阅读说明：本技术 复合结构 (Composite structure ) 是由 M·英格尔 J·吉尔梅斯 于 2019-10-01 设计创作，主要内容包括：一种复合结构(10),其包括纤维注塑部分(14)；插入材料(16)；和任选的外层(12),其中纤维注塑部分(14)至少部分地围绕插入材料(16)。本教导还考虑了形成复合结构(10)的方法,其包括将插入材料(16)定位到模具中,并通过纤维注塑工艺或吹塑工艺将纤维注入到模具中。(A composite structure (10) comprising a fiber injection molded portion (14); an insert material (16); and an optional outer layer (12), wherein the fiber injection molded portion (14) at least partially surrounds the insert material (16). The present teachings also contemplate a method of forming a composite structure (10) that includes positioning an insert material (16) into a mold and injecting fibers into the mold via a fiber injection molding process or a blow molding process.)

1. A composite structure, comprising:

a. a fiber injection molding part; and

b. an insertion material;

wherein the fiber injection molded portion at least partially surrounds the insert material.

2. The composite structure of claim 1, wherein the insert material comprises one or more vertically-laid plies.

3. The composite structure as defined in any one of the preceding claims wherein the insert material is a polyamide-based nonwoven material.

4. The composite structure as defined in any one of the preceding claims, wherein the insert material comprises a three-dimensional mat having an open structure.

5. The composite structure of claim 4, wherein the open structure allows fibers from a fiber injection molding process to enter and surround the insert material.

6. The composite structure as defined in any one of the preceding claims, wherein the insert material comprises a foam material.

7. The composite structure of any of the preceding claims, wherein the insert material comprises a heat-activatable and/or expandable material.

8. The composite structure as claimed in any preceding claim, wherein the composite structure comprises a plurality of layers forming the insert material.

9. The composite structure as claimed in any preceding claim, wherein the insert material is removable and/or interchangeable.

10. The composite structure of any of the preceding claims, wherein the composite structure further comprises an outer layer.

11. The composite structure of claim 10, wherein the outer layer is a fire retardant layer.

12. The composite structure of any of the preceding claims, wherein the composite structure further comprises one or more brackets, fasteners, or structural reinforcements.

13. The composite structure of any of the preceding claims, wherein the composite structure is free of added adhesive.

14. The composite structure as claimed in any preceding claim, wherein the composite structure comprises a plurality of injection moulded portions of fibres having different fibre composition and/or different density.

15. The composite structure of any of the preceding claims, wherein the fibers of the fiber injection molded portion comprise inorganic fibers.

16. The composite structure of claim 15, wherein the inorganic fibers are ceramic fibers and/or silica-based fibers.

17. A composite structure as claimed in any preceding claim, wherein the composite structure is a cushion for a seat.

18. The composite structure of claim 17, wherein the seat is in a transportation vehicle.

19. A method of forming the composite structure of any of the preceding claims, comprising:

a. positioning the insert material into a mold;

b. the fibers are injected into the mold by a fiber injection molding process or a blow molding process.

20. The method of claim 19, further comprising positioning an outer layer into the mold prior to injecting the fibers.

21. A method according to claim 19 or 20, wherein the injecting step comprises injecting different fibres in different regions of the mould to produce regions of different density or composition.

22. The method of any one of claims 19 to 21, wherein the method comprises forming the interposer material by a lay-up (e.g. vertical lay-up) process.

23. The method of any one of claims 19 to 22, wherein the method comprises incorporating one or more fasteners, brackets or structural reinforcements into the composite structure.

Technical Field

The present teachings relate generally to fiber composites and, more particularly, to fiber composites formed at least in part by a blow molding process with integrated technology materials or components.

Background

The industry is seeking new ways to provide structural properties, cushioning, insulation or sound absorption while still having good flame and smoke resistance and physical strength. For example in buildings, vehicles or aircraft, it is important that the materials used meet fire and flammability standards. Fire and flammability standards are important in establishing building codes, insurance requirements, and personnel safety in buildings or vehicles. The government also regulates the materials used in these buildings, vehicles and aircraft. For example, the federal aviation administration requires that interior components such as passenger seating materials, cabinets, interior side wall panels, interior ceilings, partitions, and certain exposed surfaces meet certain flammability standards. The amount of smoke generated by the material after exposure to a flame is also important.

For example, in applications such as seating or mattresses, it is important to maintain a suitable thickness and stiffness even after repeated use, while still being comfortable for the user. It is also desirable that the seat or cushion be lightweight to facilitate assembly and reduce the weight of the vehicle.

Thus, there remains a need for a material or layer thereof that is relatively high in temperature resistance (e.g., up to about 1150 ℃) that is also capable of withstanding processing without degradation or cracking. There remains a need for materials that meet required flammability, smoke and/or toxicity standards for use in, for example, vehicles, aircraft or buildings. There is also a need for materials that are safe and/or easier to handle (e.g., do not require certain protective equipment, do not worry about glass contamination in the skin, eyes, and lungs, or both). There remains a need for materials that provide thermoacoustic insulation. It is also desirable to provide spacer materials having lower (i.e., equal or better) thermal conductivities to provide thermal isolation benefits. It may also be desirable to provide an isolator that is more easily adjusted or modified (e.g., during the manufacturing process) to provide desired thermal isolation characteristics. It may therefore also be desirable to provide an isolation material with a greater freedom of adjustment. It may also be desirable to provide materials that are easily shaped to form structures that can fit within a desired or expected space. It may be desirable for the material to be flexible so that the material can bend or conform around corners and bend in the area into which the material is to be installed. It is also desirable that the material be easier to install and that the chance of delamination of the material due to stress points in the bending zone be reduced. Furthermore, it may be desirable to provide a structure that is capable of providing acoustic properties (e.g., for sound absorption) to improve the overall noise level of a vehicle or aircraft. It may also be desirable to provide materials that dry faster or do not retain moisture, thereby reducing or preventing the development of mold or mildew within the material and reducing or preventing delamination of the adhesive. It may also be desirable to provide materials that do not degrade over time, thereby extending the life of the material (e.g., as compared to fiberglass). It may also be desirable to provide a flexible material, a lighter weight material, a material made of a less toxic or non-toxic material, a moldable material, or a combination thereof.

Disclosure of Invention

The present teachings address one or more of the above needs by providing improved apparatus and methods as described herein. The present teachings contemplate composite structures that include a fiber injection molded portion and an insert material. The fiber injection molded portion may at least partially surround the insert material. The insert material may include one or more vertically laid layers (vertically laid layers), a polyamide-based nonwoven material, a three-dimensional mat having an open structure, a foam material, a heat-activatable and/or expandable material, or a combination thereof. The open or porous structure of the insert may allow fibers from the fiber injection molding process to enter and surround the insert material. The composite structure may include a plurality of layers forming an interposer material. The layers may be the same or different. The composite structure may further comprise an outer layer. The outer layer may be a fire retardant (fireblocker) layer. The composite structure may include one or more brackets, fasteners, or structural reinforcements. The composite structure may be free of added adhesive (e.g., where the fiber injection molding process sufficiently adheres the components of the structure to one another without the need for additional adhesive). The composite structure may include a plurality of fiber injection molded parts having different fiber compositions and/or different densities. The fibers of the fiber injection molded part may include inorganic fibers. The inorganic fibers may include ceramic fibers and/or silica-based fibers. The composite structure may be a cushion for a seat. The seat may be in a transport vehicle.

The present teachings also contemplate a method of forming a composite structure that includes positioning an insert material into a mold; and injecting the fiber into the mold through a fiber injection molding process or a blow molding process. The method may further comprise positioning the outer layer into a mold prior to injecting the fibers. The injecting step may include injecting different fibers in different regions of the mold to create regions having different densities or compositions. The method may further include forming the interposer material by a lay-up (e.g., vertical lay-up) process. The method may include incorporating one or more fasteners, brackets, or structural reinforcements into the composite structure.

Drawings

FIG. 1A is a cross-sectional view of an exemplary composite structure according to the present teachings.

FIG. 1B is an enlarged view of a portion of the composite structure of FIG. 1A.

FIG. 2A is a cross-sectional view of an exemplary composite structure according to the present teachings.

Fig. 2B is an enlarged view of a portion of the composite structure of fig. 2A.

FIG. 3 is a cross-sectional view of an exemplary composite structure according to the present teachings.

FIG. 4 is an exemplary seat cushion according to the present teachings.

FIG. 5 is an exemplary seat cushion according to the present teachings.

Detailed Description

The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the teachings, their principles, and their practical application. Those skilled in the art may modify and apply the present teachings in numerous forms as may be most suitable for the requirements of a particular use. Accordingly, the specific embodiments of the present teachings as set forth are not intended to be exhaustive or limiting of the present teachings. The scope of the present teachings should, therefore, be determined not with reference to the description herein, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the appended claims, which are also hereby incorporated by reference into this written description.

Cushioning, insulation, structural or sound absorbing materials (e.g., composite structures) may have a wide range of applications, such as in aerospace applications, automotive applications, generator set engine rooms, commercial vehicle engines, cab areas, construction equipment, agricultural equipment, architectural applications, flooring, floor underlayment (flooring underlayments), and even heating, ventilation and air conditioning (HVAC) applications. These materials are useful in mechanical and device insulation, motor vehicle insulation, household appliance insulation, dishwashers, and commercial wall and ceiling panels. The insulation material may be used, for example, in the engine compartment of a vehicle, on the interior and/or exterior dashboard, or under a carpet in the passenger compartment. These materials may also provide other benefits such as sound absorption, compression resilience, stiffness, structural properties, temperature or flame resistance, etc. The insulation material may also be used as a sound damping material in an aircraft or vehicle to dampen sound originating from outside the cabin and propagating towards the inside of the cabin. The materials as disclosed herein may be used in an aircraft, such as primary insulation, or in an interior component of an aircraft, such as a seat cushion. The materials as described herein may be used for cushioning in aerospace, automotive, commercial vehicles, trains, and other transportation methods. These materials may also be used in flotation devices, or may have buoyancy properties (e.g., in the case of vehicles or aircraft in close proximity to water). The materials as disclosed herein may also be used for filtration, such as hot gas filtration.

The present teachings contemplate the use of composite structures that are flame retardant, smoke resistant, safe, and/or easier to handle (e.g., without the need for certain items of protective equipment), resilient, compression resistant, buoyant, or any combination of these properties. The composite structure may be used in cushioning applications including seating. The composite structure may be used for sound and/or thermal insulation, for providing compression resistance, for providing a material that reduces or eliminates the possibility of mold or mildew therein. The composite structure may provide long-term structural stability for long-term acoustic and/or thermal performance. The composite structure may provide long-term resistance to humid environments, or may be able to withstand temperature and humidity variations and fluctuations.

The present teachings contemplate composite structures that meet flame or flammability standards. The composite structure may be located adjacent a high temperature radiant heat source or an open flame source. The composite structure may be shaped to fit within a desired location. The composite structure may be moldable or otherwise shaped. The composite structure may allow for in situ molding of mechanical features or for incorporation of fastening or assembly mechanisms. The composite structure may include multiple layers or components (e.g., higher density materials, lay-up materials, porous flexible sheets, fabrics, scrims (scrims), facings, films, meshes, adhesives, etc. the layers may be attached to one another by one or more lamination processes, one or more adhesives, one or more molding processes, or combinations thereof.

The present teachings contemplate a composite structure or composite material that includes a fiber injection molded portion and one or more insert materials. The composite structure may also include one or more facing layers or other functional layers, which may be referred to herein as outer layers. The composite structure allows for the introduction and integration of various technical materials or components into a fiber-based blow molding process. The composite structure and associated methods of forming the material may be tailored to provide desired characteristics, such as physical or chemical characteristics. The resulting three-dimensional structure may have multi-functional properties that address a variety of issues. For example, the composite structure may provide compression resistance while also providing cushioning, high temperature resistance, flame or flame retardancy, or a combination of these properties.

The composite structure may include one or more fiber injection molded parts. Although referred to herein as a fiber injection molded part, this also includes parts formed by one or more blow molding processes. This may allow for variation in density in different regions of the composite structure when using fiber injection or blow molding processes. These processes may also allow for the creation of composite structures having a desired shape.

The material fibers that make up the injection molded portion of the fibers may be selected based on a number of considerations, such as temperature resistance, desired thermal conductivity, stiffness, resiliency, cost, desired long term humidity exposure resistance, and the like. The material forming the injection molded portion of the fibers may be a blend of fibers. Any fiber selected for the fiber injection molded part can be blow molded and/or shaped to form a three-dimensional structure. Fibers of different lengths and/or deniers may be combined to provide desired properties, such as insulation and/or acoustic properties. Depending on the application; the temperature to which the composite structure is to be exposed; desired compression and/or resilience resistance; the desired isolation characteristics; desired acoustic properties; the type, size, and/or characteristics of the fibrous material (e.g., density, porosity, desired airflow resistance, thickness, size, shape, etc. of the fibrous injection molded part and/or any other layers of the composite structure); or any combination thereof, the fiber lengths may vary. The addition of shorter fibers alone or in combination with longer fibers may provide more effective fiber filling, which may allow for easier control of pore size in order to obtain desired properties (e.g., acoustic and/or insulating properties).

At least some of the fibers forming the molded portion of fibers may be of inorganic material. The inorganic material may be any material capable of withstanding a temperature of about 250 ℃ or greater, about 500 ℃ or greater, about 750 ℃ or greater, about 1000 ℃ or greater. The inorganic material may be a material capable of withstanding temperatures up to about 1200 ℃ (e.g., up to about 1150 ℃). The fibers of the fiber injection molded part may comprise a combination of fibers having different melting points. For example, fibers having a melting temperature of about 900 ℃ may be combined with fibers having a higher melting temperature (e.g., about 1150 ℃). When these fibers are heated above the melting temperature of the lower melting temperature fibers (e.g., above 900 ℃), the lower melting temperature fibers can melt and bond with the higher temperature fibers. The inorganic fibers may have a Limiting Oxygen Index (LOI) indicating low flame or smoke, for example according to ASTM D2836 or ISO 4589-2. The LOI of the inorganic fibers may be higher than the LOI of standard binder fibers. For example, the LOI of a standard PET bicomponent fiber can be from about 20 to about 23. Thus, the LOI of the inorganic fibers can be about 23 or greater. The inorganic fibers can have an LOI of about 25 or greater. The inorganic fibers may be ofAbout 60 weight percent or more, about 70 weight percent or more, about 80 weight percent or more, or about 90 weight percent or more is present in the fiber injection molded part. The inorganic fibers may be present in the fiber injection molded part in an amount of about 100 weight percent or less. The inorganic fibers may be selected based on their desired stiffness. The inorganic fibers may be crimped or uncrimped. Non-crimped organic fibers may be used when fibers with a greater flexural modulus (or higher stiffness) are desired. The modulus of the inorganic fibers may determine the size of the rings when forming the matrix. Crimped fibers may be used where it is desired that the fibers be more easily bent. The inorganic fibers may be ceramic fibers, silica-based fibers, glass fibers, mineral-based fibers, or combinations thereof. The ceramic and/or silica-based fibers may be formed from polysilicic acid (e.g., sialool or Sialoxid) or derivatives thereof. For example, the inorganic fibers may be based on amorphous alumina containing polysilicic acid. The fibers may include about 99% or less, about 95% or less, or about 92% or less of SiO₂. The remainder may comprise-OH (hydroxyl) and/or alumina groups. Siloxanes, silanes, and/or silanols can be added to or reacted into the fiber injection molding part to impart additional functionality. These modifiers may include a carbonaceous component.

The inorganic fibers of the fiber injection molded part can have an average linear mass density of about 0.4 denier or greater, about 0.6 denier or greater, or about 0.8 denier or greater. The inorganic fibers of the fiber injection molded part can have an average linear mass density of about 2.0 denier or less, about 1.7 denier or less, or about 1.5 denier or less. Other fibers of the fiber injection molded part (e.g., bicomponent binders) can have an average linear mass density of about 1 denier or greater, about 1.5 denier or greater, or about 2 denier or greater. Other fibers of the fiber injection molded portion (e.g., bicomponent binders) can have a linear mass density of about 20 denier or less, about 17 denier or less, or about 15 denier or less. The inorganic fibers of the fiber injection molded part may have a length of about 20mm or more, about 27mm or more, or about 34mm or more. The inorganic fibers of the fiber injection molded part may have a length of about 200mm or less, about 150mm or less, or about 130mm or less. Combinations of fibers having different lengths may be used. For example, a combination of lengths of about 67mm and about 100mm may be used. Varying the length may be advantageous in some cases because there may be natural cohesion of the fibers due to differences in length of the fibers, the type of fibers, or both. The blend of fibers of the fiber injection molded section can have an average denier size of about 4 denier or greater, about 5 denier or greater, or about 6 denier or greater. The blend of fibers of the fiber injection molded section can have an average denier size of about 10 denier or less, about 8 denier or less, or about 7 denier or less. For example, the average denier size may be about 6.9 denier.

The fiber injection molded part may include fibers blended with inorganic fibers. For example, the fiber injection molded part may also include natural fibers or synthetic fibers. Suitable natural fibers may include cotton fibers, jute fibers, wool fibers, cellulose fibers, glass fibers, silica-based fibers, and ceramic fibers. Suitable synthetic fibers may include polyester, polypropylene, polyethylene, nylon, aramid, imide, acrylate fibers, or combinations thereof. The fiber injection molded part material may comprise polyester fibers such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and copolyester/polyester (CoPET/PET) binder bicomponent fibers. The fibers may include Polyacrylonitrile (PAN), oxidized polyacrylonitrile (Ox-PAN, OPAN, or PANOX), olefins, polyamides, Polyetherketones (PEK), Polyetheretherketones (PEEK), Polyethersulfones (PES), or other polymeric fibers. The melting and/or softening temperature of the fibers may be selected.

The fibers may be 100% virgin fibers, or may contain fibers regenerated from post-consumer waste (e.g., up to about 90% fibers regenerated from post-consumer waste, or even up to 100% fibers regenerated from post-consumer waste). The fibers may have or may provide improved thermal insulation properties. The fibers may have a relatively low thermal conductivity. The fibers may have a non-circular or non-cylindrical geometry to alter convective flow around the fibers, thereby reducing convective heat transfer effects within the three-dimensional structure. The fiber injection molded part may include or contain an engineered aerogel structure to impart additional thermal insulation benefits. The fiber injection molded part may include or be enriched with a pyrolyzed organic bamboo additive. Fibers blended with inorganic fibers may be sacrificed after exposure to certain temperatures. For example, if the injection molded portion of the fiber is exposed to temperatures of about 250 ℃ or higher, the fiber may volatilize away, leaving only the inorganic fibers.

The fibers, or at least a portion of the fibers, may have high infrared reflectivity or low emissivity. At least some of the fibers may be metallized to provide Infrared (IR) radiant heat reflection. The fibers may be metallized in order to provide heat reflective properties to the molded fiber portion and/or to protect the molded fiber portion. For example, the fibers may be aluminized. The fibers themselves may be infrared reflective (e.g., such that an additional metallization or aluminizing step may not be required). The metallization or aluminization process may be performed by depositing metal atoms onto the fibers. As an example, aluminization may be achieved by applying an atomic layer of aluminum to the surface of the fiber. The metallization may be performed before any additional layers are applied to the fiber injection molded part. In addition to or instead of having metallized fibers within the fiber injection molded portion, it is contemplated that other layers of the composite structure may include metallized fibers.

The metallization may provide a desired reflectivity or emissivity. The metallized fibers may be about 50% IR reflective or higher, about 65% IR reflective or higher, or about 80% IR reflective or higher. The metallized fibers may be about 100% IR reflective or less, about 99% IR reflective or less, or about 98% IR reflective or less. For example, the emissivity may range from about 0.01 or greater or about 0.20 or less, or 99% to about 80% IR reflective, respectively. Emissivity may change over time as oil, dust, degradation, etc. may affect the fibers in the application.

Other coatings may be applied to the fibers (whether metallized or not) to achieve the desired characteristics. Oleophobic and/or hydrophobic treatments may be added. Flame retardants may be added. A corrosion-resistant coating may be applied to the metallized fibers to reduce or prevent oxidation and/or loss of reflectivity of the metal (e.g., aluminum). IR reflective coatings that are not based on metallization techniques may be added.

The fiber injection molded part may include additional fibers, such as staple fibers, which may be blended, for example, with inorganic fibers. Staple fibers such as binder fibers (e.g., alone or in combination with other fibers) may be used. For example, some or all of the fibers (particularly the binding fibers) can be of a powder-like consistency (e.g., fiber lengths of about 2 millimeters to about 3 millimeters or even less, such as about 200 microns or more or about 500 microns or more).

The fiber injection molded part (or any other layer of the composite structure) may include a binder or binding fibers. The binder may be present in the fiber injection molded portion in an amount of about 40 weight percent or less, about 30 weight percent or less, about 25 weight percent or less, or about 15 weight percent or less. The injection molded portion of the fibers may be substantially free of binder. The injection molded portion of the fiber may be completely free of binder. Although the binder is referred to herein as fibers, it is contemplated that it may be generally powder-like, spherical, or have any shape that can be received within interstitial spaces between other fibers (e.g., inorganic fibers) and that can bind the injection molded portions of the fibers together. The binder may have a softening and/or melting temperature of about 180 ℃ or greater, about 200 ℃ or greater, about 225 ℃ or greater, about 230 ℃ or greater, or even about 250 ℃ or greater. The fibers may be a high temperature thermoplastic material. The fibers may include one or more of the following: polyamideimide (PAI); high Performance Polyamides (HPPA), such as nylon; polyimide (PI); polyketone; a polysulfone derivative; polycyclohexanedimethylene terephthalate (PCT); a fluoropolymer; polyetherimide (PEI); polybenzimidazole (PBI); polyethylene terephthalate (PET); polybutylene terephthalate (PBT); polyphenylene sulfide; syndiotactic polystyrene; polyetheretherketone (PEEK); polyphenylene Sulfide (PPS), Polyetherimide (PEI); and so on. The fiber injection molded part may include polyacrylate and/or epoxy (e.g., thermoset and/or thermoplastic type) fibers. The fiber injection molded part may include a multiple binder system. The fiber injection molded part may include one or more sacrificial binder materials and/or binder materials having a melting temperature lower than the inorganic fibers.

The fiber injection molded part (or any other layer of the composite structure) may comprise a plurality of bicomponent fibers. The bicomponent fibers may act as a binder within the injection molded portion of the fibers. The bicomponent fibers may be thermoplastic low melt bicomponent fibers. The bicomponent fibers may have a lower melting temperature than other fibers in the mixture (e.g., a lower melting temperature than the inorganic fibers, ordinary staple fibers, or both). The bicomponent fibers may be of the flame retardant type (e.g., formed from or including a flame retardant polyester). Bicomponent fibers can enable the fiber injection molded part to be molded and/or fused into a network in space such that the material can have a structure and a body, and can be processed, laminated, fabricated, installed as cut or molded parts, and the like, to provide insulation properties, sound absorption, structural properties, flame retardant properties, smoke barrier properties, low toxicity, or combinations thereof. The bicomponent fiber may include a core material and a sheath material surrounding the core material. The sheath material may have a lower melting point than the core material. The web of fibrous material may be formed at least in part by heating the material to a temperature that softens the sheath material of at least some of the bicomponent fibers. The temperature at which the molded portion of the fiber (or other layer of the composite structure) is heated to soften the sheath material of the bicomponent fiber may depend on the physical properties of the sheath material. Some fibers or portions of the fibers (e.g., sheaths) may be crystalline or partially crystalline. Some fibers or portions of the fibers (e.g., sheaths) may be amorphous.

For example, for a polyethylene or polypropylene sheath, the temperature may be about 140 degrees celsius or greater, about 150 degrees celsius or greater, or about 160 degrees celsius or greater. The temperature may be about 220 degrees celsius or less, about 210 degrees celsius or less, or about 200 degrees celsius or less. For example, a bicomponent fiber having a polyethylene terephthalate (PET) sheath or a polybutylene terephthalate (PBT) sheath can melt at about 180 degrees celsius to about 240 degrees celsius (e.g., about 230 degrees celsius). The bicomponent fibers may be formed from short lengths cut from extruded bicomponent fibers. The bicomponent fibers can have a sheath-to-core ratio (in cross-sectional area) of about 15% or greater, about 20% or greater, or about 25% or greater. The bicomponent fibers can have a sheath-to-core ratio of about 50% or less, about 40% or less, or about 35% or less.

The fibers of the fiber injection molded part may be blended or otherwise combined with suitable additives such as, but not limited to, other forms of recycled waste, virgin (non-recycled) materials, binders, fillers (e.g., mineral fillers), adhesives, powders, thermosetting resins, colorants, flame retardants, longer staple fibers, and the like. Any, a portion, or all of the fibers used in the matrix may be of a low flame and/or smoke emission type (e.g., to meet flame and smoke standards for transportation). Powders or liquids can be incorporated into the fiber injection molded part which impart additional properties such as bonding properties, flame/smoke barrier foaming, expansion of the polymer acting under heat, induction or radiation, which improves acoustical, physical, thermal and fire performance.

The fiber injection molded part may comprise other materials instead of or in addition to the other fibers described herein. For example, foam chips (e.g., polyurethane foam chips) or pellets may be used. Expandable or heat-activatable materials are also contemplated.

The composite structure may include one or more intervening materials or layers (which are referred to herein as inserts, even when referring to multiple layers or materials). The inserts may impart additional properties to the composite, such as increased stiffness, compression resistance, resilience, reinforcement, and the like. The insert may include one or more lay-up layers (e.g., vertical lay-up layers), three-dimensional mats having an open structure, spacer fabrics, foams, heat-activatable and/or expandable materials, antimicrobial materials, or layers having open spaces (e.g., for providing flotation capability). The insert may include treatments such as with fire retardant or flame retardant additives to improve performance when exposed to fire, smoke, or toxicity.

The insert may be formed from any of the fibers in any combination as described herein for the fiber injection molded part. The fibers may be formed into a nonwoven web using a nonwoven process including, for example, fiber blending, carding, laying, air laying (air laying), mechanical forming (mechanical formation), or a combination thereof. By these processes, the fibers may be oriented in a substantially vertical or near vertical direction (e.g., in a direction substantially perpendicular to the longitudinal axis of the insert). The fibers may be opened and blended using conventional techniques. The resulting structure formed may be a lofty insert (lofted insert). The lofty insert may be engineered to have optimal weight, thickness, physical properties, thermal conductivity, insulation properties, sound absorption, or combinations thereof.

The insert may be adjusted based on the desired characteristics. For example, the insert may be adjusted to provide desired temperature resistance, weight, thickness, compression resistance, or other physical properties. The insert may be adjusted to provide the desired heat resistance. The insert may be adjusted to provide the desired thermal conductivity. The insert may be adjusted to provide desired characteristics such as flame or fire retardancy, smoke resistance, reduced toxicity, and the like. The insert may be formed from non-woven fibers. The insert may thus be a non-woven structure. The insert may be a fluffy material. The fibers forming the insert may be a unique mixture of vertically or near vertically oriented fibers. The fibers forming the insert may be a unique mixture of fibers having a generally Z-shape, C-shape, or S-shape, which may be formed by compressing fibers having a perpendicular or near perpendicular orientation. The fibers may be in a three-dimensional loop structure. The ring may extend through the thickness direction from one surface of the base to the opposite surface of the base. The fibers forming the insert may have an orientation of about ± 60 degrees from vertical, about ± 50 degrees from vertical, or about ± 45 degrees from vertical. A vertical direction may be understood as relative to a plane extending substantially transversely from the longitudinal axis of the composite structure (e.g., in the thickness direction). Thus, perpendicular fiber orientation means that the fibers are substantially perpendicular to the length of the composite structure (e.g., fibers extending in the thickness direction). The fibers forming the insert may be in a generally horizontal orientation (e.g., fibers extending in a length and/or width direction). The composite structure may include one or more intervening layers. For example, the composite structure may include an insert having fibers oriented substantially vertically and another insert having fibers oriented substantially horizontally (e.g., via a cross-lay or air-lay process).

For example, the insert may have a facing layer on the side of the insert facing the heat source. The insert may have a finishing layer on a side of the insert facing away from the heat source. The insert may be sandwiched between two (or more) facing layers. A layer (e.g., a layer having a different composition) may be sandwiched between two layers of the insert. The facing layer or intermediate layer may be substantially coextensive with the sides of the insert. The facing layer or intermediate layer may alternatively cover or be attached to only a portion of the sides of the insert. The facing or intermediate layer may comprise a solid film, a perforated film, a solid foil, a perforated foil, a woven or nonwoven scrim, or other material. The facing or intermediate layer may be made of polybutylene terephthalate (PBT); polyethylene terephthalate (PET), polypropylene (PP), cellulosic materials, or combinations thereof. The facing or intermediate layer may be formed from a nonwoven material, a woven material, or a combination thereof. The facing or intermediate layer may comprise silica-based fibers, polysilicic fibers, minerals, ceramics, glass fibers, aramid, or combinations thereof. The film may include Polyetheretherketone (PEEK), Polyethersulfone (PES), Polyetherketone (PEK), urethane (urethane), polyimide, or a combination thereof. Any of the materials described herein for forming the fiber injection molded part can be used to form one or more of the facings or interlayers as described herein. The fibers forming the facing layer (e.g., if formed as a scrim) or the surface itself may be metallized to impart infrared reflectivity, thereby providing improved thermal insulation values for the entire composite structure. Any of the layers may have a heat resistance capable of withstanding the temperatures to which the layers will be exposed.

For example, the present teachings contemplate an intervening layer sandwiched between two layers (e.g., a lay-up intervening layer). One layer may be a film layer (e.g., a PEEK film or any other material as described herein for possible fiber materials). On the opposite side of the insert layer may be an air flow resistance layer. This layer may be hydrophobic. This layer may be a spunbond (S) material, a Spunbond and Meltblown (SM) material, or a spunbond + meltblown + Spunbond (SMs) nonwoven material. Such a structure may provide a combination of properties including a built-in pressure release mechanism that enables the material to adapt to the environment as pressure changes. This may be particularly useful in insulation blankets of aircraft, as the pressure in the cabin may vary.

Inserts may include, for example, as disclosed in U.S. publication nos. 2004/0053003 (relating to thermoformable sheets), 2006/0090958 (relating to thermoformable products), 2011/0139543 (relating to acoustic materials), 2011/0293911 (relating to short fiber nonwovens), 2012/0024626 (relating to composite acoustical absorbers), 2015/0330001 (relating to moldable short fiber nonwovens), 2018/0126691 (relating to multi-layer nonwovens), and 2018/0047380 (relating to nonwovens with IR reflective fibers); international applications No. PCT/US2018/041221 and PCT/US2018/042658 (relating to nonwoven structures for high temperature applications); and any of the materials taught or described in U.S. application No. 15/988,256 (related to insulation); all of which are incorporated by reference in their entirety.

The insert may comprise or be formed from an open three-dimensional structure or foam. Such an open structure may allow fibers to enter and surround the structure to build the final shape of the composite structure. This can reduce mass while improving resilience, comfort, impact performance, and the like. Such open structures may be foams, woven spacer fabrics, three-dimensional woven materials, three-dimensional mats (woven or non-woven), and the like. Exemplary three-dimensional pads include a passable Low&Obtained by BonarOr othersSolutions products. An open structure or an insert with open spaces may also provide or improve buoyancy or flotation of the composite structure.

The insert may comprise one or more expandable materials. For example, the insert may include a heat activated expandable material (e.g., in pellet form, adhesive form, tape form). The expandable material may increase stiffness, compression resilience/recovery, or both. The expandable material may provide or enhance the buoyancy of the composite structure. It is contemplated that the insert may be baked and expanded prior to blow molding. It is also contemplated that the insert may be inflated after or during the blow molding or fiber injection molding process.

The insert may be secured within the composite structure during the molding process. The inserts may be removable, which may extend the life of the composite structure or its components. For example, if the insert has started to wear, the insert may be removed and another insert may be provided to replace it.

The composite structure may include one or more outer layers. The outer layer may cover a portion of other components of the composite structure. The outer layer may partially enclose a portion of other components of the composite structure. The outer layer may completely enclose a portion of the other components of the composite structure. The outer layer may provide additional protection to the composite structure, for example by providing additional flame resistance, puncture resistance, compression resistance. The outer layer may act as a moisture or chemical barrier. The outer layer may act as a separator. The outer layer may act as a cover. The outer layer may be removable. The outer layer may be washable or washable (e.g., via stain treatment, wiping with a cloth, hand washing, by a conventional household or industrial washing machine, etc.). In the event that an outer layer is worn, broken, damaged, or otherwise needs replacement, another outer layer may be replaced. The outer layer may be, for example, a fabric, a woven layer, a fire retardant textile, or a nonwoven material. The outer layer may be any facing layer or scrim as described herein. The outer layer may be laid within the mold during the fiber injection or blow molding process. The outer layer may be sufficiently porous to allow blowing of the fibers inside, on top of, or around the fabric. The outer layer may be formed of a material that repels moisture. The outer layer may be formed of a material that wicks moisture away. The outer layer may be a breathable material. The outer layer may have antimicrobial properties. The outer layer may include one or more features that at least temporarily hold it in place. For example, the outer layer may include one or more fasteners, zippers, hook and loop fasteners, and the like. The outer layer may be secured via one or more adhesives.

The composite structure may include additional features such as mechanical inserts, braces (braces), structural reinforcements, fasteners, braces, antimicrobial diffusers, and the like. These features may be secured to the composite structure after the composite structure is formed. These features may be integrated into a composite structure. For example, additional features may be positioned within the mold prior to the blow molding or fiber injection molding process to incorporate the features into the final structure. The fastening system can be placed in a mold and fiber injection molding can be performed. This fastening system may allow the seat cushion to be fitted directly to the seat frame in a dedicated position, for example. It is also possible to fix the seat cover directly and immediately to the seat cushion.

The configuration of the layers within the composite structure may be customized based on the desired characteristics. One or more inserts may be part of a composite structure. One or more of the inserts may be removable from the composite structure. One or more inserts may be swapped with other inserts (e.g., if different characteristics are desired, if the insert has been damaged or deformed, or if the insert has reached its operational life limit). The composite structure may be free of an outer layer. The composite structure may include one or more outer layers. The outer layer may enclose the fiber injection molded part and the insert material. The fiber injection molded portion may at least partially surround the insert material. The fiber injection molded portion may completely surround the insert material. The outer layer may directly contact the insert. The outer layer may directly contact the injection molded portion of the fiber. The density or composition of the molded portions of the fibers may vary in certain areas within the composite structure. The density or composition of the inserts may vary over certain areas within the composite structure. The fiber injection molded part may be located between two or more insert layers. Two or more intervening layers may be in direct contact with each other. The fiber injection molded portion may be located on top of the outer layer (e.g., facing away from the composite structure).

The present teachings also include methods of making layers of the composite structure and methods of making the composite structure as a whole. One or more inserts may be formed at least in part by a carding process. The carding process can separate the tufted material into individual fibers. During the carding process, the fibers may be aligned with one another in a substantially parallel orientation, and a carding machine may be used to produce a web of fibers.

The carded web may be subjected to a layup process to produce a lofty insert. The carded web can be rotary, cross-plied, or vertically plied to form a bulky or lofty nonwoven material. Carded webs may be vertically laid, for example, according to processes such as "Struto" or "vertical lay (V-Lap)". This architecture provides a web having relatively high structural integrity in the thickness direction of the insert, thereby minimizing the likelihood of the web becoming frayed during application or use, and/or providing compression resistance to the composite structure as it is installed and used. The carding and layup process can create a nonwoven fiber layer with good compression resistance through a vertical cross-section (e.g., through the thickness of the material), and can enable the production of lower quality inserts, particularly lower quality inserts that are fluffed to greater thicknesses without adding significant amounts of fiber to the insert. The layup material may have a substantially accordion-like structure. A small amount of hollow conjugate fibers (i.e., in a small percentage) can increase loft and resiliency to improve insulation, sound absorption, or both. This arrangement also provides the ability to obtain a low density web having a relatively low bulk density.

The insert may be formed by an air laid process. Such an air laying process may be used instead of carding and/or laying. In the air-laid process, the fibers are dispersed into a rapidly moving air stream and then the fibers are deposited from a suspended state onto a perforated screen to form a web. The deposition of the fibers may be performed, for example, by means of pressure or vacuum. An airlaid or mechanically formed web can be produced. The web may then be thermally bonded, air bonded, mechanically consolidated, the like, or combinations thereof, to form a cohesive nonwoven insulation material. While the air-laying process may provide a substantially random fiber orientation, there may be some fibers having an orientation substantially in the vertical direction so that resiliency in the thickness direction of the material may be achieved.

The insert may undergo additional processes during its formation. For example, during pleating of substrates, it is contemplated that a laid substrate may be needled horizontally in situ with barbed pusher needles. The fibers (e.g., surface fibers) of the insert may be mechanically entangled to bind the fibers together. This can be done by a rotating tool with a grit-type finish on the top of the head to catch and twist or entangle the fibers while rotating. The fibers (e.g., the surface of the insert) can then be entangled in the machine direction (e.g., through the tops of the peaks of the loops after lay-up). It is contemplated that the heads of the tool may be movable in the x and y directions. The top surface of the insert, the bottom surface of the insert, or both surfaces may be subjected to mechanical entanglement. The entangling may be carried out simultaneously or at separate times. The process may be performed in the absence of binder, in the presence of minimal binder, or in the presence of binder in an amount of about 40% by weight or less of the web content. Mechanical entanglement can be used to hold the insert together, for example, by tying the peaks of the three-dimensional loops together. This process can be performed without compressing the insert. The resulting surface of the insert may have improved tensile strength and stiffness in a perpendicular three-dimensional structure. The ability to tie the top surface to the bottom surface can be affected by the fiber type and length as well as the lay-up structure with integrated vertical three-dimensional loop structures from top to bottom. The mechanical entanglement process may also allow the fabric or finish to be mechanically tied to the top and/or bottom surfaces of the lay-up insert. Instead of or in addition to mechanical entanglement, the surface of the material may be melted to form a skin layer, for example by an IR heating system, a stream of hot air or a laser beam.

The layers of material forming the composite structure may be bonded together to create a finished composite structure. One or more layers may be bonded together by elements present in the layers. For example, the binder fibers in the layers may be used to bind the layers together. The outer layer (i.e., sheath) of the bicomponent fibers in one or more layers may soften and/or melt upon application of heat, which may cause the fibers of the various layers to adhere to each other and/or to the fibers of the other layers. The layers may be attached together by one or more lamination processes. The layers may be combined by operations such as heat sealing, sonic or vibration welding, pressure welding, and the like, or combinations thereof. One or more adhesives may be used to join two or more layers. The binder may be a powder or may be applied, for example, in the form of a tape, a sheet, or as a liquid. The vertical three-dimensional structure may enable a veneer or other layer to be bound to an insert layer (e.g., mechanically, thermally, or with an adhesive). Because the vertical loops are continuous through the thickness of the structure, the fabric or facing may be tied to the top and bottom of the structure. One or more layers may be bonded in situ to the insert. For example, a scrim, with or without an adhesive, may be fed through the laminator, and the insert may be laminated to the scrim. The scrim and insert may then be bonded in situ in a vertical lay-up (V-lap) oven.

The composite structure may be formed by positioning the insert in a mold and performing a fiber injection or blow molding process that injects fibers into the mold. This enables the fibers and the insert material to be joined together. It is also contemplated that fibers may be at least partially integrated into the insert during the fiber injection or blow molding process if the insert has a sufficient pore size, which may provide additional strength to the insert and/or more securely join the insert and the fiber injection molded portion. The outer layer of the composite structure may be secured to the composite structure after the composite structure has been formed. The outer layer may alternatively be positioned within the mold prior to fiber injection or blow molding. After the molding process is performed, the outer layer may become fixed or bonded to the fiber injection molded part, the insert material, or both.

During the blow molding or fiber injection molding process, one or more injection nozzles may be used. The nozzles may be placed in different positions. One or more of the nozzles may be stationary. One or more of the nozzles may be sliding or rotating. The use of multiple nozzles may allow for the creation of regions of different densities or compositions in the fiber injection molding section. This may also allow the mold to be filled to create a composite structure of a desired shape. If necessary, the composite structure or a component thereof (e.g., the outer layer) may be trimmed after the molding process.

The composite structure may comprise one or more layers. The composite structure may include two or more intervening layers. The composite structure may include one or more loft layers, one or more skin layers, one or more facing layers, one or more foils, one or more films, or a combination thereof. The one or more layers may be formed of metal, fibrous material, polymer, or a combination thereof. The skin layer may be formed by applying heat to melt a portion of the layer, the heat being applied in a manner such that only a portion of the layer (e.g., the top surface) melts and then hardens to form a substantially smooth surface. The composite structure may include multiple layers, some or all of which serve different functions or provide different properties to the composite structure (when compared to other layers of the composite structure). The ability to combine layers of materials having different properties may allow for customization of the composite structure based on the application. The additional layer may serve to provide the following: additional isolation properties, protection of an interposer or other layer, infrared reflection properties, conduction properties (or reduced conduction properties), convection properties (or reduced convection properties), structural properties, or combinations thereof. The one or more layers may be secured to each other or to the insert by a molding process, lamination, heat sealing, sonic or vibration welding, pressure welding, or the like, or combinations thereof. The one or more layers can have a temperature resistance greater than or equal to the temperature resistance of the binding fibers. The melting or softening temperature of the one or more layers may be higher than the temperature to which the layers will be exposed when installed in an assembly. One or more of the layers may act as a moisture barrier. The one or more layers may be hydrophobic layers, which may have a certain porosity to allow the composite structure to accommodate pressure changes without bursting. Such layers may be particularly important in applications such as aerospace isolation. One or more of the layers may act as a chemical barrier or as a barrier for keeping dirt, dust, debris, or other unwanted particles or matter away from the item to be isolated. For example, one or more composite structural layers may provide isolation. One or more composite structural layers may include one or more binder materials (e.g., as part of the fibers of the layer or as a separate element in or on the layer) for binding the fibers together, for binding the layers together, or both. It is contemplated that any adhesive may be of the type that can be melted, flowed, bonded, allowed to cool and then cured, or a combination thereof. One or more of the layers or the composite structure as a whole may be free of additional binders when forming the structure. One or more composite structural layers may support the skin layers, other material layers, or both. One or more of the composite structure layers may provide thermal resistance (e.g., if the composite structure is located in a region exposed to high temperatures). One or more composite structural layers may provide stiffness to the composite structure. The additional layers (or a combination of one or more layers and one or more inserts) may provide additional stiffness, structural properties, compression resistance, compression resilience, or a combination thereof. One or more composite structural layers may provide flexibility and/or softness to the composite.

The composite structure or one or more layers thereof (e.g., nonwoven material) may be formed to have a thickness and density selected according to the desired physical, insulative, and air permeability characteristics desired for the finished fibrous layer (and/or the composite structure as a whole). The layers of the composite structure may be of any thickness depending on the application, the location of installation, the shape, the fibers used (and loft of the insert), or other factors. The density of the layers of the composite structure may depend in part on the specific gravity of any additives incorporated into the materials (e.g., nonwoven materials) making up the layers and/or the proportion of the final material made up of the additives. Bulk density is generally a function of the specific gravity of the fibers and the porosity of the material produced by the fibers, which can be considered to represent the packing density of the fibers.

Any fiber or material as discussed herein (particularly with respect to the insert or fiber injection molded part) may also be used to form, or may be included within, any additional layer(s) of the composite structure (e.g., a facing layer and/or scrim layer). For example, an inorganic fiber based paper scrim may be another layer of the structure. Any of the materials described herein can be combined with other materials described herein (e.g., in the same layer or different layers of a composite structure). The layers may be formed of different materials. Some or all of the layers may be formed of the same material, or may include common materials or fibers. The type of materials forming the layers, the order of the layers, the number of layers, the positioning of the layers, the thickness of the layers, or a combination thereof may be selected based on the desired properties of each material (e.g., infrared reflectivity, insulating properties, conductive properties, convective properties, compression resistance, and/or puncture resistance), the insulating properties of the composite structure as a whole, the heat transfer properties of the composite structure as a whole, the desired air flow resistance properties of the composite structure as a whole, the desired weight, density, and/or thickness of the composite structure (e.g., based on the available space in which the fiber composite will be installed), the desired flexibility (or location of controlled flexibility) of the structure, or a combination thereof. The layers may be selected to provide different fiber orientations. The one or more composite structural layers may be any material known to exhibit sound absorption properties, insulation properties, flame retardancy, smoke resistance, or a combination thereof. One or more composite structural layers may be at least partially formed as a web of material (e.g., a fiber web). One or more of the fiber composite layers may be formed of a nonwoven material, such as a staple fiber nonwoven material. One or more of the fiber composite layers may be formed of a woven material. One or more fiber composite layers may be formed by hot-melting the surface of the fiber matrix to form a skin layer. One or more of the layers may be a fabric, a film, a foil, or a combination thereof. The one or more composite structural layers may be a porous bulk absorbent (e.g., a lofty porous bulk absorbent formed by a carding and/or lay-up process). One or more composite structural layers may be formed by air laying. The composite structure (or one or more composite structure layers) may be an engineered 3D structure. From these potential layers, it is clear that there is great flexibility in creating materials that meet the specific needs of the end user, customer, installer, etc.

Turning now to the drawings, FIG. 1A illustrates an exemplary composite 10 according to the present teachings. The exemplary composite 10 includes an outer layer 12, a fiber injection molded portion 14, and an insert 16. As illustrated in fig. 1A, the outer layer 12 encloses the fiber injection molded portion 14, and the fiber injection molded portion 14 encloses the insert 16. The portion enclosed within the box defined by the dashed lines in FIG. 1A is exaggerated in FIG. 1B to illustrate an exemplary configuration of the outer layer 12, the fiber injection molded portion 14, and the insert 16.

Figure 2A illustrates an exemplary composite 10 according to the present teachings. The exemplary composite 10 includes an outer layer 12, a fiber injection molded portion 14, and an insert 16. As illustrated in fig. 2A and 2B, the outer layer 12 surrounds the fiber injection molded portion 14 and the insert 16, but the insert 16 is not completely surrounded by or enclosed within the fiber injection molded portion 14. The portion enclosed within the box defined by the dashed lines in fig. 2A is exaggerated in fig. 2B to illustrate an exemplary configuration of the outer layer 12, the fiber injection molded portion 14, and the insert 16.

Figure 3 illustrates an exemplary composite 10 according to the present teachings. The exemplary composite 10 includes an outer layer 12, a fiber injection molded portion 14, and an insert 16. As illustrated, the outer layer 12 covers only a portion of the fiber injection molded portion 14 and the insert 16, without completely enclosing these layers.

Although fig. 1A-3 illustrate exemplary configurations of layers or components of a composite structure, other configurations are also contemplated. For example, the outer layer may cover more than one side and less than the entire composite. For clarity, the figures show layers or components as rectangular, but any component may take any shape. The order of the components may be different or additional layers or components may be added. For example, the insert may not be completely enclosed by another component or combination of components. The composite may be free of an outer layer. The insert may comprise a plurality of layers. The composite may include multiple inserts, multiple fiber injection molded portions (e.g., formed of different fibers or blends in different regions). The composite may include other features, such as fasteners, reinforcement features, and the like.

Fig. 4 illustrates an exemplary seat cushion 20. The mat 20 includes a fiber injection molded portion 14 that may be formed of the same fibers or blends or different fibers or blends in different regions. The cushion 20 also includes inserts 16 to provide additional support, cushioning, compression resistance, resiliency, or a combination thereof.

Fig. 5 illustrates an exemplary seat cushion 20. The mat 20 includes fiber injection sections 14, 14' and 14 "which may contain different fiber blends, for example, in different regions of the mat. This may allow for variations in density or may allow for the mat to be formed into a desired three-dimensional shape. The mat also includes a plurality of insert layers 16, 16', and 16 ". The different insert layers may be formed of different materials and may be selected to provide different characteristics to the cushion. The insert or blend of materials may allow the cushion to achieve desired cushioning properties.

Alternative materials and arrangements of materials are also contemplated by the present teachings. Other or additional materials and processes may be used to provide the article, such as a seat cushion. For example, polymeric and/or foam materials, such as polyurethane, may be used in addition to or in place of the fiber injection portion. The foam may be injection molded. Cavities may be formed in the material (e.g., manually removed during or after injection molding). The cavity may be adapted to receive one or more insert materials as described herein. As discussed, the article may include one or more interchangeable components. Insertion materials such as lay-up materials, three-dimensional open structures, or other fibrous materials may be manually inserted and replaced (e.g., due to wear or deterioration from use). It is contemplated that an outer material may be used to at least partially surround the foam and insert material. This outer material may be permanently attached. This outer material may be at least partially removable (e.g., to allow access to the removable insert material).

Parts by weight as used herein are 100 parts by weight with reference to the specifically mentioned composition. Any numerical value recited in the above application includes all values from the lower value to the upper value, in increments of one unit, provided that there is a separation of at least 2 units between any lower value and any upper value. As an example, if it is stated that the amount of a component or a value of a process variable (such as temperature, pressure, time, etc.) is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, the present specification intends to explicitly list values such as from 15 to 85, from 22 to 68, from 43 to 51, from 30 to 32, etc. For values less than 1, one unit is considered as 0.0001, 0.001, 0.01, or 0.1, as appropriate. These are only examples of what is specifically intended, and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be expressly stated in this application in a similar manner. Unless otherwise indicated, all ranges are inclusive of the two endpoints and all numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both endpoints of the range. Thus, "about 20 to 30" is intended to encompass "about 20 to about 30," including at least the endpoints specified. The term "consisting essentially of …" describing a combination is intended to include the identified element, ingredient, component or step as well as other elements, ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising" or "including" herein to describe combinations of elements, ingredients, components or steps also contemplates embodiments that consist essentially of the elements, ingredients, components or steps. A plurality of elements, components, means or steps may be provided by a single integrated element, component, means or step. Alternatively, a single integrated element, component, or step may be divided into multiple separate elements, components, or steps. The disclosure of "a" or "an" to describe an element, ingredient, component or step is not intended to exclude additional elements, ingredients, components or steps.