Patent Application
20230166481
The accompanying drawings illustrate a number of exemplary embodiments and are a part of the specification. Together with the following description, these drawings demonstrate and explain various principles of the present disclosure.
Throughout the drawings, identical reference characters and descriptions indicate similar, but not necessarily identical, elements. While the exemplary embodiments described herein are susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and will be described in detail herein. However, the exemplary embodiments described herein are not intended to be limited to the particular forms disclosed. Rather, the present disclosure covers all modifications, equivalents, and alternatives falling within the scope of the appended claims.
Glass laminates may be used as windows and glazings in architectural and transportation applications, and as coversheets and lenses for various electronic and electro-optic systems and devices, including head-mounted displays. In applications where strength is important, the toughness of glass can be enhanced by several methods, including thermal and chemical tempering, and the addition of one or more layers to the laminate architecture. Notwithstanding recent developments, it would be advantageous to provide optically transparent and lightweight glass laminates having high toughness and high fracture resistance.
As disclosed herein, a glass laminate may include a pair of opposing glass sheets and a polymer multilayer sandwiched therebetween. The polymer multilayer may be configured to induce a compressive stress in the near surface region of each sheet of glass. In particular embodiments, the compressive stress may be achieved through the photothermal actuation of ultra-drawn ultra-high molecular weight polyethylene (UHMWPE) or high density polyethylene (HDPE) layer(s).
In one example, a glass laminate may include a polymer multilayer that includes two or more laminated layers of ultra-drawn, ultra-high molecular weight polyethylene (UHMWPE) or ultra-drawn high density polyethylene (HDPE). As used herein, “ultra-drawn” polyethylene may refer to a polyethylene thin film that has been stretched to a draw ratio of at least approximately 10 along at least one in-plane dimension. Reference to “ultra-high molecular weight” polyethylene may include polyethylene having an average molecular weight of at least approximately 200,000 g/mol, e.g., 200,000, 500,000, 1,000,000, 2,000,000, or 5,000,000 g/mol or more, including ranges between any of the foregoing values. The term “high density” polyethylene may be used in reference to polyethylene having a density of at least approximately 0.93 g/cm3.
Example ultra-drawn UHMWPE or ultra-drawn HDPE layers may have a tensile strength of at least approximately 0.2 GPa, e.g., 0.2, 0.4, 0.6, 0.8, or 1.0 GPa, including ranges between any of the foregoing values, and a tensile modulus of at least approximately 10 GPa, e.g., 10, 20, 30, 40, 50, 100, or 150 GPa, including ranges between any of the foregoing values.
In some embodiments, a polymer multilayer may be disposed between transparent substrates to form a transparent glass laminate having a total thickness of from approximately 0.2 mm to approximately 1.0 mm and a minimum areal dimension of at least approximately 1 cm. In further embodiments, a polymer multilayer may be disposed between non-transparent substrates.
A polymer multilayer may include alternating layers of polyethylene (e.g., UHMWPE or HDPE) and a suitable adhesive, which may be laminated to one or more glass substrates using compression molding, for example. A polymer multilayer may include two or more layers of polyethylene, e.g., 2, 4, 6, 8, 10, or more polymer layers. The laminated structure may be optically transparent and exhibit high tensile strength and high fracture toughness. In some examples, a glass laminate may have a fracture toughness of at least approximately 5 MPa·m1/2, e.g., 5, 7, 10, 12, or 15 MPa·m1/2, including ranges between any of the foregoing values, and an absorbed energy of at least approximately 5 J/mm, e.g., 5, 10, or 20 J/mm, including ranges between any of the foregoing values.
An individual polyethylene layer may have a thickness of at least approximately 10 micrometers, e.g., 10, 15, 20, or 50 micrometers, including ranges between any of the foregoing values. A polyethylene layer may be optically transparent and may exhibit, for example, near field transparency of at least approximately 85% (e.g., at least approximately 90%) and far field transparency of at least approximately 80% (e.g., at least approximately 85% or approximately 90%). In some embodiments, the bulk haze of a polyethylene layer may be less than approximately 10%, e.g., less than 10, 5, 2, 1, 0.5, or 0.2%, including ranges between any of the foregoing values.
Example adhesives that may be incorporated into a polymer multilayer include optically clear adhesives (OCAS), liquid optically clear adhesives (LOCAs), thermoplastic polyurethanes (TPUs), polyvinyl butyrals (PVBs), or ethylene-vinyl acetates (EVAs), although further adhesive compositions are contemplated. In some embodiments, an adhesive layer may have a refractive index ranging from approximately 1.49 to approximately 1.60. The adhesive layers may be applied using a roll-to-roll process, such as calendaring, and the interfacial energy between the adhesive layer and a neighboring layer of polyethylene may be less than approximately 20 mN/m, e.g., 10, 15, or 20 mN/m, including ranges between any of the foregoing values. An adhesive may be used to laminate a polymer multilayer between transparent substrates. Example transparent substrates may include glass, polycarbonate, a cyclic olefin copolymer (COC), etc. The interfacial energy between an adhesive layer and a substrate may be less than approximately 40 mN/m, e.g., 40, 30, 20, or 10 mN/m, including ranges between any of the foregoing values.
In accordance with various embodiments, the polyethylene layers may be manufactured using melt extrusion, solvent casting, gel casting, calendaring, solid state extrusion, compression molding, although additional forming methods are contemplated.
The polyethylene layer(s) may be stretched such that the polymer molecules within the polyethylene may be preferentially reoriented, e.g., along the stretch direction. The act of stretching may include the application of a uniaxial stress or a biaxial stress. In certain embodiments, the draw ratio for an ultra-drawn polyethylene layer may be at least approximately 10, e.g., approximately 10, approximately 20, approximately 30, approximately 40, approximately 50, approximately 60, approximately 70, approximately 80, approximately 90, or approximately 100, including ranges between any of the foregoing values.
As will be appreciated, the optical, thermal, and mechanical response of a polymer thin film may be determined by its chemical composition, the chemical structure of the polymer repeat unit, its density and extent of crystallinity, as well as the alignment of the crystals and/or polymer chains throughout the polymer matrix. Among these factors, the crystal or polymer chain alignment may dominate. In crystalline or semi-crystalline polymer thin films, an optical, thermal, or mechanical property or condition may be correlated to the degree or extent of crystal orientation, whereas the degree or extent of chain entanglement may create comparable optical, thermal, or mechanical properties in amorphous polymer thin films.
An applied stress may be used to form a preferred alignment of crystals or polymer chains within a polymer thin film and induce a corresponding modification of the optical, thermal, and/or mechanical properties along different directions of the film. As disclosed further herein, during processing where a polymer thin film is stretched to induce a preferred alignment of crystals/polymer chains and an attendant modification of the refractive index/birefringence, thermal, and mechanical properties, Applicants have shown that one approach to forming an anisotropic material is to modify the kinetics of the stretching process.
Stretching may include the application of a uniaxial or biaxial stress. Stretching may include a single act of stretching or plural, successive stretching events, such as along different in-plane directions of a polymer thin film. The act of stretching may be velocity limited or strain rate limited. In some embodiments, a polymer thin film may be stretched at a variable or constant velocity. In some embodiments, the polymer may be stretched using a variable strain rate or a constant strain rate (e.g., 0.5 s−1, 1 s−1, 5 s−1, or 10 s−1, including ranges between any of the foregoing values). By way of example, the strain rate may decrease throughout an act of stretching and/or amongst different stretching events from an initial strain rate (e.g., 5 s−1) to a final strain rate (e.g., 0.5 s−1).
In accordance with particular embodiments, Applicants have developed a polymer thin film manufacturing method for forming an oriented polyethylene (PE) thin film having desired optical clarity and strength. Applicants have demonstrated that high quality, high performance single layer and multilayer polymer thin films having improved drawability and enhanced optical, thermal, and mechanical properties may be formed by implementing stretching processes throughout one or more stages of thin film manufacture, including the acts of forming, pre-orienting, and final stretching. Such polymer thin films and multilayers may be incorporated into optically transparent laminated structures having high toughness.
Polymer thin films may be formed using casting operations such as melt extrusion, compression molding, solvent casting, gel casting, and the like. Applicants have demonstrated that enhanced drawability may be achieved by tuning one or more of the draw temperature and the draw rate of a cast polymer thin film. In some examples, the draw temperature may be correlated to the thin film's primary (glass, or alpha) relaxation and/or its low temperature (beta) relaxation.
In some embodiments, polyethylene may be provided in particulate or powder form. Example polyethylene powders may have a particle size distribution (d90) greater than approximately 50 micrometers, e.g., greater than 50, 100, 200, or 300 micrometers, including ranges between any of the foregoing values.
A low molecular weight additive may be provided in particulate or powder form. Example additives, e.g., waxes, may have a particle size distribution (d90) less than approximately 30 micrometers, e.g., 5, 10, 15, 20, or 25 micrometers, including ranges between any of the foregoing values.
In some embodiments, particulate or powdered polyethylene may be mixed with a particulate or powdered wax in a long continuous mixer (LCM) at any suitable temperature. For instance, a mixing temperature may be less than, equal to, or greater than a melting temperature of the wax. The mixing may be adapted to impregnate the polyethylene with the wax to form a homogeneous mixture prior to casting.
In some examples, a mixture of “unentangled” polyethylene and low molecular weight additive may be extruded at a temperature less than approximately 140° C. (e.g., 120° C. or 130° C.) and above the melting point of the additive to form a polymer thin film. An extruded thin film may have a thickness of less than approximately 2 mm (e.g., 500 micrometers, 750 micrometers, or 1 mm, including ranges between any of the foregoing values) and a porosity of less than approximately 10% (e.g., less than 5%, less than 2%, or less than 1%).
In example melt extrusion methods, the melt may undergo pre-orientation with a draw down ratio (DDR) of at least approximately 1, e.g., approximately 1, approximately 2, approximately 3, or approximately 4, including ranges between any of the foregoing values. The melt may be collected on a chilled roller. The roller temperature may be less than (e.g., at least approximately 10° C. less than) the lowest melting point of any additive included in the melt. The cast polymer may undergo a machine direction orientation (MDO) process to form a hard cast film having a draw ratio along the machine direction (MDX) of at least approximately 2, e.g., at least approximately 2, at least approximately 4, or at least approximately 6, including ranges between any of the foregoing values.
According to further embodiments, a polymer thin film may be formed via gel casting from a dilute solution including a polymer composition and a first solvent followed by removal of the solvent. Example solvents include poor solvents such as mineral oils, paraffin oil, stearic acid, p-xylene, dodecanol, and the like. The first solvent may be removed prior to, during, and/or after the act(s) of stretching. The first solvent may be removed directly by evaporation, or through contact with a miscible second solvent followed by evaporation of the resulting co-solvent.
A cast polymer thin film may be stretched using single or multiple stretching events. Some stretching processes may include two successive stretching events. For instance, orthogonal consecutive stretching (OCS) may be used to develop structural fingerprints, such as smaller lamellar thicknesses and higher degrees of polymer chain orientation at draw ratios less than the draw ratios used to achieve similar structural fingerprints via comparative single stretching (SS) or parallel consecutive stretching (PCS) techniques. Orthogonal consecutive stretching may include first stretching a polymer thin film along a first in-plane axis, and then subsequently stretching the polymer thin film along a second in-plane axis that is orthogonal to the first in-plane axis.
In an example method, a cast polymer thin film may be stretched along a first in-plane axis to a stretch ratio of up to approximately 4 (e.g., 2, 3, or 4, including ranges between any of the foregoing values) with an attendant relaxation in the cross-stretch direction having a relaxation ratio of at least approximately 0.2 (e.g., 0.2, 0.3, 0.4, or 0.5, including ranges between any of the foregoing values). Subsequently, the polymer thin film may be stretched along a second in-plane axis orthogonal to the first in-plane axis to a stretch ratio of at least approximately 10 (e.g., 10, 20, 30, 40, 50, or 60, including ranges between any of the foregoing values) with a relaxation ratio in the cross-stretch direction of at least approximately 0.2 (e.g., 0.2, 0.3, 0.4, or 0.5, including ranges between any of the foregoing values).
In some examples, the draw ratio in the first stretching step may be less than the draw ratio in the second stretching step. According to further embodiments, the temperature of the polymer thin film during the second stretching step may be greater than the polymer thin film temperature during the first stretching step. The temperature during the second stretching step may be at least approximately 5° C. greater than the temperature during the first stretching step (e.g., 5, 10, 15, or 20° C. greater, including ranges between any of the foregoing values).
In some embodiments, a polymer thin film may be heated and stretched along a first direction, cooled, and then heated and stretched along a second direction. In some embodiments, a polymer thin film may be heated and stretched along a first direction, cooled, and then heated and stretched again along the first direction. Following the second stretching step, the polymer thin film may be cooled. The acts of cooling may immediately follow the first (or second) stretching steps, where the polymer thin film may be cooled within approximately 10 seconds following completion of the first (or second) stretching step. In some examples, the temperature of the polymer thin film during an act of stretching may be greater than the glass transition temperature of the polymer. In some examples, the temperature of the polymer thin film during an act of stretching may be less than, equal to, or greater than the melting onset temperature of the polymer.
In various examples, the extent of relaxation perpendicular to the stretch direction may be approximately equal to the square root of the stretch ratio in the stretch direction. In some embodiments, the extent of relaxation may be substantially constant throughout the stretching process(es). In further embodiments, the extent of relaxation may decrease, with greater relaxation associated with the beginning of a stretch step and lesser relaxation associated with the end of a stretch step.
An example polymer may include ultra-high molecular weight polyethylene (UHMWPE) or high density polyethylene (HDPE). According to some embodiments, various properties of UHMWPE or HDPE may be improved in conjunction with the processing methods disclosed herein by decreasing or eliminating surface and/or bulk defects. In some embodiments, one or more low melting point additives may be incorporated into the polymer matrix of a polymer thin film.
Example polyethylene materials include ultra-high molecular weight polyethylene and high density polyethylene, as well as derivatives and mixtures thereof, and may have a molecular weight (e.g., weight-averaged molecular weight) of at least approximately 200,000 g/mol, e.g., at least approximately 200,000 g/mol, or at least approximately 250,000 g/mol. Ultra-high molecular weight polyethylene may have a molecular weight of at least approximately 300,000 g/mol, e.g., approximately 300,000 g/mol, approximately 400,000 g/mol, approximately 500,000 g/mol, approximately 600,000 g/mol, approximately 700,000 g/mol, approximately 800,000 g/mol, approximately 900,000 g/mol, approximately 1,000,000 g/mol, approximately 2,000,000 g/mol, or approximately 5,000,000 g/mol, including ranges between any of the foregoing values.
In some embodiments, a polymer thin film may include a low molecular weight additive. The additive may include a low molecular weight polyethylene or polyethylene oligomer and may constitute from approximately 1 wt. % to approximately 90 wt. % of the polymer matrix forming the polymer thin film. An additive may be homogeneously or non-homogeneously dispersed. Additives may have good solubility in, and may be index matched with ultra-high molecular weight polyethylene or high density polyethylene.
Example additives may include one or more of hydrocarbon waxes, e.g., polyethylene-wax molecules or amide waxes, mineral oils, fluoropolymers, etc. If used, polyethylene-wax molecules may have a molecular weight of at least approximately 400 g/mol, e.g., 400, 1000, 2000, or 3000 g/mol, including ranges between any of the foregoing values. The wax content within the polyethylene matrix may be at least approximately 2 wt. %, e.g., 2, 5, 10, 20, 50, or 80 wt. %, including ranges between any of the foregoing values. Suitable mineral oils may have a molecular weight of at least approximately 200 g/mol, e.g., 200, 400, or 600 g/mol, including ranges between any of the foregoing values. In some embodiments, up to approximately 1000 ppm (e.g., 200, 400, 600, 800, or 1000 ppm) of a fluoropolymer or other processing aid may be incorporated into the polymer matrix. An additive may be characterized by a refractive index of approximately 1.5 to approximately 1.6, e.g., 1.55.
In some embodiments, an additive incorporated into the polymer matrix may include a photothermal material such as a photothermal dye. Accordingly, thermal energy or incident electromagnetic radiation may be used to create a compressive stress and the associated interfacial stresses due to the high tensile modulus of the polyethylene layers.
Example photothermal dyes include 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (BZT), azobenzene, coronatine dye, graphene, quaterrylene-based dyes, and metal nanoparticles such as gold nanoparticles, as well as mixtures thereof. A photothermal dye such as azobenzene or metal nanoparticles may be functionalized by ethylene oligomers having a molecular weight of at least approximately 500 g/mol, e.g., 500, 1000, 2000, or 3000 g/mol, including ranges between any of the foregoing values. In some examples, a concentration of a photothermal additive within the polymer matrix may be at least approximately 0.5 wt. %, e.g., 0.5, 1, 2, or 5 wt. %, including ranges between any of the foregoing values. A functionalized photothermal dye may be added to polyethylene prior to or during formation of a thin film, which may be stretched to form a dichroic arrangement of dye in the polyethylene matrix.
In some embodiments, optical and mechanical properties may be specifically targeted, and the polymer thin film may contain approximately 60 wt. % to approximately 90 wt. % of a low molecular weight polyethylene or polyethylene oligomer. In some embodiments, thermal conductivity may be specifically targeted, and the polymer thin film may contain approximately 1 wt. % to approximately 10 wt. % of a low molecular weight polyethylene or polyethylene oligomer.
An additive may be thermally conductive. A thermally conductive additive may have a thermal conductivity of at least approximately 5 W/mK, e.g., 5, 10, 15, or 20 W/mK, including ranges between any of the foregoing values. Example thermally conductive additives include particles of graphene or borophene, carbon nanotubes, silver nanowires, and metal nanoparticles, such as high aspect ratio metallic nanoparticles. According to some embodiments, the loading of a thermally conductive additive may range from approximately 0.01 wt. % to approximately 1 wt. %.
The “low molecular weight” additive may have a molecular weight of less than approximately 4,000 g/mol, e.g., less than approximately 4,000 g/mol, less than approximately 2,000 g/mol, less than approximately 1,000 g/mol, less than approximately 500 g/mol, or less than approximately 200 g/mol. An example low molecular weight additive may be characterized by a melting temperature (Tm) of at least approximately 40° C., e.g., approximately 40° C., approximately 60° C., approximately 80° C., approximately 100° C., or approximately 120° C., including ranges between any of the foregoing values. Reference herein to a melting temperature may include reference to a temperature corresponding to the onset of melting.
Example polyethylene polymer and oligomer-based additives may include a reactive group such as vinyl, acrylate, methacrylate, epoxy, isocyanate, hydroxyl, amine, and the like. Such additives may be cured in situ, i.e., within a polymer thin film by applying one or more of heat or light, or by reaction with a suitable catalyst.
In some embodiments, plural additives may be used. According to particular embodiments, an original additive can be used during processing of a thin film (e.g., during extrusion, stretching, and/or calendaring). Thereafter, the original additive may be removed such as by washing or evaporation and replaced by a secondary additive. A secondary additive (e.g., various phenolic benzotriazoles) may be index matched to the crystalline polyethylene polymer and may, for example, have a refractive index ranging from approximately 1.45 to approximately 1.6. By way of example, phenolic benzotriazoles can form π-π interactions with polymer chains in the polyethylene polymer and enable phonons to pass at extremely low loading amounts without affecting optical quality. A secondary additive can be added by soaking the thin film under melting conditions or in a solvent bath. A secondary additive may have a melting point of less than approximately 100° C.
A secondary additive, if used, may be a poor solvent to polyethylene. Example poor solvents may include stearic acid or saturated hydrocarbons such as mineral oils (e.g., Kaydol® mineral oil, paraffin oil, Primol™ oil, and the like). The secondary additive may be removed before, during, or after a film stretching process such as by evaporation or solvent exchange.
The presently disclosed polyethylene thin films may be characterized as optical quality polymer thin films and may form, or be incorporated into, an optical element, including an optically transparent laminated structure having high toughness. Such optical elements may be used in various display devices, such as virtual reality (VR) and augmented reality (AR) glasses and headsets. The efficiency of these and other optical elements may depend on the degree of optical clarity and/or one or more mechanical properties of the polymer thin film(s).
According to various embodiments, an “optical quality” polymer thin film or an “optical” thin film may, in some examples, be characterized by transmissivity within the visible light spectrum of at least approximately 20%, e.g., 20, 30, 40, 50, 60, 70, 80, 90 or 95%, including ranges between any of the foregoing values, and less than approximately 10% bulk haze, e.g., 0, 1, 2, 4, 6, or 8% bulk haze, including ranges between any of the foregoing values.
A material or element that is “transparent” or “optically transparent” may, for a given thickness, have a transmissivity within the visible light spectrum of at least approximately 80%, e.g., approximately 80, 90, 95, 97, 98, 99, or 99.5%, including ranges between any of the foregoing values, and less than approximately 5% bulk haze, e.g., approximately 0.1, 0.2, 0.5, 1, 2, or 5% bulk haze, including ranges between any of the foregoing values. Transparent materials will typically exhibit very low optical absorption and minimal optical scattering.
As used herein, the terms “haze” and “clarity” may refer to an optical phenomenon associated with the transmission of light through a material, and may be attributed, for example, to the refraction of light within the material, e.g., due to secondary phases or porosity and/or the reflection of light from one or more surfaces of the material. As will be appreciated by those skilled in the art, haze may be associated with an amount of light that is subject to wide angle scattering (i.e., at an angle greater than 2.5° from normal) and a corresponding loss of transmissive contrast, whereas clarity may relate to an amount of light that is subject to narrow angle scattering (i.e., at an angle less than 2.5° from normal) and an attendant loss of optical sharpness or “see through quality.”
After extrusion or casting, a polyethylene film can be oriented either uniaxially or biaxially as a single layer or multilayer to form a mechanically anisotropic and optically clear film that may exhibit anisotropy also in its thermal conductivity. An anisotropic polymer thin film may be formed using a thin film orientation system configured to heat and stretch a polymer thin film in at least one in-plane direction in one or more distinct regions thereof. In some embodiments, a thin film orientation system may be configured to stretch a polymer thin film, i.e., a crystallizable polymer thin film, along only one in-plane direction. For instance, a thin film orientation system may be configured to apply an in-plane stress to a polymer thin film along the x-direction while allowing the thin film to relax along an orthogonal in-plane direction (e.g., along the y-direction). As used herein, the relaxation of a polymer thin film may, in certain examples, accompany the absence of an applied stress along a relaxation direction.
According to some embodiments, within an example orientation system, a polymer thin film may be heated and stretched transversely to a direction of film travel through the system. In such embodiments, a polymer thin film may be held along opposing edges by plural movable clips slidably disposed along a diverging track system such that the polymer thin film is stretched in a transverse direction (TD) as it moves along a machine direction (MD) through heating and deformation zones of the thin film orientation system. In some embodiments, the stretching rate in the transverse direction and the relaxation rate in the machine direction may be independently and locally controlled. In certain embodiments, large scale production may be enabled, for example, using a roll-to-roll manufacturing platform.
In certain aspects, the tensile stress may be applied uniformly or non-uniformly along a lengthwise or widthwise dimension of the polymer thin film. Heating of the polymer thin film may accompany the application of the tensile stress. For instance, a semi-crystalline polymer thin film may be heated to a temperature greater than room temperature (˜23° C.) to facilitate deformation of the thin film and the formation and realignment of crystals and/or polymer chains therein.
The temperature of the polymer thin film may be maintained at a desired value or within a desired range before, during and/or after the act of stretching, i.e., within a pre-heating zone or a deformation zone downstream of the pre-heating zone, in order to improve the deformability of the polymer thin film relative to an un-heated polymer thin film. The temperature of the polymer thin film within a deformation zone may be less than, equal to, or greater than the temperature of the polymer thin film within a pre-heating zone.
In some embodiments, the polymer thin film may be heated to a constant temperature throughout the act of stretching. In some embodiments, a region of the polymer thin film may be heated to different temperatures, i.e., during and/or subsequent to the application of a tensile stress. In some embodiments, different regions of the polymer thin film may be heated to different temperatures. In certain embodiments, the strain realized in response to the applied tensile stress may be at least approximately 20%, e.g., approximately 20%, approximately 50%, approximately 100%, approximately 200%, approximately 400%, approximately 500%, approximately 1000%, approximately 2000%, approximately 3000%, or approximately 4000% or more, including ranges between any of the foregoing values.
The crystalline content within the polymer thin film may increase during the act of stretching. In some embodiments, stretching may alter the orientation of crystals within a polymer thin film without substantially changing the crystalline content.
In some embodiments, a protective layer may be formed over one or both major surfaces of a polymer thin film. The protective layer(s) may include an organic or an inorganic material, and may shield the polymer thin film against surface damage or debris, such as scratches or dust. The protective layer(s), if provided, may be removed prior to one or more acts of stretching, or the protective layer(s) may be removed following stretching. In various examples, the removable protective layer(s) may have a 90° peel strength of at least approximately 10 g/cm width (e.g., 10, 20, 50, 100, 200, 500, 1000 g/cm width or greater).
Following the act(s) of stretching, one or more thin film properties may be refined through hot pressing or hot calendaring. Uniaxial hot pressing, for example, may be performed in a rigid die with loading applied along a common axis. Some pressing systems may include a graphite die, which may be enclosed in a protective atmosphere or vacuum chamber. During hot pressing, temperature and pressure may be applied simultaneously to the stretched polymer thin film. Heating may be achieved using induction coils that surround the graphite die, and pressure may be applied hydraulically. Calendaring is a process of compressing a thin film during production by passing a polymer thin film between one or more pairs of heated rollers.
In some embodiments, a stretched polymer thin film may be pressed or calendared to at least approximately 50% of its initial thickness (e.g., 50%, 60%, 70%, or 80% of its initial thickness, including ranges between any of the foregoing values) under an applied pressure of at least approximately 2 MPa (e.g., 2, 3, 4, 5, or 10 MPa, including ranges between any of the foregoing values) and at a temperature of less than approximately 140° C. (e.g., 120° C., 125° C., 130° C., or 135° C., including ranges between any of the foregoing values).
A pressed or calendared polymer thin film may have a thickness of less than approximately 500 micrometers, e.g., less than 400 micrometers, less than 300 micrometers, or less than 200 micrometers. According to some embodiments, following hot pressing or hot calendaring, a polymer thin film may be stretched further using one or more additional stretching steps. In a post-hot pressing or post-hot calendaring stretching step, a polymer thin film may be stretched to a draw ratio of approximately 5 or greater (e.g., 5, 10, 20, 40, 60, 80, 100, 120, or 140, including ranges between any of the foregoing values).
Hot pressing or hot calendaring may increase transmissivity and/or thermal conductivity of a polymer thin film. According to some embodiments, the applied pressure may collapse voids within the polymer thin film, thus decreasing the overall void volume and increasing the density of the polymer matrix.
Following deformation of the polymer thin film, the heating may be maintained for a predetermined amount of time, followed by cooling of the polymer thin film. The act of cooling may include allowing the polymer thin film to cool naturally, at a set cooling rate, or by quenching, such as by purging with a low temperature gas, which may thermally stabilize the polymer thin film.
Following deformation, the crystals or chains may be at least partially aligned with the direction of the applied tensile stress. As such, a polymer thin film may exhibit a high degree of optical clarity and mechanical anisotropy, including one or any combination of: transmissivity within the visible spectrum (380-750 nm) of at least approximately 80% (e.g., 80, 90, 95, 97, or 99%, including ranges between any of the foregoing values), bulk haze of less than approximately 5% (e.g., 0, 1, 2, 3, 4, or 5%, including ranges between any of the foregoing values), a Young's modulus of at least approximately 30 GPa (e.g., 30, 40, 50, 60, 70, 80, 90, 100, or 150 GPa, including ranges between any of the foregoing values), tensile strength of at least approximately 0.5 GPa (e.g., 0.5, 1, or 1.5 GPa, including ranges between any of the foregoing values), thermal conductivity of at least approximately 5 W/mK (e.g., 5, 10, 20, 30, 40, 50, 60, 70, or 80 W/mK, including ranges between any of the foregoing values), void volume of less than approximately 25% (e.g., 0, 1, 2, 3, 4, 5, 10, 15, 20, or 25%, including ranges between any of the foregoing values) and an average void size of less than approximately 100 nm (e.g., 10, 20, 50, or 100 nm, including ranges between any of the foregoing values). In some embodiments, the modulus of a polymer thin film may be invariant or substantially invariant as a function of frequency (e.g., over a range of 0.1 to 100 Hz, for example). These and other properties may exhibit an in-plane anisotropy ranging from approximately 2:1 to approximately 100:1 or more, e.g., 2:1, 3:1, 4:1, 5:1, 10:1, 20:1, 50:1, or 100:1.
Polyethylene thin films may include fibrous, amorphous, partially crystalline, or wholly crystalline materials. In various embodiments, an UHMWPE thin film or a HDPE thin film may be at least approximately 50% crystalline, e.g., 50, 60, 70, 80, 90, 92, 94, 96, 98, or 100% crystalline, including ranges between any of the foregoing values. Such materials may also exhibit anisotropy with respect to one or more further characteristics, which may include compressive strength, shear strength, yield strength, stiffness, hardness, toughness, ductility, machinability, thermal expansion, and creep behavior.
In a polymer multilayer, plural layers of polyethylene may be oriented such that the stretch axes are aligned in parallel. Alternatively, alternating layers of polyethylene within a polymer multilayer may be oriented such that the stretch axes are aligned perpendicular to one another. According to still further embodiments, a polymer multilayer may include a repeat sequence of (n) polyethylene layers where the orientation of each successive layer is rotationally offset by an angle
Features from any of the embodiments described herein may be used in combination with one another in accordance with the general principles described herein. These and other embodiments, features, and advantages will be more fully understood upon reading the following detailed description in conjunction with the accompanying drawings and claims.
The following will provide, with reference to
Referring to
In some embodiments, pre-tension may be created in each polyethylene layer incident to lamination. That is, an external in-plane tensile stress may be applied to a polyethylene layer 210 prior to and during lamination with the substrate 205, whereupon the external tensile stress may be removed.
As illustrated in
Referring to
Referring to
A further example polymer multilayer is shown in
angle where n is the number of repeating polyethylene layers in the multilayer. In the polymer multilayer of
According to various embodiments, actuation of a polymer multilayer may be driven thermally or by exposure to electromagnetic radiation (e.g., UV radiation, visible light, or near-infrared radiation). In some examples, and with reference to
As will be appreciated, a polymer multilayer may induce a state of compressive stress in a substrate through pre-tensioning of one or more the polymer layers, by exposing the polymer layer(s) to heat and/or radiation, or by a combination thereof.
In conjunction with various embodiments, a polymer thin film may be described with reference to three mutually orthogonal axes that are aligned with the machine direction (MD), the transverse direction (TD), and the normal direction (ND) of a thin film orientation system, and which may correspond respectively to the length, width, and thickness dimensions of the polymer thin film. Throughout various embodiments and examples of the instant disclosure, the machine direction may correspond to the y-direction of a polymer thin film, the transverse direction may correspond to the x-direction of the polymer thin film, and the normal direction may correspond to the z-direction of the polymer thin film.
Referring to
By way of example, and referring still to
During a second stretching step, the polymer thin film may be stretched along the first axis or, as illustrated in
Prior to the acts of stretching, a polymer thin film may be pre-aligned, i.e., with respect to the stretch axes of a thin film orientation system. Pre-alignment of the polymer thin film may allow polymer chains within the polymer thin film to form a cross-linked crystal network. This cross-linked crystal network may allow the polymer film to be stretched to higher draw ratios compared to thin films that are stretched only in a single direction and without pre-alignment.
Referring still to
During a first stretching process, an inter-clip spacing 750 within clip array 710 may increase, while an inter-clip spacing 745 within clip array 720 may be fixed. A tensile stress may be applied to the polymer thin film 705 along the machine direction while the polymer thin film is unstressed along the transverse direction, thus forming a uniaxially stretched polymer thin film 740. During a second and subsequent stretching process, an inter-clip spacing 755 within clip array 720 may increase, while an inter-clip spacing 760 within clip array 710 may be fixed. Thus, a tensile stress may be applied to the polymer thin film 740 along the transverse direction while the polymer thin film is unstressed along the machine direction, thus forming an OCS processed polymer thin film 765.
Referring now to
During operation, a resin typically provided in powder or pellet form may be fed into extruder 805 from a hopper 810. One or more optional additives may be blended with the resin within hopper 810 or incorporated using a separate downstream hopper 815. The temperature of extruder 805 along its length (L) may be controlled by heating elements 820. Extruder 805 may include a screw or other element (not shown) for mixing, homogenizing, and driving feedstock from hoppers 810, 815 to an extrusion die 825.
As shown in the inset, extrusion die 825 may include plural inputs A, B, C, that are configured to receive feedstock from plural respective extruders (e.g., extruder 805, etc.). In some embodiments, the temperature of the extrusion die 825 may be greater than the melting point of the feedstock. The melted feedstock may be output through extrusion die 825 to form a multilayer thin film 840 that may include, for example, a central layer 835 and a pair of outer layers 830 that sandwich the central layer 835. Central layer 835 may include a polymer layer. Multilayer thin film 840 may be initially collected on a chilled roller 845 and output as a pre-oriented cast thin film 842. The temperature of the chilled roller 845 may be selected based on the type of additive(s) used in the process. The rotational rate of the chilled roller 845 (i.e., relative to the output rate of the extrusion die 825) may be adjusted to pre-orient multilayer thin film 840.
In some embodiments, the central layer 835 may include ultra-high molecular weight polyethylene (UHMWPE) or high density polyethylene (HDPE). Each outer layer 830 may include a material having a high surface energy relative to polyethylene (e.g., fluoropolymers such as polyvinylidene fluoride or polyesters such as polyethylene terephthalate) or materials having a low surface energy relative to polyethylene (e.g., polyolefins such as polypropylene).
Prior to an act of stretching, one or both of the outer layers 830 may be removed from the multilayer thin film 840. By way of example, the outer layer(s) 830 may be removed prior to stretching the central layer 835, removed after one stage of the stretching (e.g., removed after stretching along the machine direction), or removed following two stages of stretching (e.g., removed following an OCS process). In some embodiments, the outer layers 830 may be removed from the central layer 835 by peeling. In some embodiments, the outer layers 830 may have a 90° peel strength of at least approximately 10 g/cm width, e.g., 10, 20, 50, 100, 500, or 1000 g/cm width, including ranges between any of the foregoing values.
A single stage thin film orientation system for forming an optically and mechanically anisotropic polymer thin film is shown schematically in
Polymer thin film 905 may include a single polymer layer or multiple (e.g., alternating) layers of first and second polymers, such as a multilayer ABAB . . . structure. Alternately, polymer thin film 905 may include a composite architecture having a crystallizable polymer thin film and a high Poisson's ratio polymer thin film directly overlying the crystallizable polymer thin film (not separately shown). In some embodiments, a polymer thin film composite may include a high Poisson's ratio polymer thin film reversibly laminated to, or printed on, a single crystallizable polymer thin film or a multilayer polymer thin film.
During operation, proximate to input zone 930, clips 924, 926 may be affixed to respective edge portions of polymer thin film 905, where adjacent clips located on a given track 925, 927 may be disposed at an inter-clip spacing 950, 955. For simplicity, in the illustrated view, the inter-clip spacing 950 along the first track 925 within input zone 930 may be equivalent or substantially equivalent to the inter-clip spacing 955 along the second track 927 within input zone 930. As will be appreciated, in alternate embodiments, within input zone 930, the inter-clip spacing 950 along the first track 925 may be different than the inter-clip spacing 955 along the second track 927.
In addition to input zone 930 and output zone 947, system 900 may include one or more additional zones 935, 940, 945, etc., where each of: (i) the translation rate of the polymer thin film 905, (ii) the shape of first and second tracks 925, 927, (iii) the spacing between first and second tracks 925, 927, (iv) the inter-clip spacing 950, 952, 954, 955, 957, 959, and (v) the local temperature of the polymer thin film 905, etc. may be independently controlled.
In an example process, as it is guided through system 900 by clips 924, 926, polymer thin film 905 may be heated to a selected temperature within each of zones 930, 935, 940, 945, 947. Fewer or a greater number of thermally controlled zones may be used. As illustrated, within zone 935, first and second tracks 925, 927 may diverge along a transverse direction such that polymer thin film 905 may be stretched in the transverse direction while being heated, for example, to a temperature greater than its glass transition temperature (Tg) but less than the onset of melting.
Referring still to
A temperature of the polymer thin film may be controlled within each heating zone. Withing stretching zone 935, for example, a temperature of the polymer thin film 905 may be constant or independently controlled within sub-zones 965, 970, for example. In some embodiments, the temperature of the polymer thin film 905 may be decreased as the stretched polymer thin film 905 enters zone 940. Rapidly decreasing the temperature (i.e., thermal quenching) following the act of stretching within zone 935 may enhance the conformability of the polymer thin film 905. In some embodiments, the polymer thin film 905 may be thermally stabilized, where the temperature of the polymer thin film 905 may be controlled within each of the post-stretch zones 940, 945, 947. A temperature of the polymer thin film may be controlled by forced thermal convection or by radiation, for example, IR radiation, or a combination thereof.
Downstream of stretching zone 935, according to some embodiments, a transverse distance between first track 925 and second track 927 may remain constant or, as illustrated, initially decrease (e.g., within zone 940 and zone 945) prior to assuming a constant separation distance (e.g., within output zone 947). In a related vein, the inter-clip spacing downstream of stretching zone 935 may increase or decrease relative to inter-clip spacing 952 along first track 925 and inter-clip spacing 957 along second track 927. For example, inter-clip spacing 955 along first track 925 within output zone 947 may be less than inter-clip spacing 952 within stretching zone 935, and inter-clip spacing 959 along second track 927 within output zone 947 may be less than inter-clip spacing 957 within stretching zone 935. According to some embodiments, the spacing between the clips may be controlled by modifying the local velocity of the clips on a linear stepper motor line, or by using an attachment and variable clip spacing mechanism connecting the clips to the corresponding track.
To facilitate cross-stretch relaxation while stretching in the TD direction, the inter-clip spacings 952, 957 withing stretching zone 935 may be decreased by at least approximately 20% (e.g., 20%, 30%, 40%, or 50% or more) relative to respective inter-clip spacings 950, 955 within input zone 930. The relaxation profile may be constant or variable, i.e., as a function of position, across stretching zone 935. According to some embodiments, a maximum TD draw ratio within stretching zone 935 be at least approximately 2 and less than approximately 4. The stretched and oriented polymer thin film 915 may be removed from system 900 and stretched in a further stretching step, such as via length orientation with relaxation as shown in
Referring to
In an example process, proximate to input zone 1030, first and second clips 1024, 1026 may be affixed to edge portions of polymer thin film 1005, where adjacent clips located on a given track 1025, 1027 may be disposed at an initial inter-clip spacing 1050, 1055, which may be substantially constant or variable along both tracks within input zone 1030. Within input zone 1030 a distance along the transverse direction between first track 1025 and second track 1027 may be constant or substantially constant.
System 1000 may additionally include one or more zones 1035, 1040, etc. The dynamics of system 1000 allow independent control over: (i) the translation rate of the polymer thin film 1005, (ii) the shape of first and second tracks 1025, 1027, (iii) the spacing between first and second tracks 1025, 1027 along the transverse direction, (iv) the inter-clip spacing 1050, 1055 within input zone 1030 as well as downstream of the input zone (e.g., inter-clip spacings 1052, 1054, 1057, 1059), and (v) the local temperature of the polymer thin film, etc.
In an example process, as it is guided through system 1000 by clips 1024, 1026, polymer thin film 1005 may be heated to a selected temperature within each of zones 1030, 1035, 1040, 1045. A temperature greater than the glass transition temperature of a component of the polymer thin film 1005 may be used during deformation (i.e., within zone 1035), whereas a lesser temperature, an equivalent temperature, or a greater temperature may be used within each of one or more downstream zones.
As in the previous embodiment, the temperature of the polymer thin film 1005 within stretching zone 1035 may be locally controlled. According to some embodiments, the temperature of the polymer thin film 1005 may be maintained at a constant or substantially constant value during the act of stretching. According to further embodiments, the temperature of the polymer thin film 1005 may be incrementally increased within stretching zone 1035. That is, the temperature of the polymer thin film 1005 may be increased within stretching zone 1035 as it advances along the machine direction. By way of example, the temperature of the polymer thin film 1005 within stretching zone 1035 may be locally controlled within each of heating zones a, b, and c.
The temperature profile may be continuous, discontinuous, or combinations thereof. As illustrated in
Referring still to
Within stretching zone 1035, the inner-clip spacings 1052, 1057 may increase linearly such that the primary mode of deformation may be at constant velocity. For example, a strain rate of the polymer thin film may decrease along the machine direction. In further embodiments, the polymer thin film 1005 may be stretched at a constant strain-rate where the inter-clip spacing may increase exponentially.
In certain examples, a progressively decreasing strain rate may be implemented with thin film orientation system 1000 to generate a high refractive index polymer thin film. For instance, within stretching zone 1035 an inter-clip spacing may be configured such that a distance between each successive pair of clips 1024, 1026 increases along the machine direction. The inter-clip spacing between each successive pair of clips may be independently controlled to achieve a desired strain rate along the machine direction.
In response to the tensile stress applied along the machine direction, system 1000 is configured to inhibit the generation of stresses and an attendant realignment of crystals along the machine direction. As illustrated, within zone 1035, first and second tracks 1025, 1027 may converge along a transverse direction such that polymer thin film 1005 may relax in the transverse direction while being stretched in the machine direction. Using a single stretching step or multiple stretching steps, polymer thin film 1005 may be stretched by a factor of at least approximately 4 (e.g., 4, 5, 6, 7, 8, 9, 10, 20, 40, 100, or more, including ranges between any of the foregoing values).
Within stretching zone 1035, an angle of inclination of first and second tracks 1025, 1027 (i.e., with respect to the machine direction) may be constant or variable. In particular examples, the inclination angle within stretching zone 1035 may decrease along the machine direction. That is, according to certain embodiments, the inclination angle within heating zone a may be greater than the inclination angle within heating zone b, and the inclination angle within heating zone b may be greater than the inclination angle within heating zone c. Such a configuration may be used to provide a progressive decrease in the relaxation rate (along the transverse direction) within the stretching zone 1035 as the polymer thin film advances through system 1000.
In some embodiments, the temperature of the polymer thin film 1005 may be decreased as the stretched polymer thin film 1005 exits zone 1035. In some embodiments, the polymer thin film 1005 may be thermally stabilized, where the temperature of the polymer thin film 1005 may be controlled within each of the post-deformation zones 1040, 1045. A temperature of the polymer thin film may be controlled by forced thermal convection or by radiation, for example, IR radiation, or a combination thereof.
Downstream of deformation zone 1035, the inter-clip spacing may increase or remain substantially constant relative to inter-clip spacing 1052 along first track 1025 and inter-clip spacing 1057 along second track 1027. For example, inter-clip spacing 1055 along first track 1025 within output zone 1045 may be substantially equal to the inter-clip spacing 1052 as the clips exit zone 1035, and inter-clip spacing 1059 along second track 1027 within output zone 1045 may be substantially equal to the inter-clip spacing 1057 as the clips exit zone 1035. Following the act of stretching, polymer thin film 1005 may be annealed, for example, within one or more downstream zones 1040, 1045.
The strain impact of the thin film orientation system 1000 is shown schematically by unit segments 1060, 1065, which respectively illustrate pre- and post-deformation dimensions for a selected area of polymer thin film 1005. In the illustrated embodiment, polymer thin film 1005 has a pre-stretch width (e.g., along the transverse direction) and a pre-stretch length (e.g., along the machine direction). As will be appreciated, a post-stretch width may be less than the pre-stretch width and a post-stretch length may be greater than the pre-stretch length.
In some embodiments, a roll-to-roll system may be integrated with a thin film orientation system, such as thin film orientation system 900 or thin film orientation system 1000, to manipulate a polymer thin film. In further embodiments, as illustrated herein with reference
An example roll-to-roll polymer thin film orientation system is depicted in
While controlling the temperature of the polymer thin film, rollers 1105, 1115 may be engaged and the polymer thin film may be stretched. For instance, first roller 1105 may rotate at a first rate and second roller 1115 may rotate at a second rate greater than the first rate to stretch the polymer thin film along a machine direction therebetween. Within a deformation zone between rollers, system 1100 may be configured to locally control the temperature and the strain rate of the polymer thin film. In some examples, as the polymer thin film advances from roller 1105 to roller 1115, a temperature of the polymer thin film may increase, and a strain rate of the polymer thin film may decrease. Downstream of roller 1115, the polymer thin film may then be cooled while maintaining the applied stress. System 1100 may be used to form a uniaxially oriented polymer thin film. Additional rollers may be added to system 1100 to control the conveyance and take-up of the polymer thin film.
Referring to
During calendaring, voids 1217 present in stretched polyethylene thin film 1215 may be compressed, and the overall void fraction within the thin film may be decreased. Moreover, voids exposed at a surface of the thin film may be smoothed, resulting in decreased surface roughness and, together with compression of voids within the bulk of the thin film, higher transmissivity and higher thermal conductivity.
According to some embodiments, a composite laminated structure having improved mechanical properties, including enhanced tensile strength and fracture toughness, may be formed by laminating optical grade ultra-drawn polyethylene layers between optically transparent substrates. The laminated structure may be incorporated into optical systems and devices. In conjunction with a negative coefficient of thermal expansion, the incorporation of a photothermal material into the relatively stiff polymer layers may be leveraged to form a self-stiffening laminated structure via the introduction of large interfacial stresses, which may further improve the mechanical properties of the stack upon actuation.
As disclosed herein, a transparent laminated structure includes a polymer multilayer formed between a pair of optically transparent substrates. The substrates may include glass or polymer sheets, for example. The polymer multilayer may include alternating layers of an ultra-drawn, ultra-high molecular weight polyethylene (PE) or ultra-drawn high density polyethylene and a suitable adhesive. In example structures, an interfacial energy between a PE layer and an adhesive layer within the polymer multilayer may be less than approximately 20 mN/m.
In some embodiments, the polymer layers may be uniaxially or biaxially stretched and then stacked and bonded with the stretch axes aligned mutually parallel, perpendicular, or at any suitable orientation to form the polymer multilayer. An example draw ratio for uniaxial or biaxial stretching may be 10 or more. Example polyethylene layers may have a molecular weight of at least approximately 200,000 g/mol, as well as a high tensile modulus (>10 GPa) and a high tensile strength (>0.2 GPa).
The polymer multilayer may be laminated to each substrate and, in certain embodiments, may be configured to exert interfacial compressive stresses that improve the mechanical properties of the laminated structure. In some examples, a photothermal dye may be incorporated into the PE polymer matrix and the interfacial compressive stresses may be achieved using photothermal actuation of the dye-containing polyethylene layer(s). Actuation may be achieved by exposure to heat and/or one or more of UV, visible, and near-IR radiation. As will be appreciated, the incorporation of a compressive stress in a near surface region of a substrate may inhibit crack propagation and fracture of the substrate.
In particular embodiments, the laminated structure may be characterized by a high tensile strength and a high fracture toughness. According to further embodiments, additional additives, such as low molecular weight polyethylene, mineral oil, and/or one or more fluoropolymer, may be incorporated into the polymer matrix and, in some examples, the polymer multilayer and the substrates may be refractive index matched and/or birefringence matched. An adhesive layer may be refractive index matched and/or birefringence matched with a polyethylene layer and/or a substrate. In lieu of incorporating the polymer multilayer into a laminated structure, in some embodiments, the polymer multilayer may be used independently as a stand-alone architecture.
Example 1: A multilayer structure includes a polymer multilayer having two or more laminated layers of ultra-drawn, ultra-high molecular weight polyethylene or high density polyethylene.
Example 2: The multilayer structure of Example 1, where draw axes of adjacent polyethylene layers are parallel.
Example 3: The multilayer structure of Example 1, where draw axes of adjacent polyethylene layers are rotationally offset.
Example 4: The multilayer structure of any of Examples 1-3, where at least one of the polyethylene layers includes a photothermal material.
Example 5: The multilayer structure of any of Examples 1-4, where the polymer multilayer is optically transparent.
Example 6: The multilayer structure of any of Examples 1-5, where the polymer multilayer has a near field transparency of at least approximately 80%, a far field transparency of at least approximately 85%, and bulk haze of less than approximately 10%.
Example 7: The multilayer structure of any of Examples 1-6, where the polymer multilayer includes a layer of an optical grade adhesive between adjacent polyethylene layers.
Example 8: The multilayer structure of any of Examples 1-7, where the polymer multilayer is disposed between a pair of substrates.
Example 9: The multilayer structure of Example 8, where the polymer multilayer is configured to induce a compressive stress in a near surface region of at least one of the substrates.
Example 10: The multilayer structure of any of Examples 8 and 9, where the substrates are optically transparent.
Example 11: The multilayer structure of any of Examples 1-10, where the multilayer structure is optically transparent.
Example 12: The multilayer structure of any of Examples 1-11, where the polymer multilayer has a thickness of from approximately 0.1 mm to approximately 2 mm.
Example 13: A heads-up display including the multilayer structure of any of examples 1-12.
Example 14: A method includes forming a polymer multilayer having two or more laminated layers of ultra-drawn, ultra-high molecular weight polyethylene or ultra-drawn high density polyethylene over a substrate, and processing the polymer multilayer to cause contraction of polymer chains within the polymer multilayer along an in-plane direction, where the contraction creates a compressive stress in a near surface region of the substrate.
Example 15: The method of Example 14, where the processing includes heating the polymer multilayer or illuminating the polymer multilayer with electromagnetic radiation.
Example 16: The method of any of Examples 14 and 15, further including tensioning at least one polyethylene layer prior to forming the polymer multilayer over the substrate.
Example 17: An optically transparent laminated structure includes a transparent substrate, and a polymer multilayer disposed over the transparent substrate, where the polymer multilayer includes two or more layers of ultra-drawn, ultra-high molecular weight polyethylene or ultra-drawn high density polyethylene.
Example 18: The optically transparent laminated structure of Example 17, where at least one of the polyethylene layers includes a photothermal material.
Example 19: The optically transparent laminated structure of any of Examples 17 and 18, where the polymer multilayer is configured to create a compressive stress in a near surface region of the transparent substrate.
Example 20: The optically transparent laminated structure of any of Examples 17-19, where the polymer multilayer has a near field transparency of at least approximately 80%, a far field transparency of at least approximately 85%, and bulk haze of less than approximately 10%.
Embodiments of the present disclosure may include or be implemented in conjunction with various types of artificial-reality systems. Artificial reality is a form of reality that has been adjusted in some manner before presentation to a user, which may include, for example, a virtual reality, an augmented reality, a mixed reality, a hybrid reality, or some combination and/or derivative thereof. Artificial-reality content may include completely computer-generated content or computer-generated content combined with captured (e.g., real-world) content. The artificial-reality content may include video, audio, haptic feedback, or some combination thereof, any of which may be presented in a single channel or in multiple channels (such as stereo video that produces a three-dimensional (3D) effect to the viewer). Additionally, in some embodiments, artificial reality may also be associated with applications, products, accessories, services, or some combination thereof, that are used to, for example, create content in an artificial reality and/or are otherwise used in (e.g., to perform activities in) an artificial reality.
Artificial-reality systems may be implemented in a variety of different form factors and configurations. Some artificial-reality systems may be designed to work without near-eye displays (NEDs). Other artificial-reality systems may include an NED that also provides visibility into the real world (such as, e.g., augmented-reality system 1300 in
Turning to
In some embodiments, augmented-reality system 1300 may include one or more sensors, such as sensor 1340. Sensor 1340 may generate measurement signals in response to motion of augmented-reality system 1300 and may be located on substantially any portion of frame 1310. Sensor 1340 may represent one or more of a variety of different sensing mechanisms, such as a position sensor, an inertial measurement unit (IMU), a depth camera assembly, a structured light emitter and/or detector, or any combination thereof. In some embodiments, augmented-reality system 1300 may or may not include sensor 1340 or may include more than one sensor. In embodiments in which sensor 1340 includes an IMU, the IMU may generate calibration data based on measurement signals from sensor 1340. Examples of sensor 1340 may include, without limitation, accelerometers, gyroscopes, magnetometers, other suitable types of sensors that detect motion, sensors used for error correction of the IMU, or some combination thereof.
In some examples, augmented-reality system 1300 may also include a microphone array with a plurality of acoustic transducers 1320(A)-1320(J), referred to collectively as acoustic transducers 1320. Acoustic transducers 1320 may represent transducers that detect air pressure variations induced by sound waves. Each acoustic transducer 1320 may be configured to detect sound and convert the detected sound into an electronic format (e.g., an analog or digital format). The microphone array in
In some embodiments, one or more of acoustic transducers 1320(A)-(J) may be used as output transducers (e.g., speakers). For example, acoustic transducers 1320(A) and/or 1320(B) may be earbuds or any other suitable type of headphone or speaker.
The configuration of acoustic transducers 1320 of the microphone array may vary. While augmented-reality system 1300 is shown in
Acoustic transducers 1320(A) and 1320(B) may be positioned on different parts of the user's ear, such as behind the pinna, behind the tragus, and/or within the auricle or fossa. Or, there may be additional acoustic transducers 1320 on or surrounding the ear in addition to acoustic transducers 1320 inside the ear canal. Having an acoustic transducer 1320 positioned next to an ear canal of a user may enable the microphone array to collect information on how sounds arrive at the ear canal. By positioning at least two of acoustic transducers 1320 on either side of a user's head (e.g., as binaural microphones), augmented-reality device 1300 may simulate binaural hearing and capture a 3D stereo sound field around about a user's head. In some embodiments, acoustic transducers 1320(A) and 1320(B) may be connected to augmented-reality system 1300 via a wired connection 1330, and in other embodiments acoustic transducers 1320(A) and 1320(B) may be connected to augmented-reality system 1300 via a wireless connection (e.g., a BLUETOOTH connection). In still other embodiments, acoustic transducers 1320(A) and 1320(B) may not be used at all in conjunction with augmented-reality system 1300.
Acoustic transducers 1320 on frame 1310 may be positioned in a variety of different ways, including along the length of the temples, across the bridge, above or below display devices 1315(A) and 1315(B), or some combination thereof. Acoustic transducers 1320 may also be oriented such that the microphone array is able to detect sounds in a wide range of directions surrounding the user wearing the augmented-reality system 1300. In some embodiments, an optimization process may be performed during manufacturing of augmented-reality system 1300 to determine relative positioning of each acoustic transducer 1320 in the microphone array.
In some examples, augmented-reality system 1300 may include or be connected to an external device (e.g., a paired device), such as neckband 1305. Neckband 1305 generally represents any type or form of paired device. Thus, the following discussion of neckband 1305 may also apply to various other paired devices, such as charging cases, smart watches, smart phones, wrist bands, other wearable devices, hand-held controllers, tablet computers, laptop computers, other external compute devices, etc.
As shown, neckband 1305 may be coupled to eyewear device 1302 via one or more connectors. The connectors may be wired or wireless and may include electrical and/or non-electrical (e.g., structural) components. In some cases, eyewear device 1302 and neckband 1305 may operate independently without any wired or wireless connection between them. While
Pairing external devices, such as neckband 1305, with augmented-reality eyewear devices may enable the eyewear devices to achieve the form factor of a pair of glasses while still providing sufficient battery and computation power for expanded capabilities. Some or all of the battery power, computational resources, and/or additional features of augmented-reality system 1300 may be provided by a paired device or shared between a paired device and an eyewear device, thus reducing the weight, heat profile, and form factor of the eyewear device overall while still retaining desired functionality. For example, neckband 1305 may allow components that would otherwise be included on an eyewear device to be included in neckband 1305 since users may tolerate a heavier weight load on their shoulders than they would tolerate on their heads. Neckband 1305 may also have a larger surface area over which to diffuse and disperse heat to the ambient environment. Thus, neckband 1305 may allow for greater battery and computation capacity than might otherwise have been possible on a stand-alone eyewear device. Since weight carried in neckband 1305 may be less invasive to a user than weight carried in eyewear device 1302, a user may tolerate wearing a lighter eyewear device and carrying or wearing the paired device for greater lengths of time than a user would tolerate wearing a heavy standalone eyewear device, thereby enabling users to more fully incorporate artificial-reality environments into their day-to-day activities.
Neckband 1305 may be communicatively coupled with eyewear device 1302 and/or to other devices. These other devices may provide certain functions (e.g., tracking, localizing, depth mapping, processing, storage, etc.) to augmented-reality system 1300. In the embodiment of
Acoustic transducers 1320(1) and 1320(J) of neckband 1305 may be configured to detect sound and convert the detected sound into an electronic format (analog or digital). In the embodiment of
Controller 1325 of neckband 1305 may process information generated by the sensors on neckband 1305 and/or augmented-reality system 1300. For example, controller 1325 may process information from the microphone array that describes sounds detected by the microphone array. For each detected sound, controller 1325 may perform a direction-of-arrival (DOA) estimation to estimate a direction from which the detected sound arrived at the microphone array. As the microphone array detects sounds, controller 1325 may populate an audio data set with the information. In embodiments in which augmented-reality system 1300 includes an inertial measurement unit, controller 1325 may compute all inertial and spatial calculations from the IMU located on eyewear device 1302. A connector may convey information between augmented-reality system 1300 and neckband 1305 and between augmented-reality system 1300 and controller 1325. The information may be in the form of optical data, electrical data, wireless data, or any other transmittable data form. Moving the processing of information generated by augmented-reality system 1300 to neckband 1305 may reduce weight and heat in eyewear device 1302, making it more comfortable to the user.
Power source 1335 in neckband 1305 may provide power to eyewear device 1302 and/or to neckband 1305. Power source 1335 may include, without limitation, lithium ion batteries, lithium-polymer batteries, primary lithium batteries, alkaline batteries, or any other form of power storage. In some cases, power source 1335 may be a wired power source. Including power source 1335 on neckband 1305 instead of on eyewear device 1302 may help better distribute the weight and heat generated by power source 1335.
As noted, some artificial-reality systems may, instead of blending an artificial reality with actual reality, substantially replace one or more of a user's sensory perceptions of the real world with a virtual experience. One example of this type of system is a head-worn display system, such as virtual-reality system 1400 in
Artificial-reality systems may include a variety of types of visual feedback mechanisms. For example, display devices in augmented-reality system 1300 and/or virtual-reality system 1400 may include one or more liquid crystal displays (LCDs), light emitting diode (LED) displays, microLED displays, organic LED (OLED) displays, digital light project (DLP) micro-displays, liquid crystal on silicon (LCoS) micro-displays, and/or any other suitable type of display screen. These artificial-reality systems may include a single display screen for both eyes or may provide a display screen for each eye, which may allow for additional flexibility for varifocal adjustments or for correcting a user's refractive error. Some of these artificial-reality systems may also include optical subsystems having one or more lenses (e.g., conventional concave or convex lenses, Fresnel lenses, adjustable liquid lenses, etc.) through which a user may view a display screen. These optical subsystems may serve a variety of purposes, including to collimate (e.g., make an object appear at a greater distance than its physical distance), to magnify (e.g., make an object appear larger than its actual size), and/or to relay (to, e.g., the viewer's eyes) light. These optical subsystems may be used in a non-pupil-forming architecture (such as a single lens configuration that directly collimates light but results in so-called pincushion distortion) and/or a pupil-forming architecture (such as a multi-lens configuration that produces so-called barrel distortion to nullify pincushion distortion).
In addition to or instead of using display screens, some of the artificial-reality systems described herein may include one or more projection systems. For example, display devices in augmented-reality system 1300 and/or virtual-reality system 1400 may include micro-LED projectors that project light (using, e.g., a waveguide) into display devices, such as clear combiner lenses that allow ambient light to pass through. The display devices may refract the projected light toward a user's pupil and may enable a user to simultaneously view both artificial-reality content and the real world. The display devices may accomplish this using any of a variety of different optical components, including waveguide components (e.g., holographic, planar, diffractive, polarized, and/or reflective waveguide elements), light-manipulation surfaces and elements (such as diffractive, reflective, and refractive elements and gratings), coupling elements, etc. Artificial-reality systems may also be configured with any other suitable type or form of image projection system, such as retinal projectors used in virtual retina displays.
The artificial-reality systems described herein may also include various types of computer vision components and subsystems. For example, augmented-reality system 1300 and/or virtual-reality system 1400 may include one or more optical sensors, such as two-dimensional (2D) or 3D cameras, structured light transmitters and detectors, time-of-flight depth sensors, single-beam or sweeping laser rangefinders, 3D LiDAR sensors, and/or any other suitable type or form of optical sensor. An artificial-reality system may process data from one or more of these sensors to identify a location of a user, to map the real world, to provide a user with context about real-world surroundings, and/or to perform a variety of other functions.
The artificial-reality systems described herein may also include one or more input and/or output audio transducers. Output audio transducers may include voice coil speakers, ribbon speakers, electrostatic speakers, piezoelectric speakers, bone conduction transducers, cartilage conduction transducers, tragus-vibration transducers, and/or any other suitable type or form of audio transducer. Similarly, input audio transducers may include condenser microphones, dynamic microphones, ribbon microphones, and/or any other type or form of input transducer. In some embodiments, a single transducer may be used for both audio input and audio output.
In some embodiments, the artificial-reality systems described herein may also include tactile (i.e., haptic) feedback systems, which may be incorporated into headwear, gloves, body suits, handheld controllers, environmental devices (e.g., chairs, floormats, etc.), and/or any other type of device or system. Haptic feedback systems may provide various types of cutaneous feedback, including vibration, force, traction, texture, and/or temperature. Haptic feedback systems may also provide various types of kinesthetic feedback, such as motion and compliance. Haptic feedback may be implemented using motors, piezoelectric actuators, fluidic systems, and/or a variety of other types of feedback mechanisms. Haptic feedback systems may be implemented independent of other artificial-reality devices, within other artificial-reality devices, and/or in conjunction with other artificial-reality devices.
By providing haptic sensations, audible content, and/or visual content, artificial-reality systems may create an entire virtual experience or enhance a user's real-world experience in a variety of contexts and environments. For instance, artificial-reality systems may assist or extend a user's perception, memory, or cognition within a particular environment. Some systems may enhance a user's interactions with other people in the real world or may enable more immersive interactions with other people in a virtual world. Artificial-reality systems may also be used for educational purposes (e.g., for teaching or training in schools, hospitals, government organizations, military organizations, business enterprises, etc.), entertainment purposes (e.g., for playing video games, listening to music, watching video content, etc.), and/or for accessibility purposes (e.g., as hearing aids, visual aids, etc.). The embodiments disclosed herein may enable or enhance a user's artificial-reality experience in one or more of these contexts and environments and/or in other contexts and environments.
The process parameters and sequence of the steps described and/or illustrated herein are given by way of example only and may be varied as desired. For example, while the steps illustrated and/or described herein may be shown or discussed in a particular order, these steps do not necessarily need to be performed in the order illustrated or discussed. The various exemplary methods described and/or illustrated herein may also omit one or more of the steps described or illustrated herein or include additional steps in addition to those disclosed.
The preceding description has been provided to enable others skilled in the art to best utilize various aspects of the exemplary embodiments disclosed herein. This exemplary description is not intended to be exhaustive or to be limited to any precise form disclosed. Many modifications and variations are possible without departing from the spirit and scope of the present disclosure. The embodiments disclosed herein should be considered in all respects illustrative and not restrictive. Reference should be made to the appended claims and their equivalents in determining the scope of the present disclosure.
Unless otherwise noted, the terms “connected to” and “coupled to” (and their derivatives), as used in the specification and claims, are to be construed as permitting both direct and indirect (i.e., via other elements or components) connection. In addition, the terms “a” or “an,” as used in the specification and claims, are to be construed as meaning “at least one of.” Finally, for ease of use, the terms “including” and “having” (and their derivatives), as used in the specification and claims, are interchangeable with and have the same meaning as the word “comprising.”
It will be understood that when an element such as a layer or a region is referred to as being formed on, deposited on, or disposed “on” or “over” another element, it may be located directly on at least a portion of the other element, or one or more intervening elements may also be present. In contrast, when an element is referred to as being “directly on” or “directly over” another element, it may be located on at least a portion of the other element, with no intervening elements present.
As used herein, the term “substantially” in reference to a given parameter, property, or condition may mean and include to a degree that one of ordinary skill in the art would understand that the given parameter, property, or condition is met with a small degree of variance, such as within acceptable manufacturing tolerances. By way of example, depending on the particular parameter, property, or condition that is substantially met, the parameter, property, or condition may be at least approximately 90% met, at least approximately 95% met, or even at least approximately 99% met.
As used herein, the term “approximately” in reference to a particular numeric value or range of values may, in certain embodiments, mean and include the stated value as well as all values within 10% of the stated value. Thus, by way of example, reference to the numeric value “50” as “approximately 50” may, in certain embodiments, include values equal to 50±5, i.e., values within the range 45 to 55.
While various features, elements or steps of particular embodiments may be disclosed using the transitional phrase “comprising,” it is to be understood that alternative embodiments, including those that may be described using the transitional phrases “consisting” or “consisting essentially of,” are implied. Thus, for example, implied alternative embodiments to an adhesive that comprises or includes BZT include embodiments where an adhesive consists essentially of BZT and embodiments where an adhesive consists of BZT.
This application claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Application No. 63/284,785, filed Dec. 1, 2021, the contents of which are incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63284785 | Dec 2021 | US |
