the bottom layer 96a, the core layer 96b, and/or the top layer 96c may not need to include as much fiber (e.g., polymeric fiber and/or glass fiber) and/or filler materials. For example, compared to embodiments that do not include a polyurethane foam binding agent (e.g., composites that include a polyurea binding agent formed using MDI and water, without a polyol), the resulting composite can have a weight percentage of fiber and/or filler materials that is lower by 10%, 20%, 30%, 40%, 50%, or more. The polyurethane foam can result in composite materials are not as heavy as non-foamed composites (e.g., lighter or lower in density by 10%, 20%, 30%, 40%, 50%, or more). For example, foamed composites can have a density from about 20 lb/ft3 (320 kg/m3) to about 45 lb/ft3 (721 kg/m3). Non-foamed composites can have a density from about 35 lb/ft3 (561 kg/m3) to about 70 lb/ft3 (1120 kg/m3). Additionally or alternatively, the polyurethane foam can be more water resistant than other binding agents described herein. In some instances, for example, the closed cells of the polyurethane foam can prevent water from infiltrating into the composite materials described herein. Further, composite materials produced using a rigid polyurethane foam can be stronger or stiffer than other composite materials described herein. The added strength or stiffness can be due to the polyurethane foam connecting fibers and/or fillers in a single matrix. Similar advantages can be achieved using a polyurea foam as the binding agent, which can be formed from MDI, water, and an accelerant, as described herein.


In other examples, rather than passing the phenolic paper (or other resin-impregnated paper, or fiberglass film) through the pre-press 110 and/or the hydraulic press 118, the phenolic paper can be applied after the bottom layer 96a, the core layer 96b, and the top layer 96c have been heated and pressed by the pre-press 110 and/or the hydraulic press 118 to form a composite. The phenolic paper (or fiberglass film) can be bonded to the resulting composite (e.g., using a glue) and the resin in the phenolic paper (or fiberglass film) can be cured (e.g., by applying heat). In some examples, the composite materials described herein do not include the phenolic paper, other resin-impregnated paper, or fiberglass film.


Additionally or alternatively, the composite materials described herein can be formed using a single layer of binding agent, polymeric and/or glass fibers, polymeric films, and/or other fillers or additives, as described herein and shown in FIG. 5B. For example, the manufacturing process 80 can be modified to form or include the core layer 96b but not the bottom layer 96a and the top layer 96c. In other examples, the manufacturing process 80 can be modified to form or include the core layer 96b and only one of the bottom layer 96a and the top layer 96c.


After the sheets of composite material have been formed, the sheets can be cooled and cut to desired shapes and sizes, and various finishing processes can be utilized to form a finished product. For example, edges or other portions of the composite sheet can be subjected to thermal or heat treatments in which an open flame, infrared radiation, or a hot roller melts polymeric material and/or closes any open structures or pores of the composition, thereby reducing or eliminating pathways for moisture absorption. Additionally or alternatively, the composite material can be coated with one or more coatings, such as water-based paint (e.g., latex paint or acrylic paint), solvent based paint, two-part catalyst paint, nano-based coatings, and/or UV cured coatings. Additionally or alternatively, one or more sealants (e.g., silicone-based sealant materials) and/or laminate or film banding can be applied. In some examples, the finishing processes can include surface treatments, such as embossing (inside or after the hydraulic press 118), molding, and/or digital printing (e.g., performed on the phenolic paper or fiberglass film before or after the hydraulic press 118). Embossing can be performed using one or more engraved plates or belts in the hydraulic press 118. The engraved plates can emboss a realistic wood pattern into a top or bottom layer of phenolic paper or fiberglass film. Alternatively or additionally, embossing can be performed after the hydraulic press, for example, in a finishing process using a flat press and/or a roll embosser. The digital printing can be performed, for example, to add a printed texture resembling natural wood, stone, tile, brick, or other building material. One or more coatings can be applied (e.g., to the phenolic paper or fiberglass film), such as a powder coating or a clear coat. In some implementations, a masonry finish can be obtained or simulated by gluing or affixing aggregate materials, stucco, and/or cementitious materials or products to an exterior surface of the composite materials described herein. Alternatively or additionally, metal materials (e.g., aluminum sheets) can be attached to the composite materials to obtain a metal surface layer.


In various implementations, the finishing processes can include one or more of the following steps, in any combination. The cooled panels from the hydraulic press can be ripped or cut into boards of various widths, for example, using a multi-gang rip saw. The boards can be transferred automatically to a linear finishing line, which can align the boards from side-to-side and/or end-to-end. The boards can then be processed using various finishing steps, which can depend on the specific product being manufactured. These finishing steps can include, for example, deburring (sanding), thermal treatment (e.g., flame treatment tunnel or hot roller), edge banding or other edge application, and/or molding (e.g., in a shaper). Once the finishing steps are complete, the composite product can go through a laser QA system, for example, to confirm dimensions (e.g., width and thickness) and/or detect any surface imperfections. Boards can be rejected automatically based on the QA system.


In some examples, the resulting boards can go through as many as three cycles of painting and drying. Two coats of primer or sealer can be applied to edges or an entire board, with each coat preferably being dried in an infrared thermal oven. A final coating of top paint can then be applied and dried. A cooling step can be used to remove heat from the product prior to automatic packaging, to prevent sticking of boards. Protective coatings or packing materials can be applied prior to shipment. Boards can be sub-bundled, if desired, and/or automatically palletized, and pallets can be wrapped and labeled.



FIG. 10 is a flowchart of an example method 130 of manufacturing a composite building material. A core layer having a first type of polymeric fibers (e.g., carpet fibers) and a first binding agent is formed (step 132). The first type of polymeric fibers has a first average fiber length. A top layer having a second type of polymeric fibers (e.g., carpet fibers) and a second binding agent is formed (step 134). The second type of polymeric fibers has a second average fiber length different than the first average fiber length. A bottom layer having the second type of polymeric fibers and the second binding agent is formed (step 136). At least one surface layer of resin-impregnated paper (or fiberglass film) is applied (step 138) above the top layer or below the bottom layer. The composite building material is formed by heating and pressing (step 140) the core layer and the at least one surface layer of resin-impregnated paper (or fiberglass film), with the core layer positioned between the top layer and the bottom layer. In some examples, step 136 is performed before step 132, which is performed before step 134. In certain implementations, the first type of polymeric fibers and the second type of polymeric fibers can include fibers having the same or similar chemical composition and/or fiber diameters. The polymeric fibers used for the core layer, the top layer, and/or the bottom layer can be replaced in whole or in part by glass fibers, as described herein.



FIG. 11 is a flowchart of an example method 150 of manufacturing a composite building material. A core layer is formed (step 152) that includes a binding agent at least one of polymeric fibers or polymeric film particles (e.g., polymeric fibers, polymeric film particles, or both polymeric fibers and polymeric film particles). At least one surface layer of resin-impregnated paper (or fiberglass film) is applied (step 154) above or below the core layer. The core layer and the at least one surface layer of resin-impregnated paper (or fiberglass film) are heated and pressed (step 156) to form the composite building material.


In certain examples, a variety of polymeric or glass fiber lengths can be used to achieve composite building materials having a variety of performance characteristics. In general, longer fibers (e.g., average length of about 12 mm, about 25 mm, or longer) can be used to produce boards that are stiffer or higher in strength. Additionally or alternatively, shorter fibers (e.g., average length less than about 25 mm, less than about 12 mm, or less than about 6 mm) can be used to produce boards that have smoother exterior surfaces and/or may be easier to mold and/or shape in a finishing process. For example, the shorter fibers (and/or higher fiber densities) can be used to produce boards that are easier to mold and/or shape (e.g., using a router, shaper, etc.). The shorter fibers can be used to achieve smoother exterior surfaces, as described herein.


EXAMPLES

A variety of composite materials having carpet fiber and optionally a top and/or bottom surface layer of phenolic paper were produced in accordance with the composites and methods described herein. Table F lists various parameters related to the composition and structure of two examples of these composite materials that were used for performance testing. Samples of the composite materials were produced using a two daylight, hydraulic press from DIEFFENBACHER, with cycle times of approximately 10 minutes. Platen temps in the press for Example A were approximately 410-420° F. (210-216° C.) and for Example B were approximately 390° F. (199° C.). The phenolic paper for the top and bottom surface layers was obtained from PANELTECH (of Hoquiam, WA).









TABLE F







Parameter values for example composite materials.









Composition
Example A
Example B












Core Layer




Carpet Fiber (wt %)
94
70


Carpet Fiber Average Length (mm)
7
10


Binding Agent (MDI + water) (wt %)
6
7


Natural Fiber Filler (wt %)
0
0


Polymeric Filler (BOPP) (wt %)
0
23


Inorganic Filler (wt %)
0
0


Fiberglass (wt %)
0
0


Additives (wt %)
0
0


Average Thickness (% of Combined
70
60


Thickness of Core Layer, Top Layer,


and Bottom Layer)


Average Thickness (mm)
13.3
11.4


Top and Bottom Layers


Carpet Fiber (wt. %)
91
93


Carpet Fiber Average Length (mm)
2
6


Binding Agent (MDI + water) (wt %)
9
7


Natural Fiber Filler (wt %)
0
0


Polymeric Filler (BOPP) (wt %)
0
0


Inorganic Filler (wt %)
0
0


Fiberglass (wt %)
0
0


Additives (wt %)
0
0


Top Layer Average Thickness (% of
15
20


Combined Thickness of Core Layer,


Top Layer, and Bottom Layer)


Top Layer Average Thickness (mm)
2.85
3.8


Bottom Layer Average Thickness (%
15
20


of Combined Thickness of Core Layer,


Top Layer, and Bottom Layer)


Bottom Layer Average Thickness (mm)
2.85
3.8


Top and Bottom Surface Layers


Paper Weight (without Resin) (gsm)
N/A
200


Number of Paper Sheets per Layer
0
1


Resin Content (wt %)
N/A
35









Table G illustrates results from performance tests that were performed on the example composite materials listed in Table F. The results indicate that the coefficient of thermal expansion (CTE; as measured using ASTM D6341-16) for Example A was 0.00003 to 0.00006 m/m ° C., and the CTE for Example B was 0.000006 to 0.000008 m/m ° C. The results also indicate that linear expansion of a 6.1 m (20 ft) board due to a 50° C. temperature change (from −10° C. to 40° C.) was 1.7 to 3.3 cm for Example A and 0.33 to 0.43 cm for Example B. The significant reduction in CTE and linear thermal expansion (e.g., as much as a factor of 10) achieved with Example B (and with other similar samples in other experiments) is believed to be primarily due to the use of phenolic paper, rather than any other differences between the samples). As Table F indicates, Example B included phenolic paper on the top and bottom surfaces while Example A did not include any phenolic paper. Advantageously, this reduction in CTE and linear thermal expansion can significantly improve the performance of the composite materials described herein for various building applications, particularly where substantial temperature variations (e.g., of 30° C. or more) may be encountered. Such building applications can include, for example, exterior decking, siding, trim boards, and/or roofing. In some instances, the reduction in CTE achieved through the use of phenolic paper can render the composite materials commercially viable. For example, composite materials that do not utilize phenolic paper on top and/or bottom surfaces may be susceptible to large or excessive amounts of thermal expansion, which can cause installed products to bend, warp, become unfastened or loose, become less visibly attractive, and/or destroy or damage neighboring installed materials.









TABLE G







Performance parameters for the example composite materials.









Performance Parameter
Example A
Example B





Coefficient of Thermal Expansion
3.0E−05 to
6.0E−06 to


(m/m ° C.)
6.0E−05
8.0E−06


Linear Thermal Expansion of 6.1 m
1.7 to 3.3
0.33 to 0.43


Board due to 50° C. Temperature


Change (cm)


Linear Expansion of 6.1 m Board due to
1.3
0.23


Submersion in Water for 24 hours (cm)


Linear Expansion of 6.1 m Board due to
2.5
0.33


Submersion in Water for 144 hours (cm)









The results in Table G also indicate that expansion due to moisture absorption was significantly lower for Example B, compared to Example A. For example, linear expansion of a 6.1 m (20 ft) board due to submersion in water at 20° C. for 24 hours was 1.3 cm for Example A and 0.23 cm for Example B. Likewise, linear expansion of a 6.1 m (20 ft) board due to submersion in water at 20° C. for 144 hours was 2.5 cm for Example A and 0.33 cm for Example B. The significant reduction in expansion due to moisture absorption (e.g., as much as a factor of about 8) achieved with Example B (and with similar samples in other experiments) is believed to be primarily due to the use of phenolic paper, rather than any other differences between the samples). Advantageously, this reduction in moisture expansion can significantly improve the performance of the composite materials described herein for various building applications where exposure to moisture may be encountered. Such building applications can include, for example, exterior decking, siding, trim boards, and/or roofing. In some instances, the reduction in CTE achieved through the use of phenolic paper can render the composite materials commercially viable. For example, composite materials that do not utilize phenolic paper on top and/or bottom surfaces may be susceptible to large or excessive amounts of moisture expansion, which can cause installed products to bend, warp, become unfastened or loose, become less visibly attractive, and/or destroy neighboring installed materials.


Additional experiments indicate that use of phenolic paper, as described herein, can significantly improve various performance parameters related to mechanical strength. For example, such experiments indicate that modulus of elasticity, modulus of rupture, and/or yield strength can increase by a factor of 2, 5, 10, or more, due to the use of phenolic paper (e.g., on top and/or bottom surfaces) in the composite materials described herein. Use of the fiberglass mats or films described herein can similarly improve or modify various performance parameters related to mechanical strength (e.g., modulus of elasticity and modulus of rupture), thermal expansion, and/or moisture expansion. The use of fiberglass mats or films can improve fire resistance (e.g., achieve a Class A fire rating), increase water resistance, increase hardness, and/or increase puncture resistance. Composite materials that do not utilize phenolic paper and/or fiberglass films may have inadequate stiffness or mechanical strength. This can result in product failure or excessive product bending or displacement, and/or may present a safety hazard.


A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.


Each numerical value presented herein, for example, in a table, a chart, or a graph, is contemplated to represent a minimum value or a maximum value in a range for a corresponding parameter. Accordingly, when added to the claims, the numerical value provides express support for claiming the range, which may lie above or below the numerical value, in accordance with the teachings herein. Absent inclusion in the claims, each numerical value presented herein is not to be considered limiting in any regard.


The terms and expressions employed herein are used as terms and expressions of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof. In addition, having described certain embodiments of the invention, it will be apparent to those of ordinary skill in the art that other embodiments incorporating the concepts disclosed herein may be used without departing from the spirit and scope of the invention.


The features and functions of the various embodiments may be arranged in various combinations and permutations, and all are considered to be within the scope of the disclosed invention. Accordingly, the described embodiments are to be considered in all respects as only illustrative and not restrictive. Furthermore, the configurations, materials, and dimensions described herein are intended as illustrative and in no way limiting. Similarly, although physical explanations have been provided for explanatory purposes, there is no intent to be bound by any particular theory or mechanism, or to limit the claims in accordance therewith.


TERMINOLOGY

The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.


The term “about”, the term “approximately”, the phrase “approximately equal to”, and other similar phrases, as used in the specification and the claims (e.g., “X has a value of approximately Y” or “X is approximately equal to Y”), should be understood to mean that one value (X) is within a predetermined range of another value (Y). The predetermined range may be plus or minus 20%, 10%, 5%, 3%, 1%, 0.1%, or less than 0.1%, unless otherwise indicated.


As used herein, “substantially nonuniform thickness” can refer to one or more layers having a ratio of a minimum thickness to a maximum thickness that is less than 0.5, less than 0.4, less than 0.3, less than 0.2, less than 0.1, or less than 0.05. Likewise, “substantially uniform thickness” can refer to one or more layers having a ratio of a minimum thickness to a maximum thickness that is greater than 0.5, greater than 0.6, greater than 0.7, greater than 0.8, greater than 0.9, or greater than 0.95.


The indefinite articles “a” and “an,” as used in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.” The phrase “and/or,” as used in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.


As used in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.


As used in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.


Use of ordinal terms such as “first,” “second,” “third,” etc., in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed. Ordinal terms are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term), to distinguish the claim elements.

Claims
  • 1. A composite building material, comprising: a core layer comprising a first binding agent and fibers; anda top layer disposed above the core layer and comprising a second binding agent and fibers, wherein the fibers in the core layer and the fibers in the top layer comprise fibers derived from at least one of a scrap fiber source, a used fiber source, a recycled fiber source, or any combination thereof,wherein at least one of the fibers in the core layer or the fibers in the top layer comprise glass fibers,wherein the fibers in the top layer have an average length less than about 6 mm and shorter than an average length of the fibers in the core layer,wherein the first binding agent and the second binding agent each comprises a thermoset cured by applying heat,wherein the first binding agent and the second binding agent are not foamed,wherein the core layer and the top layer form a board or a sheet,wherein the core layer has a substantially nonuniform thickness, the top layer has a substantially nonuniform thickness, and the core layer and the top layer together have a substantially uniform thickness due at least in part to shorter fibers in the top layer filling in valleys and covering thickness irregularities formed by longer fibers in the core layer, andwherein an average combined thickness of the core layer and the top layer is from about 6 mm to about 40 mm.
  • 2. The composite building material of claim 1, wherein at least one of (i) the fibers in the core layer or (ii) the fibers in the top layer comprise fibers derived from at least one of carpet, automotive headliners, automotive sidewalls, automotive fabrics, insulation materials, or any combination thereof.
  • 3. The composite building material of claim 1, wherein at least one of (i) the fibers in the core layer or (ii) the fibers in the top layer comprise glass fibers derived from at least one of fiberglass insulation materials, recycled wind turbine fan blades, boat hulls, machine components, or construction materials.
  • 4. The composite building material of claim 1, wherein at least one of the first binding agent or the second binding agent comprises polyurea, polyurethane, epoxy, acrylic resin, unsaturated polyester resin, isocyanate, MDI, pMDI, phenol formaldehyde (PF), a product derived therefrom, or any combination thereof.
  • 5. The composite building material of claim 1, wherein the first binding agent and the second binding agent are different.
  • 6. The composite building material of claim 1, wherein the first binding agent and the second binding agent are identical.
  • 7. The composite building material of claim 1, wherein the fibers in the core layer have an average length less than about 6 mm.
  • 8. The composite building material of claim 1, wherein at least one of the core layer or the top layer comprises a polymeric filler comprising particles formed from at least one of biaxially oriented polypropylene, a polymeric film, a packaging film, a barrier packaging film, a MRF residual, or any combination thereof.
  • 9. The composite building material of claim 1, wherein at least one of the core layer or the top layer comprises at least one of an inorganic filler or a natural fiber filler.
  • 10. The composite building material of claim 1, wherein the fibers in the core layer and the fibers in the top layer are compressed.
  • 11. The composite building material of claim 1, wherein the board or the sheet is configured for use in a building product, and wherein the building product comprises at least one of siding, trim, molding, panels, roofing, or decking.
  • 12. The composite building material of claim 1, further comprising a resin-impregnated paper disposed above the top layer.
  • 13. The composite building material of claim 1, further comprising a fiberglass film disposed above the top layer.
  • 14. A method of manufacturing a composite building material, the method comprising the steps of: forming a core layer comprising a first binding agent and fibers;forming a top layer comprising a second binding agent and fibers; andheating and pressing the core layer and the top layer to form the composite building material, wherein the fibers in the core layer and the fibers in the top layer comprise fibers derived from at least one of a scrap fiber source, a used fiber source, a recycled fiber source, or any combination thereof,wherein at least one of the fibers in the core layer or the fibers in the top layer comprise glass fibers,wherein the fibers in the top layer have an average length less than about 6 mm and shorter than an average length of the fibers in the core layer,wherein the first binding agent and the second binding agent each comprises a thermoset cured by the heating,wherein the first binding agent and the second binding agent are not foamed,wherein the core layer and the top layer form a board or a sheet,wherein the core layer has a substantially nonuniform thickness, the top layer has a substantially nonuniform thickness, and the core layer and the top layer together have a substantially uniform thickness due at least in part to shorter fibers in the top layer filling in valleys and covering thickness irregularities formed by longer fibers in the core layer, andwherein an average combined thickness of the core layer and the top layer is from about 6 mm to about 40 mm.
  • 15. The method of claim 14, wherein forming the core layer comprises mixing the first binding agent with fibers, and wherein forming the top layer comprises mixing the second binding agent with fibers.
  • 16. The method of claim 14, further comprising applying at least one surface layer above the top layer, the at least one surface layer comprising resin-impregnated paper or a fiberglass film.
  • 17. The composite building material of claim 1, wherein the glass fibers are at least partially coated with an organofunctional silane.
  • 18. The composite building material of claim 1, wherein the fibers in the top layer have an average length less than about 5 mm.
  • 19. The composite building material of claim 1, wherein the thermoset was cured while applying pressure in at least one of a hydraulic press, a cycle press, or a continuous roll press.
  • 20. The composite building material of claim 1, wherein the fibers in the core layer comprise polymeric fibers.
  • 21. The composite building material of claim 12, wherein the resin-impregnated paper provides the composite building material with increased resistance to expansion caused by at least one of temperature changes or moisture exposure.
  • 22. The composite building material of claim 1, wherein the core layer comprises clumps or balls of fiber that form peaks or valleys in the core layer, and wherein the top layer covers the peaks or valleys in the core layer to achieve the substantially uniform thickness.
  • 23. The composite building material of claim 1, wherein the fibers in the core layer have a greater tendency to form clumps or balls during formation of the core layer, compared to a tendency for the fibers in the top layer to form clumps or balls during formation of the top layer.
  • 24. The composite building material of claim 1, wherein the shorter fibers in the top layer fill in voids or interstitial spaces formed by longer fibers in the core layer.
  • 25. The composite building material of claim 1, wherein the shorter fibers in the top layer were spread onto the core layer to fill in the valleys and cover the thickness irregularities.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is (i) a continuation-in-part of International Patent Application No. PCT/US2021/059863, filed Nov. 18, 2021, which is a continuation-in-part of U.S. patent application Ser. No. 17/216,858, filed Mar. 30, 2021, and claims priority to and the benefit of U.S. Provisional Patent Application No. 63/115,318, filed Nov. 18, 2020, and (ii) a continuation-in-part of U.S. patent application Ser. No. 17/216,858, filed Mar. 30, 2021, which claims priority to and the benefit of U.S. Provisional Patent Application No. 63/115,318, filed Nov. 18, 2020, the entire contents of each of which are incorporated by reference herein.

US Referenced Citations (389)
Number Name Date Kind
3170832 Wilson et al. Feb 1965 A
3471355 Truesdell et al. Oct 1969 A
3478134 Gruss et al. Nov 1969 A
3511750 Hider May 1970 A
3560324 Quackenbush Feb 1971 A
3669823 Wood Jun 1972 A
3717534 Duling et al. Feb 1973 A
3801417 Shanok et al. Apr 1974 A
3804693 Nichols, Jr. Apr 1974 A
3856724 O'Connor et al. Dec 1974 A
3864201 Susuki et al. Feb 1975 A
3936554 Squier Feb 1976 A
3959434 Squier May 1976 A
3970324 Howat Jul 1976 A
3995980 Smith Dec 1976 A
4025686 Zion May 1977 A
4028159 Norris Jun 1977 A
4029839 Lesti Jun 1977 A
4044188 Segal Aug 1977 A
4045603 Smith Aug 1977 A
4154893 Goldman May 1979 A
4158646 Benkowski et al. Jun 1979 A
4212703 D'Amico et al. Jul 1980 A
4212928 Arney, Jr. Jul 1980 A
4315048 Beghelli et al. Feb 1982 A
4382108 Carroll et al. May 1983 A
4388435 Loch Jun 1983 A
4405752 Recker et al. Sep 1983 A
4438166 Gluck et al. Mar 1984 A
4459334 Blanpied et al. Jul 1984 A
4463043 Reeves et al. Jul 1984 A
4469741 Akao Sep 1984 A
4480061 Coughlin et al. Oct 1984 A
4503115 Hemels et al. Mar 1985 A
4567987 Lepisto et al. Feb 1986 A
4680214 Frisch Jul 1987 A
4695501 Robinson Sep 1987 A
4942084 Prince Jul 1990 A
5002624 Howell et al. Mar 1991 A
5045389 Campagna Sep 1991 A
5130352 Chow Jul 1992 A
5134026 Melcher Jul 1992 A
5160772 Futami et al. Nov 1992 A
5217655 Schmidt et al. Jun 1993 A
5275862 Ramadan et al. Jan 1994 A
5294384 David et al. Mar 1994 A
5373674 Winter, IV Dec 1994 A
5393536 Brandt et al. Feb 1995 A
5441801 Deaner et al. Aug 1995 A
5486553 Deaner et al. Jan 1996 A
5496648 Held Mar 1996 A
5498667 David et al. Mar 1996 A
5516472 Laver May 1996 A
5534590 Horiie et al. Jul 1996 A
5535945 Sferrazza et al. Jul 1996 A
5539027 Deaner et al. Jul 1996 A
5578370 Ferrar et al. Nov 1996 A
5591802 David et al. Jan 1997 A
5601912 Ellingson Feb 1997 A
5626939 Kotlair et al. May 1997 A
5641553 Tingley Jun 1997 A
5648138 Tingley Jul 1997 A
5662994 Funger et al. Sep 1997 A
5695874 Deaner et al. Dec 1997 A
5707571 Reedy Jan 1998 A
5722603 Costello et al. Mar 1998 A
5725939 Nishibori et al. Mar 1998 A
5728741 Zegler et al. Mar 1998 A
5735092 Clayton et al. Apr 1998 A
5738935 Turk et al. Apr 1998 A
5773138 Seethamraju et al. Jun 1998 A
5786279 Funger et al. Jul 1998 A
5786280 Funger et al. Jul 1998 A
5789477 Nosker et al. Aug 1998 A
5792529 May Aug 1998 A
5804641 Iwakawa Sep 1998 A
5827462 Brandt et al. Oct 1998 A
5827607 Deaner et al. Oct 1998 A
5836128 Groh et al. Nov 1998 A
5840773 Booij et al. Nov 1998 A
5847016 Cope Dec 1998 A
5858522 Turk et al. Jan 1999 A
5866264 Zehner et al. Feb 1999 A
5869138 Nishibori et al. Feb 1999 A
5883191 Hughes Mar 1999 A
5912315 Horiie et al. Jun 1999 A
5919575 Bowns, IV et al. Jul 1999 A
5932334 Deaner et al. Aug 1999 A
5948524 Seethamraju et al. Sep 1999 A
5951927 Cope Sep 1999 A
5981067 Seethamraju et al. Nov 1999 A
5981612 Keppeler Nov 1999 A
6004668 Deaner et al. Dec 1999 A
6007590 Sanders, Jr. Dec 1999 A
6011091 Zehner Jan 2000 A
6015611 Deaner et al. Jan 2000 A
6015612 Deaner et al. Jan 2000 A
6015856 Matsushita et al. Jan 2000 A
6017830 Brown et al. Jan 2000 A
6054207 Finley Apr 2000 A
6059207 Costello et al. May 2000 A
6063473 Zafiroglu May 2000 A
6066367 Nishibori et al. May 2000 A
6066680 Cope May 2000 A
6083601 Prince et al. Jul 2000 A
6096403 Wycech Aug 2000 A
6103791 Zehner Aug 2000 A
6106654 Velin et al. Aug 2000 A
6117924 Brandt Sep 2000 A
6122877 Hendrickson et al. Sep 2000 A
6132840 Lee et al. Oct 2000 A
6133349 Hughes Oct 2000 A
6180211 Held Jan 2001 B1
6194051 Gagas et al. Feb 2001 B1
6210792 Seethamraju et al. Apr 2001 B1
6211275 Xanthos et al. Apr 2001 B1
6217967 Bobrowicz Apr 2001 B1
6241168 Young et al. Jun 2001 B1
6248813 Zehner Jun 2001 B1
6265037 Godavarti et al. Jul 2001 B1
6271270 Muzzy et al. Aug 2001 B1
6274637 Schallenberg et al. Aug 2001 B1
6280667 Koenig et al. Aug 2001 B1
6305920 Kean et al. Oct 2001 B1
6306318 Ricciardelli et al. Oct 2001 B1
6316016 Iwakawa Nov 2001 B1
6342172 Finley Jan 2002 B1
6344268 Stucky et al. Feb 2002 B1
6344504 Zehner et al. Feb 2002 B1
6344515 Parikh et al. Feb 2002 B1
6352784 Katagiri Mar 2002 B1
6357197 Serino et al. Mar 2002 B1
6375777 Sjolin et al. Apr 2002 B1
6383652 Templeton et al. May 2002 B1
6387967 Muzzy et al. May 2002 B2
6465046 Hansson et al. Oct 2002 B1
6498205 Zehner Dec 2002 B1
6511757 Brandt et al. Jan 2003 B1
6517935 Kornfalt et al. Feb 2003 B1
6526712 Brooks et al. Mar 2003 B2
6534592 Chou et al. Mar 2003 B1
6558754 Velin et al. May 2003 B1
6565919 Hansson et al. May 2003 B1
6579605 Zehner Jun 2003 B2
6592962 Edwards et al. Jul 2003 B2
6605245 Dubelsten et al. Aug 2003 B1
6632387 Archuletta et al. Oct 2003 B2
6632863 Hutchison et al. Oct 2003 B2
6662515 Buhrts et al. Dec 2003 B2
6673207 Nishibori et al. Jan 2004 B1
6680090 Godavarti et al. Jan 2004 B2
6682789 Godavarti et al. Jan 2004 B2
6682814 Hendrickson et al. Jan 2004 B2
6685993 Hansson Feb 2004 B1
6692815 Edgman Feb 2004 B2
6702259 Pratt Mar 2004 B2
6723424 Ricciardelli et al. Apr 2004 B2
6749921 Edwards et al. Jun 2004 B1
6756412 Muzzy Jun 2004 B2
6758996 Monovoukas et al. Jul 2004 B2
6761794 Mott et al. Jul 2004 B2
6784230 Patterson et al. Aug 2004 B1
6786988 Bell Sep 2004 B1
6814826 Bell Nov 2004 B1
6821613 Kagi et al. Nov 2004 B1
6821614 Dubelsten et al. Nov 2004 B1
6841101 Nakos et al. Jan 2005 B2
6844049 Amin-Javaheri Jan 2005 B2
6860953 Grizzle et al. Mar 2005 B1
6863972 Burger et al. Mar 2005 B2
6865849 Mollinger et al. Mar 2005 B1
6866081 Nordgard et al. Mar 2005 B1
6867322 Kato et al. Mar 2005 B1
6872674 Williams et al. Mar 2005 B2
6939496 Maine et al. Sep 2005 B2
6953501 Kelley et al. Oct 2005 B2
6958185 Zehner Oct 2005 B1
6971211 Zehner Dec 2005 B1
6972144 Roth et al. Dec 2005 B2
6984676 Brandt Jan 2006 B1
7022751 Zhang et al. Apr 2006 B2
7025408 Jones et al. Apr 2006 B2
7030179 Patterson et al. Apr 2006 B2
7037459 Easter May 2006 B2
7045590 Bell May 2006 B2
7169464 Semmens Jan 2007 B2
7175905 Curtis et al. Feb 2007 B2
7186457 Zehner et al. Mar 2007 B1
7258913 Jo et al. Aug 2007 B2
7279058 Morgan Oct 2007 B2
7335424 Domine et al. Feb 2008 B2
7348067 Hoffman Mar 2008 B1
7405008 Domine et al. Jul 2008 B2
7409796 Sacks Aug 2008 B2
7410687 Dolinar Aug 2008 B2
7414084 Yamaguchi et al. Aug 2008 B2
7416779 Hashiba et al. Aug 2008 B2
7473722 Guiselin et al. Jan 2009 B2
7507464 Walrath Mar 2009 B2
7754120 Kessing Jul 2010 B2
7862746 Kaspers et al. Jan 2011 B2
7875655 Mancosh et al. Jan 2011 B2
7887726 Tsai Feb 2011 B1
7913960 Herr et al. Mar 2011 B1
7923477 Murdock et al. Apr 2011 B2
7976655 Bacon et al. Jul 2011 B2
8065849 Douglass Nov 2011 B2
8075987 Ricciardelli et al. Dec 2011 B2
8167275 Bizzarri et al. May 2012 B1
8216659 Zafiroglu Jul 2012 B2
8268737 Kumar Sep 2012 B1
8278365 Murdock et al. Oct 2012 B2
8439161 Bliton et al. May 2013 B2
8455558 Mancosh et al. Jun 2013 B2
8518312 Katz Aug 2013 B2
8563137 Genz et al. Oct 2013 B2
8809406 Murdock et al. Aug 2014 B2
8957120 Berthevas et al. Feb 2015 B2
8980145 Baroux Mar 2015 B2
9028731 Weyant et al. May 2015 B2
9056444 Moeller Jun 2015 B1
9221104 Moore et al. Dec 2015 B2
9254624 Calkins Feb 2016 B2
9289085 Thrush Mar 2016 B2
9404221 Hagiopol et al. Aug 2016 B2
9410026 Rees et al. Aug 2016 B1
9447547 Penland, Jr. et al. Sep 2016 B2
9637920 Murdock et al. May 2017 B2
9695601 Whispell et al. Jul 2017 B2
10227470 Li et al. Mar 2019 B2
10822798 Murdock et al. Nov 2020 B2
11060290 Rayman, Jr. et al. Jul 2021 B1
20010051243 Godavarti et al. Dec 2001 A1
20010051249 Gagas et al. Dec 2001 A1
20020007899 Mott et al. Jan 2002 A1
20020009936 North et al. Jan 2002 A1
20020014297 Mott et al. Feb 2002 A1
20020025414 Desai et al. Feb 2002 A1
20020031653 Ricciardelli et al. Mar 2002 A1
20020031659 Gansen et al. Mar 2002 A1
20020038924 Nilsson et al. Apr 2002 A1
20020092256 Hendrickson et al. Jul 2002 A1
20020096255 Mott Jul 2002 A1
20020106498 Deaner et al. Aug 2002 A1
20020153107 Roffael Oct 2002 A1
20020192401 Matsumoto et al. Dec 2002 A1
20020192431 Edgman Dec 2002 A1
20030021915 Rohatgi et al. Jan 2003 A1
20030075824 Moore et al. Apr 2003 A1
20030087079 Okabe et al. May 2003 A1
20030087572 Balthes et al. May 2003 A1
20030087574 Latimer et al. May 2003 A1
20030096094 Hayduke May 2003 A1
20030104124 Pavey et al. Jun 2003 A1
20030124940 Michael Jul 2003 A1
20030125399 Zhang et al. Jul 2003 A1
20030138616 Englert Jul 2003 A1
20030154662 Bruchu et al. Aug 2003 A1
20030191227 Grove Oct 2003 A1
20030198775 Roth et al. Oct 2003 A1
20030207634 Holeschovsky Nov 2003 A1
20030229160 Williams et al. Dec 2003 A1
20040003888 Mott et al. Jan 2004 A1
20040038002 Franco et al. Feb 2004 A1
20040058163 Gansen et al. Mar 2004 A1
20040062920 Guilbert et al. Apr 2004 A1
20040076820 Hodgson Apr 2004 A1
20040076846 Domine et al. Apr 2004 A1
20040096628 Saathoff et al. May 2004 A1
20040101674 Ross May 2004 A1
20040126515 Yarmoska Jul 2004 A1
20040126568 Deaner et al. Jul 2004 A1
20040142160 Cannon et al. Jul 2004 A1
20040161623 Domine et al. Aug 2004 A1
20040161993 Tripp et al. Aug 2004 A1
20040191617 Visco et al. Sep 2004 A1
20040192794 Patterson et al. Sep 2004 A1
20040224589 Bacon et al. Nov 2004 A1
20040241392 Sorrentino Dec 2004 A1
20040242108 Russell et al. Dec 2004 A1
20040247845 Abe et al. Dec 2004 A1
20040259973 Sakuma et al. Dec 2004 A1
20050003221 Walrath Jan 2005 A1
20050008814 Bell Jan 2005 A1
20050019539 Pike Jan 2005 A1
20050029709 Jo et al. Feb 2005 A1
20050037176 Domine Feb 2005 A1
20050042413 Bell Feb 2005 A1
20050049329 Faulkner Mar 2005 A1
20050058818 West Mar 2005 A1
20050058822 Ittel Mar 2005 A1
20050115182 Heiland Jun 2005 A1
20050132643 Flanery et al. Jun 2005 A1
20050136272 VanRheenen Jun 2005 A1
20050164580 Holeschovsky Jul 2005 A1
20050170141 Bacon et al. Aug 2005 A1
20050170157 Armela et al. Aug 2005 A1
20050176833 Tay Aug 2005 A1
20050187315 Dean Aug 2005 A1
20050206029 Moore et al. Sep 2005 A1
20050233126 Pike Oct 2005 A1
20050287347 Sorrentino Dec 2005 A1
20060006564 Maldas et al. Jan 2006 A1
20060032175 Chen et al. Feb 2006 A1
20060099393 Woodman et al. May 2006 A1
20060147669 Mano et al. Jul 2006 A1
20060147687 Ricciardelli et al. Jul 2006 A1
20060147693 Przybylinski et al. Jul 2006 A1
20060165972 Chimelak et al. Jul 2006 A1
20060183821 Kaspers et al. Aug 2006 A1
20060188734 Valentage et al. Aug 2006 A1
20060191655 Nunn et al. Aug 2006 A1
20060229381 Bartko Oct 2006 A1
20060234026 Huusken Oct 2006 A1
20060257597 Gleich Nov 2006 A1
20060267238 Wang Nov 2006 A1
20070007682 Maldas et al. Jan 2007 A1
20070009729 Kessing Jan 2007 A1
20070009743 Kessing et al. Jan 2007 A1
20070012414 Kajander Jan 2007 A1
20070043128 Jenkines et al. Feb 2007 A1
20070092701 Jeng Apr 2007 A1
20070098972 Balthes May 2007 A1
20070104930 Grohman May 2007 A1
20070113759 Roth et al. May 2007 A1
20070128428 Moriya et al. Jun 2007 A1
20070141316 McGrath et al. Jun 2007 A1
20070154669 Schneider et al. Jul 2007 A1
20070154689 Hughes et al. Jul 2007 A1
20070173551 Mancosh et al. Jul 2007 A1
20070212531 Mclntyre et al. Sep 2007 A1
20070235705 Burger et al. Oct 2007 A1
20070275207 Higgins et al. Nov 2007 A1
20080010924 Pietruczynik et al. Jan 2008 A1
20080064794 Murdock et al. Mar 2008 A1
20080075915 Wening et al. Mar 2008 A1
20080093763 Mancosh et al. Apr 2008 A1
20080098935 Roth et al. May 2008 A1
20080102263 Slywchuk et al. May 2008 A1
20080128933 Przybylinski et al. Jun 2008 A1
20080213562 Przybylinski et al. Sep 2008 A1
20080233336 Giannopoulos et al. Sep 2008 A1
20080263994 Kain Oct 2008 A1
20080287576 Nichols et al. Nov 2008 A1
20080289295 Waters et al. Nov 2008 A1
20080293837 Toft et al. Nov 2008 A1
20090053490 Clausi et al. Feb 2009 A1
20090130355 Chen et al. May 2009 A1
20090202803 Poloso et al. Aug 2009 A1
20090288582 Glessner et al. Nov 2009 A1
20100003431 Raybuck Jan 2010 A1
20100021753 Hojabr et al. Jan 2010 A1
20100058957 Boxley Mar 2010 A1
20100159213 Przybylinski et al. Jun 2010 A1
20100310893 Derbyshire et al. Dec 2010 A1
20110020619 Van Den Bossche et al. Jan 2011 A1
20110045250 De Zen Feb 2011 A1
20110097552 Mancosh et al. Apr 2011 A1
20110185662 Mollinger et al. Aug 2011 A1
20120003462 Wong Jan 2012 A1
20120031543 Bacon et al. Feb 2012 A1
20120052760 Doyle et al. Mar 2012 A1
20120077890 Mancosh et al. Mar 2012 A1
20120315471 Mancosh et al. Dec 2012 A1
20130046049 Ono et al. Feb 2013 A1
20130280976 McCann et al. Oct 2013 A1
20140212653 Slywchuk et al. Jul 2014 A1
20140287145 Brown et al. Sep 2014 A1
20150024171 Murdock et al. Jan 2015 A1
20150044434 Kotiadis et al. Feb 2015 A1
20150152650 Cernohous et al. Jun 2015 A1
20150354143 Pike Dec 2015 A1
20160032098 Sherga Feb 2016 A1
20160082706 Przybylinski et al. Mar 2016 A1
20160207283 Wang et al. Jul 2016 A1
20180002934 Pervan et al. Jan 2018 A1
20180094763 Ragiel Apr 2018 A1
20180319942 Kumar et al. Nov 2018 A1
20190066062 Lilly et al. Feb 2019 A1
20190070680 Lilly et al. Mar 2019 A1
20190161594 Li et al. May 2019 A1
20190338517 Murdock et al. Nov 2019 A1
20200061725 Lilly Feb 2020 A1
20200338789 Whitaker et al. Oct 2020 A1
20210238855 Rayman, Jr. et al. Aug 2021 A1
20210390518 Cochrane et al. Dec 2021 A1
20220064403 Winterowd et al. Mar 2022 A1
20220205774 Wan et al. Jun 2022 A1
20220250288 Winterowd et al. Aug 2022 A1
Foreign Referenced Citations (103)
Number Date Country
2028527 Mar 1992 CA
2353036 Jan 2002 CA
2594258 Jul 2006 CA
2538539 Sep 2006 CA
2607928 Apr 2008 CA
1821295 Aug 2006 CN
101015929 Aug 2007 CN
201295961 Aug 2009 CN
101538356 Sep 2009 CN
201420361 Mar 2010 CN
101830070 Sep 2010 CN
102555003 Jul 2012 CN
207432396 Jun 2018 CN
109397807 Mar 2019 CN
2444420 Mar 1976 DE
2722774 Nov 1978 DE
4338199 Feb 1995 DE
19734338 Jan 1999 DE
102008046481 Mar 2010 DE
114409 Aug 1984 EP
0473379 Mar 1992 EP
548696 Jun 1993 EP
00688644 Dec 1995 EP
950510 Oct 1999 EP
1016558 Jul 2000 EP
1022400 Jul 2000 EP
2952344 Dec 2015 EP
3001914 Aug 2014 FR
2071007 Sep 1981 GB
51 062883 May 1976 JP
02150303 Jun 1990 JP
6155432 Jun 1994 JP
H105096 Jan 1998 JP
2000263624 Sep 2000 JP
2001072817 Mar 2001 JP
2002241514 Aug 2002 JP
2003003018 Jan 2003 JP
2005 312782 Nov 2005 JP
2013537492 Oct 2013 JP
2016068300 May 2016 JP
20070111293 Nov 2007 KR
504501 Feb 1997 SE
WO-9612857 May 1996 WO
WO-9735700 Oct 1997 WO
WO-98025983 Jun 1998 WO
WO-9907786 Feb 1999 WO
WO-9916984 Apr 1999 WO
WO-99035364 Jul 1999 WO
WO-0024577 May 2000 WO
WO-0036218 Jun 2000 WO
WO-0036242 Jun 2000 WO
WO-0049246 Aug 2000 WO
WO-00073037 Dec 2000 WO
WO-2001028760 Apr 2001 WO
WO-0147717 Jul 2001 WO
WO-0147718 Jul 2001 WO
WO-0148333 Jul 2001 WO
WO-01058663 Aug 2001 WO
WO-0178981 Oct 2001 WO
WO-2001076869 Oct 2001 WO
WO-0204206 Jan 2002 WO
WO-0204207 Jan 2002 WO
WO-0204208 Jan 2002 WO
WO-0247906 Jun 2002 WO
WO-02057692 Jul 2002 WO
WO-02072367 Sep 2002 WO
WO-02090129 Nov 2002 WO
WO-03002338 Jan 2003 WO
WO-03047858 Jun 2003 WO
WO-03061967 Jul 2003 WO
WO-03064520 Aug 2003 WO
WO-03080337 Oct 2003 WO
WO-03095537 Nov 2003 WO
WO-04041534 May 2004 WO
WO-04083541 Sep 2004 WO
WO-05007384 Jan 2005 WO
WO-05021656 Mar 2005 WO
WO-05039843 May 2005 WO
WO-05063479 Jul 2005 WO
WO-05080496 Sep 2005 WO
WO-05123380 Dec 2005 WO
WO-2006001717 Jan 2006 WO
WO-2006037538 Apr 2006 WO
WO-06074276 Jul 2006 WO
WO-07056629 May 2007 WO
WO-07084822 Jul 2007 WO
WO-08066751 Jun 2008 WO
WO-09153324 Dec 2009 WO
WO-2010056250 May 2010 WO
WO-2010144969 Dec 2010 WO
WO-2011007184 Jan 2011 WO
WO-2011098470 Aug 2011 WO
WO-2012007703 Jan 2012 WO
WO-2012031131 Mar 2012 WO
WO-12103378 Aug 2012 WO
WO-2012168563 Dec 2012 WO
WO-2014108465 Jul 2014 WO
WO-2014137972 Sep 2014 WO
WO-2014144193 Sep 2014 WO
WO-2015196134 Dec 2015 WO
WO-2017082914 May 2017 WO
WO-2019094411 May 2019 WO
WO-2020028914 Feb 2020 WO
Non-Patent Literature Citations (42)
Entry
“ExactTM Plastomers,” published by Exxon Mobil, available at: http://www.exxonmobilchemical.com/Chem-English/brands/exact-plastomers.aspx?ln=pr, 1 page.
“Fact Sheet: ENGAGE™ Polyolefin Elastomers—A product of Dow's Specialty Plastics and Elastomers business, ENGAGE™ is bridging the gap between rubber and plastic, and inspiring new design possibilities,” published by The Dow Chemical Company, available at: http://www.dow.com/elastomers/products/engage.htm., 2 pages.
“Geon Duracap Vinyl Capstock,” downloaded on Jun. 13, 2012 from http://www.polyone.com/en-us/products/vinylextrusionmold/Pages/Duracap VinylCapstockCompounds.aspx, 2 pages.
“New Wood Plastic Composite Products Strengthen CertainTeed's Position as one-stop-shop for Railing and Decking,” downloaded on Jun. 13, 2012 from http://www.certainteed.com/pressroom/pressRelease.aspx?id=301#, 2 pages.
“Polyolefin Elastomers,” published by the International Institute of Synthetic Rubber Producers, available at: www.iisrp.com/WebPolymers/05ModPolyolefinElast_v1-2.pdf?, 3 pages.
“Reclaim and Resin Prices Skyrocket,” Sep. 2004, http://www.principiaconsulting.com/publishing/pdf/WPCNewsSept04.pdf, 8 pages.
“The Fast Growing Wood Plastic Composites WPC,” downloaded on Jun. 13, 2012 from, http://www.steerworld.com/downloads/KnowledgeCenter/Review%20Articles/THE%20FAST%20GROWING%20WPC.pdf, 5 pages.
“Wood-Filled Composites Jump off the Deck,” downloaded on Jun. 13, 2012 from http://www.compositesworld.com/articles/wood-filled-composites-jump-off-the-deck, 6 pages.
“Wood-Plastic Composites need protection, too.” downloaded on Jun. 13, 2012 from http://www.freepatentsonline.com/article/Plastics-Engineering/166824015.html, 4 pages.
280P Technical Data Sheet, Medium Density Overlay (MDO), available at https://paneltechintl.com>20-280-P_TDS, downloaded on Apr. 19, 2021.
Anonymous: “Separation Process,” Research Disclosure, Mason Publications, Hampshire, GB, vol. 388, No. 13, Aug. 1, 1996, ISSN: 0374-4353, 1 page.
Douglas J. Gardener, Adhesion Between Wood & Fiber Reinforced Polymers: Bonding Issues, Power Point Presentation, Advance Engineered Wood Composites Center.
European Office Action for 07862186.9 dated May 4, 2010 (7 pages).
Everboard High-Performance Roof Board, available at: <https://www.continuusmaterials.com/wp-content/uploads/2020/05/EverboardInformationSheet.pdf>, downloaded on Apr. 19, 2021.
International Search Report & Written Opinion for PCT/US2009/32552, mailed Sep. 15, 2009 (22 pages).
International Search Report and Written Opinion for International Patent Application for PCT/US2021/059863, mailed Mar. 11, 2022 (13 pages).
International Search Report and Written Opinion for PCT/US2009/068964 mailed Aug. 10, 2010 (14 pages).
International Search Report and Written Opinion for PCT/US2011/046798 mailed Feb. 3, 2012 (13 pages).
International Search Report and Written Opinion for PCT/US2012/042248, mailed Feb. 19, 2013 (27 pages).
International Search Report for International application PCT/US2007/024313, mailed from the International Search Authority on Apr. 15, 2008, 13 pgs.
International Search Report for PCT/US07/60381 dated Oct. 1, 2007, 8 pp.
Jan H. Schut, Foaming Expands Possibilities for Wood-Fiber Composites, Plastics Technology, www.ptonline.com, Oct. 17, 2008.
Jan H. Schut, Wood is Good for Compounding, Sheet & Profile, Plastics Technology, www.ptonline.com, Oct. 17, 2008.
Jennifer Markarian, Wood Plastic Composites Need Protection, Too, Plastics Engineering, www.4spe.org., Jul. 2007.
K. Oksman, Improved interaction between wood and synthetic polymers in wood/polymer composites, Department of Wood Technology, Lulea University, Skelleftea, Sweden, Wood Science an Technology, vol. 30, Issue 3, Jun. 1996, pp. 197-205.
Kelly Williams, New Technology for Protecting Wood/Polymer Composites, Power Point Presentation, INFIN Coating Technology.
Krzysik et al., Wood-Polymer Bonding in Extruded and Non-Woven Web Composite Panels, Wood Adhesives 1990: Proceedings of a Symposium, Madison, WI, Forest Products Research Soicety, p. 183-189, 1991.
Maged Botros, Ph.D., Development of New Generation Coupling Agents for Wood-Plastic Composites, Equistar, Intertech Conference Dec. 3-5, 2003.
Mao et al., “Recycling Polyurethane Materials: A Comparison of Polyol from Glycolysis with Micronized Polyurethane Powder in Particleboard Applications,” College of Forestry, Shandong Agriculture, University, Taian, China, 2014.
Nicole M. Stark and Laurent M. Matuana, Coating WPCS using Co-Extrusion to improve Durability, Coating Wood & Wood Composites: Designing for Durability, Federation of Societies for Coatings Technology, Jul. 23-25, 2007.
Nimz et al., “Wood,” Ullmann's Encyclopedia of Industrial Chemistry, 2000, 454-505.
Partial International Search for PCT/US2012/042248 dated Oct. 8, 2012, 3 pages.
Partial International Search Report for PCT/US09/032552 dated Jun. 6, 2009, 2 pgs.
Preliminary Report with Written Opinonfor International application PCT/US2011/046798, mailed from the International Search Authority on Feb. 21, 2013, 9 pgs.
Qiao et al., “Effect of particle size and vol. fraction on tensile properties of fly ash/polyurea composites,” Proceeding of Spie, XP055090624, vol. 7644, Mar. 19, 2010, p. 76441X-76441X-4.
San Diego Plastics, “Celuka Procedure,” website: www.sdplastics.com/celukaprocess.html, undated, accessed Dec. 11, 2008, 1 pg.
Scott Gibson, Wood Substitutes Cost More but Promise Less Maintenance, Professional Deck Builder Online/Hanldy Wood, www.deckmagazine.com, Oct. 17, 2008.
Sotayo et al., “Carpet recycling: A review of recycled carpets for structural composites,” Engineering Department, Lancaster University, Lancaster, UK, Mar. 9, 2015.
Techwoodn decking, Technical sheet, downloaded on Sep. 17, 2013 from http://www.google.com/url?sa=t&rct=j&q=&esrc=s&frm=1&source=web&cd=1&cad=rja&ved=0CCkQFjAA&url=http%3A%2F%2Fwww.techwoodn.com%2Fdata%2Fshwh%2F110222%2F110222010854tajktw.pdf&ei=wnw4UsKyLJWj4APC20DQAw&usg=AFQjCNFIXJ5CdkRTOyPz-12A3D8cTEeTyQ, 6 pages.
Tieq Li and Ning Yan, lonomer as a multi-functional ingredient for value-added wood-plastic composites, Faculty of Forestry, University of Toronto.
Tieqi Li and Ning Yan, Mechanical properties of wood flour/HDPE/Ionomer composites, Faculty of Forestry, University of Toronto, Toronto Ontario Canada, Composites Part A: Applied Science and Manufacturing, vol. 38, Issue 1, Jan. 2007, pp. 1-12.
Wisegeek, “What are Foam Extrusions?,” website: www.wisegeek.com/what-are-foam-extrusions.htm, 2003-2008, accessed Dec. 11, 2008, 2 pges.
Related Publications (1)
Number Date Country
20230182435 A1 Jun 2023 US
Provisional Applications (1)
Number Date Country
63115318 Nov 2020 US
Continuation in Parts (3)
Number Date Country
Parent PCT/US2021/059863 Nov 2021 WO
Child 18164893 US
Parent 17216858 Mar 2021 US
Child PCT/US2021/059863 US
Parent 17216858 Mar 2021 US
Child 18164893 US