MATERIALS FOR PIEZOELECTRIC IMPLANTS, AND METHODS OF POLING MATERIALS FOR PIEZOELECTRIC RESPONSE

FOR BONE GROWTH STIMULATION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63/156, 192 filed March 3, 2021, U.S. Provisional Patent Application No. 63/196,137 filed June 2, 2021, U.S. Provisional Patent Application No. 63/243901 filed September 14, 2021, and U.S. Provisional Patent Application No. 63/299540 filed January 14, 2022. The entire disclosures of these provisional applications are incorporated herein by reference.

FIELD

[0002] The present disclosure relates to materials for piezoelectric implants. The present disclosure also relates to methods of poling for piezoelectric response for bone growth stimulation. The present disclosure further relates to piezoelectric implants comprising such materials.

BACKGROUND

[00031 This section provides background information related to the present disclosure which is not necessarily prior art.

[00041 Piezoelectric refers to the ability of certain materials to generate an electric charge in response to applied mechanical stress or pressure. For example, a piezoelectric spinal fusion implant will generate electricity to stimulate bone growth when the piezoelectric spinal fusion implant is subjected to applied stress and compressive loads during normal activities, such as walking, etc.

SUMMARY

[00051 This section provides a general summary of the disclosure and is not a comprehensive disclosure of its full scope or all of its features.

[0006] Disclosed are exemplary embodiments of materials for piezoelectric implants. Also disclosed are exemplary methods of poling materials for piezoelectric response for bone growth stimulation. Additional exemplary embodiments are disclosed of piezoelectric implants comprising such materials.

[0007] Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

DRAWINGS

[0008] The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations and is not intended to limit the scope of the present disclosure.

[0009] FIG. 1 is a perspective view of a material including barium titanate (BaTiCh) and polyetheretherketone (PEEK) according to an exemplar)' embodiment in which tunnels or closed-ended holes have been formed (e.g., drilled, etc.) in the BaTiOVPEEK material.

[0010] FIG. 2 is a cross-sectional view of the BaTiOr /PEEK material shown in FIG. 1 taken along the tunnels and illustrating the negative charge along the top and bottom surfaces of the BaTiOVPEEK material.

[0011] FIG. 3 is a front end view of the BaTiCh /PEEK material shown in FIG. 1 and illustrating the negative charge along the top and bottom surfaces of the BaTiOVPEEK material.

[0012] FIG. 4 is a side view of the BaTiOa /PEEK material shown in FIG. 1 and illustrating the negative charge along the top and bottom surfaces of the BaTiOVPEEK material. [00131 FIGS. 5 and 6 are perspective views of a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplary embodiment

[00141 FIG. 7 is a side view of the piezoelectric implant shown in FIG. 5.

[00151 FIG. 8 is a front view of the piezoelectric implant shown in FIG. 5.

[00161 FIG. 9 is a top view of the piezoelectric implant shown in FIG. 5.

[00171 FIG. 10 is a cross-sectional view taken along the line A-A in FIG. 8.

[00181 FIG. 11 is a detailed view of the portion C in FIG. 10 at a scale of 10:1.

[00191 FIG. 12 is a cross-sectional view taken along the line B-B in FIG. 9.

[00201 FIG. 13 is a perspective view of the piezoelectric implant shown in FIG. 5 without an electrode or electrically- conductive coating to illustrate the location of piezoelectric elements (e.g., pre-poled piezoelectric PVDF films laminated, etc.) along at least the outermost protruding portions of ridges defined by abase (e.g., PEEK or other suitable material, etc).

[0021] FIG. 14 is a perspective view illustrating an electrically -conductive coating shown as a shell (e.g., a titanium or other electrically-conductive coating provided via stuttering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc.) for the piezoelectric implant shown in FIG. 13 such that an entire outside of the piezoelectric implant has a negative charge.

[0022] FIGS. 15 and 16 are cross-sectional views (not to scale) of a piezoelectric implant according to an exemplary embodiment including an electrode coating or shell (e.g., a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc ) such that an entire outside of the piezoelectric implant has a negative charge as shown in FIG. 15.

[0023] FIG. 17 is a cross-sectional views (not to scale) of a piezoelectric implant according to an exemplary embodiment including an electrically-conductive coating (e.g., a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc) such that an entire outside of the piezoelectric implant has a negative charge.

[0024[ FIGS. 18 and 19 are perspective views of a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplary embodiment

[00251 FIG. 20 is a side view of the piezoelectric implant shown in FIG. 18.

[00261 FIG. 21 is a front view of the piezoelectric implant shown in FIG. 18.

[00271 FIG. 22 is a top view of the piezoelectric implant shown in FIG. 18.

[00281 FIG. 23 is a cross-sectional view taken along the line A-A in FIG. 21.

[00291 FIG. 24 is a detailed view of the portion C in FIG. 23 at a scale of 10:1.

[00301 FIG. 25 is a cross-sectional view taken along the line B-B in FIG. 22.

[00311 FIG. 26 is an exploded perspective view illustrating the electrically-conductive coating shown as a shell (e.g., a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc), the piezoelectric inserts (e.g., piezoelectric poled PVDF inserts, etc.) and base (e.g., PEEK base, etc.) of the piezoelectric implant shown in FIGS. 18-25. The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge.

[0032] FIGS. 27 and 28 are perspective views of a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplary embodiment.

[0033[ FIG. 29 is a side view of the piezoelectric implant shown in FIG. 27.

[00341 FIG. 30 is a front view of the piezoelectric implant shown in FIG. 27.

[00351 FIG. 31 is a top view of the piezoelectric implant shown in FIG. 27.

[00361 FIG. 32 is a cross-sectional view taken along the line A-A in FIG. 30.

[00371 FIG. 33 is a detailed view of the portion C in FIG. 32 at a scale of 10:1. [00381 FIG. 34 is a cross-sectional view taken along the line B-B in FIG. 31.

[00391 FIG. 35 is an exploded perspective view illustrating the electrically-conductive coating shown as a shell (e.g, a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc.) and the piezoelectric base (e.g., piezoelectric poled PVDF base, etc.) of the piezoelectric implant shown in FIGS. 27- 34. The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge.

[00401 FIGS. 36 and 37 are perspective views of a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplaiy embodiment

[00411 FIG. 38 is a side view of the piezoelectric implant shown in FIG. 36.

[00421 FIG. 39 is a front view of the piezoelectric implam shown in FIG. 36.

[00431 FIG. 40 is a top view of the piezoelectric implant shown in FIG. 36.

[00441 FIG. 41 is a cross-sectional view taken along the line A-A in FIG. 39.

[00451 FIG. 42 is a detailed view of the portion C in FIG. 41 at a scale of 10:1.

[00461 FIG. 43 is a cross-sectional view taken along the line B-B in FIG. 40.

[00471 FIG. 44 is an exploded perspective view illustrating the electrically-conductive coating shown as a shell (e.g, a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc,), the piezoelectric coating (e.g., piezoelectric poled PVDF dipped coating, etc.), and the base (e.g., PEEK base, etc.) of the piezoelectric implam shown in FIGS. 38-45. The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge.

[0048] FIGS. 45 and 46 are perspective views of a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplaiy embodiment

[00491 FIG. 47 is a side view of the piezoelectric implant shown in FIG. 45.

[00501 FIG. 48 is a front view of the piezoelectric implant shown in FIG. 45.

[00511 FIG. 49 is a top view of the piezoelectric implam shown in FIG. 45.

[00521 FIG. 50 is a cross-sectional view taken along the line A-A in FIG. 48.

[00531 FIG. 51 is a detailed view of the portion C in FIG. 50 at a scale of 10:1.

[00541 FIG. 52 is a cross-sectional view taken along the line B-B in FIG. 49.

[00551 FIG. 53 is an exploded perspective view illustrating the electrically-conductive coating shown as a shell (e.g., a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, pltysical vapor deposition, or other suitable process, etc), the piezoelectric inserts (e.g., piezoelectric poled PVDF inserts, etc.) and the base (e.g., PEEK base, etc) of the piezoelectric implant shown in FIGS. 38-45. The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge. The piezoelectric inserts may be bonded to the base with electrically non-conductive or dielectric adhesive.

DETAILED DESCRIPTTON

[0056[ Example embodiments will now be described more fully with reference to the accompanying drawings.

[00571 Disclosed are exemplaiy etribodimems of materials for piezoelectric implants. In exemplary embodiments, a material for a piezoelectric implam comprises a compounded material including barium titanate. In other exemplary embodiments, a material for a piezoelectric implam comprises a homogeneous material including ceramic material(s) doped with barium titanate. In additional exemplary embodiments, a material for a piezoelectric implam comprises polylactide (PolyQactic acid), PLA) (e.g., PLLA, PDLA, PDLLA, etc) poled to be piezoelectric. In further exemplary embodiments, a material for a piezoelectric implam comprises polyvinylidene fluoride (PVDF) poled to be piezoelectric. In other exemplaiy' etribodimems, a material for a piezoelectric implam comprises potassium sodium niobate (KNN) poled to be piezoelectric. [0058] In yet other exemplary embodiments, the structural substrate or base (e.g, PEEK, etc.) of a piezoelectric implant may be dipped into a liquid material to thereby coat and encapsulate the structural substrate or base with the material, which material would thereafter be poled to be piezoelectric. The liquid material may comprise liquid polyvinylidene fluoride (PVDF), liquid polylactide (Poly(lactic acid), PLA) (e.g., PLLA, PDLA, PDLLA, etc.), liquid potassium sodium niobate (KNN, etc. The structural substrate or base of the piezoelectric implant may comprise polyetheretherketone (PEEK), polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic potymer(s), other thermoplastic material(s), zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, and/or other ceramic materials), etc.

[0059] Also disclosed are exemplary methods of poling materials (e.g., compounded materials including barium titanate, ceramic material(s) doped with barium titanate, PVDF, PLLA, KNN, etc.) for piezoelectric response for bone growth stimulation. Additional exemplary embodiments are disclosed of piezoelectric implants (e.g., a piezoelectric spinal fusion implant, a piezoelectric cranial implant, other orthopedic piezoelectric implant, veterinary/animal piezoelectric implant, etc.) comprising (e.g., injection molded from, etc.) one or more materials disclosed herein, such as a compounded material including barium titanate, a homogeneous material including ceramic materials) doped with barium titanate, PVDF, PLA, KNN, other materials disclosed herein.

[0060] In exemplary embodiments, a compounded material comprises barium titanate and a thermoplastic material, such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic polymers), other thermoplastic material(s), etc. The compounded material comprising barium titanate and thermoplastic material may be annealed in exemplary embodiments.

[0061] In other exemplary embodiments, a homogeneous material comprises one or more of zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic material(s) that has been doped with barium titanate. The homogeneous material comprising ceramic material doped with barium titanate may be sintered in exemplary embodiments.

[0062] In additional exemplary embodiments, a material for a piezoelectric implant comprises polylactide (Poly(lactic acid), PLA) (e.g., PLLA, PDLA, PDLLA. etc ) poled to be piezoelectric. For example, PLLA may' be poled to be dielectric independent of or without needing barium titanate. The PLLA may be usable as a single homogeneous piezoelectric material for a piezoelectric implant, e.g., instead of or in addition to using a compounded material including barium titanate, etc. By way of further example, piezoelectric poled PLLA may be bonded to surfaces of a compounded material including barium titanate and thermoplastic and/or to surfaces of a homogeneous material including ceramic material doped with barium titanate.

[0063] In further exemplary embodiments, a material for a piezoelectric implant comprises polyvinylidene fluoride (PVDF) poled to be piezoelectric. PVDF may be poled to be dielectric independent of or without needing barium titanate. The poled PVDF may be used for a piezoelectric implant, e.g., instead of or in addition to using a compounded material including barium titanate, etc. For example, one or more poled piezoelectric PVDF films, sheets, or layers may bonded to (e.g., wrapped around and/or fused, etc) to surfaces of a compounded material including barium titanate and thermoplastic and/or to surfaces of a homogeneous material including ceramic material doped with barium titanate.

[0064] In other exemplary embodiments, a material for a piezoelectric implant comprises potassium sodium niobate (KNN) poled to be piezoelectric. KNN may be poled to be dielectric independent of or without needing barium titanate. The poled KNN may be used for a piezoelectric implant, e.g., instead of or in addition to using a compounded material including barium titanate, etc. For example, one or more poled piezoelectric KNN films, sheets, or layers may bonded to (e.g., wrapped around and/or fused, etc) to surfaces of a compounded material including barium titanate and thermoplastic and/or to surfaces of a homogeneous material including ceramic material doped with barium titanate.

[0065] Generally, compounding is a process of mixing or blending a base resin and one or more additives. Compounding is typically performed in the molten state to achieve a homogeneous blend of the base resin and additives. In exemplary embodiments disclosed herein, PEEK (or other thermoplastic polymer) is compounded with barium titanate to provide a homogeneous compounded blend of the PEEK and barium titanate. By way of example, the barium titanate may be in the form of spheres and/or fibers, etc. The PEEK and barium titanate may be fed through an extmder (e.g., twin screw extruder, etc.) or other suitable compounder in which the PEEK and barium titanate are blended. The melted homogeneous blend of the PEEK and barium titanate may exit the extmder in strands. After the strands have cooled, the strands may be pelletized and formed into pellets suitable for injection molding of piezoelectric implants (e.g., an injection molded single-piece piezoelectric spinal fusion, cranial, orthopedic, or veterinary/animal implant having a monolithic construction, etc.). In this example, the PEEK was compounded with barium titanate. But in other exemplary embodiments, other materials may be compounded with barium titanate, such as polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic polymers), other thermoplastic material(s). Accordingly, all exemplary embodiments disclosed herein do not necessarily require or are not limited to PEEK. In addition, all exemplary embodiments disclosed herein do not necessarily require or are not limited to barium titanate.

[0066] In exemplary embodiments, one or more films, sheets, or layers of material (e.g., polyvinylidene fluoride (PVDF), poly lactide (Poly (lactic acid) PL A), potassium sodium niobate (KNN), etc. ) that has been poled to be piezoelectric is bonded (e.g. , wrapped around and/or fused, etc.) to surfaces of a compounded material including barium titanate and thermoplastic and/or to surfaces of a homogeneous material including ceramic material doped with barium titanate.

[0067] For example, a relatively thin film, sheet, or layer of PVDF may be poled to be piezoelectric. The PVDF film, sheet, or layer may be piezoelectric without needing barium titanate to be piezoelectric. The piezoelectric PVDF film, sheet, or layer may then be bonded to a compounded material that comprises barium titanate and thermoplastic material and/or to a homogeneous material that comprises ceramic material doped with barium titanate.

[0068] By way of further example, a relatively thin film, sheet, or layer of PLA (e.g., PLLA, PDLA, PDLLA, etc.) may be poled to be piezoelectric. The PLA film, sheet, or layer film may then be bonded to a compounded material that comprises barium titanate and thermoplastic material and/or to a homogeneous material that comprises ceramic material doped with barium titanate.

[0069] As a further example, a relatively thin film, sheet, or layer of KNN may be poled to be piezoelectric. The KNN film, sheet, or layer may then be bonded to a compounded material that comprises barium titanate and thermoplastic material and/or to a homogeneous material that comprises ceramic material doped with barium titanate.

[0070] In exemplary embodiments, a compounded material comprises the barium titanate and polyetheretherketone (PEEK). The compounded material may comprise a homogeneous conpounded blend of the polyetheretherketone and the barium titanate.

[0071] In exemplary embodiments, the compounded material comprises the barium titanate and at least one other material. For example, the compounded material may comprise the barium titanate and at least one other material including one or more of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic polymer(s), other thermoplastic material(s), etc.

[0072] In an exemplary embodiment, a compounded material includes about 40 percent by weight of the barium titanate, and/or the conpounded material includes about 12.62 percent by volume of the barium titanate.

[0073] In an exemplary embodiment, a compounded material includes about 50 percent by weight of the barium titanate, and/or the conpounded material includes about 17.8 percent by volume of the barium titanate.

[0074] In an exemplary embodiment, a conpounded material includes about 60 percent by weight of the barium titanate, and/or the conpounded material includes about 24.52 percent by volume of the barium titanate.

[0075] In an exemplary' embodiment, a conpounded material includes about 70 percent by weight of the barium titanate, and/or the conpounded material includes about 33.57 percent by volume of the barium titanate.

[0076] In an exemplary embodiment, a conpounded material includes about 80 percent by weight of the barium titanate, and/or the conpounded material includes about 46.42 percent by volume of the barium titanate.

[0077] In an exemplary embodiment, a conpounded material includes about 30 percent by weight of polyetheretherketone; and/or the conpounded material includes about 66.5 percent by volume of polyetheretherketone. [0078] In exemplary embodiments, the compounded material includes a top surface and a bottom surface. The compounded material is poled or configured to have a negative charge along the top and bottom surfaces.

[0079] In exemplary embodiments, the compounded material includes a top surface, a bottom surface, and at least one tunnel. The at least one tunnel has an open end in one of a top or bottom surface and extending fiom the one of said top or bottom surface towards the other one of said top or bottom surface. The at least one tunnel does not extend completely through the other one of said top or bottom surface such that the at least one tunnel has a closed end adjacent the other one of said top or bottom surface. The compounded material is configured to have a negative charge along the top and bottom surfaces.

[0080] In exemplary embodiments, the compounded material includes first and second comers diagonally opposite each other and third and fourth diagonally opposite each other. The compounded material also includes first, second, third, and fourth tunnels respectively adjacent the first, second, third, and fourth comers of the compounded material. Each of the first and second tunnels starts at an opening defined in the top surface and extends downwardly fiom the top surface towards the bottom surface. The first and second tunnels do not extend completely through the bottom surface such that each of the first and second tunnels has a closed end adjacent the bottom surface. Each of the third and fourth tunnels starts at an opening defined in the bottom surface and extends upwardly fiom the bottom surface towards the top surface. The third and fourth tunnels do not extend completely through the top surface such that each of the third and fourth tunnels has a closed end adjacent the top surface.

[0081] In exemplary embodiments, the compounded material is poled at a temperature less than the Curie temperature of the barium titanate, and the poled compounded material is piezoelectric.

[0082] In exemplary embodiments, the compounded material is poled at room temperature within a range from about 20 °C to 22 °C, and the poled compounded material is piezoelectric.

[0083] In exemplary embodiments, the compounded material has a piezoelectric modulus or piezoelectric coefficient (D33) within a range fiom 4 to 33 (e.g., from 5 to 23, etc?). The D33 range from 4 to 33 is an example as other exemplary embodiments may be configured differently, such that the compounded material has a piezoelectric modulus or piezoelectric coefficient (D33) less than 4 or greater than 33.

[0084] In exemplaty embodiments, the compounded material consists only of poly etheretherketone and the barium titanate.

[00851 In exemplary embodiments, a piezoelectric implant comprises a compounded material as disclosed herein. The piezoelectric implant may be injection molded from the compounded material such that the piezoelectric implant has a monolithic, singlepiece construction. The piezoelectric implant may comprise a spinal fusion piezoelectric implant, cranial piezoelectric implant, orthopedic piezoelectric implant, a veterinary /animal piezoelectric implant, eta

[0086] In exemplary embodiments, a method comprises prepoling a material that includes barium titanate by annealing the material during which pressure and electrical current is applied to the compounded material; or extruding the material during which electrical current is applied to the compounded material.

[0087] In exemplary embodiments, a method includes compounding polyetheretherketone with the barium titanate to thereby provide a homogeneous compounded blend of the poiyetheretherketone and the barium titanate; and thereafter poling the homogeneous compounded blend of the polyetheretheiketone and the barium titanate for piezoelectric response.

[0088] In exemplary embodiments, a method comprises poling a material including barium titanate and thermoplastic polymer for piezoelectric response at a temperature less than the Curie temperature of the barium titanate and less than the glass transition temperature of the thermoplastic polymer.

[0089] In exemplary embodiments, the thermoplastic polymer comprises polyetheretherketone, potyetherketoneketone, another thermoplastic polymer in the polyaryletherketone family, other thermoplastic polymer(s).

[0090] In exemplary embodiments, the method includes poling the material at room temperature within a range from about 20 °C to 22 °C. [0091] hi exemplary embodiments, the poling includes applying an electric charge of about 75 kilovolts to the material for about 5 minutes at room temperature in a silicone oil bath without first heating the material.

[0092] In exemplary embodiments, the method includes compounding polyetheretherketone with the barium titanate to thereby provide a homogeneous compounded blend of the polyetheretherketone and the barium titanate; and thereafter poling the homogeneous compounded blend of the polyctherctherketone and the barium titanate for piezoelectric response at the temperature less than the Curie temperature of the barium titanate and less than the glass transition temperature of the polyetheretherketone. The homogeneous compounded blend of the polyetheretherketone and the barium titanate may consist only of the polyetheretherketone and the barium titanate. The method may further include injection molding the homogeneous compounded blend of the polyetheretherketone and the barium titanate into a single-piece piezoelectric implant having a monolithic construction.

[0093] In exemplary embodiments, the material includes about 33.5 percent by volume of the barium titanate; and/or the material includes about 70 percent by' weight of the barium titanate. The material may include about 66.5 percent by volume of polyetheretherketone; and/or the material may include about 30 percent by weight of polyetheretherketone.

[0094] In an exemplary' embodiment, a compounded material includes about 40 percent by weight of the barium titanate, and/or the compounded material includes about 12.62 percent by volume of the barium titanate. In an exemplary embodiment, a compounded material includes about 50 percent by weight of the barium titanate, and/or the compounded material includes about 17.8 percent by volume of the barium titanate. In an exemplary embodiment, a compounded material includes about 60 percent by weight of the barium titanate, and/or the confounded material includes about 24.52 percent by volume of the barium titanate. In an exemplary embodiment, a confounded material includes about 80 percent by weight of the barium titanate, and/or the confounded material includes about 46.42 percent by volume of the barium titanate.

[0095] In exemp lary embodiments, the method includes poling the material to have a negative charge along top and bottom surfaces of the material.

[0096] In exemplar)' embodiments, the method includes forming at least one tunnel in the material having an open end in one of a top or bottom surface of the compounded material and that extends from the one of said top or bottom surface towards the other one of said top or bottom surface. The at least one tunnel does not extend completely through the other one of said top or bottom surface such that the at least one tunnel has a closed end adjacent the other one of said top or bottom surface.

[0097] In exemplary embodiments, the material includes first and second comers diagonally opposite each other and third and fourth diagonally opposite each other. The method includes forming first, second, third, and fourth tunnels respectively adjacent the first, second, third, and fourth comers of the compounded material. Each of the first and second tunnels starts at an opening defined in the top surface and extends downwardly from the top surface towards the bottom surface. The first and second tunnels do not extend completely through the bottom surface such that each of the first and second tunnels has a closed end adjacent the bottom surface. Each of the third and fourth tunnels starts at an opening defined in the bottom surface and extends upwardly from the bottom surface towards the top surface. The third and fourth tunnels do not extend completely through the top surface such that each of the third and fourth tunnels has a closed end adjacent the top surface.

[0098] In exemplary embodiments, the material including the barium titanate and thermoplastic polymer has a piezoelectric modulus or piezoelectric coefficient (D33) within a range from 4 to 33 (e.g., from 5 to 23, etc). The D33 range from 4 to 33 is an example as other exemplary embodiments may be configured differently, such that the material including the barium titanate and thermoplastic polymer a piezoelectric modulus or piezoelectric coefficient (D33) less than 4 or greater than 33.

[0099] In exemplary embodiments, the material further includes one or more functional fillers. For example, the material may include hydroxyapatite (HA). Or, for example, the material may include one or more functional fillers that may be added to the compounder for extending the life of a compounded material for bioresorbable (e.g.. PLLA) implants to a predetermined time period for the piezoelectric implant to be made from the compounded material. [0100] In exemplar} embodiments, a piezoelectric implant comprises a material including barium titanate compounded with thermoplastic polymer and/or ceramic material doped with barium titanate. The piezoelectric implant may be injection molded from the material such that the piezoelectric implant has a monolithic, single-piece construction. The piezoelectric implant may comprise a spinal fusion piezoelectric implant, a cranial. In other exemplary embodiments, the piezoelectric implant may comprise a cranial piezoelectric implant, other orthopedic piezoelectric implant, a piezoelectric implant for veterinary /animal purposes. Accordingly, aspects of the present disclosure should not be limited to arty particular type of piezoelectric implant or be limited to use with only humans or animals.

[0101] FIGS. 1-4 illustrate a material including barium titanate (BaTiOs) and polyetheretherketone (PEEK) according to an exemplary embodiment in which tunnels or closed-ended holes have been formed (e.g., drilled, etc) in the BaTiOa/PEEK material. As shown, each of the four tunnels is adjacent a corresponding one of the four comers of the BaTiOa/PEEK material. As shown in FIGS. 2-4, a negative charge is along the top and bottom surfaces of the BaTiOa/PEEK material, thereby providing a negative charge for a contacting surfaces of a piezoelectric implant Although the example illustrated in FIGS. 1-4 includes PEEK, the material with the tunnels may include one or more other materials with barium titanate, such as polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaiylelheiketone (PAEK) family, polylactide (PolyOactic acid), PLA) (e.g, PLLA, PDLA, PDLLA, etc), other thermoplastic polymer(s), other thermoplastic material(s), etc.

[0102] With continued reference to FIGS. 1-4, first and second tunnels are formed in the top surface of the BaTiOa/PEEK at diagonally opposite first and second comers, respective!}'. Each of first and second tunnels starts at an opening defined in the top surface and extends downward!}’ from the top surface towards the bottom surface of the BaTiOa/PEEK material. The first and second tunnels are closed ended and do not extend completely through the bottom surface of the BaTiOa/PEEK material.

[0103] Third and fourth tunnels are formed in the bottom surface of the BaTiOa/PEEK at diagonally opposite third and fourth comers, respectively. Each of the third and fourth tunnels starts at an opening defined in the bottom surface and extends upwardly from the bottom surface towards the top surface of the BaTiOa/PEEK material. The third and fourth tunnels are closed ended and do not extend completely through the top surface of the BaTiOa/PEEK material. The tunnels may be operable for voltage spreading.

[0104] In exemplary embodiments, a metal with elasticity (e.g. , porous titanium, etc ) may be used to create an electrode along the top and/or bottom surfaces and help disperse voltage from the tunnels. In exemplary embodiments, titanium or other suitable electrode coating may be sprayed, sputtered, applied via a sol-gel process, applied via a physical vapor deposition process, or otherwise coated or provided along at least portions of the top and bottom surfaces of an implant, which may promote better bone growth and voltage spreading. In some exemplar}’ embodiments, titanium or other suitable coating encapsulates the entirety of the piezoelectric implant such that the entire outside of the piezoelectric implant has a negative charge (e.g., FIG. 15, FIG. 17, etc.).

[0105] In exemplary embodiments, the compounded material includes about 20 volume percent to about 30 volume percent of the barium titanate. In such exemplar}' embodiments, the compounded material may also include about 70 volume percent to about 80 volume percent of the PEEK.

[0106] In exemplary embodiments, the compounded material includes about 30 weight percent to about 80 weight percent of the barium titanate. In such exemplary embodiments, the compounded material may also include about 20 weight percent to about 70 weight percent of the PEEK.

[0107] In an exemplary embodiment, the compounded material may include about 8 volume percent of the barium titanate and about 92 volume percent of the polyetheretherketone. In such exemplary embodiment, the compounded material includes about 30 weight percent of the barium titanate and about 70 weight percent of the polyetheretherketone.

[0108] In an exemplary embodiment, the compounded material includes about 40 weight percent of the barium titanate and about 60 weight percent of the polyetheretherketone. In another exemplary embodiment, the compounded material includes about 50 weight percent of the barium titanate and about 50 weight percent of the polyetheretherketone. In a further exemplary embodiment, the compounded material includes about 60 weight percent of the barium titanate and about 40 weight percent of the polyetheretherketone. In an additional exemplary embodiment, the compounded material includes about 70 weight percent of the barium titanate and about 30 weight percent of the polyetheretherketone. In yet another exemplary embodiment, the compounded material includes about 80 weight percent of the barium titanate and about 20 weight percent of the poly etheretherketone.

[0109] By way of example, the barium titanate may comprise a barium titanate powder that does not include lead or cadmium and is biocompatible. The barium titanate may have a Curie temperature of about 120 °C.

[0110] By way of further example, the PEEK may comprise polyetherctherketone supplied in pellet form. The PEEK may be highly dielectric with a dielectric strength of about 15 kilovolts per millimeter (kV/mm), a dielectric constant of about 0.001 at a frequency of 60 hertz (Hz), a dielectric constant of about 0.001 at a frequency of 1 kilohertz (kHz), and a dielectric constant of about 0.003 at a frequency of 1 megahertz (MHz). The PEEK may have a glass transition temperature of about 147 °C.

[0111] Embodiments disclosed herein also include poling the compounded PEEK and barium titanate material for piezoelectric response for bone growth stimulation. Conventional poling methods typically include heating a specimen in a silicone oil bath and applying an electric charge to activate the specimen to produce a piezoelectric response. Contrary to the conventional methods, however, exemplary embodiments disclosed herein include poling the compounded PEEK and barium titanate material at room temperature (e.g., about 20 °C, from about 20 °C to about 22 °C, etc.) without first heating the compounded PEEK and barium titanate material in a silicone oil bath. Given that PEEK is highly dielectric with a glass transition temperature that is considerably higher than the Curie temperature of barium titanate, poling the compounded PEEK and barium titanate material at room temperature well below the Curie temperature of barium titanate is counterintuitive and contrary to conventional wisdom.

[0112] In exemplary methods, poling the compounded PEEK and barium titanate material may include applying an electric charge of about 75 kdlovolts/75000 watts to the compounded material for about 5 minutes in a silicone oil bath at room temperature without heating. The poled compounded PEEK and barium titanate material produced a piezoelectric response within a range from about 1.5 picocoulombs per newton (pC/N) to about 2.5 pC/N. In other exemplary embodiments, the poling may produce a different piezoelectric response from the compounded PEEK and barium titanate material, e.g., ftom about 1.8 pC/N to about 3 pC/N, less than 30 pC/N, etc.

[0113] In exemplary embodiments, compounded PEEK and barium titanate material (or other materials disclosed herein) may be used to make piezoelectric implants. For example, a single-piece piezoelectric implant having a monolithic construction may be injection molded from compounded PEEK and barium titanate material or from another material disclosed herein. The single-piece piezoelectric implant may provide one or more (but not necessarily arty or all) of the following advantages as compared to multi-piece piezoelectric implant assemblies. For example, a single-piece piezoelectric implant may be less prone to failure than multi-piece piezoelectric implant assemblies. A single-piece piezoelectric implant may require less time for sterilization as compared to having to sterilize multiple pieces of a multi-piece piezoelectric implant assembly. A single-piece piezoelectric implant made of a homogeneous blend of materials (e.g., a homogeneous blend of PEEK and barium titanate, etc.) may also avoid problems associated with different mismatched material properties (e.g., strength, elasticity, biocompatibility, etc.) of the different materials used for the different pieces in multi-piece piezoelectric implant assemblies. The single-piece piezoelectric implant may include only a single relatively large piece, thereby avoiding the use of the very small pieces and the time required to assemble the various small pieces into the multi-piece piezoelectric implant assembly.

[0114] In exemplary embodiments, one or more films, sheets, or layers of material (e.g., polyvinylidene fluoride (PVDF), potassium sodium niobate (KNN), polylactidc (Poly(lactic acid) PLA) etc.) that have been poled to be piezoelectric are bonded to the surface of a compounded and/or homogeneous material as disclosed herein. For example, a relatively thin film, sheet, or layer of PVDF is poled to be piezoelectric. The PVDF film, sheet, or layer may be piezoelectric without needing barium titanate to be piezoelectric. The piezoelectric PVDF film, sheet, or layer is bonded to a compounded material that comprises barium titanate and at least one other material, including one or more of polyetheretherketone (PEEK), polyetheiketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic polymers), other thermoplastic materials), etc. Or, for example, the piezoelectric PVDF film, sheet, or layer is bonded to a homogeneous material that comprises ceramic material (e.g., zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic material(s), etc.) doped with barium titanate. [0115] In other exemplary embodiments, one or more relatively thins films, sheets, or layers of PLA (e.g., PLLA, PDLA, PDLLA, etc.) are poled to be piezoelectric. For example, a relatively thin film, sheet, or layer of PLLA is poled to be piezoelectric. The PLLA film, sheet, or layer may be piezoelectric without needing barium titanate to be piezoelectric. The piezoelectric PLLA is bonded to a compounded material that comprises barium titanate and at least one other material, including one or more of polyetheretherketone (PEEK), pofyetherketoneketone (PEKK), a thermoplastic polymer in the poiyaryletherketone (PAEK) family, other thermoplastic pofymer(s), other thermoplastic materials), etc. Or, for example, the piezoelectric PLLA film, sheet, or layer is bonded to a homogeneous material that comprises ceramic material ( e.g., zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic material(s), etc.) doped with barium titanate.

[0116] In further exemplary embodiments, a relatively thin film, sheet, or layer of KNN is poled to be piezoelectric. The KNN film, sheet, or layer may be piezoelectric without needing barium titanate to be piezoelectric. The piezoelectric KNN film, sheet, or layer is bonded to a compounded material that comprises barium titanate and at least one other material, including one or more of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), a thermoplastic polymer in the poiyaryletherketone (PAEK) family, other thermoplastic polymers), other thermoplastic materials), etc. Or, for example, the piezoelectric KNN film, sheet, or layer is bonded to a homogeneous material that comprises ceramic material (e.g., zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic material(s), etc.) doped with barium titanate.

[0117] In exemplary embodiments, titanium or other suitable electrode coating may be plasma sprayed, sputtered, applied via a sol-gel process, applied via a physical vapor deposition process, or otherwise coated or provided along one or more portions or along an entire outer surface a piezoelectric implant. The titanium or other electrode coating may be operable for spreading the charge/voltage that results as a piezoelectric response to strain. The titanium coating or other electrode coaling will amplify the electric charge and carry the charge over a greater surface area than just where the piezoelectric elements are located. In these exemplary embodiments, the piezoelectric implant may be made from a compounded material including barium titanate, a homogeneous material including ceramic material doped with barium titanate, or other material.

[0118] In exemplary embodiments, a piezoelectric implant may' include a titanium coating or other electrode coating along only predetermined portions of the piezoelectric implant that are configured to make physical contact with bone and/or that are configured to be compressed generally between the piezoelectric implant and bone. For example, the titanium coating or other electrode coating may be provided along outwardly protruding portions or ridges along the piezoelectric implant’s top and bottom surfaces.

[0119] In other exemplary embodiments, a piezoelectric implant may include a titanium coating or other electrode coating (broadly, an electrically-conductive coating) that defines and/or is disposed over the entire outside of the piezoelectric implant The titanium coating or other electrode coating (e.g., a titanium shell encapsulation, etc.) may fully encapsulate the entire piezoelectric implant The titanium or other electrically-conductive coating may be configured such that the entire outside of the piezoelectric implant has a negative charge (e.g., FIG. 15, FIG. 17, etc.). The amplified negative side is much more negative than the inverse positive side. This inhibits or prevents short circuiting because the positive charge is very small relative to the negative charge, and the negatively charged side has a sufficiently high enough negative charge to overtake the positively charged side.

[0120] FIG. 15 shows a negative charge around the entire outer surface of the piezoelectric implant even though the electrode grounded out the positive charge. With reference to FIG. 16, A references an electrode coating (e.g., titanium, other electrically-conductive coating, etc.) around entire outside, B references piezoelectric elements having their negative sides facing outwardty/away, C references an electrically non-conductive or dielectric adhesive without ary electrode coating, and D references a base or substrate structure of the piezoelectric implant.

[0121] FIG. 17 also shows a negative charge around the entire outer surface of the piezoelectric implant according to another exemplary embodiment In FIG. 17, E references a thermal polymer (e.g.. PEEK, other materials disclosed herein, etc.), F references an electrically non-conductive or dielectric adhesive (e.g., light cured biocompatible epoxy , etc), G references piezoelectric elements, and H references an electrically -conductive coating (e.g., a titanium or other electrically -conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition, or other suitable process, etc).

[0122] A references an electrode coating (e.g., titanium, other electrically -conductive coating, etc.) around entire outside, B references piezoelectric elements having their negative sides facing outwardly/away, C references an electrically non-conductive or dielectric adhesive without atty electrode coating, and D references a base or substrate structure of the piezoelectric implant

[0123] FIGS. 5-14 illustrate a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplary embodiment In this exemplary embodiment, the piezoelectric implant includes a base (e.g., PEEK or other suitable material, etc.), piezoelectric elements (e.g., pre-poled piezoelectric PVDF films laminated, etc.) along at least the outermost protruding portions of one more ridges defined by the base, and an electrode coating or shell encapsulation (e.g., a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition process, or other suitable process, etc).

[0124] In this exemplary embodiment, the base comprises polyetherctherketone (PEEK). But other suitable materials may also be used for the base, such as polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic potymer(s), other thermoplastic material(s), zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic materials), etc.

[0125] As shown in FIGS. 10-13, the piezoelectric elements are disposed along at least the outermost protruding portions of ridges defined by the base. Accordingly, the piezoelectric elements are thus disposed along portions of the piezoelectric implant that are configured to make pltysical contact with bone and/or that are configured to be compressed generally between the piezoelectric implant and bone.

[0126] In this exemplary embodiment, the piezoelectric elements comprise polyvinylidene fluoride (PVDF) films poled to be piezoelectric. The PVDF films ate laminated or otherwise bonded to the PEEK base such that the PVDF films’ negative sides face outward and positive sides face inward. The PVDF films are along the outermost protruding portions of the ridges where compression occurs. In this exemplary embodiment, the PVDF films are not disposed in the valleys, troughs, or channels or along sidewalls of the piezoelectric implant In other exemplary embodiments, the PVDF films or other piezoelectric elements may be disposed within the valleys, troughs, or channels. One or more other materials (e.g., electrically non-conductive or dielectric adhesive, etc.) may also be provided in the valleys, troughs, or channels to strengthen and/or to reinforce he piezoelectric implant for distribution of forces. As a further example, the PVDF films or other piezoelectric elements may be disposed over the entire top and bottom sides of the piezoelectric implant, e.g., within the valleys, troughs, or channels and along the entirety of the ridges. In this latter example, an electrically non-conductive or dielectric adhesive or other suitable material(s) may be disposed over the PVDF films and/or may fill up the valleys, troughs, or channels to address and/or inhibit delamination of the PVDF films from the PEEK base.

[0127] This exemplary embodiment includes piezo lamination in the form of PVDF films laminated to the base. Alternative processes besides lamination may be used for providing or bonding the piezoelectric elements to the base and/or other materials besides PVDF films may be used for the piezoelectric elements. For example, the piezoelectric elements may comprise potassium sodium niobate (KNN) poled to be piezoelectric. Or, for example, the piezoelectric elements may comprise polylactide (Poty(lactic acid), PLA) (e.g., PLLA, PDLA, PDLLA, etc) poled to be piezoelectric.

[0128] FIG. 13 illustrates the piezoelectric implant shown in FIG. 5 without an electrode coating to illustrate the location of piezoelectric elements (e.g., pre-poled piezoelectric PVDF films laminated, etc.) along at least the outermost protruding portions of ridges defined by the base (e.g. , PEEK or other suitable material, etc). FIG. 14 illustrates an electrically -conductive coating shown as a shell (e.g. , a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, pltysical vapor deposition, or other suitable process, etc) for the piezoelectric implant shown in FIG. 13 such that an entire outside of the piezoelectric inplant has a negative charge as discussed above and shown in FIG. 15.

[0129] FIGS. 18-26 illustrate a piezoelectric inplant (e.g., for use as a spinal fusion implant, etc.) according to an exemplary embodiment In this exemplary embodiment, the piezoelectric inplant includes a base (e.g., PEEK or other suitable material, etc), piezoelectric elements (e.g., pre-poled piezoelectric PVDF inserts, etc.'), and an electrically -conductive coating or shell encapsulation (e.g., a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition process, or other suitable process, etc.). The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge.

[0130] In this exemplary embodiment the base comprises polyetheretherketone (PEEK). But other suitable materials may also be used for the base, such as polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic polymers), other thermoplastic materials), zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic materials), etc.

[0131] In this exemplary embodiment the piezoelectric elements comprise poiyvinylidene fluoride (PVDF) inserts poled to be piezoelectric. The PEEK base is between the piezoelectric inserts as shown in FIG. 25, such that the piezoelectric inserts’ negative sides face outward and positive sides face inward. The piezoelectric inserts define protruding portions or ridges where compression occurs. Other materials besides PVDF may be used for the piezoelectric elements. For example, the piezoelectric elements may comprise potassium sodium niobate (KNN) poled to be piezoelectric. Or, for example, the piezoelectric elements may comprise polylactide (Poty(lactic acid), PLA) (e.g., PLLA, PDLA, PDLLA, etc.) poled to be piezoelectric.

[0132] FIGS. 27-35 illustrate a piezoelectric implant (e.g., for use as a spinal fusion implant, etc.) according to an exemplary embodiment In this exemplary embodiment the piezoelectric implant includes a piezoelectric base (e.g, a piezoelectric poled PVDF base, other suitable material, etc.) and an electrically -conductive coating or shell encapsulation (e.g., a titanium or other electrically -conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition process, or other suitable process, etc). The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge.

[0133] In this exemplary embodiment, the piezoelectric base comprises piezoelectric poled PVDF base. But other materials besides PVDF may be used for the piezoelectric base. For example, the piezoelectric base may comprise potassium sodium niobate (KNN) poled to be piezoelectric. Or. for example, the piezoelectric base may' comprise polylactide (Poly(lactic acid), PLA) (e.g, PLLA, PDLA, PDLLA, etc.) poled to be piezoelectric.

[0134] FIGS. 36-44 illustrate a piezoelectric implant (e.g, for use as a spinal fusion implant, etc) according to an exemplary embodiment. In this exemplary embodiment, the piezoelectric implant includes a base (e.g, PEEK or other suitable material, etc), a piezoelectric coating (e.g, piezoelectric poled PVDF dipped coating, etc), and an electrically-conducting or shell encapsulation (e.g, a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel physical vapor deposition process, or other suitable process, etc). The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge.

[0135] In this exemplary embodiment, the base comprises polyetheretheiketone (PEEK). Bin other suitable materials may also be used for the base, such as polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic polymers), other thermoplastic material(s), zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic materials), etc.

[0136] In this exemplary embodiment, the piezoelectric coating comprises piezoelectric poled PVDF dipped coating. Alternative processes besides dip coating may be used for providing the piezoelectric coating along the base and/or other materials besides PVDF may be used for the piezoelectric coating.

[0137] FIGS. 45-54 illustrate a piezoelectric implant (e.g, for use as a spinal fusion implant, etc) according to an exemplary embodiment. In this exemplary embodiment, the piezoelectric implant includes a base (e.g, PEEK or other suitable material, etc), piezoelectric elements (e.g, pre-poled piezoelectric PVDF inserts, etc), and an electrically-conductive coating or shell encapsulation (e.g, a titanium or other electrically-conductive coating provided via sputtering, plasma spraying, sol-gel, physical vapor deposition process, or other suitable process, etc). The electrically-conductive coating may be configured such that an entire outside of the piezoelectric implant has a negative charge. The piezoelectric elements may be bonded to the base with electrically non-conductive or dielectric adhesive. [0138] In this exemplary' embodiment, the base comprises polyetheretherketone (PEEK). But other suitable materials may also be used for the base, such as polyetherketoneketone (PEKK), a thermoplastic polymer in the polyaryletherketone (PAEK) family, other thermoplastic poiymer(s). other thermoplastic material(s), zirconium, zirconia, ZTA (zirconia toughen alumina), silicon, other ceramic material(s), etc.

[0139] In this exemplary embodiment, the piezoelectric elements comprise polyvinylidene fluoride (PVDF) inserts poled to be piezoelectric. The PEEK base is between the piezoelectric inserts as shown in FIG. 52, such that the piezoelectric inserts’ negative sides face outward and positive sides face inward. The piezoelectric inserts define protruding portions or ridges where compression occurs. Other materials besides PVDF may be used for the piezoelectric elements. For example, the piezoelectric elements may comprise potassium sodium niobate (KNN) poled to be piezoelectric. Or, for example, the piezoelectric elements may comprise polylactide (Poly(lactic acid), PLA) (e.g., PLLA, PDLA, PDLLA, etc.) poled to be piezoelectric.

[0140] Example embodiments are provided so that this disclosure will be thorough and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms, and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail. In addition, advantages and improvements that may be achieved with one or more exemplary embodiments of the present disclosure are provided for purpose of illustration only and do not limit the scope of the present disclosure, as exemplary embodiments disclosed herein may provide all or none of the above mentioned advantages and improvements and still fall within the scope of the present disclosure.

[0141] Specific dimensions, specific materials, and/or specific shapes disclosed herein are example in nature and do not limit the scope of the present disclosure. The disclosure herein of particular values and particular ranges of values for given parameters are not exclusive of other values and ranges of values that may be useful in one or more of the examples disclosed herein. Moreover, it is envisioned that any two particular values for a specific parameter stated herein may define the endpoints of a range of values that may be suitable for the given parameter (i.e., the disclosure of a first value and a second value for a given parameter can be interpreted as disclosing that any value between the first and second values could also be employed for the given parameter). For example, if Parameter X is exemplified herein to have value A and also exemplified to have value Z, it is envisioned that parameter X may have a range of values from about A to about Z. Similarly, it is envisioned that disclosure of two or more ranges of values for a parameter (whether such ranges are nested, overlapping, or distinct) subsume all possible combination of ranges for the value that might be claimed using endpoints of the disclosed ranges. For example, if parameter X is exemplified herein to have values in the range of 1 - 10, or 2 - 9, or 3 - 8, it is also envisioned that Parameter X may have other ranges ofvalues including 1 - 9, 1 - 8, 1 - 3, 1 -2, 2 - 10, 2 - 8, 2 - 3, 3 - 10, and 3 - 9.

[0142] The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. For example, when permissive phrases, such as “may comprise”, “may include”, and the like, are used herein, at least one embodiment comprises or includes the features). As used herein, the singular forms “a”, “an” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising.” “including,” and “having,” are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiting their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed.

[0143] When an element or layer is referred to as being “on”, “engaged to”, “connected to” or “coupled to” another element or layer, it may be directly on, engaged, connected, or coupled to the other element or layer, or intervening elements or layers may be present, hi contrast, when an element is referred to as being “directly on,” “directly engaged to”, “directly connected to” or “directly coupled to” another element or layer, there may be no intervening elements or layers present Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between,” “adjacent’ versus “directly adjacent" etc.). As used herein, the term “and/or” includes ary and all combinations of one or more of the associated listed items.

[0144] The term “about” when applied to values indicates that the calculation or the measurement allows some slight imprecision in the value (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If, for some reason, the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates at least variations that may arise from ordinary methods of measuring or using such parameters. For example, the terms “generally”, “about”, and “substantially” may be used herein to mean within manufacturing tolerances. Or for example, the term “about” as used herein when modifying a quantity of an ingredient or reactant of the invention or employed refers to variation in the numerical quantity that can happen through typical measuring and handling procedures used, for example, when making concentrates or solutions in the real world through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, equivalents to the quantities are included.

[0145] Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer, or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context Thus, a first element component region, layer, or section discussed below could be termed a second element component, region, layer, or section without departing from the teachings of the example embodiments.

[0146] Spatially relative terms, such as “inner,” “outer," “beneath”, “below”, “lower", “above", “upper” and the like, may be used herein for ease of description to describe one element or feature’s relationship to another element(s) or features) as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

[0147] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements, intended or stated uses, or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.