Composites, methods of making and using the same

Abstract

Disclosed herein is a composite material comprising: one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer; a second sublayer having a second thickness and comprising a first amorphous polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a second amorphous polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite. Also disclosed are methods of making the same composites and articles comprising the same.

Description

Attorney Docket No.10046-647WO1 UT Ref.8487 TEH COMPOSITES, METHODS OF MAKING AND USING THE SAME CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application No.63 / 708,414, filed October 17, 2024, which is incorporated by reference herein in its entirety. STATEMENT OF GOVERNMENT SUPPORT

[0002] This invention was made with government support under Grant No. 80NSSC22K1203, awarded by NASA. The government has certain rights in the invention. BACKGROUND

[0003] The growing demand for large-scale thermoplastic composites has sparked increased interest in their manufacturability across various industries. Unlike thermosetting composites, thermoplastics can be melted, reshaped, and reprocessed, offering high versatility in manufacturing processes. Over recent decades, thermoplastic composites have gained prominence in the marine, automotive, and aerospace fields.

[0004] These materials offer numerous advantages in aerospace, including weight reduction, faster production cycles, improved damage tolerance, and recyclability. Additionally, their ability to be welded eliminates the need for conventional fasteners, providing greater manufacturing flexibility and easier repair. However, producing large-scale thermoplastic composites presents challenges, particularly in controlling the cooling rates during manufacturing. Sensitivity to cooling rates can affect material properties, complicate quality control, and slow production. Achieving the right balance between crystallinity and toughness requires precise cooling management, adding complexity and cost, especially in aerospace applications. Addressing this issue is crucial for fully harnessing the benefits of thermoplastic composites in large-scale, high-performance aerostructures.

[0005] Developing new thermoplastic composites is critical for addressing the evolving demands of modern aerospace. As the industry seeks to reduce fuel consumption, emissions, and operational costs, the need for lighter, stronger, and more durable materials grows. Moreover, advances in thermoplastics can helpAttorney Docket No.10046-647WO1 UT Ref.8487 TEH overcome current challenges in processing, cost, and joining techniques, paving the way for more efficient, sustainable aircraft structures in the future.

[0006] Thus, novel thermoplastic composites, easy methods of producing the same, and articles made of the same are disclosed herein. SUMMARY

[0007] Disclosed herein is a composite material comprising: one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer; a second sublayer having a second thickness and comprising a first amorphous polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a second amorphous polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

[0008] In some aspects, the semicrystalline polymer of the first sublayer is impregnated with a plurality of reinforcing materials. In such exemplary and unlimiting aspects, the reinforcing materials can have a volume fraction of 40-60 vol%.

[0009] In some aspects, the plurality of reinforcing materials comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof. While some aspects, the reinforcing materials comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof.

[0010] Also disclosed herein is a composite material comprising: one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a first semicrystalline polymer; a second sublayer having a second thickness and comprising a second semicrystalline polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a third semicrystalline polymer, wherein the first sublayer overlays the third sublayerAttorney Docket No.10046-647WO1 UT Ref.8487 TEH such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

[0011] Also disclosed herein are articles comprising any of the disclosed herein thermoplastic composites. In such exemplary and unlimiting aspects, the article can comprise an aircraft component, a spacecraft component, a component of a military article, an automotive component, a recreation component, a turbine component, construction & infrastructure, a satellite component, marine component, medical components, chemical storage / transport, or any combination thereof.

[0012] Also disclosed is method of forming a composite comprising: (a) forming one or more layers, wherein each layer comprises a first sublayer having a first thickness and comprising a semicrystalline polymer having a Tm; a second sublayer having an initial second thickness and comprising a first amorphous polymer having a Tg, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a second amorphous polymer having a Tg, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that such that an overlaying portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and c) reducing the thickness of the second sublayer and the third sublayer to form a second thickness and a third thickness to be less than 10 microns.

[0013] Still further disclosed herein is method of forming a composite comprising: method of forming a composite comprising: (a) forming one or more layers, wherein each layer comprises a first sublayer having a first thickness and comprising a semicrystalline polymer having a first Tm; a second sublayer having an initial second thickness and comprising a second semicrystalline polymer having a second Tm, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a third semicrystalline polymer having a third Tm, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that such that an overlayingAttorney Docket No.10046-647WO1 UT Ref.8487 TEH portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and c) reducing the thickness of the second sublayer and the third sublayer to form a second thickness and a third thickness to be less than 10 microns.

[0014] In accordance with the purposes of the disclosed materials, compounds, compositions, and methods, as embodied and broadly described herein, the disclosed subject matter, in one aspect, relates to compounds and compositions and methods for preparing and using such compounds and compositions.

[0015] Additional advantages will be set forth in part in the description that follows and in part will be obvious from the description or may be learned by practice of the aspects described below. The advantages described below will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive. BRIEF DESCRIPTION OF THE FIGURES

[0016] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects described below.

[0017] FIGURE 1A depicts an exemplary schematic of prior art composites.

[0018] FIGURE 1B depicts a schematic of an exemplary composite according to one aspect.

[0019] FIGURE 2 depicts a photograph of a typical composite (PEEK) and an exemplary composite according to one aspect (OATMEAL).

[0020] FIGURE 3 depicts a schematic representation of Goldilocks conditions where the amorphous polymer can heal above its own glass transition temperature and below the semi-crystalline polymer’s melt to produce an exemplary composite in one aspect.

[0021] FIGURE 4 depicts photographs of the large-scale production of an exemplary composite in one aspect.

[0022] FIGURE 5 depicts photographs of large-scale production, specifically the ablation of an exemplary composite in one aspect.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0023] FIGURES 6A-6B depict optical microscope images comparing a standard composite (FIG.6A) and an exemplary composite according to one aspect of the disclosure (FIG.6B). These are optical microscope images of polished cross- sections showing that the ablation process helped remove excess PEI.

[0024] FIGURES 7A-7B depict optical microscope images of an exemplary composite according to one aspect of the disclosure (FIG.7A) and its magnification (FIG.7B).

[0025] FIGURES 8A-8F depict simulations to demonstrate the degrees of healing as a function of the tool’s temperature, velocity, and time.

[0026] FIGURES 9A-9C depict healing analysis. FIGS.9A-9B show simulations demonstrating healing as a function of the tool’s temperature, velocity, and time. FIG.9C shows a ratio of the maximum degree of healing vs the velocity of the automated fiber placement (AFP) apparatus.

[0027] FIGURES 10A-10B present a spatial map of an absorption spectrum (1448 cm-1) unique to PEI, illustrating the interdiffusion of the amorphous polymer into a semi-crystalline PEEK prepreg. This data was measured using atomic force microscopy and infrared spectrometry.

[0028] FIGURES 11A-11D depict a schematic overviewing the process of healing amorphous polymer (PEI) and semi-crystalline prepreg (CF / PEEK) before slow-cooling (FIG.11A), a Goldilocks processing zone with PEI sheaths (FIG.11B), laser ablation of PEI surface leaving behind PEI–PEEK blend (FIG.11C), and sub- melt consolidation enabling a cooling-rate independent process (FIG.11D).

[0029] FIGURES 12A-12E depict distinctions between the laminates. FIG. 12A shows mid-infrared FT-IR spectra of neat PEI and PEEK, highlighting distinct peaks used to differentiate the polymers. FIG.12B presents optical cross-sectional microscopy of polished laminates, highlighting interfacial regions. FIG.12C shows spatial FT-IR mapping of the absorption ratio between characteristic PEI and PEEK peaks. FIG.12D shows AFM-IR nanoscale mapping of healed PEI–PEEK films. FIG.12D shows corresponding absorption spectra across a 40 m blending region. FIG.12E shows AFM-IR mapping of the OATMEAL interface between 0° / 90° oriented plies.

[0030] FIGURES 13A-13D depict characterization of the laminates. FIG.13A presents representative DSC heating curves that indicate a shift in the PEI glass transition temperature and the appearance of double and triple melting peaks inAttorney Docket No.10046-647WO1 UT Ref.8487 TEH hybrid and OATMEAL laminates. FIG.13B shows calculated crystallinity percentages for each system, averaged over six specimens. FIG.13C shows SBS strength for quasi-isotropic and unidirectional laminates consolidated at 300°C (hybrid and OATMEAL) compared to the CF / PEEK reference processed at 380°C. FIG.13D shows fiber-volume fractions quantified via image analysis of optical cross- sectional micrographs.

[0031] FIGURE 14 depicts post-mortem SEM imaging of failed interfaces in SBS samples showing a convergence to CF / PEEK failure modes after laser ablation of the neat PEI.

[0032] FIGURES 15A-15C depict details of the production methods. FIG.15A shows a table detailing the processing in the autoclave and VBO oven during cooling, highlighting reduced processing temperatures and increased cooling rates. FIG.15B shows that both laminates maintain high crystallinity, yet OATMEAL preserves superior SBS even after rapid cooling. FIG.15C shows theoretical OATMEAL-enabled continuous VBO oven production rates with shuttle in / out and air cooling, demonstrating up to a 5 times increase in throughput.

[0033] FIGURES 16A-16D depict details of laser ablation. FIG.16A shows the Ekspla AtlanticTM20 Nd:YVO4picosecond laser setup. FIG.16B shows the hybrid surface with a square ablated region. FIG.16C shows Keyence laser confocal height measurement before / after ablation. FIG.16D shows an average material removal depth during ablation.

[0034] FIGURE 17 depicts C-Scans of the tested laminates.

[0035] FIGURES 18A-18D depict an example of sub-melt bonding for a deployable space structure. Figure 18A shows the Goldilocks zone between the glass transition temperature of PEI and the melt temperature of PEEK. Figure 18B details the deployable boom structure. Figure 18C shows the miscibility of the two polymers. Figure 18D illustrates the amorphous bonding concept, depicting the finished structure after welding below the melt temperature.

[0036] FIGURES 19A-19C depict short beam strength results from laser- assisted automated fiber placement of hybrid and OATMEAL materials. Figure 19A shows the robot used in the automated fiber placement process. Figure 19B details the results showing improved performance using amorphous bonding. Figure 19C details the thermal physics during processing, where the fiber absorbs the laser energy and subsequently conductively heat the polymers.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0037] FIGURES 20A-20B depict the characterization of a hybrid material manufactured on a typical slurry-based prepregger machine. The machine was modified to laminate PEI film onto AS4-PEEK prepreg. Figure 20A shows differential scanning calorimetry heating curves. Figure 20B details the measured crystallinity, highlighting that using a typical prepregger to produce a hybrid material does not fully crystallize the PEEK.

[0038] FIGURE 21 depicts a micrograph of the hybrid material manufactured on a typical slurry-based prepregger machine. The machine was modified to laminate PEI film onto AS4-PEEK prepreg. The PEI and PEEK appear to be well consolidated, but the tape’s surface is rough.

[0039] FIGURE 22 depicts a micrograph of a hybrid material laminate consolidated below the melt temperature of PEEK. The hybrid material was manufactured on a typical slurry-based prepregger machine. The machine was modified to laminate PEI film onto AS4-PEEK prepreg.

[0040] FIGURE 23 depicts a micrograph of a hybrid material laminate consolidated below the melt temperature of PEEK. The hybrid material was manufactured on a typical slurry-based prepregger machine. The machine was modified to laminate PEI film onto AS4-PEEK prepreg.

[0041] FIGURE 24 depicts a theoretical heating history for using a continuous compression molding machine to manufacture a hybrid material. A thermal hold above the semi-crystalline polymer’s melt temperature ensures full healing of the amorphous and semi-crystalline polymers. Subsequently, the controlled cooling rate is engineered to maximize crystallinity in the prepreg.

[0042] FIGURE 25 depicts a theoretical pressure history for using a continuous compression molding machine to manufacture a hybrid material. The pressure ensures that the amorphous film is fully healed to the semi-crystalline prepreg. DETAILED DESCRIPTION

[0043] The materials, compounds, compositions, articles, and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter, and the examples included therein.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0044] Before the present materials, compounds, compositions, kits, and methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0045] Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entirety are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon. DEFINITIONS

[0046] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

[0047] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance can or cannot occur and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0048] It is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate aspects, can also be provided in combination in a single aspect. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single aspect, can also be provided separately or in any suitable subcombination.

[0049] As used in the description and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0050] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" can include the aspects "consisting of" and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In thisAttorney Docket No.10046-647WO1 UT Ref.8487 TEH specification and in the claims which follow, reference will be made to a number of terms that shall be defined herein.

[0051] For the terms "for example" and "such as" and grammatical equivalences thereof, the phrase "and without limitation" is understood to follow unless explicitly stated otherwise. It is further understood that these phrases are used for explanatory purposes only. It is further understood that the term "exemplary," as used herein, means "an example of" and is not intended to convey an indication of a preferred or ideal aspect.

[0052] The term "or" means "and / or." Recitation of ranges of values is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. The endpoints of all ranges are included within the range and independently combinable. All methods described herein can be performed in a suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

[0053] All disclosed values also include values that fall within ±10% variation from the disclosed value unless otherwise indicated or inferred. In other words, if a range of 1 to 10 is disclosed, then a range of about 1 to about 10 is disclosed. In such aspects, it is understood that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, amounts, sizes, formulations, parameters, and other quantities and characteristics include both exact values but also approximate, larger, or smaller values as desired, reflecting tolerances, conversion factors, rounding, measurement error, and the like, and other factors known to those of skill in the art, such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In general, an amount, size, formulation, parameter, or other quantity or characteristic is "about," "approximate," or "at or about," whether or not expressly stated to be such. Where "about," "approximate," or "at or about" is used before a quantitative value, the parameter also includes the specific quantitative value itself unless expressly stated otherwise.

[0054] As used herein, the term or phrase "effective," "effective amount," or "conditions effective to" refers to such amount or condition that is capable of performing the function or property for which an effective amount or condition isAttorney Docket No.10046-647WO1 UT Ref.8487 TEH expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact "effective amount" or "condition effective to." However, it should be understood that an appropriate, effective amount will be readily determined by one of ordinary skill in the art.

[0055] When a range is expressed, a further aspect includes from the one particular value and to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase "x to y" includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. The range can also be expressed as an upper limit, e.g., 'x, y, z, or less' and should be interpreted to include the specific ranges of 'x,' 'y,' 'z,' 'about x,' 'about y,' and 'about z' as well as the ranges of 'less than x,' 'less than y, or 'less than z,' or 'less than about x,' 'less than about y, and 'less than about z.' Likewise, the phrase ' x, y, z, or greater' should be interpreted to include the specific ranges of 'x,' 'y,' 'z,' 'about x,' 'about y,' and 'about z' as well as the ranges of 'greater than x,' greater than y,' 'greater than z,' or 'greater than about x,' greater than about y,' 'greater than about z.' In addition, the phrase " 'x' to 'y'," where 'x' and 'y' are numerical values, also includes "about 'x' to about 'y'."

[0056] Such a range format is used for convenience and brevity and, thus, should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of " 0.1% to 5%" should be interpreted to include not only the explicitly recited values of 0.1% to 5% but also include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range.

[0057] Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value recited or falling within the range unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited. Ranges provided herein are understood to be shorthand for all of the values within the range. ForAttorney Docket No.10046-647WO1 UT Ref.8487 TEH example, a range of 1 to 50 is understood to include any number, or combination of numbers, from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 or sub-ranges from the group consisting of 10-40, 20-50, 5-35, etc. Similarly, numerical ranges recited herein by endpoints include subranges subsumed within that range (e.g., 1 to 5 includes 1-1.5, 1.5-2, 2-2.75, 2.75-3, 3-3.90, 3.90-4, 4-4.24, 4.24-5, 2-5, 3-5, 1-4, and 2-4).

[0058] As used herein, the term "composition" is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product that results, directly or indirectly, from a combination of the specified ingredients in the specified amounts.

[0059] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a mixture containing 2 parts by weight of component X and 5 parts by weight, components Y, X, and Y are present at a weight ratio of 2:5 and are present in such a ratio regardless of whether or not additional components are contained in the mixture.

[0060] A weight percent (wt.%) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0061] As used herein, “compound” is intended to refer to a chemical entity, whether as a solid, liquid, or gas, and whether in a crude mixture or isolated and purified.

[0062] As used herein, “composite” refers to a combination of two or more distinct constituent materials into one. The individual components, on an atomic level, remain separate and distinct within the finished structure. The materials may have different physical or chemical properties that, when combined, produce a material with characteristics different from the original components. In some embodiments, a composite may have at least two constituent materials that comprise the same empirical formula but are distinguished by different densities, crystal phases, or a lack of a crystal phase (i.e., an amorphous phase).Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0063] It will be understood that although the terms "first," "second," 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 are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. 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 example embodiments.

[0064] As used herein, the term "substantially" means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.

[0065] Still further, the term "substantially" can, in some aspects, refer to at least about 80 %, at least about 85 %, at least about 90 %, at least about 91 %, at least about 92 %, at least about 93 %, at least about 94 %, at least about 95 %, at least about 96 %, at least about 97 %, at least about 98 %, at least about 99 %, or about 100 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount. It is understood that this definition also includes the ranges when no word "about" is present.

[0066] In other aspects, as used herein, the term "substantially free," when used in the context of a composition or component of a composition that is substantially absent, is intended to refer to an amount that is then about 1 % by weight, e.g., less than about 0.5 % by weight, less than about 0.1 % by weight, less than about 0.05 % by weight, or less than about 0.01 % by weight of the stated material, based on the total weight of the composition or based on any other calculations as disclosed. It is understood that this definition also includes the ranges when no word "about" is present.

[0067] As used herein, the term "substantially," in, for example, the context "substantially identical" or "substantially similar," refers to a method or a system, or a component that is at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% by similar to the method, system, or the component it is compared to. It is understood that this definition also includes the ranges when no word "about" is present.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0068] As used herein, the terms "substantially identical reference composition" and "substantially identical reference article" refer to a reference composition or article comprising substantially identical components in the absence of an inventive component. In another exemplary aspect, the term "substantially," in, for example, the context "substantially identical reference composition" or "substantially identical reference article," refers to a reference composition or an article comprising substantially identical components, and wherein an inventive component is absent or is substituted with a common in the art component.

[0069] By "contact" or other forms of the word, such as "contacted" or "contacting," it is meant to add, combine, or mix two or more compounds, compositions, or materials under appropriate conditions to produce a desired product or effect. The term "react" is sometimes used when "contacting" results in a chemical reaction.

[0070] The terms “interdiffusion” and / or “healing” are used herein interchangeably to refer to bonding or interaction between various sublayers within the composite. To start the interdiffusion, two or more sublayers need to be brought into intimate contact. It is understood that such interaction between various sublayers results in the absence of clear interface boundaries between the sublayers.

[0071] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only, and one of ordinary skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred in any respect. This holds for any possible non- express basis for interpretation, including matters of logic with respect to the arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0072] The present invention may be understood more readily by reference to the following detailed description of various aspects of the invention and the examples included therein, and to the Figures and their previous and following description. COMPOSITE

[0073] In certain aspects disclosed herein is a composite material comprising: one or more layers, wherein each layer of the one or more layers comprises one or more sublayers. In certain aspects, each layer of the one or more layers can comprise a first sublayer having a first thickness and comprising a semicrystalline polymer. In still further aspects, each layer of the one or more layers comprises a second sublayer having a second thickness and comprising a first amorphous polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness. In still further aspects, each layer of the one or more layers comprises a third sublayer having a third thickness and comprising a second amorphous polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

[0074] In such exemplary and unlimiting aspects, the second thickness and the third thickness can be the same. Yet in other aspects, the second thickness and the third thickness are different. In still further aspects, the second and third thicknesses are less than 10 microns, less than 9 microns, less than 8 microns, less than 7 microns, less than 6 microns, less than 5 microns, less than 4 microns, less than 3 microns, less than 2 microns, less than 1 micron, or less than 0.5 microns. In still further aspects, the second and third thicknesses are in a range of 10 microns to 0.1 microns, 8 microns to 0.1 microns, 5 microns to 0.1 microns, 3 microns to 0.1 microns, 1 micron to 0.1 microns, 0.5 microns to 0.1 microns, 10 microns to 0.5 microns, 10 microns to 1 micron, 10 microns to 3 microns, 10 microns to 5 microns, 10 microns to 8 microns, 8 microns to 1 micron, 5 microns to 3 microns, and so on.

[0075] In still further aspects, the composite can comprise two or more layers. Yet in still further aspects, the composite can comprise a plurality of layers. In certain aspects, when the composite comprises two or more layers, the two or more layersAttorney Docket No.10046-647WO1 UT Ref.8487 TEH are positioned such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of an adjacent layer.

[0076] In such exemplary and unlimiting aspects, it is understood that when the interdiffusion between adjacent portions of the sublayers occurs, the interdiffused portion is substantially free of an interface boundary. In such aspects, the term “substantially free of an interface boundary” can be understood as no substantially visual interface is observed on cross-section optical or electronic images of the composite. It is understood that while the various sublayers can be observed, a clear boundary indicating the interface between various sublayers is substantially invisible.

[0077] In still further aspects, when the second sublayer of one layer and the third sublayer of the adjacent layer are interdiffused, they form one sublayer having a fourth thickness. In such exemplary and unlimiting aspects, the fourth thickness is less than 20 microns, less than 18 microns, less than 15 microns, less than 13 microns, less than 10 microns, less than 5 microns, or less than 1 micron. In still further aspects, the fourth thickness can be in a range of 20 microns to 1 micron, 15 microns to 1 micron, 10 microns to 1 micron, 5 microns to 1 micron, 20 microns to 5 microns, 20 microns to 10 microns, 20 microns to 15 microns, 15 microns to 3 microns, 12 microns to 8 microns, and so on.

[0078] It is further understood that the configuration disclosed above assumes that the one layer is positioned below the adjacent layer. However, it is understood that the one layer can also overlay the adjacent layer. In such aspects, the third sublayer of the one layer is interdiffused with the second sublayer of the adjacent layer. It is further understood that if the plurality of layers are present, the one layer can both overlay one adjacent layer and be positioned beneath a second adjacent layer.

[0079] In still further aspects, the first and second amorphous polymers can be the same or different.

[0080] In certain aspects, the first and / or second amorphous polymers exhibit a glass transition temperature Tgsmaller than a melting temperature Tmof the semicrystalline polymer. It is understood that if the first and second amorphous polymers are not the same, their individual Tg are still smaller than the melting temperature Tm of the semicrystalline polymer.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0081] In certain aspects, the Tg is in a range of 0°C-300°C, including exemplary values of 25°C, 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, and 275°C. In still further aspects, Tg can fall between any foregoing values or within a range formed by any foregoing values. For example, and without limitations, the Tgcan be in a range of 0°C-300°C, 25°C-300°C, 50°C-300°C, 75°C- 300°C, 100°C-300°C, 150°C-300°C, 200°C-300°C, 225°C-300°C, 250°C-300°C, 275°C-300°C, 0°C-300°C, 0°C-275°C, 0°C-250°C, 0°C-225°C, 0°C-200°C, 0°C- 150°C, 0°C-100°C, 80°C-170°C, 90°C-205°C, and so on.

[0082] In certain aspects, the Tm is in a range of 100°C-430°C, including exemplary values of 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 200°C, 325°C, 350°C, 375°C, 400°C, and 425°C. In still further aspects, Tg can fall between any foregoing values or within a range formed by any foregoing values. For example, and without limitations, the Tg can be in a range of 100°C-430°C, 150°C-430°C, 200°C- 430°C, 250°C-430°C, 300°C-430°C, 350°C-430°C, 100°C-350°C, 100°C-300°C, 100°C-250°C, 100°C-200°C, and so on.

[0083] In still further aspects, the amorphous polymers present in the second and third sublayers can be any amorphous polymers known in the art and suitable for the desired application. In certain aspects, the first and / or second amorphous polymers comprise polyethyleneimine (PEI), polyamide-imide (PAI) polyphenylsulfone (PPSU), polysulfone (PSU), polyether sulfone (PESU), acrylonitrile butadiene styrene (ABS), amorphous polyetheretherketone (PEEK), polymethyl methacrylate (acrylic), polyimide (PI), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), or any combinations thereof. In yet other aspects, the first and / or second amorphous polymers can be PEI.

[0084] In still further aspects, disclosed herein are composites where the semicrystalline polymers comprise polyetheretherketone (PEEK), polyaryletherketones (PAEKs), polyetherketoneketone (PEKK), polypheylenesulfide (PPS), nylon-11, nylon-6, perfluoroalkoxy (PFA), polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), polylactic acid (PLA), liquid crystal polymers (LCP), polyethylene (PE), or any combinations thereof.

[0085] In still further aspects, the composite disclosed herein can have a first layer comprising a semicrystalline polymer comprising PEEK and the first and / or second amorphous polymer comprising PEI.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0086] In still further aspects, the first thickness is 20 microns to 400 microns, including exemplary values of 25 microns, 50 microns, 75 microns, 100 microns, 125 microns, 150 microns, 175 microns, 200 microns, 225 microns, 250 microns, 275 microns, 300 microns, 325 microns, 350 microns, and 375 microns. In still further aspects, the first thickness can fall between any foregoing values or within a range formed by any foregoing values. For example, and without limitations, the first thickness can be in a range 20 microns to 400 microns, 50 microns to 400 microns, 100 microns to 400 microns, 150 microns to 400 microns, 200 microns to 400 microns, 250 microns to 400 microns, 300 microns to 400 microns, 20 microns to 300 microns, 20 microns to 250 microns, 20 microns to 200 microns, 20 microns to 150 microns, 20 microns to 100 microns, 20 microns to 60 microns, 50 microns to 150 microns, 100 microns to 250 microns, and so on.

[0087] In certain aspects, the semicrystalline polymer of the first sublayer is impregnated with a plurality of reinforcing materials. In certain aspects, the first sublayer can be called a pre-impregnated material or prepreg. In such aspects, it is understood that this prepreg is also a composite material comprising reinforcing materials and a resin matrix. In such exemplary aspects, the resin matrix is disclosed herein semicrystalline polymer. The reinforcing materials can have a volume fraction of 40-60 vol%, including exemplary values of 41 vol%, 42 vol%, 43 vol%, 44 vol%, 45 vol%, 46 vol%, 47 vol%, 48 vol%, 49 vol%, 50 vol%, 51 vol%, 52 vol%, 53 vol%, 54 vol%, 55 vol%, 56 vol%, 57 vol%, 58 vol%, and 59 vol%. In still further aspects, the reinforcing materials can have a volume fraction between any foregoing values or fall within a range formed by any foregoing values. For example, and without limitations, the reinforcing materials can have a volume fraction of 40-60 vol%, 42-60 vol%, 45-60 vol%, 47-60 vol%, 50-60 vol%, 52-60 vol%, 55-60 vol%, 40-57 vol%, 40- 55 vol%, 40-52 vol%, 40-50 vol%, 40-47 vol%, 42-55 vol%, 44-53 vol%, and so on.

[0088] In still further aspects, the plurality of reinforcing materials can comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof.

[0089] In certain aspects, the fibers are embedded within the semicrystalline polymer in various configurations. For example, the reinforcing materials can comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof. In yet still further aspects, the fibers can be arranged in a unidirectional layer, in two layers having different orientations, or as fabric.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0090] One of the primary challenges in current thermoplastic composites lies in the crystallization of semi-crystalline polymers. During interdiffusion, polymer chains at the interface of each sublayer diffuse and entangle, forming a strong bond. For amorphous polymers, this process continues up to the glass transition temperature (Tg), but in semicrystalline polymers, it ceases when crystallization occurs. While crystallization enhances fiber-matrix adhesion and chemical resistance, it restricts interdiffusion, especially in high-rate manufacturing settings, necessitating tight control over crystallization. To form a plurality of large crystals in the first sublayer, the cooling rate from the melt needs to be around 10°C per minute, which reduces the processing rate of composites. However, for future production environments (i.e., automated fiber placement), cooling rates likely need to exceed 1000°C per minute, which can adversely impact the composite’s performance by not allowing time for interdiffusion or slow enough cooling rates to grow crystals. The disclosed herein processes and the formed composites minimize or eliminate these issues. Specifically, in certain aspects, the semi-crystalline polymer present in the first sublayer does not undergo recrystallization (does not melt) during processing, allowing better bonding and more uniform properties. Moreover, in some aspects, the composite is designed to be agnostic to cooling rates, meaning it maintains its properties regardless of the rate applied, ensuring consistent performance even under rapid production conditions.

[0091] In still further aspects, the composite disclosed herein and comprising 1-500, 2-500, 5-500, 10-500, 50-500, 100-500, 1-200, 2-200, 5-200, 1-400, 1-300, 1- 200, 2-400, 2-500, 5-100, 5-300,10-500, 20-500, 50-500, 1-50, 2-50, and on layers exhibits a short beam strength of 50-110 MPa, 55-110 MPa, 60-110 MPa, 70-110 MPa, 80-110 MPa, 50-100 MPa, 50-80 MPa, 50-70 MPa, 55-100 MPa, 55-80 MPa, and so on.

[0092] It is understood that the overall strength of a composite is generally determined by the individual strength of each sublayer and their collective influence on the composite's performance. In current thermoplastic composites, the presence of amorphous sublayers significantly reduces the strength, with actual performance showing a 20% to 50% higher reduction in strength than the theoretical prediction. The theoretical reduction in strength accounts for the inclusion of both the first and second amorphous polymer sublayers in the composite.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0093] In contrast, the composites disclosed herein demonstrate a significantly lower reduction in strength. For example, the composites disclosed herein exhibit less than 25%, 20%, 15%, 10%, 5%, 3%, 1%, or even less than 0.5% reduction in strength compared to the theoretical reduction. This theoretical reduction is similarly based on the incorporation of the first and second amorphous polymers. In other words, the composites disclosed herein exhibit strength that is nearly identical or substantially equal to the calculated theoretical strength of the composite.

[0094] In still further aspects, also disclosed additional composites comprising one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a first semicrystalline polymer; a second sublayer having a second thickness and comprising a second semicrystalline polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a third semicrystalline polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

[0095] In such exemplary and unlimiting aspects, the second thickness and the third thickness can be the same. Yet in other aspects, the second thickness and the third thickness are different. In still further aspects, the second and third thicknesses are less than 10 microns, less than 9 microns, less than 8 microns, less than 7 microns, less than 6 microns, less than 5 microns, less than 4 microns, less than 3 microns, less than 2 microns, less than 1 micron, or less than 0.5 microns. In still further aspects, the second and third thicknesses are in a range of 10 microns to 0.1 microns, 8 microns to 0.1 microns, 5 microns to 0.1 microns, 3 microns to 0.1 microns, 1 micron to 0.1 microns, 0.5 microns to 0.1 microns, 10 microns to 0.5 microns, 10 microns to 1 micron, 10 microns to 3 microns, 10 microns to 5 microns, 10 microns to 8 microns, 8 microns to 1 micron, 5 microns to 3 microns, and so on.

[0096] In such aspects, all of the sublayers can comprise a semicrystalline polymers. In yet still further aspects, the first semicrystalline polymer is impregnated with a plurality of reinforcing materials. Yet in other aspects, the second and the third semicrystalline polymers are not impregnated by the reinforcing materials. YetAttorney Docket No.10046-647WO1 UT Ref.8487 TEH aspects, where the second and / or third semicrystalline polymers are impregnated with reinforcing materials, are also contemplated. In still further aspects, the second semicrystalline polymer and the third semicrystalline polymer are the same or different and are free of reinforcing materials.

[0097] Yet in still further aspects, the first, second and the third semicrystalline polymers can be the same or different and can comprise any of the disclosed above semicrystalline polymers. For example, and without limitations, the first, second, and / or third semicrystalline polymers can comprise polyetheretherketone (PEEK), polyaryletherketones (PAEKs), polyetherketoneketone (PEKK), polypheylenesulfide (PPS), nylon-11, nylon-6, perfluoroalkoxy (PFA), polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), polylactic acid (PLA), liquid crystal polymers (LCP), polyethylene (PE), or any combinations thereof.

[0098] In still further aspects, the first thickness is 20 microns to 400 microns, including exemplary values of 25 microns, 50 microns, 75 microns, 100 microns, 125 microns, 150 microns, 175 microns, 200 microns, 225 microns, 250 microns, 275 microns, 300 microns, 325 microns, 350 microns, and 375 microns. In still further aspects, the first thickness can fall between any foregoing values or within a range formed by any foregoing values. For example, and without limitations, the first thickness can be in a range 20 microns to 400 microns, 50 microns to 400 microns, 100 microns to 400 microns, 150 microns to 400 microns, 200 microns to 400 microns, 250 microns to 400 microns, 300 microns to 400 microns, 20 microns to 300 microns, 20 microns to 250 microns, 20 microns to 200 microns, 20 microns to 150 microns, 20 microns to 100 microns, 20 microns to 60 microns, 50 microns to 150 microns, 100 microns to 250 microns, and so on.

[0099] In certain aspects, the semicrystalline polymer of the first sublayer is impregnated with a plurality of reinforcing materials. Again, while in certain aspects, the second and the third semicrystalline polymers are not impregnated, the actual impregnation of these sublayers is also contemplated.

[0100] The reinforcing materials can have a volume fraction of 40-70 vol%, including exemplary values of 41 vol%, 42 vol%, 43 vol%, 44 vol%, 45 vol%, 46 vol%, 47 vol%, 48 vol%, 49 vol%, 50 vol%, 51 vol%, 52 vol%, 53 vol%, 54 vol%, 55 vol%, 56 vol%, 57 vol%, 58 vol%, 59 vol%, 60 vol%, 61 vol%, 62 vol%, 63 vol%, 64 vol%, 65 vol%, 66 vol%, 67 vol%, 68 vol%, and 69 vol%. In still further aspects, theAttorney Docket No.10046-647WO1 UT Ref.8487 TEH reinforcing materials can have a volume fraction between any foregoing values or fall within a range formed by any foregoing values. For example, and without limitations, the reinforcing materials can have a volume fraction of 40-70 vol%, 42-70 vol%, 45- 70 vol%, 47-70 vol%, 50-70 vol%, 52-70 vol%, 55-70 vol%, 60-70 vol%, 65-70 vol%, 40-67 vol%, 40-65 vol%, 40-62 vol%, 40-60 vol%, 40-57 vol%, 40-55 vol%, 40-50 vol%, 40-47 vol%, 42-55 vol%, 44-53 vol%, and so on.

[0101] In still further aspects, the plurality of reinforcing materials can comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof.

[0102] In certain aspects, the fibers are embedded within the semicrystalline polymer in various configurations. For example, the reinforcing materials can comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof. In yet still further aspects, the fibers can be arranged in a unidirectional layer, in two layers having different orientations, or as fabric.

[0103] In still further aspects, in any of the disclosed herein composites (whether it has the second and third sublayers be amorphous materials or semicrystalline materials), the second and / or the third sublayer are at least partially ablated.

[0104] Also disclosed herein are articles comprising any of the disclosed herein composite materials. For example, and without limitations, the article can comprise an aircraft component, a spacecraft component, a component of a military article, an automotive component, a recreation component, a turbine component, construction & infrastructure, a satellite component, a marine component, a medical component, chemical storage / transport, or any combination thereof. For example, the article can be an aircraft wing, car doors or sides, tennis rackets, bikes, composite materials used in building materials, etc. METHODS

[0105] Also disclosed are methods of forming the described above composites.

[0106] In certain aspects, the methods disclosed herein comprise (a) forming one or more layers, wherein each layer comprises a first sublayer having a first thickness and comprising a semicrystalline polymer having a Tm; a second sublayer having an initial second thickness and comprising a first amorphous polymer having a Tg, wherein the second sublayer overlays the first sublayer; and a third sublayerAttorney Docket No.10046-647WO1 UT Ref.8487 TEH having an initial third thickness and comprising a second amorphous polymer having a Tg, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that such that an overlaying portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and c) reducing the thickness of the second sublayer and the third sublayer to form a second thickness and a third thickness to be less than 10 microns

[0107] It is understood that the first sublayer can comprise any of the disclosed above semicrystalline polymers. In certain aspects, such semicrystalline polymers can be impregnated by any of the aforementioned reinforcing materials. It is understood that impregnation can be preformed by any known in the art methods. For example, laser-assisted automated fiber placement.

[0108] It is understood that the first sublayer can be formed by any method known in the art. Some of the methods of making such prepregs are disclosed in the U.S. Patent Application Publication No.20100170637 and U.S. Patent No. 10259175, the contents of which are incorporated by reference in their entirety.

[0109] In still further aspects, the second sublayer can comprise any of the first amorphous polymers disclosed above. In yet other aspects, the third sublayer can comprise any of the disclosed above second amorphous polymers. In still further aspects, the initial second thickness and initial third thickness are greater than 10 microns to 100 microns, 11 microns to 100 microns, 15 microns to 100 microns, 20 microns to 100 microns, 25 microns to 100 microns, 30 microns to 100 microns, 35 microns to 100 microns, 40 microns to 100 microns, 45 microns to 100 microns, 50 microns to 100 microns, 55 microns to 100 microns, 60 microns to 100 microns, 70 microns to 100 microns, 80 microns to 100 microns, 11 microns to 80 microns, 15 microns to 60 microns, 15 microns to 50 microns, 15 microns to 20 microns, and so one.

[0110] In still further aspects, the second and third thicknesses are less than 10 microns, less than 9 microns, less than 8 microns, less than 7 microns, less than 6 microns, less than 5 microns, less than 4 microns, less than 3 microns, less than 2 microns, less than 1 micron, or less than 0.5 microns. In still further aspects, the second and third thicknesses are in a range of 10 microns to 0.1 microns, 8 micronsAttorney Docket No.10046-647WO1 UT Ref.8487 TEH to 0.1 microns, 5 microns to 0.1 microns, 3 microns to 0.1 microns, 1 micron to 0.1 microns, 0.5 microns to 0.1 microns, 10 microns to 0.5 microns, 10 microns to 1 micron, 10 microns to 3 microns, 10 microns to 5 microns, 10 microns to 8 microns, 8 microns to 1 micron, 5 microns to 3 microns, and so on.

[0111] In still further aspects, the reduction of the initial second and third thickness to obtain the second and third thicknesses can be done by known in the art methods. For example, it can be done by a laser ablation, radiofrequency ablation, chemical etching, laser-induced-plasma-assisted ablation (LIPAA), plasma etching, mechanical ablation, ultrasonic ablation, photoablation, electrical ablation, cryoablation, microwave ablation, ion beam etching, reactive ion etching or any combinations thereof.

[0112] In still further aspects, the second and the third sublayer can be disposed by any methods known in the art. In the disclosed herein aspects, the first sublayer is sandwiched between the second and third sublayers. In still further aspects, the second and the third sublayers can be disposed as films, tapes, and powders, which can be directly grown on the first sublayer. In still further aspects, the second and / or the third layers can be formed by a polymer growth, spray coating, disposing a powder, disposing polymer fibers, laying one or more polymer films, dispersing polymer flakes, solvent coating, dip coating, grafting, polymerizing, hot pressing, thermal lamination, or by any combination thereof before interdiffusing respective surfaces with the first sublayer.

[0113] In still further aspects, the interdiffusion can be done by applying pressure and / or temperature, or any combination thereof.

[0114] In still further aspects, when the sublayers are disposed on each other, the pressure can be applied to bring those sublayers into intimate contact to allow efficient interdiffusion during the heating step. In such aspects, when the layer is formed, the step of heating occurs at a temperature above or near the Tmof the semicrystalline polymer. After the layer is formed, the composite is cooled down slowly at temperatures of less than 1,000°C / min, less than 500°C / min, less than 100°C / min, or less than 10°C / min. In still further aspects, the colling at this stage is done in a range of 1°C / min to 10°C / min, 5°C / min to 15°C / min, 1°C / min to 50°C / min, or 1°C / min to 100°C / min.

[0115] In certain aspects, the composite only comprises one layer.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0116] In yet further aspects, the methods disclosed herein further comprise: (d) positioning a first layer of the one or more layers on a second layer of the one or more layers to form two or more layers; optionally positioning further one or more layers between the first and the second layer of two or more layers, or optionally positioning the further one or more layers on a final layer of the two or more layers, wherein the further one or more layers are different from the first layer, the second layer, and / or the final layer; (e) heating the two or more layers to a temperature that is greater than Tg of the first and / or second amorphous polymer but such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of the second layer; and (f) cooling the two or more layers to form a composite, wherein the cooling is rate- agnostic.

[0117] In a still further aspect, wherein the shape of each of the two or more layers is not changed after step e).

[0118] In still further aspects, the temperature is less than Tmof the semicrystalline polymer. Yet in still further aspects, the layers can be heated to a temperature greater than the first Tgor the second Tgor greater than the first and the second Tgas long as it is less than Tm.

[0119] In still further aspects, the composite can have three or more layers.

[0120] Formation of the plurality of layers can be done by any known in the art methods. For example, in some aspects, each layer is formed separately (by disposing the sublayers in the desired way and interdiffusing the sublayers as disclosed above), and then the layers are superimposed and heated to form a laminate. In still further aspects, each layer is added sequentially to form the laminate. In other aspects, a number of layers can be compiled together and then laminated. In still further aspects, the laminate or the plurality of layers can be formed by a tape laying, compression molding, oven processing, thermoforming, and the like. The interdiffusion can occur above the Tgof the amorphous polymers present in the second and / or third sublayers of the individual layers.

[0121] In still further aspects, the interdiffused portions in any of the layers present in the composite are substantially free of an interface boundary. Again, it is understood that the skilled person reviewing the images of the laminate can define different layers, however, a clear interface boundary is substantially not observant.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0122] In still further aspects, the second sublayer of one layer and the third sublayer of an adjacent layer are interdiffused to form one sublayer having a fourth thickness. In such exemplary and unlimiting aspects, the fourth thickness is less than 20 microns, less than 18 microns, less than 15 microns, less than 13 microns, less than 10 microns, less than 5 microns, or less than 1 micron. In still further aspects, the fourth thickness can be in a range of 20 microns to 1 micron, 15 microns to 1 micron, 10 microns to 1 micron, 5 microns to 1 micron, 20 microns to 5 microns, 20 microns to 10 microns, 20 microns to 15 microns, 15 microns to 3 microns, 12 microns to 8 microns, and so on.

[0123] It is further understood that the configuration disclosed above assumes that the one layer is positioned below the adjacent layer. However, it is understood that the one layer can also overlay the adjacent layer. In such aspects, the third sublayer of the one layer is interdiffused with the second sublayer of the adjacent layer. It is further understood that if the plurality of layers are present, the one layer can both overlay one adjacent layer and be positioned beneath a second adjacent layer.

[0124] In still further aspects, the semicrystalline polymer present in the first sublayer when the plurality of layers is formed does not melt or undergo recrystallization.

[0125] In still further aspects, the step of heating is performed for 1 microsecond to 20 hours, 30 microseconds to 20 hours, 50 microseconds to 20 hours, 100 microseconds to 20 hours, 500 microseconds to 20 hours, 1 milliseconds to 20 hours, 10 milliseconds to 20 hours, 1 second to 20 hours, 10 seconds to 20 hours, 30 seconds to 20 hours, 1 min to 20 hours, 5 min to 20 hours, 10 min to 20 hours, 30 min to 20 hours, 1 hour to 20 hours, 5 hours to 20 hours, 10 hours to 20 hours, 1 microsecond to 15 hours, 1 microsecond to 10 hours, 1 microsecond to 5 hours, 1 microsecond to 2 hours, 1 microsecond to 1.5 hours, 1 microsecond to 1 hours, 1 microsecond to 40 min, 1 microsecond to 30 min, 1 microsecond to 20 min, 1 microsecond to 10 min, 1 microsecond to 5 min, 1 microsecond to 1 min, 1 microsecond to 30 sec, 1 microsecond to 1 sec, 1 microsecond to 500 milliseconds, 1 microsecond to 100 milliseconds, 1 microsecond to 50 milliseconds, 1 microsecond to 10 milliseconds, 1 microsecond to 1 milliseconds, and so on.

[0126] In still further aspects, the heating is performed under 0.1 MPa to 10 MPa, 0.1 MPa to 8 MPa, 0.1 MPa to 5 MPa, 0.1 MPa to 3 MPa, 0.1 MPa to 1 MPa,Attorney Docket No.10046-647WO1 UT Ref.8487 TEH 0.1 MPa to 0.5 MPa, 0.5 MPa to 10 MPa, 1 MPa to 10 MPa, 3 MPa to 10 MPa, 5 MPa to 10 MPa, and so on.

[0127] In still further aspects, the methods of forming the composite are cooling rate agnostic. In other words, the composite properties are not affected by the cooling rate. In still further aspects, the cooling is performed at any rate within 1°C / min to 1,000°C / min, 1°C / min to 900°C / min, 1°C / min to 500°C / min, 1°C / min to 300°C / min, 1°C / min to 100°C / min, 1°C / min to 50°C / min, 10°C / min to 1,000°C / min, 50°C / min to 1,000°C / min, 100°C / min to 1,000°C / min, 300°C / min to 1,000°C / min, 500°C / min to 1,000°C / min, and so on.

[0128] In still further aspects, the methods also can comprise steps where an amount of the first amorphous polymer and the second amorphous polymer removed during the reducing the thickness step is collected and recycled.

[0129] In still further aspects, the second and the third thicknesses in the reducing step are controlled with a profilometer.

[0130] In still further aspects, the method comprises monitoring and analyzing a chemical composition of a material removed during the reducing the thickness step.

[0131] In still further aspects, the composite formed by the disclosed herein methods exhibits any of the disclosed above properties.

[0132] In still further aspects, the method further comprises forming any of the disclosed above articles.

[0133] In still further aspects, also disclosed are methods where instead of the second and third sublayers comprising the first and the second amorphous polymers, the second and the third sublayers comprise a second and third semicrystalline polymers. In such aspects, a method of forming a composite comprising: : (a) forming one or more layers, wherein each layer comprises a first sublayer having a first thickness and comprising a semicrystalline polymer having a first Tm; a second sublayer having an initial second thickness and comprising a second semicrystalline polymer having a second Tm, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a third semicrystalline polymer having a third Tm, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that such that an overlaying portion of the initial second thickness isAttorney Docket No.10046-647WO1 UT Ref.8487 TEH interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and c) reducing the thickness of the second sublayer and the third sublayer to form a second thickness and a third thickness to be less than 10 microns.

[0134] The methods further comprise (d) positioning one layer on a second layer to form two or more layers; (e) heating the two or more layers such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of the second layer; and (f) cooling the two or more layers to form a composite, wherein the cooling is rate- agnostic.

[0135] In yet still further aspects, the heating is to a temperature that is higher than the first Tm, the second Tm, and the third Tm.

[0136] Also disclosed herein are layers, wherein the first sublayer and at least one of the second or third sublayers comprise any of the disclosed above semicrystalline polymers. In such exemplary aspects, only one of the sublayers can be any of the disclosed above amorphous polymers.

[0137] Also disclosed herein are composites comprising a plurality of layers where one layer can comprise the first sublayer comprising any of the disclosed above semicrystalline polymers sandwiched between any of the disclosed above amorphous polymers, and wherein one or more layers comprise a composite where all three sublayers comprise the semicrystalline polymers as described above and / or where one layer comprises a composite the first sublayer and at least one of the second or third sublayers comprise any of the disclosed above semicrystalline polymers and where at least one sublayer is an amorphous layer. It is understood that the plurality of layers can comprise any variety of the disclosed herein layers disposed in any order.

[0138] It is understood that the methods of forming such a composite comprise the temperatures, pressures, and steps disclosed above. In yet still further aspects, the first, second, and third semicrystalline polymers used in these methods can be any of the disclosed above materials. Any of the methods disclosed above for reducing the thickness can be utilized. In still further aspects, the formed composites can have any of the disclosed above properties.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH EXAMPLES

[0139] The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention, which are apparent to one skilled in the art.

[0140] Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, the temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction ranges and conditions, which can be used to optimize the purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions. EXAMPLE 1:

[0141] FIG.1A shows a traditional method of forming thermoplastic composites. During this process, the crystallization stops the healing process, which results in the composite with diminishing properties.

[0142] One exemplary composite formed according to the methods disclosed herein is shown in FIG.1B.

[0143] In the examples disclosed herein, one of the disclosed above semicrystalline composite prepregs (130 microns) was sandwiched between thick amorphous polymers (25-micron). The excess of the amorphous polymer was reduced to less than a micron. This results in an ultra-thin, smooth amorphous sheath that is readily available for bonding without melting the parent material. The amorphous polymer can be bonded beneath the melt temperature of the semi- crystalline composite but above the healing temperature of the amorphous polymer. This gives the prepreg a cooling-rate agnostic nature by not requiring slow cooling of the semi-crystalline polymer. The laser ablation process minimizes mechanical knockdown from adding the amorphous sheath.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0144] Currently, significant global efforts, totaling over $500 million, are underway to demonstrate the viability of TPC aircraft structures and their assembly. The goal is to manufacture 80 single-aisle airliners per month by 2040, as part of initiatives like NASA's Hi-Rate Composite Aircraft Manufacturing (HiCAM) project. In contrast, current thermoset autoclave methods only allow to produce of 10-14 composite airplanes per month. By developing a cooling-rate agnostic composite, this study offers a solution that may hit these desired target production rates. There is a race to build a composite alternative to the single-aisle (737), and the winner will have a serious competitive advantage. Moreover, high-rate composite manufacturing is necessary for the automotive industry.

[0145] The interest in the manufacturability of large-scale (fuselages, wing structures, etc.) thermoplastic composite (TPCs) aerostructures stems from their exceptional toughness, recyclability, and chemical resistance. Notably, TPCs can be welded to eliminate the need for conventional fasteners and offer manufacturing flexibility and repair. This has led to an emphasis on high-rate technologies (>60 airplanes / month) like thermoplastic automated fiber placement (AFP), thermal welding, and filament winding. Central to these methods is fusion bonding, which involves intimate contact, interdiffusion, and solidification. Intimate contact refers to the polymer-polymer contact necessary for interdiffusion, where polymer chains cross interfaces and entangle. Interdiffusion (healing) continues in amorphous polymers until the glass transition temperature (Tg), but ceases in semi-crystalline polymers upon a critical crystallization. Crystallization, while crucial for fiber-matrix adhesion and chemical resistance, limits interdiffusion in high-rate settings. Additionally, for crystallinity to develop large crystals, the cooling rate from the melt is required to be ~10°C / min, but in AFP settings, the cooling rate can be >100010°C / min. The current disclosure aims to address the reduced processing window due to the onset temperature of critical crystallization by adding an amorphous polymer at the bonding interface.

[0146] A concept of amorphous bonding was introduced in the 1980s with a dual-bonding process called Thermabond©, where an amorphous polymer, Polyetherimide (PEI), was added to the surface of Aromatic Polymer Composite (APC-2) composites during hot pressing before subsequent welding. More recently, hybrid composite tapes have been developed by sandwiching CF-PEEK (127 μm) between neat PEI (50 μm) to promote amorphous bonding in high-rate settings. AAttorney Docket No.10046-647WO1 UT Ref.8487 TEH key benefit of the PEI film is that interdiffusion can occur below the melt temperature of the PEEK, such that existing crystallinity does not melt during processing. The limitation of these approaches is that adding PEI reduces the relative fiber volume fraction of the composite (FIG.4), which leads to a decrease in mechanical performance. It was shown that the short beam strength (SBS) decreases by ~40% as resin-rich interlayer thickness increases from 5 to 13 μm. The in-plane properties would suffer as well.

[0147] Given the strength of CF-PEEK (~425 MPA) and neat PEI (~95 MPA), adding 50 and 25 microns of PEI to each layer of the prepreg reduces the tensile strength by 34% and 22% by the rule of mixtures, respectively. Whereas, when adding only 5 and 1 micron, there is only a 3% and .5% theoretical reduction in strength, respectively.

[0148] FIG.2 shows a conventional PEEK thermoplastic composite and an Out-of-autoclave Amorphous / semicrystalline Thermoplastic Material for Energy- efficient Aerospace-grade Laminates (OATMEAL) composite disclosed herein.

[0149] There is a trade-off between adding enough PEI to promote fusion bonding at the interface and not corrupting the mechanical performance. It was found that handling a thin PEI film is challenging. The film was prone to wrinkling, leaving voids between the film and composite, and it would rip easily. It was also found that using semi-crystalline polymers with higher melting temperatures results in composites with higher performance. In this example, the PEEK with Tm of 343°C was found to be useful because PEI fully heals in less than a second at 320°C.

[0150] Initially, the 25-micron PEI on both sides of PEEK-CF (carbon fiber) was positioned in a vacuum bag in an autoclave and cooled at a rate of 10°C / min. Then, a 16-ply quasi plate was consolidated at 320°C (see FIG.6A). Cross-sectional microscopy revealed resin-rich interfaces and strong bonding, even though the plate was processed below the melt temperature of the PEEK. It was found that leveraging the healing behavior of the PEI, the crystal history of the PEEK is not erased. It was also found that the process is not limited by the necessary slow-cooling nature of PEEK. To reduce the mechanical impact of the thick PEI interfaces, the ablating homemade tape (FIG.5). Laser ablation uses a high frequency laser to vaporize and eject desired amounts of material from the surface without damaging underlying material. This was done using an Ekspla Atlantic 20 Nd:YVO4 picosecond laser on a PhotoMachining, Inc. system with a galvanometer to move the laser spot across theAttorney Docket No.10046-647WO1 UT Ref.8487 TEH surface. The tuning parameters are laser power (limited through attenuation), frequency, overlap between passes and scan speed. This study investigated fusion bonding (at 320°C, beneath the melt temperature of PEEK laser-ablated surfaces of varying power. It was found that regardless of the laser power, all of the surfaces bonded. Under cross-sectional microscopy it was found that after 15% power, the cross-sections looked the same: almost zero excess resin between layers (FIG.4 and FIG.6B and FIGS.7A-7B). In FIGS.7A-7B, it can be seen that the composites obtained by the disclosed herein methods have less than 1 micron of PEI sublayer bond the sublayers without melting the PEEK and without clear interface boundaries being observed.

[0151] FIG.3 shows a known heating behavior of PEI and PEEK polymers. The temperature range where PEI is above its Pg but below Tm of PEEK can be defined as a range where the Goldilocks effect of the effective interdiffusion and healing occurs.

[0152] FIG.4 shows exemplary processing steps where the PEI films and PEEK-CF (carbon fiber) prepregs are arranged together to form one layer. These sublayers are then disposed into a vacuum bag and into an autoclave to heal them together.

[0153] FIGS.8A-8F show simulations of the healing process of PEI and PEEK under different thermal histories that are representative of the automated fiber placement process.

[0154] FIGS.9A-9C are analytical expressions predicting that when the composites are formed using AFP processes and are disposed onto a heated tool, the OATMEAL composites can be formed super-fast (1 m / s) without melting the PEEK.

[0155] FIGS.10A-10B show a spatial map of an absorption spectrum (1448 cm-1) unique to PEI, illustrating the interdiffusion of the amorphous polymer into a semi-crystalline PEEK prepreg. This data was measured using atomic force microscopy and infrared spectrometry. EXAMPLE 2:

[0156] The processing of thermoplastic composites is often limited by high energy demands and slow cycle times. Out-of-autoclave amorphous / crystalline thermoplastic materials for energy-efficient aerospace-grade laminates (OATMEAL)Attorney Docket No.10046-647WO1 UT Ref.8487 TEH address these challenges through a unique prepreg architecture. OATMEAL includes slow-cooled carbon fiber-reinforced semicrystalline polyetheretherketone (PEEK) tape sheathed in thin amorphous polyetherimide (PEI) layers. The PEI sheaths are miscible with PEEK and enable interfacial healing below the melting point of PEEK — preserving pre-existing crystallinity and reducing processingtemperatures by 80 °C. The sheaths are thinned via high-frequency laser ablation tothe PEEK–PEI blending regions, thereby reducing residual stresses, and promoting chemical resistance. Fast-cooled vacuum bag only oven processing of OATMEAL laminates yields aerospace-quality laminates while enabling processing speeds over five times faster than conventional methods. These results represent a significant advancement and a step towards truly high-rate, large-scale aerostructure manufacturing. Introduction

[0157] The high energy demands and lengthy processing times of advanced composite structures present a significant barrier to the aerospace industry’s emerging need to scale production to ~80 single-aisle aircraft per month and to support future air taxi markets. Potential high-throughput manufacturing methods with thermoplastic composites (TPCs), such as in situ consolidation via automated fiber placement (AFP), fall short of these ambitious targets, constrained by rapid cooling, short processing windows, and high equipment costs. Although TPCs offer compelling advantages, including weldability, chemical resistance, and damage tolerance, their commercial adoption is slow. Leading candidates for next-generation TPC structures include carbon fiber (CF)–reinforced polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and low-melt polyaryletherketone (LM PAEK), often combined with thermoforming to achieve complex geometries. However, press size limitations necessitate welding of subcomponents into large assemblies, adding further complexity. Another path forward could be processing of preforms through vacuum-bag-only (VBO) consolidation in an oven or on a heated tool to improve the performance. These techniques are carried out at relatively high temperatures and for extended periods to reduce porosity, enhance the crystallinity of the matrix, and most importantly, enhance bonding between the layers. The temperature cycle is constrained by crystallinity growth. This study addresses the challenges discussed so far by enabling rapid, energy-efficient manufacturing of large-scale TPCs structures.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0158] Thermoplastic fusion bonding includes intimate contact, polymer healing (interdiffusion or autohesion), and eventual solidification. Intimate contact refers to the extent to which polymer interfaces come into contact, enabling healing to occur. Insufficient intimate contact leads to the formation of interlaminar voids. Resin percolation during intimate contact leads to resin-rich interfaces. Once intimate contact is achieved, the process of interdiffusion or healing begins. This involves the motion of polymer chains across polymer-polymer interfaces. The extent of interdiffusion depends on both the depth of chain penetration and the degree of entanglement. Notably, the polymer chains need to be mobile, and crystallinity retards interdiffusion by restricting local chain motion. Therefore, processing temperatures are 10-15% above the matrix’s melting temperature to ensure that any crystallinity is removed and chains are mobile across interfaces. During solidification, semi-crystalline polymer regions form, building strength but inhibiting further interdiffusion. It is apparent that crystallization, while essential for mechanical performance and fiber-matrix adhesion, reduces the processing window.

[0159] Unlike semi-crystalline polymers, amorphous polymers can heal above their glass transition temperature, Tg, and may be better suited at the interfaces between plies to circumnavigate their constraint. Polyetherimide (PEI) is a high- performance amorphous polymer that is miscible with PEEK. At 300°C, the welding time of a PEI–PEI interface was measured to be 63 to 321 seconds and 0.7 to 3 seconds at 320°C. In comparison, for a PEEK–PEEK interface, the measured welding times are 0.30 to 1.60 seconds at 420°C and 782 to 3957 seconds at 380°C. The PEEK melting temperature is measured to be 343°C, but crystallinity effects appear to persist above the melt. Imaging spherulites with polarized optical microscopy after holding them for 3 minutes at various temperatures above the melting point revealed that spherulites nucleated at the same location at 360 °C and 370°C, displaying melt memory, but at 380°C, the ordering was erased. The temperature for PEEK healing is, therefore, around 380°C because the melt memory restricts polymer motion. Comparatively, the healing time for a PEI–PEEK interface is sufficiently lower at 380°C, 82 to 414 seconds.

[0160] A “dual bonding” ThermabondTMprocess was introduced previously, in which a 75 μm polyetherimide (PEI, Tg 260°C) layer is hot pressed onto semi- crystalline PEEK laminates to enable subsequent welding below the PEEK melting point (Tm 343°C). By restricting weld temperatures beneath the Tm of PEEK,Attorney Docket No.10046-647WO1 UT Ref.8487 TEH existing crystalline domains remain intact, and PEI–PEI interfacial healing achieves lap shear strengths comparable to conventional PEEK–PEEK welds, exceeding those attainable with structural adhesives. However, its reliance on a relatively thick, pure PEI film carries penalties: resin-rich interlayers reduce fiber-volume fraction, degrade both inter- and intralaminar mechanical properties, and inherit PEI’s limited chemical resistance and creep performance. For example, Thermabond™’s PEIweld strength falls by 60 % after exposure to Skydrol hydraulic fluid, whereas PEEK–PEI blends endure the same chemical attack for at least 1,000 h with minimal loss ofstrength.

[0161] As discussed above in Example 1, more recently, laser-assisted in-situconsolidation AFP was applied to a 127 μm CF / PEEK prepreg sandwiched between50 μm PEI plies: a 980 nm laser penetrates the semi-transparent PEI, heats thecarbon fibers, and conductively fuses the PEEK–PEI interface. In that study, mechanical properties were not reported, but it was found that the process still leaves a thick amorphous PEI layer, one that is predicted to compromise stiffness and strength and remain chemically vulnerable. Indeed, it was found that increasingresin-rich interlayer thickness from 5 to 13 μm in cross-ply CF / PEKK laminatescauses over a 30 % drop in short beam strength, even at constant void content andcrystallinity. (See Arquier et al., “Role of the inter-ply microstructure in the consolidation quality of high-performance thermoplastic composites,” Polym Compos, vol.45, no.2, pp.1218–1227, Jan.2024, doi: 10.1002 / pc.27847).

[0162] In contrast, this study employs a high-frequency laser to remove PEI down to the PEI / PEEK blending at micrometer thickness, thereby preserving high fiber-volume fraction, minimizing interlayer resin content, and improving both solvent and creep resistance. By tailoring blend chemistry and reducing interlayerdimensions, the material retains the rapid, low energy bonding advantages ofamorphous polymers while overcoming the shortcomings of pure PEI films – achieving full interlaminar fusion with minimal compromise of in-plane or transverse mechanical performance. The PEEK composites with thin PEI–PEEK sheaths are aptly named out-of-autoclave amorphous / crystalline thermoplastic materials for energy-efficient aerospace-grade laminates (OATMEAL) because they are processed within the "Goldilocks Zone," balancing the right amount of amorphous and crystalline polymer content. FIGS.11A-11D provides an overview of processing OATMEAL by healing 25 μm of PEI to the surface of CF / PEEK tapes (similar toAttorney Docket No.10046-647WO1 UT Ref.8487 TEH Example 1), resulting in the blending of the two polymers. Laser ablation of neat PEI at the surface significantly improves interlaminar bonding, increases the volume fraction, and thermal analysis confirms that the crystallinity of PEEK is preserved when processed within the Goldilocks Zone. The healing of PEI to PEEK was investigated through spatial chemical mapping, where Fourier transform infrared spectroscopy (FT-IR) and atomic force microscopy infrared spectroscopy (AFM-IR) are used together to generate spatial maps of the polymer interfaces, revealing that the blended polymer region maintains the Goldilocks zone healing domain. Results and Discussion

[0163] A PEI–PEEK blend sheath enables processing below the melt temperature of PEEK. FIG.11D demonstrates a 16-ply quasi-isotropic laminate, [0 / 45 / -45 / 90]2S, of AS4 CF / PEEK and OATMEAL processed in an autoclave at 300°C for 30 minutes under 0.8 MPa of absolute pressure, where only the OATMEAL laminate consolidated. Two chemical species mapping techniques are investigated (microscale FT-IR and nanoscale AFM-IR) to measure the PEI–PEEK distributions at interlaminar regions. As shown in FIGS.12A-12F, the findings demonstrate that reducing interlaminar resin-rich regions via laser ablation and PEI– PEEK blending is sufficient for consolidation below the melt temperature of PEEK. By measuring an FT-IR spectrum across a polished cross-section, the polymer distribution is mapped via peak amplitudes at two characteristic wavenumbers: 1351 cm-1for PEI and 925 cm-1for PEEK (see FIG.12A). The optical micrograph in FIG. 12B shows the exact region scanned. Notably, the OATMEAL laminate exhibits reduced resin content in its interlaminar region, an effect of the laser ablation step, compared to the hybrid, which is 25 m of PEI healed to CF / PEEK. In FIG.12C, the absorption at 1351 cm-1and 925 cm-1is normalized against bulk polymer measurements, then the ratio of the normalized absorption (PEI over PEEK) is calculated to highlight local blending behavior.

[0164] The hybrid laminates are characterized by distinct 20-30 m thick interlaminar regions of neat PEI (1351 cm-1absorption matches that of neat PEI). Although nominally 50 m of PEI was added (25 m to each side), only ~20 m interface width is measured due to interdiffusion into the PEEK as well as fiber repopulation during the initial PEI–PEEK consolidation (FIGS.12B-12C). In contrast, OATMEAL samples show neither neat PEI absorption nor full resin richness; instead, their interlaminar regions contain a PEI–PEEK blend (FIGS.12B-12D). WithoutAttorney Docket No.10046-647WO1 UT Ref.8487 TEH wishing to be bound by any theory, it was hypothesized that laser ablation strips away surface PEI, leaving behind a partially mixed polymer layer. Where fiber repopulation was more pronounced, less PEI was removed. Crucially, as shown earlier, this residual PEI–PEEK blend can still consolidate below the PEEK melting point at 300°C, 80°C below its processing temperature.

[0165] Interdiffusion of neat PEI–PEEK films was investigated using nanoscale AFM-IR (FIG.12D). The films were healed together at 380°C under 0.8 MPa of absolute pressure and then polished. There are no fibers present in this sample. During AFM-IR, single-wavenumber irradiation (1448 cm-1, which is absorbed by PEI) was aimed at the AFM tip (via an optimization procedure automated by the instrument software). Where PEI was present, the thermal expansion pulses excited the AFM cantilever at the contact resonance frequency, enabling chemical mapping. A clear blending gradient forms across the interface (measured to be ~40 m). Additionally, across the interface, full IR spectra were collected and plotted together (see FIG.12E) to observe a smooth transition region across the 40 m where the two polymers are blended. A distinct transition in absorption spectra is observed, confirming chemical blending.

[0166] Finally, AFM-IR was used to measure the blending of PEI and PEEK across a 0 / 90 (in / out-of-plane) interface of an OATMEAL specimen. Similarly, the thermal response to an IR laser at 1448 cm-1is plotted on a 3D topographic map, shown in FIG.12F. Directly at the interface, about 4 m of PEI (or a PEI–PEEK blend) is measured before the first out-of-plane fiber. This fiber is thought to have repopulated during the healing of the polymers, as there is a nearly 15 m PEI-rich region before the next fiber. Fiber repopulation is predicted to influence the laser ablation behavior and corresponds with the FT-IR observations. Regions near fibers exhibit a contrast gradient likely arising from a variable photothermal expansion signal, due to differing thermal conduction of absorbed pulse energy over domains at various distances from the highly conductive fibers. Moving into the CF / PEEK, the PEI concentration decreases over ~20 m (roughly three fiber diameters), indicating slowed interdiffusion in the presence of fibers compared to the neat films.

[0167] Representative heating differential scanning calorimetry (DSC) curves are presented in FIG.13A, together with the average crystallinity percentages (FIG. 13B) measured for six replicates of each laminate. Identical overall crystallinity percentages were exhibited by all laminates; in particular, hybrid and OATMEALAttorney Docket No.10046-647WO1 UT Ref.8487 TEH specimens, both consolidated at 300°C, below PEEK’s melt temperature, showed crystallinity preservation. Two glass transition events were observed in the hybrid and OATMEAL heating curves. The second transition, associated with PEI, was shifted from ~220°C in the hybrid laminate to ~200°C in the OATMEAL. This downward shift is attributed to a reduction in neat PEI content and increased PEI– PEEK intermixing at the interlaminar regions, in agreement with chemical mapping results. By comparison, fully homogeneous PEI–PEEK blends exhibit a single Tgthat moves from 217°C to 180°C to 143°C as the PEI fraction decreases (100 / 0, 60 / 40, 0 / 100 by weight).

[0168] Distinct melting peak behavior was revealed for hybrid and OATMEAL laminates, in contrast to the single endotherm of the CF / PEEK reference. The hybrid laminate produced a double peak, and the OATMEAL produced a triple peak, with its third peak extending beyond the melting window observed in the other systems. Such multi-peak melting profiles have been linked to PEI being trapped in interlaminar regions during fast cooling and rejected into interspherulitic regions during slow cooling. The introduction of PEI is, therefore, inferred to cause additional melting events. Ideally, PEI rejection into amorphous interlaminar layers is promoted to support sub-melt bonding, and this behavior was enabled by consolidation below PEEK’s melting temperature.

[0169] Another factor for the double and triple peak behavior may lie in the prepreg manufacturing process: a 10°C / min ramp to 380°C (with a 30-minute isothermal hold for PEI healing) followed by a 5°C / min cool. PEEK is known to exhibit double melting peaks under slow heating, with the first peak melting before recrystallization. The presence of blended PEI–PEEK during the isothermal hold (interdiffused over ~20 m, as shown by FT IR / AFM-IR) could give rise to a third endotherm. To reduce the impact of PEI on PEEK crystallization while maintaining sub-melt interlaminar consolidation, it is recommended that future studies explore shorter healing times for the PEI–PEEK system.

[0170] Short beam strength (SBS) tests were conducted to probe the interlaminar regions of the thermoplastic laminates, following the sensitivity to resin rich interlayer thickness for off-axis CF / PEKK systems. In the present work, nominally 50 μm of PEI was added to the interlayer of the hybrid laminates; the actual interlaminar thickness was measured at ~20 μm by optical microscopy andFT-IR, and corresponding fiber volume fractions were determined via image analysisAttorney Docket No.10046-647WO1 UT Ref.8487 TEH (FIG.13D). While all laminates were manufactured in an autoclave under 0.8 MPa, the OATMEAL / hybrid were processed at 300°C compared to 380°C for CF / PEEK reference. For the quasi-isotropic layup, the CF / PEEK reference exhibited an average SBS of 87 ± 4 MPa; the hybrid panels fell to 52 ± 3 MPa (–40%), and the OATMEAL panels reached 67 ± 2 MPa (–23%). In unidirectional specimens, the reference recorded 110 ± 2 MPa, the hybrid laminate decreased to 88 ± 4 MPa (– 20%), and OATMEAL measured 96 ± 4 MPa (–13%). After laser ablation (OATMEALprocessing), the interlaminar thickness was reduced to ~5-10 μm, and fiber volumefraction recovered by ~20%, but ~22% less than the CF / PEEK material.

[0171] The reduction in resin rich interlayer thickness is also inferred toalleviate residual stresses generated by the coefficient of thermal expansion (CTE) mismatch between polymer and carbon fiber, which can differ by 3–4 orders of magnitude. During cooling, differential shrinkage in thick resin layers pre-stresses the interlaminar regions. By contrast, removing or thinning resin-rich interfaces via laser ablation is seen to reduce this effect by preserving fiber reinforcement and reducing stress concentrations. Under these conditions, the SBS reduction waslimited to 29%, indicating that removal of excess resin rich zones andreestablishment of higher fiber volume mitigates SBS loss with amorphous bonding. These values are consistent with aerospace-grade laminates and exceed reported values for amorphous bonding.

[0172] Scanning electron microscopy (SEM) examination of failed surfaces (FIG.14) further corroborates these findings. In hybrid laminates, large resin-rich pockets were imaged, and ductile polymer failure dominated crack propagation within a single interlaminar layer (aligned with the span direction of the SBS specimen). Polymer adherence to the few visible fiber surfaces was noted, suggesting strong fiber–matrix bonding despite the thick PEI layer. In OATMEAL specimens, the interlaminar surfaces displayed a mix of fiber and polymer, and the crack path traversed between off-axis plies rather than through a single thick interlaminar layer. Both ductile and brittle polymer failure modes were observed, andsingle fiber breakage was imaged where the crack jumped between plies. Thisbehavior closely resembles that of the CF / PEEK reference, wherein brittle failure andoff-axis ply to ply crack paths are typical. Thus, it is demonstrated that reducingexcess PEI thickness leads to interlaminar performance approaching that of theAttorney Docket No.10046-647WO1 UT Ref.8487 TEH unmodified PEEK system. For future optimization, it is imperative that interlaminarthicknesses be reduced even further below 10 μm and fiber volume fractionsmaximized, achieved by shortening the PEI–PEEK healing cycle just enough to form a continuous interface, followed by controlled laser ablation, to fully realize the benefits of sub-melt bonding without sacrificing interlaminar shear strength.

[0173] Future aerospace markets are projected to require production rates of approximately 80 aircraft per month, a rate that exceeds the throughput capabilities of the current thermoplastic composite consolidation method. The OATMEAL concept was therefore devised to circumvent the need for slow cooling through crystallization after melt consolidation, enabling lower temperature processing of high-performance thermoplastics. To evaluate a VBO oven process, which is extendable to large aerostructures due to not being constrained by platen size, unidirectional hybrid and OATMEAL laminates were consolidated at 300°C for30 minutes inside sealed vacuum bags (0.1 MPa absolute pressure). A thermocoupleplaced within the bag recorded temperature during the hold and subsequent air cooling stage. Cooling rates of approximately 45°C / min were measured initially (FIG. 15A), slowing thereafter, contrasting with the controlled 5°C / min rate used in prior autoclave cycles.

[0174] Despite full PEEK crystallinity being confirmed by DSC in both VBO specimens, SBS values (FIG.15B) were found to decrease markedly under fast- cooled VBO conditions. In the hybrid laminate, SBS fell from 88 ± 4 MPa (autoclave) to 41 MPa (VBO), a 53% reduction, attributed to elevated residual stresses in thick, resin-rich interlayers combined with rapid cooling. The fast cooling reduces the time for polymer relaxation, leading to higher residual stresses. By contrast, the OATMEAL laminate’s SBS remained higher — 96 ± 4 MPa (autoclave) to 82 ± 8 MPa (VBO). The slight reduction is attributed to the reduced processing pressure (0.1 MPa vs.0.8 MPa). It is predicted to be less impacted by the residual stress from fast cooling due to the reduction of resin-rich interfaces. And micron-sized ridges between laser ablation passes could promote rapid air removal during VBO (FIGS. 16A-16C). These factors led to a 98% improvement over the hybrid in SBS for fast cooling, achieving the fastest consolidation of fully crystallized aerospace-grade thermoplastic laminates outside of a press / autoclave.

[0175] These results show that VBO consolidation can slash cycle times by unconstrained cooling rates. Consider an oven held at a temperature with two pass-Attorney Docket No.10046-647WO1 UT Ref.8487 TEH through doors: parts can be loaded and unloaded continuously without thermal cycling of the oven before air cooling, all while maintaining their crystallinity history. This OATMEAL-enabled continuous VBO process leads to an unprecedented production rate for large-scale aerostructures. A thermal analysis model quantifiesthe throughput gains enabled by this continuous flow approach. The simple modelassumes only one part in the oven at a time, and a second part can be shuttled in immediately afterward (FIG.15C), leading to a predicted fivefold increase in throughput. Higher throughput is realized with multiple parts on a conveyor. This gain would grow further with the addition of rapid-entry IR heating. In such a scenario, cycle time could approach just the hold-time limit for healing of interfaces. OATMEAL may enable high-rate manufacturing of large-scale thermoplastic composite aerostructures by circumnavigating crystallinity at interfaces.

[0176] Furthermore, it is understood that laser ablation can selectively remove surface polymer. Engineered patterns could be used for air removal during any method steps disclosed herein, and more particularly, methods of forming the stack material. Patterns could be engineered for any desired process. In certain aspects, in a laser-assisted automated fiber placement, the surface patterns could be engineered to best absorb the laser’s energy.

[0177] Without wishing to be bound by any theory, the study of the integration of OATMEAL into in-situ consolidation platforms (e.g., automated fiber placement) can be evaluated.

[0178] The PEI–PEEK dwell times for precisely controlling interlayer thickness require further study and tuning. Similarly, the extension of the “Goldilocks zone” by exploring higher melting temperature polymers needs to be studied and evaluated.

[0179] Additionally, comprehensive fatigue and environmental durability tests are needed to verify long-term performance, with particular attention to any changes in the chemical resistance to PEEK introduced by PEI. Conclusions

[0180] Blending amorphous polymer with semi crystalline prepreg surfaceshas been shown to enable sub-melt consolidation of high-performance thermoplastic composites, preserving crystallinity at lower processing temperatures to reduce cycle times dramatically. In this work, a 25 μm PEI film was healed onto 125 μm CF / PEEK plies (hybrid), then selectively removed by laser ablation. Chemical mapping via FTAttorney Docket No.10046-647WO1 UT Ref.8487 TEH IR and AFM-IR demonstrated that ablation leaves behind PEI–PEEK interlayers approximately 5–10 μm thick, which retain the ability to interdiffuse and heal at 300°C. Removing the excess PEI is crucial in a continuous VBO process where the laminates are air-cooled.

[0181] SBS testing revealed that OATMEAL laminates preserve 77–87% of the interlaminar strength of autoclave consolidated panels in both quasi-isotropic and unidirectional layups, whereas hybrid (nonablated) specimens retained only 56–80%. This improvement is attributed to reduced residual stresses, arising from CTE mismatch, and to the elevated fiber-volume fraction within the interlayers. Fast VBO oven trials further confirmed that OATMEAL laminates maintain over 85% of autoclave SBS performance under rapid cooling (~45°C / min) and low bag pressure (0.1 MPa), in contrast to only 40% observed in hybrid panels due to thick resin-rich PEI interfaces. Collectively, these results demonstrate that OATMEAL meets the aerospace demands of rapid production and robust mechanical performance by operating within complementary “Goldilocks zones.” This zone defines an interlaminar thickness that is neither too thick to generate residual stresses nor too thin to undermine healing. Without wishing to be bound by any theory, it is understood that the PEI–PEEK blending at the interface is beneficial. The zone further defines a preferred range of the processing temperature, which enables sub- melt consolidation within an optimal window.

[0182] By holding interlaminar layers to 5–10 μm through targeted PEI–PEEK blending, preserving PEEK crystallinity, and exploiting amorphous bonding chemistry, structural integrity is achieved for aerospace-grade quality, and manufacturing throughput is increased. OATMEAL thus represents a pathway to next-generation thermoplastic composite manufacturing. Experimental Section / Methods

[0183] This study leverages the ability of PEI and PEEK to form a fully miscible blend, which facilitates the formation of a coherent interface between the CF / PEEK composite and the bulk PEI film. The PEEK prepreg (nominal thickness of 125 m), reinforced with AS4 fibers, was sourced from Toray as Cetex TC1200, while the PEI film (nominal thickness of 25 m) was provided by CS Hyde. An autoclave with a vacuum bag setup was used to bond PEI film to the PEEK prepreg; materials designed for processing at thermoplastic temperatures (>350°C) were sourced from Airtech. The bagging film, breather, and sealant tape were Thermflex,Attorney Docket No.10046-647WO1 UT Ref.8487 TEH Airweave UHT 800, and Fast Tack HT, respectively. The vacuum port / socket and hose were Vac Valve 429 and Airflow 800. A steel mold was prepared by applying three layers of Frekote to clean and seal surface cracks on the tool surface. The hybrid prepreg, including a single layer of CF / PEEK sandwiched between PEI film, was processed in an oven. The temperature was ramped up at 10°C / min until the tool thermocouple reached 380°C. The total absolute pressure was approximately 0.1 MPa. The temperature was maintained at 380°C for 30 minutes to ensure complete healing of the PEI and PEEK layers, and then it was cooled at 5°C / minute. This processing cycle follows the vendor’s recommended procedure for PEEK– PEEK consolidation, though it may have been excessive, using more pressure and time than likely required. The prepreg manufacturing was a conservative approach to ensure sufficient fusion bonding of the PEI–PEEK.

[0184] Reducing the PEI thickness enhances the volume fraction of the prepreg material, but it is necessary to retain enough PEI at the interlaminar surface to ensure proper consolidation. This study investigates laser ablation as a method for removing excess PEI. Laser ablation has demonstrated rapid, precise, and reproducible surface treatment capabilities for composites and is suitable for automation. NASA Langley has explored its use for removing surface contaminants, increasing surface roughness, and chemically activating composite laminate surfaces. During ablation, the surface absorbs laser radiation, vaporizes, and is ejected rapidly. It is predicted that very minimal thermal transfer occurs through the thickness due to the high laser frequency.

[0185] A Ekspla AtlanticTM20 Nd:YVO4 picosecond laser (355 nm) from PhotoMachining, Inc.TMis used to reduce the PEI and is shown in FIGS.16A-16D. The laser speed is controlled by a galvanometer, with the ablation process performed perpendicular to the fiber direction. The initial investigation into laser ablation for PEI removal utilized parameters based on NASA Langley’s previous research: laser speed of 76.2 cm / s (30 in / s), line pitch of 20.32 m (0.0008 in) for overlap between passes (laser spot size ~25 m), pulse frequency of 326 kHz, and 300 mW. These parameters were selected based on experience and initially tested on a sample shown in FIGS.16A-16D to ensure repeatability, but future work should optimize these parameters. Laser confocal measurements (FIG.16C) indicated anaverage material removal depth of 10.0 ± 0.2 m (measured across five samples)(FIG.16D) while a previous study using the same laser ablated 11.5 m onAttorney Docket No.10046-647WO1 UT Ref.8487 TEH CF / PEEK. At the edge where the laser first activates, a pronounced basin forms due to the longer dwell time. To avoid this in the prepreg ablation, the laser is activated just off the ply surface. Even though the line pitch is smaller than the laser spot size, there is slight ridging between passes. While future studies might explore whether eliminating these ridges improves surface uniformity, it is hypothesized that they may facilitate void evacuation during laminate consolidation.

[0186] Three quasi-isotropic, [0 / 45 / -45 / 90]2S, and unidirectional, [0]16, laminates were consolidated in the autoclave using the same vacuum bag layup as in the prepreg fabrication process, but with varying recipes:

[0187] Hybrid: Each lamina includes 125 m CF / PEEK sandwiched between 25 m PEI. The laminate was consolidated at 300°C for 30 minutes in the autoclave under 0.8 MPa. The cooling rate was 5°C / min. The total time was 130 minutes.

[0188] OATMEAL: Each lamina is made from laser-ablated hybrid prepreg, reducing the PEI thickness. The laminate was consolidated at 300°C for 30 minutes in the autoclave under 0.8 MPa. The cooling rate was 5°C / min. The total time was 130 minutes.

[0189] PEEK: The reference laminate is CF / PEEK, consolidated at 380°C for 30 minutes in the autoclave under 0.8 MPa. The cooling rate was 2.5°C / min. The total time was 229 minutes.

[0190] Lastly, to verify the hypothesis that OATMEAL can be fast cooled after consolidation below the melt temperature of PEEK, a rapid VBO experiment was done in an oven. The layup used the same bagging procedure as before, but a thermocouple was added on the part. The laminate was consolidated at 300°C for 20 minutes, and then the layup was immediately removed from the oven and cooled in open air.

[0191] Short beam strength (SBS) testing was carried out following the ASTM D2344 standard (sample size was 5.7 × 18.6 mm). This test was selected because thermoplastic composite laminates are known to be sensitive to SBS. On post- mortem SBS samples, FEI Quanta 650 scanning electron microscopy (SEM) was used to examine the failed interface. The SBS result is measured following the ASTM standard of 30% load drop-off, but the test was continued until catastrophic failure to expose an interlaminar surface for SEM imaging. To prevent charging during imaging, the surface was sputter-coated with gold for 60 seconds.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0192] Cross-sectional optical microscopy of the consolidated laminates was performed by first cutting the samples with a diamond saw, putting them in epoxy, and then grinding progressively from 80 to 2000 grit using a Struers polishing machine. The final polish was achieved with a 1 m suspension fluid. Volume fraction measurements were calculated using Ostu thresholding in ImageJ across samples.

[0193] Crystallinity measurements were conducted using a TA Discovery DSC25. Samples (~10-15 mg) were heated at a rate of 10°C / min to 400°C to observe cold crystallization and the melting enthalpy. Six samples were measured for each laminate after consolidation. Crystallinity was calculated with a fiber weight fraction of 66% and a fusion enthalpy of 130 J / g.

[0194] Here, Xc is the crystallinity of the material, Hf is the enthalpy of fusion, Hc is the enthalpy of cold crystallization, and Hf° is the fusion enthalpy for hypothetically completely crystalline PEEK.

[0195] WPEEK is the weight fraction of PEEK in the sample. The addition of PEI and fibers needs to be considered.where V°PEEK and V°fibers are the original volume fractions of PEEK (41%) and fibers (59%). The densities, r, are 1.30 g / cm3, 1.27 g / cm3and 1.79 g / cm3for PEEK, PEI, and CF, respectively. The laminate thickness is measured without, to, and with PEI, t. For this study, WPEEK for the hybrid, OATMEAL, and reference CF / PEEK laminates were calculated to be 0.27, 0.31, and 0.34, respectively.

[0196] Polished specimens were analyzed using a Bruker LUMOS II Fourier Transform Infrared Spectroscopy (FT-IR); This microscope handles spatial chemical species characterization using a retractable attenuated total reflectance (ATR) crystal probe along with a motorized stage. Spectra were first collected on neat PEI and PEEK and compared to find peaks unique to each polymer species. For theseAttorney Docket No.10046-647WO1 UT Ref.8487 TEH scans, 10 spectra were acquired, baseline corrected using the “rubber band” method, and then averaged together. Unique chemical peaks were identified as 1351.5 cm-1 and 924.6 cm-1, corresponding to PEI and PEEK, respectively. When scanning polished laminate cross-sections, 500 × 25 spectra were acquired across a 625 × 250 m mapping area using the motorized stage. Each measurement had a resolution of 15 × 15 m. Each spectrum was baseline corrected using the “rubber band” method.2D plots of the magnitude of the absorption across the mapping area were developed to distinguish where each polymer is present. To assist with comparison between specimens, the spectra are normalized by the magnitude of the absorption peaks measured for the bulk polymers.2D plots of the ratio (1351.5 over 924.6) of the unique chemical peaks are presented.

[0197] The PEI films were healed to the CF / PEEK prepreg with a vacuum bag in an oven (totaling ~0.1 MPa) and held at 380°C for 30 minutes. This recipe was chosen based on the CF / PEEK supplier’s recommendation for consolidating PEEK to PEEK. At 380°C, it is known that the PEEK polymer chains are fully amorphous and sufficiently mobile for interdiffusion to occur. Barroeta Robles et al. measured that only 82 to 414 seconds (about 7 minutes) is necessary for full healing of PEI– PEEK at 380°C, suggesting that 30 minutes is potentially five times longer than necessary. (See Barroeta Robles et al., “Healing study of poly (ether-imide) and poly ether ether ketone using resin films and a parallel plate rheometer,” Compos Part A Appl Sci Manuf, vol.174, Nov.2023, doi: 10.1016 / j.compositesa.2023.107736).

[0198] In addition to FT-IR, atomic force microscopy-based infrared spectroscopy (AFM-IR, using a Bruker NanoIR3) was used to investigate PEI–PEEK blending at a finer spatial resolution. The AFM-IR was operated in contact resonance under phase-locked-loop feedback (to remain on resonance) by altering the IR laser pulse frequency at primarily 72+-2 kHz, and at a force setpoint of a few tenths of a V (of raw cantilever deflection transducer signal relative to undeflected baseline) employing gold-coated Bruker probes of type PR-EX-NIR2. IR laser pulse radiation is locally absorbed based on surface chemistry, generating a photothermal expansion pulse that is detected by the AFM tip (at the above frequencies, which are well above the bandwidth of the Z feedback circuit that simultaneously tracks topography). The Bruker NanoIR3 employed a MIRCAT quantum cascade laser using three of its chips (spanning 914-1778 cm-1). While the NanoIR3 provided sub- 100 nm resolution, compared to the 15 × 15 m resolution of FT-IR, it was limited toAttorney Docket No.10046-647WO1 UT Ref.8487 TEH 50 × 50 m images, which were montaged (via a digital stage motor) up to a 250 × 100 m mapping area. The first sample tested was a neat PEI film (approximately 25 m thick) bonded to a neat PEEK film (also 25 m) using the same procedure described in the manufacturing section. The second sample was an OATMEAL laminate. Together with FT-IR, AFM-IR provides a comprehensive view of PEI– PEEK healing.

[0199] Non-Destructive C-Scans: A MISTRASTMUPK-T60-HS high-speed C-scan system, equipped with an OlympusTM10.0 MHz / 6 mm (0.25 in.) immersion transducer (I3-1004-S-SU), was utilized to conduct ultrasonic inspection in pulse- echo mode at a scan speed of 127 mm / s with a 0.5 mm × 0.5 mm per pixel resolution, and a constant 18.7 dB receiver gain. C-scan images were generated for each panel by evaluating the maximum ultrasonic amplitude from the back wall (bottom of the laminate). Qualitative observation of processing methods provides insight into consolidation behavior, as through-thickness variations in material properties alter the scans.

[0200] Non-Destructive Ultrasonic C-Scans & Optical Microscopy: Additionally, the incorporation of PEI into the interlaminar regions was found to affect through-thickness material uniformity. After consolidation, nondestructive ultrasonic C-scan measurements were performed (FIG.17). The maximum back-wall amplitude increased from 80% in the hybrid laminates to 100% in the OATMEAL laminates, reflecting thinning of the resin-rich interlayers as excess PEI was removed. Where back wall amplitude deficits were observed, they were attributed to residual resin-rich zones rather than interlaminar voids, since representative optical micrographs (FIGS. 12A-12F) confirmed full consolidation of the interlaminar regions. Corresponding B scans reveal localized ultrasonic attenuation at each interlayer, consistent with acoustic impedance mismatches introduced by thick polymer layers. These results underscore further the necessity of minimizing excess PEI: industry certification of composite integrity relies heavily on non-destructive evaluation, and thick resin-rich interfaces present a challenge.

[0201] FIGs.18A-18D shows a demonstration of the welding of the materials prepared according to the aspects disclosed herein. Without wishing to be bound by any theory, it was hypothesized that the surface amorphous polymer enables sub- melt healing with subsequent layers; the material does not warp during welding. ITAttorney Docket No.10046-647WO1 UT Ref.8487 TEH can be especially beneficial in welding skins and stringers for airplanes, as they typically require complex tooling to prevent the stringers from deforming during welding, but the disclosed herein material might enable tool-less welding.

[0202] So, these deployable structures are made with specific geometries that you do not want to disturb during welding. This is a game changer for composite manufacturing and deployable booms were a nice demonstration part.

[0203] Mathematical Model of Thermal Cycling:

[0204] Lumped Capacitance Assumption: Each part is treated as a thermally“lumped” body (i.e., its internal temperature is spatially uniform at any given time). This is valid whenever the Biot number where h is the convective heattransfer coefficient, L is the half thickness, and k is the thermal conductivity. Thissimplification is reasonable for the goal of the analysis: to compare cycle rates between an autoclave with controlled ramping versus an oven where the part can be removed directly from the processing temperature.

[0205] Governing Energy Balance: Under the lumped capacitanceassumption:

[0206] Introducing a thermal time constantthe ODE simplifies to:

[0207] Analytical Solution: For constant T :Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0208] Discrete-Time Integration Scheme: Using explicit Euler with time step t:

[0209] Thermal-Cycle Definitions:

[0210] 1) Oven Cycle: Part enters at T(0) = 35°C and heats in oven (T =380°C) until reaches 295°C for 20 min hold. Part is shuttled out of the oven and iscooled to room temperature (T = 35°C). A second part can enter the oven as soonas the previous part begins to cool outside.

[0211] 2) Autoclave Cycle: Ramp T from 35°C20

[0212] Parameter Choices: The numerical values for density ( ), specific heat(c ), heat transfer coefficient (h), and geometric thickness (L) were chosen to berepresentative of typical thermoplastic composite parts. However, the absolute values are not critical for the comparative analysis. The goal is to contrast the ovenand autoclave heating / cooling profiles under identical lumped capacitanceconditions. Thus, any reasonable set of parameters yielding similar time constants would produce a similar qualitative comparison of the two methods.

[0213] = 1600 kg / m3

[0214] c = 1000 J / (kg·K)

[0215] h = 20 W / (m2·K)

[0216] L = 0.01 m.EXAMPLE 3

[0217] A laser-automated fiber placement was investigated. The hybrid material measured a very high short beam strength (SBS) compared to existing materials. It was found that the OATMEAL material absorbed the laser energy more easily and degraded more quickly. It was determined that further research is needed to identify preferable laser powers that would lead to full healing. Without wishing to be bound by any theory, it was hypothesized that OATMEAL can have SBS in the range of 100 MPa. OATMEAL’s crystallinity is determined when the prepreg is manufactured and preserved in subsequent lamination. Ablation is used to removeAttorney Docket No.10046-647WO1 UT Ref.8487 TEH excess surface polymer and reduce roughness for quicker intimate contact. Preliminary ICAT results shown in FIGs.19A-19C demonstrate high potential (>85 MPa at 50 mm / s) with a 25-micron sheath. Without wishing to be bound by any theory, consideration needs to be given to how the fiber absorbs energy and then conducts heat locally. The patterns shown in FIGs.19A-19C are likely contributing to the energy absorption.

[0218] A roll-to-roll manufacturing trial to laminate a 5-micron PEI film onto the surface of AS4 / PEEK was investigated. An existing prepregger line was modified so that AS4 / PEEK prepreg was sandwiched between 5-micron film, passed through three IR ovens set to 400 °C, and then through a 400 °C heated die before the compaction nip rollers. This process did not control the cooling rate, so DSC measurements found that the PEEK only partially crystallized after the PEI interdiffused in. Additionally, cross-sectional microscopy of the tape found intralayer voids + rough surfaces. The results can be seen in FIGs.20A-20B and 21.

[0219] SEM images of a compression-molded tape at 300 °C from trial lamination on a prepreg line are shown in FIGs.22 and 23. These tapes are manufactured below the melt temperature of the PEEK polymer. The voids were regions with poor bonding. These results motivate a more robust method for roll-to- roll manufacturing.

[0220] Continuous compression molding as a method to heal the amorphous polymer to the surface of the semi-crystalline is also considered. Typical heating / pressure curves that could represent this process, resulting in well interdiffused PEI into PEEK and then controlled cooling to crystallize the PEEK, are shown in FIGs.24 and 25. It is hypothesized that a sufficient time (~10-30 seconds) above melt for the PEI and PEEK is needed to interdiffused. The cooling can be controlled using the different sections of the CCM (continuous casting) machine.

[0221] Disclosed herein are materials, compounds, compositions, and components that can be used in conjunction with, can be used in preparation for, or are products of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed, specific reference to each individual and collective combination and permutation of these compounds may notAttorney Docket No.10046-647WO1 UT Ref.8487 TEH be explicitly disclosed; each is specifically contemplated and described herein. For example, if a composition is disclosed and a number of modifications that can be made to a number of components of the composition are discussed, each and every combination and permutation that is possible is contemplated explicitly unless specifically indicated to the contrary. Thus, if a class of components A, B, and C is disclosed and a class of components D, E, and F, and an example of a combination composition A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F is specifically contemplated and should be considered disclosed from the disclosure of A, B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E is specifically contemplated and should be considered disclosed from the disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this disclosure, including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the disclosed methods and that each such combination is specifically contemplated and should be considered disclosed. EXEMPLARY ASPECTS

[0222] Example 1. A composite material comprising: one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer; a second sublayer having a second thickness and comprising a first amorphous polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a second amorphous polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0223] Example 2. The composite material of any one of the examples herein, particularly Example 1, wherein the second thickness and / or third thickness are less than 5 microns.

[0224] Example 3. The composite material of any one of the examples herein, particularly Example 1 or 2, wherein the second thickness and / or third thickness are less than 1 micron.

[0225] Example 4. The composite material of any one of the examples herein, particularly any one of Examples 1-3, wherein when two or more layers are present, the two or more layers are positioned such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of an adjacent layer.

[0226] Example 5. The composite material of any one of the examples herein, particularly any one of Examples 1-4, wherein the interdiffused portions are substantially free of an interface boundary.

[0227] Example 6. The composite material of any one of the examples herein, particularly any one of Examples 4-5, wherein the second sublayer of one layer and the third sublayer of an adjacent layer are interdiffused to form one sublayer having a fourth thickness.

[0228] Example 7. The composite material of any one of the examples herein, particularly Example 6, wherein the fourth thickness is less than 20 microns.

[0229] Example 8. The composite material of any one of the examples herein, particularly Example 6 or 7, wherein the fourth thickness is less than 15 microns.

[0230] Example 9. The composite material of any one of any one of the examples herein, particularly Examples 6-8, wherein the fourth thickness is less than 10 microns.

[0231] Example 10. The composite material of any one of any one of the examples herein, particularly Examples 1-9, wherein the first and / or second amorphous polymers are the same or different.

[0232] Example 11. The composite material of any one of any one of the examples herein, particularly Examples 1-10, wherein the first and / or second amorphous polymers exhibit a glass transition temperature Tgsmaller than a melting temperature Tm of the semicrystalline polymer.

[0233] Example 12. The composite material of any one of the examples herein, particularly Example 11, wherein Tg is in a range of 0-300oC.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0234] Example 13. The composite material of any one of the examples herein, particularly Example 11 or 12, wherein Tm is in a range of 100-430oC.

[0235] Example 14. The composite material of any one of the examples herein, particularly any one of Examples 1-13, wherein the first and / or second amorphous polymers comprise polyethylenimide (PEI), polyamide-imide (PAI) polyphenylsulfone (PPSU), polysulfone (PSU), polyether sulfone (PESU), acrylonitrile butadiene styrene (ABS), amorphous polyetheretherketone (PEEK), polymethyl methacrylate (Acrylic), polyimide (PI), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), or any combinations thereof.

[0236] Example 15. The composite material of any one of the examples herein, particularly any one of Examples 1-14, wherein the semicrystalline polymers comprise polyetheretherketone (PEEK), polyaryletherketones (PAEKs), polyetherketoneketone (PEKK), polypheylenesulfide (PPS), nylon -11, nylon-6, perfluoroalkoxy (PFA), polyeterfluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), polylactic acid (PLA), liquid crystal polymers (LCP), polyethylene (PE) or any combinations thereof.

[0237] Example 16. The composite of any one of the examples herein, particularly any one of Examples 1-15, wherein the first thickness is 20 microns to 400 microns.

[0238] Example 17. The composite material of any one of the examples herein, particularly any one of Examples 1-16, wherein the semicrystalline polymer of the first sublayer is impregnated with a plurality of reinforcing materials.

[0239] Example 18. The composite material of any one of the examples herein, particularly Example 17, wherein the reinforcing materials have a volume fraction of 40-70 vol%.

[0240] Example 19. The composite of any one of the examples herein, particularly Example 17 or 18, wherein the plurality of reinforcing materials comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof.

[0241] Example 20. The composite of any one of the examples herein, particularly any one of Examples 17-19, wherein the reinforcing materials comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0242] Example 21. The composite material of any one of the examples herein, particularly any one of Examples 1-20, wherein the semicrystalline polymer present in the first sublayer when the composite is formed does not undergo recrystallization.

[0243] Example 22. The composite material of any one of the examples herein, particularly any one of Examples 1-21, wherein the composite comprising 1- 500 layers exhibits a short beam strength of 50-110 MPa.

[0244] Example 23. The composite material of any one of the examples herein, particularly any one of Examples 1-22, wherein the composite exhibits less than 25% theoretical reduction in strength, wherein the theoretical reduction in strength is calculated due to the addition of the first and the second amorphous polymers.

[0245] Example 24. A composite material comprising: one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a first semicrystalline polymer; a second sublayer having a second thickness and comprising a second semicrystalline polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a third semicrystalline polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

[0246] Example 25. The composite material of any one of the examples herein, particularly Example 24, wherein the first semicrystalline polymer is impregnated with a plurality of reinforcing materials.

[0247] Example 26. The composite material of any one of the examples herein, particularly Example 24 or 25, wherein the second semicrystalline polymer and the third semicrystalline polymer are the same or different and are free of reinforcing materials.

[0248] Example 27. The composite material of any one of the examples herein, particularly any one of Examples 25-26, wherein the reinforcing materials have a volume fraction of 40-70 vol%.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0249] Example 28. The composite of any one of the examples herein, particularly any one of Examples 25-27, wherein the plurality of reinforcing materials comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof.

[0250] Example 29. The composite of any one of the examples herein, particularly any one of Examples 25-28, wherein the reinforcing materials comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof.

[0251] Example 30. The composite material of any one of the examples herein, particularly any one of Examples 1-29, the second and / or the third sublayers are at least partially ablated.

[0252] Example 31. An article comprising the composite material of any one of the examples herein, particularly any one of Examples 1-30.

[0253] Example 32. The article of any one of the examples herein, particularly Example 31, wherein the article comprises an aircraft component, a spacecraft component, a component of a military article, an automotive component, a recreation component, a turbine component, a construction & infrastructure, a satellite component, marine component, medical components, chemical storage / transport, or any combination thereof.

[0254] Example 33. A method of forming a composite comprising: (a) forming one or more layers, wherein each layer comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer having a Tm; a second sublayer having an initial second thickness and comprising a first amorphous polymer having a Tg, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a second amorphous polymer having a Tg, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that an overlaying portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and c) reducing the initial second thickness of the second sublayer and the initial thickness of the third sublayer to form a second thickness and a third thickness, respectively, to be less than 10 microns.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0255] Example 34. The method of any one of the examples herein, particularly Example 33, further comprising: (d) positioning a first layer of the one or more layers on a second layer of the one or more layers to form two or more layers; optionally positioning further one or more layers between the first and the second layer of two or more layers, or optionally positioning the further one or more layers on a final layer of the two or more layers, wherein the further one or more layers are different from the first layer, the second layer, and / or the final layer; (e) heating the two or more layers to a temperature that is greater than Tg of the first and / or second amorphous polymer, such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of the second layer; and (f) cooling the two or more layers to form a composite, wherein the cooling is rate-agnostic.

[0256] Example 35. The method of any one of the examples herein, particularly Example 34, wherein a shape of each of the two or more layers is not changed after step e).

[0257] Example 36. The method of any one of the examples herein, particularly Example 34 or 35, wherein the temperature is less than Tmof the semicrystalline polymer.

[0258] Example 37. The method of any one of the examples herein, particularly any one of Examples 33-36, wherein the heating is conducted under pressure.

[0259] Example 38. The method of any one of the examples herein, particularly Example 37, wherein the pressure is 0.1-0.8 MPa of absolute pressure.

[0260] Example 39. The method of any one of Examples 33-38, wherein the interdiffused portions are substantially free of an interface boundary.

[0261] Example 40. The method of any one of the examples herein, particularly any one of Examples 34-39, wherein the second sublayer of one layer and the third sublayer of an adjacent layer are interdiffused to form one sublayer having a fourth thickness.

[0262] Example 41. The method of any one of the examples herein, particularly Example 40, wherein the fourth thickness is less than 20 microns.

[0263] Example 42. The method of any one of the examples herein, particularly Example 40 or 41, wherein the fourth thickness is less than 15 microns.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0264] Example 43. The method of any one of the examples herein, particularly any one of Examples 40-42, wherein the fourth thickness is less than 10 microns.

[0265] Example 44. The method of any one of the examples herein, particularly any one of Examples 33-43, wherein the second and / or the third layers are formed by a polymer growth, spray coating, disposing a powder, disposing polymer fibers, laying one or more polymer films, dispersing polymer flakes, solvent coating, dip coating, grafting, polymerizing, hot pressing, thermal lamination, or by any combination thereof before interdiffusing respective surfaces with the first sublayer.

[0266] Example 45. The method of any one of the examples herein, particularly any one of Examples 33-44, wherein the first and / or second amorphous polymers are the same or different.

[0267] Example 46. The method of any one of the examples herein, particularly any one of Examples 33-45, wherein Tgis in a range of 0-300°C.

[0268] Example 47. The method of any one of the examples herein, particularly any one of Examples 33-46, wherein Tmis in a range of 100-430°C.

[0269] Example 48. The method of any one of the examples herein, particularly any one of Examples 33-47, wherein the first and / or second amorphous polymers comprise polyethylenimide (PEI), polyamide-imide (PAI) polyphenylsulfone (PPSU), polysulfone (PSU), polyether sulfone (PESU), acrylonitrile butadiene styrene (ABS), amorphous polyetheretherketone (PEEK), polymethyl methacrylate (Acrylic), polyimide (PI), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), or any combinations thereof.

[0270] Example 49. The method of any one of the examples herein, particularly any one of Examples 33-48, wherein the semicrystalline polymers comprise polyetheretherketone (PEEK), polyaryletherketones (PAEKs), polyetherketoneketone (PEKK), polypheylenesulfide (PPS), nylon -11, nylon-6, perfluoroalkoxy (PFA), polyeterfluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), polylactic acid (PLA), liquid crystal polymers (LCP), polyethylene (PE) or any combinations thereof.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0271] Example 50. The method of any one of the examples herein, particularly any one of Examples 33-49, wherein the first sublayer has a thickness of 20 microns to 400 microns.

[0272] Example 51. The method of any one of the examples herein, particularly any one of Examples 33-50, wherein the semicrystalline polymer of the first sublayer is impregnated with a plurality of reinforcing materials.

[0273] Example 52. The method of any one of the examples herein, particularly Example 51, wherein the reinforcing materials have a volume fraction of 40-70 vol%.

[0274] Example 53. The method of any one of the examples herein, particularly Example 51 or 52, wherein the plurality of reinforcing materials comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof.

[0275] Example 54. The method of any one of the examples herein, particularly any one of Examples 51-53, wherein the reinforcing materials comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof.

[0276] Example 55. The method of any one of the examples herein, particularly any one of Examples 33-54, wherein the semicrystalline polymer present in the first sublayer when the one or more layers are formed does not melt or undergo recrystallization.

[0277] Example 56. The method of any one of the examples herein, particularly any one of Examples 33-55, wherein the step of reducing the thickness comprises a laser ablation, radiofrequency ablation, chemical etching, laser-induced- plasma-assisted ablation (LIPAA), plasma etching, mechanical ablation, ultrasonic ablation, photoablation, electrical ablation, cryoablation, microwave ablation, ion beam etching, reactive ion etching or any combinations thereof.

[0278] Example 57. The method of any one of the examples herein, particularly of any one of Examples 33-56, wherein the step of heating is performed for 1 microsecond to 20 hours.

[0279] Example 58. The method of any one of the examples herein, particularly any one of Examples 33-57, wherein the cooling is performed at any rate within 1°C / min to 1,000°C / min.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH

[0280] Example 59. The method of any one of the examples herein, particularly any one of Examples 33-58, wherein the cooling is performed at any rate within 10°C / min to 1,000°C / min.

[0281] Example 60. The method of any one of the examples herein, particularly any one of Examples 33-59, wherein the cooling is performed at any rate within 100°C / min to 1,000°C / min.

[0282] Example 61. The method of any one of the examples herein, particularly any one of Examples 33-60, wherein an amount of the first amorphous polymer and the second amorphous polymer removed during the reducing the thickness step is collected and recycled.

[0283] Example 62. The method of any one of the examples herein, particularly any one of Examples 33-61, wherein the thickness in the reducing step is controlled with a profilometer.

[0284] Example 63. The method of any one of the examples herein, particularly any one of Examples 33-62, wherein the method comprises monitoring and analyzing a chemical composition of a material removed during the reducing the thickness step.

[0285] Example 64. The method of any one of the examples herein, particularly any one of Examples 33-63, wherein the composite comprising 1 to 500 layers exhibits a short beam strength of 50-110 MPa.

[0286] Example 65. The method of any one of the examples herein, particularly any one of Examples 33-64, wherein the composite exhibits less than 25% theoretical reduction in strength, wherein the theoretical reduction in strength is calculated due to the addition of the first and / or second amorphous polymer.

[0287] Example 66. The method of any one of the examples herein, particularly any one of Examples 33-65, further comprises a step of forming an article comprising the composite.

[0288] Example 67. A method of forming a composite comprising: (a) forming one or more layers, wherein each layer comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer having a first Tm; a second sublayer having an initial second thickness and comprising a second semicrystalline polymer having a second Tm, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a third semicrystalline polymer having a third Tm, wherein the first sublayer overlays theAttorney Docket No.10046-647WO1 UT Ref.8487 TEH third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that such that an overlaying portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and (c) reducing the thickness of the second sublayer and the third sublayer to form a second thickness and a third thickness to be less than 10 microns.

[0289] Example 68. The method of any one of the examples herein, particularly Example 67, further comprising: (d) positioning one layer on a second layer to form two or more layers; (e) heating the two or more layers such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of the second layer; and (f) cooling the two or more layers to form a composite, wherein the cooling is rate- agnostic.

[0290] Example 69. The method of any one of the examples herein, particularly any one of Examples 67-68, wherein the heating is to a temperature that is higher than the first Tm, the second Tm, and the third Tm.

Claims

Attorney Docket No.10046-647WO1 UT Ref.8487 TEH CLAIMS What is claimed is:

1. A composite material comprising: one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer; a second sublayer having a second thickness and comprising a first amorphous polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a second amorphous polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

2. The composite material of claim 1, wherein the second thickness and / or third thickness are less than 5 microns or less than 1 micron.

3. The composite material of any one of claims 1-2, wherein when two or more layers are present, the two or more layers are positioned such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of an adjacent layer, and or wherein the second sublayer of one layer and the third sublayer of an adjacent layer are interdiffused to form one sublayer having a fourth thickness, and wherein the fourth thickness is less than 20 microns.

4. The composite material of any one of claims 1-3, wherein the interdiffused portions are substantially free of an interface boundary.

5. The composite material of any one of claims 1-4, wherein the first and / or second amorphous polymers exhibit a glass transition temperature TgsmallerAttorney Docket No.10046-647WO1 UT Ref.8487 TEH than a melting temperature Tm of the semicrystalline polymer, wherein Tg is in a range of 0-300oC, and wherein Tm is in a range of 100-430oC.

6. The composite material of any one of claims 1-5, wherein the first and / or second amorphous polymers comprise polyethylenimide (PEI), polyamide- imide (PAI) polyphenylsulfone (PPSU), polysulfone (PSU), polyether sulfone (PESU), acrylonitrile butadiene styrene (ABS), amorphous polyetheretherketone (PEEK), polymethyl methacrylate (Acrylic), polyimide (PI), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), or any combinations thereof.

7. The composite material of any one of claims 1-6, wherein the semicrystalline polymers comprise polyetheretherketone (PEEK), polyaryletherketones (PAEKs), polyetherketoneketone (PEKK), polypheylenesulfide (PPS), nylon- 11, nylon-6, perfluoroalkoxy (PFA), polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), polylactic acid (PLA), liquid crystal polymers (LCP), polyethylene (PE), or any combinations thereof.

8. The composite of any one of claims 1-7, wherein the first thickness is 20 microns to 400 microns.

9. The composite material of any one of claims 1-8, wherein the semicrystalline polymer of the first sublayer is impregnated with a plurality of reinforcing materials, wherein the reinforcing materials have a volume fraction of 40-70 vol%.

10. The composite of claim 9, wherein the plurality of reinforcing materials comprise carbon fibers, glass fibers, aramid fibers, basalt fibers, natural fibers, boron fibers, ceramic fibers, quartz fibers, acrylic fibers, or any combination thereof; and / or wherein the reinforcing materials comprise unidirectional fibers, woven fibrous material, nonwoven fibrous material, or any combination thereof.

11. The composite material of any one of claims 1-10, wherein the semicrystalline polymer present in the first sublayer when the composite is formed does not undergo recrystallization.

12. A composite material comprising:Attorney Docket No.10046-647WO1 UT Ref.8487 TEH one or more layers, wherein each layer of the one or more layers comprises: a first sublayer having a first thickness and comprising a first semicrystalline polymer; a second sublayer having a second thickness and comprising a second semicrystalline polymer, wherein the second sublayer overlays the first sublayer such that an overlaying portion of the second thickness is interdiffused with an underlying portion of the first thickness; and a third sublayer having a third thickness and comprising a third semicrystalline polymer, wherein the first sublayer overlays the third sublayer such that an overlaying portion of the first thickness is interdiffused with an underlying portion of the third thickness; wherein the second thickness and third thickness are less than 10 microns; and wherein the composite is a thermoplastic composite.

13. The composite material of claim 12, wherein the first semicrystalline polymer is impregnated with a plurality of reinforcing materials, wherein the reinforcing materials have a volume fraction of 40-70 vol%.

14. The composite material of any one of claims 1-13, the second and / or the third sublayers are at least partially ablated.

15. An article comprising the composite material of any one of claims 1-14, wherein the article comprises an aircraft component, a spacecraft component, a component of a military article, an automotive component, a recreation component, a turbine component, a construction & infrastructure component, a satellite component, a marine component, a medical component, a chemical storage / transport component, or any combination thereof.

16. A method of forming a composite comprising: a) forming one or more layers, wherein each layer comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer having a Tm;Attorney Docket No.10046-647WO1 UT Ref.8487 TEH a second sublayer having an initial second thickness and comprising a first amorphous polymer having a Tg, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a second amorphous polymer having a Tg, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that an overlaying portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; and c) reducing the initial second thickness of the second sublayer and the initial thickness of the third sublayer to form a second thickness and a third thickness, respectively, to be less than 10 microns.

17. The method of claim 16, further comprising: d) positioning a first layer of the one or more layers on a second layer of the one or more layers to form two or more layers; optionally positioning further one or more layers between the first and the second layer of two or more layers, or optionally positioning the further one or more layers on a final layer of the two or more layers, wherein the further one or more layers are different from the first layer, the second layer, and / or the final layer; e) heating the two or more layers to a temperature that is greater than Tgof the first and / or second amorphous polymer, such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of the second layer; and f) cooling the two or more layers to form a composite, wherein the cooling is rate-agnostic.

18. The method of claim 16 or 17, wherein the temperature is less than Tm of the semicrystalline polymer.Attorney Docket No.10046-647WO1 UT Ref.8487 TEH 19. The method of any one of claims 16-18, wherein the second and / or the third layers are formed by a polymer growth, spray coating, disposing a powder, disposing polymer fibers, laying one or more polymer films, dispersing polymer flakes, solvent coating, dip coating, grafting, polymerizing, hot pressing, thermal lamination, or by any combination thereof before interdiffusing respective surfaces with the first sublayer.

20. The method of any one of claims 16-19, wherein the step of reducing the thickness comprises a laser ablation, radiofrequency ablation, chemical etching, laser-induced-plasma-assisted ablation (LIPAA), plasma etching, mechanical ablation, ultrasonic ablation, photoablation, electrical ablation, cryoablation, microwave ablation, ion beam etching, reactive ion etching, or any combination thereof.

21. The method of any one of claims 16-20, wherein the step of heating is performed for 1 microsecond to 20 hours, and / or wherein the cooling is performed at any rate within 1°C / min to 1,000°C / min.

22. A method of forming a composite comprising: a) forming one or more layers, wherein each layer comprises: a first sublayer having a first thickness and comprising a semicrystalline polymer having a first Tm; a second sublayer having an initial second thickness and comprising a second semicrystalline polymer having a second Tm, wherein the second sublayer overlays the first sublayer; and a third sublayer having an initial third thickness and comprising a third semicrystalline polymer having a third Tm, wherein the first sublayer overlays the third sublayer; wherein the initial second thickness and the initial third thickness are greater than 10 microns to 100 microns; b) heating the layer such that an overlaying portion of the initial second thickness is interdiffused with an underlying portion of the first thickness and an overlaying portion of the first thickness is interdiffused with an underlying portion of the initial third thickness; andAttorney Docket No.10046-647WO1 UT Ref.8487 TEH c) reducing the thickness of the second sublayer and the third sublayer to form a second thickness and a third thickness to be less than 10 microns.

23. The method of claim 22, further comprising: d) positioning one layer on a second layer to form two or more layers; e) heating the two or more layers such that a portion of the second thickness of the second sublayer of one layer is interdiffused with a portion of the third thickness of the third sublayer of the second layer; and f) cooling the two or more layers to form a composite, wherein the cooling is rate-agnostic.

24. The method of any one of claims 22-23, wherein the heating is to a temperature that is higher than the first Tm, the second Tm, and the third Tm.

Images