Continuous fiber reinforced ribbon

Abstract

The continuous fiber reinforced ribbon includes from 20% to 50% by weight of a polyketone component and from 50% to 80% by weight of a plurality of unidirectional continuous fibers embedded in the polyketone component, based on the total weight of the continuous fiber reinforced ribbon.

Description

CLAIM OF PRIORITY

[0001] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 469,046, filed May 25, 2023, attorney docket number 1202310, which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate to continuous fiber reinforced tapes, and in particular to continuous fiber reinforced tapes comprising a polyketone component and unidirectional continuous fibers embedded within the polyketone component. BACKGROUND

[0003] Continuous fiber reinforced tapes can have desirable properties, such as flexibility, for use in fiber reinforced pipes. However, conventional continuous fiber reinforced tapes formed from semi-crystalline thermoplastic materials or amorphous thermoplastic materials can not have sufficient shear strength at elevated temperatures (i.e., greater than or equal to 100 °C) nor the chemical resistance (e.g., oil resistance) required for certain applications, such as those in the oil and gas industry.

[0004] Accordingly, there is a continuing need for continuous fiber reinforced tapes having excellent shear strength and chemical resistance at elevated temperatures (i.e., greater than or equal to 100 °C). SUMMARY

[0005] Embodiments of the present disclosure relate to continuous fiber reinforced tapes.

[0006] According to some embodiments, a continuous fiber reinforced tape is provided. The continuous fiber reinforced tape comprises, based on the total weight of the continuous fiber reinforced tape, from 20 wt% to 50 wt% of a polyketone component and from 50 wt% to 80 wt% of a plurality of unidirectional continuous fibers embedded in the polyketone component.

[0007] Additional features and advantages of the embodiments described herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art who practice the embodiments, including the best mode contemplated herein, as described more fully below. It is intended that what is described herein be considered patentable subject matter including all components and methods alone and in combination. BRIEF DESCRIPTION OF DRAWINGS

[0008] Figure 1 is a schematic view of a continuous fiber reinforced tape according to one or more embodiments described herein;

[0009] Figure 2 is a schematic view of a continuous fiber reinforced tape laminate according to one or more embodiments described herein;

[0010] Figure 3is a cross-sectional view of a continuous fiber-reinforced pipe according to one or more embodiments described herein;

[0011] Figure 4 is a cross-sectional view of another continuous fiber-reinforced pipe according to one or more embodiments described herein;

[0012] Figure 5 is a plot of temperature (x-axis; in °C) versus shear strength (y-axis; in MPa) for a control CFR tape and an exemplary CFR tape according to one or more embodiments described herein;

[0013] Figure 6 is a plot of temperature (x-axis; in °C) versus shear strength retention (y-axis; in percent (%)) for a control CFR tape and an exemplary CFR tape according to one or more embodiments described herein;

[0014] Figure 7 is a plot of immersion time (x-axis; in hours) versus dry weight change (y-axis; in percent (%)) and flexural strength (y-axis; in MPa) for a control CFR tape and an exemplary CFR tape according to one or more embodiments described herein;

[0015] Figure 8 is a scanning electron microscope (SEM) image of glass fibers including a polyamide sizing composition according to one or more embodiments described herein, magnified 1500x;

[0016] Figure 9 is a SEM image of glass fibers including a polypropylene sizing composition according to one or more embodiments described herein, magnified 500x; Figure 8

[0017] Figure 10 is a SEM image of glass fibers including a polyethylene terephthalate / polybutylene terephthalate sizing composition according to one or more embodiments described herein, magnified 1500x;

[0018] Figure 11 is a SEM image of glass fibers including a polypropylene sizing composition according to one or more embodiments described herein, magnified 500x; Figure 10

[0019] Figure 12 is a SEM image of glass fibers including a polypropylene sizing composition according to one or more embodiments described herein, magnified 1500x; and

[0020] Figure 13 is a SEM image of glass fibers including a polypropylene sizing composition according to one or more embodiments described herein, magnified 500x. Figure 12 DETAILED DESCRIPTION

[0021] ​​​Reference will now be made in detail to various embodiments of continuous fiber reinforced (“CFR”) tapes.

[0022] This disclosure should not be construed as limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the subject matter to those skilled in the art.

[0023] Definitions

[0024] Unless otherwise defined, 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 disclosure belongs. The terminology used in the disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0025] Unless specifically stated otherwise, no embodiment disclosed herein is intended to be interpreted, in accordance with the doctrine of equivalents, as incorporating the equivalent step(s) of any method or process previously known in the art unless explicitly indicated otherwise.

[0026] Unless specifically stated otherwise, any composition or mixture disclosed herein can comprise, consist essentially of, or consist of, the disclosed components.

[0027] As used herein, the singular form of a term includes the plural unless the context clearly dictates otherwise.

[0028] As used herein, numerical values do not strictly limit the exact value to the recited exact number. Rather, each numerical value should be construed in light of the stated description and explicitly contemplated so that any differing value falling within the range defined by the stated value will be considered to be within the scope of the embodiments disclosed herein.

[0029] As used herein, the term “flexural strength” refers to the maximum flexural stress sustained during testing, measured according to ASTM D790.

[0030] As used herein, the term “flexural modulus” refers to the ratio of stress to strain at flexural deformation, measured according to ASTM D790.

[0031] As used herein, the term “tensile strength” refers to the longitudinal tensile stress at break or the maximum stress that a material can withstand when stretched longitudinally before breaking, measured according to ASTM D3039.

[0032] As used herein, the term “tensile modulus” refers to the tensile chord modulus, measured according to ASTM D3039.

[0033] As used herein, the term "tensile elongation" refers to the ratio of the increase in length after breakage to the initial length, measured according to ASTM D3039.

[0034] As used herein, the term "in-plane shear strength" refers to the in-plane shear response of the CFR tape, measured according to ASTM D3518.

[0035] As used herein, the term "interlaminar shear strength" refers to the interlaminar shear strength of the parallel fibers within the CFR tape, measured according to ASTM D2344.

[0036] As used herein, the term "retained shear strength" refers to the retention of the in-plane shear strength of the CFR tape at 100°C compared to the in-plane shear strength of the same CFR tape at 21°C, greater than 65%.

[0037] As used herein, the term "melt flow index" refers to the ease of flow of a polymer melt, measured according to ASTM D1238.

[0038] As used herein, the term "continuous fiber" refers to a fiber spanning all or substantially all of the dimensions of the CFR tape. As used herein, the term "substantially all of the dimensions" refers to greater than 75% of the dimensions of the CFR tape.

[0039] As used herein, the term "average diameter" refers to the average of the diameters of the individual fibers in a plurality of continuous fibers.

[0040] As noted above, CFR tapes can have desirable properties, such as flexibility, for use in, for example, fiber-reinforced tubing. However, conventional continuous fiber-reinforced tapes formed from semi-crystalline thermoplastic materials (such as PA6, PA66, PA1 1, PA12, polyethylene, terephthalate, and polyvinylidene fluoride) or amorphous thermoplastic materials (such as polycarbonate) can not have sufficient shear strength at elevated temperatures (i.e., greater than or equal to 100°C) nor the chemical resistance (such as oil resistance) required for certain applications, such as those in the oil and gas industry.

[0041] Disclosed herein are CFR tapes. In particular, the CFR tapes disclosed herein include a polyketone component and a plurality of unidirectional continuous fibers embedded within the polyketone component. During formation of the CFR tape, the polyketone component can interact with and bind to the unidirectional continuous fibers, causing the fibers to bond together, which can result in the retention of shear strength at elevated temperatures (i.e., greater than or equal to 100°C). Additionally, the polyketone component can impart chemical resistance to the CFR tape.

[0042] Accordingly, the CFR tapes disclosed herein can be used to manufacture any CFR article that requires strength and / or chemical resistance at elevated temperatures. The CFR tapes disclosed herein are particularly suitable for use in manufacturing CFR articles for oil and gas applications, such as, but not limited to, laminates and fiber reinforced pipe.

[0043] The CFR tapes disclosed herein can generally be described as comprising a polyketone matrix and a plurality of unidirectional continuous fibers.

[0044] Polyketone component

[0045] As noted above, the CFR tapes comprise a polyketone component into which a plurality of unidirectional continuous fibers are embedded.

[0046] The CFR tape can include a minimum amount of the polyketone component (e.g., greater than or equal to 20 wt%) to ensure that there is a sufficient amount of the polyketone component to sufficiently coat, interact with, and bond together the plurality of unidirectional continuous fibers to form the CFR tape. The amount of the polyketone component in the CFR tape can be limited (e.g., less than or equal to 50 wt%) to ensure that there is sufficient improvement in mechanical properties (e.g., shear strength) relative to the polyketone component being reinforced. Thus, in some embodiments, the amount of the polyketone in the CFR tape can be greater than or equal to 20 wt%, greater than or equal to 23 wt%, greater than or equal to 25 wt%, or even greater than or equal to 27 wt%, based on the total weight of the CFR tape. In some embodiments, the amount of the polyketone component in the CFR tape can be less than or equal to 50 wt%, less than or equal to 45 wt%, less than or equal to 40 wt%, less than or equal to 35 wt%, less than or equal to 33 wt%, or even less than or equal to 30 wt%, based on the total weight of the CFR tape. In some embodiments, the amount of the polyketone component in the CFR tape can be from 20 wt% to 50 wt%, from 20 wt% to 45 wt%, from 20 wt% to 40 wt%, from 20 wt% to 35 wt%, from 20 wt% to 33 wt%, from 20 wt% to 30 wt%, from 23 wt% to 50 wt%, from 23 wt% to 45 wt%, from 23 wt% to 40 wt%, from 23 wt% to 35 wt%, from 23 wt% to 33 wt%, from 23 wt% to 30 wt%, from 25 wt% to 50 wt%, from 25 wt% to 45 wt%, from 25 wt% to 40 wt%, from 25 wt% to 35 wt%, from 25 wt% to 33 wt%, from 25 wt% to 30 wt%, from 27 wt% to 50 wt%, from 27 wt% to 45 wt%, from 27 wt% to 40 wt%, from 27 wt% to 35 wt%, from 27 wt% to 33 wt%, or even from 27 wt% to 30 wt%, or any and all subranges formed from any of these endpoints. Without wishing to be bound by theory, it is believed that the polyketone component can impart chemical resistance to the CFR tape. For example, the presence of the polyketone component can impart oil resistance to the CFR tape.

[0047] In some embodiments, the polyketone component can include a polyketone polymer. In some embodiments, the polyketone polymer can include a minimum amount of polyketone monomer units (e.g., greater than or equal to 50 wt%) to ensure that a sufficient amount of polyketone interacts with and bonds to the plurality of unidirectional continuous fibers coated with a compatible sizing. Without wishing to be bound by theory, it is believed that the carbon-oxygen bonds of the polyketone can interact with the sizing on the fibers to form chemical bonds, which can strengthen the connection between the polyketone component and the plurality of unidirectional continuous fibers, thereby providing retained shear strength. In some embodiments, the polyketone component can include a polyketone polymer including greater than or equal to 50 wt% polyketone monomer units, based on the total weight of the polyketone polymer, for example, greater than or equal to 55 wt%, greater than or equal to 60 wt%, greater than or equal to 65 wt%, greater than or equal to 70 wt%, greater than or equal to 75 wt%, greater than or equal to 80 wt%, greater than or equal to 85 wt%, greater than or equal to 90 wt%, greater than or equal to 95 wt%, or even greater than or equal to 99 wt%.

[0048] In some embodiments, the polyketone polymer includes polypropylene monomer units in an amount less than or equal to 15 wt%, based on the total weight of the polyketone polymer, to reduce the crystallinity and melting point of the polyketone component, which can improve the processability of the resulting CFR tape. For example, the polyketone polymer can include polypropylene monomer units in an amount less than or equal to 14 wt%, less than or equal to 13 wt%, less than or equal to 12 wt%, less than or equal to 11 wt%, less than or equal to 10 wt%, less than or equal to 9 wt%, less than or equal to 8 wt%, less than or equal to 7 wt%, less than or equal to 6 wt%, less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, or even less than or equal to 1 wt%, based on the total weight of the polyketone polymer. In some embodiments, the polyketone polymer can not include polypropylene monomer units.

[0049] Suitable commercially available embodiments of the polyketone component are available from Hyosung Corporation, such as polyketone polymer grade M330F, M330A, or M930F.

[0050] In some embodiments, the polyketone polymer has a melt flow index of greater than or equal to 50 g / 10 min, for example, greater than or equal to 75 g / 10 min, greater than or equal to 100 g / 10 min, greater than or equal to 125 g / 10 min, greater than or equal to 150 g / 10 min, greater than or equal to 175 g / 10 min, greater than or equal to 200 g / 10 min, greater than or equal to 225 g / 10 min, greater than or equal to 250 g / 10 min, greater than or equal to 275 g / 10 min, greater than or equal to 300 g / 10 min, greater than or equal to 325 g / 10 min, greater than or equal to 350 g / 10 min, greater than or equal to 375 g / 10 min, or even greater than or equal to 400 g / 10 min at 240 °C / 2.16 kg, as measured according to ASTM D1238.

[0051] In some embodiments, the polyketone component can include a thermal stabilizer to improve the mechanical properties of the CFR tape at elevated temperatures (e.g., greater than or equal to 100 °C). In some embodiments, the thermal stabilizer can include calcium hydroxyapatite. In some embodiments, the polyketone component can include 0.20 wt% to 1.0 wt% calcium hydroxyapatite, for example, 0.20 wt% to 0.9 wt%, 0.2 wt% to 0.8 wt%, 0.2 wt% to 0.7 wt%, 0.2 wt% to 0.6 wt%, 0.2 wt% to 0.5 wt%, 0.2 wt% to 0.4 wt%, 0.2 wt% to 0.3 wt%, 0.3 wt% to 1.0 wt%, 0.3 wt% to 0.9 wt%, 0.3 wt% to 0.8 wt%, 0.3 wt% to 0.7 wt%, 0.3 wt% to 0.6 wt%, 0.3 wt% to 0.5 wt%, 0.3 wt% to 0.4 wt%, 0.4 wt% to 1.0 wt%, 0.4 wt% to 0.9 wt%, 0.4 wt% to 0.8 wt%, 0.4 wt% to 0.7 wt%, 0.4 wt% to 0.6 wt%, 0.4 wt% to 0.5 wt%, 0.5 wt% to 1.0 wt%, 0.5 wt% to 0.9 wt%, 0.5 wt% to 0.8 wt%, 0.5 wt% to 0.7 wt%, 0.5 wt% to 0.6 wt%, 0.6 wt% to 1.0 wt%, 0.6 wt% to 0.9 wt%, 0.6 wt% to 0.8 wt%, 0.6 wt% to 0.7 wt%, 0.7 wt% to 1.0 wt%, 0.7 wt% to 0.9 wt%, 0.7 wt% to 0.8 wt%, 0.8 wt% to 1.0 wt%, 0.8 wt% to 0.9 wt%, or even 0.9 wt% to 1.0 wt%, or any and all subranges formed from any of these endpoints, based on the total weight of the polyketone component.

[0052] Suitable commercially available embodiments of heat stabilizers are available under the brand EPSOLUTE from the company Budenheim, for example calcium hydroxyapatite grade C13-09.

[0053] Multiple continuous fibers

[0054] As described above, the CFR tape includes a plurality of unidirectional continuous fibers embedded in a polyketone component.

[0055] The CFR tape can include a minimum amount of the plurality of unidirectional continuous fibers (e.g., greater than or equal to 50 wt.%) to ensure adequate improvement in mechanical properties (e.g., shear strength) relative to the polyketone component being reinforced. The amount of the plurality of continuous fibers in the CFR tape can be limited (e.g., less than or equal to 80 wt.%) to ensure that there is a sufficient amount of the polyketone component to sufficiently coat, interact with, and bond together the plurality of continuous fibers to form the CFR tape. Thus, in some embodiments, the CFR tape can include 50 wt.% to 80 wt.% of the plurality of unidirectional continuous fibers, based on the total weight of the CFR tape. In some embodiments, the amount of the plurality of unidirectional continuous fibers in the CFR tape can be greater than or equal to 50 wt.% or even greater than or equal to 60 wt.%, based on the total weight of the CFR tape. In some embodiments, the amount of the plurality of unidirectional continuous fibers in the CFR tape can be less than or equal to 80 wt.% or even less than or equal to 70 wt.%, based on the total weight of the CFR tape. In some embodiments, the amount of the plurality of unidirectional continuous fibers in the CFR tape can be 50 wt.% to 80 wt.%, 50 wt.% to 75 wt.%, 50 wt.% to 70 wt.%, 50 wt.% to 65 wt.%, 50 wt.% to 60 wt.%, 50 wt.% to 55 wt.%, 55 wt.% to 80 wt.%, 55 wt.% to 75 wt.%, 55 wt.% to 70 wt.%, 55 wt.% to 65 wt.%, 55 wt.% to 60 wt.%, 60 wt.% to 80 wt.%, 60 wt.% to 75 wt.%, 60 wt.% to 70 wt.%, 60 wt.% to 65 wt.%, 65 wt.% to 80 wt.%, 65 wt.% to 75 wt.%, 65 wt.% to 70 wt.%, 70 wt.% to 80 wt.%, 70 wt.% to 75 wt.%, or even 75 wt.% to 80 wt.%, or any and all subranges formed by any of these endpoints.

[0056] In some embodiments, the plurality of unidirectional continuous fibers can span all or substantially all of the dimensions of the CFR tape. For example, in some embodiments, the plurality of unidirectional continuous fibers can span all or substantially all of the length of the CFR tape. In some embodiments, each unidirectional continuous fiber of the plurality of unidirectional continuous fibers can have a length, and the lengths of the unidirectional continuous fibers of the plurality of unidirectional continuous fibers can be substantially parallel. For example, in some embodiments, the lengths of the unidirectional continuous fibers can extend along and parallel to the length of the CFR tape.

[0057] In some embodiments, the plurality of unidirectional continuous fibers can include at least one of glass fibers, aramid fibers, basalt fibers, and carbon fibers. In one or more embodiments, the plurality of unidirectional continuous fibers can be continuous glass fibers.

[0058] In some embodiments, the plurality of unidirectional continuous fibers can have an average diameter of 10 pm to 30 pm to ensure that the desired shear strength is achieved. In some embodiments, the plurality of unidirectional continuous fibers can have an average diameter of 13 pm to 17 pm. In some embodiments, the plurality of unidirectional continuous fibers can have an average diameter of greater than or equal to 10 pm, greater than or equal to 13 pm, or even greater than or equal to 15 pm. In some embodiments, the plurality of unidirectional continuous fibers can have an average diameter of less than or equal to 30 pm, less than or equal to 27 pm, less than or equal to 25 pm, less than or equal to 23 pm, less than or equal to 20 pm, or even less than or equal to 17 pm. In some embodiments, the plurality of unidirectional continuous fibers can have an average diameter of 10 pm to 30 pm, 10 pm to 27 pm, 10 pm to 25 pm, 10 pm to 23 pm, 10 pm to 20 pm, 10 pm to 17 pm, 10 pm to 15 pm, 10 pm to 13 pm, 13 pm to 30 pm, 13 pm to 27 pm, 13 pm to 25 pm, 13 pm to 23 pm, 13 pm to 20 pm, 13 pm to 17 pm, 13 pm to 15 pm, 15 pm to 30 pm, 15 pm to 27 pm, 15 pm to 25 pm, 15 pm to 23 pm, 15 pm to 20 pm, 15 pm to 17 pm, 17 pm to 30 pm, 17 pm to 27 pm, 17 pm to 25 pm, 17 pm to 23 pm, 17 pm to 20 pm, 20 pm to 30 pm, 20 pm to 27 pm, 20 pm to 25 pm, 20 pm to 23 pm, 23 pm to 30 pm, 23 pm to 27 pm, 23 pm to 25 pm, 25 pm to 30 pm, 25 pm to 27 pm, 27 pm to 30 pm, or any and all subranges formed from any of these endpoints. Without being bound by theory, it is believed that unidirectional continuous fibers having an average diameter of 10 pm to 30 pm can allow for a greater total fiber surface area to be provided within the CFR tape as compared to tapes using continuous unidirectional fibers having an average diameter greater than 30 pm, which can improve the bonding between the fibers and the matrix polymer, thereby increasing the shear strength of the CFR tape.

[0059] In some embodiments, the plurality of unidirectional continuous fibers can have an average linear mass density of 4400 TEX to 276 TEX. In some embodiments, the plurality of unidirectional continuous fibers can have an average linear mass density of less than or equal to 4400 TEX, less than or equal to 4000 TEX, less than or equal to 3600 TEX, less than or equal to 3200 TEX, less than or equal to 2800 TEX, less than or equal to 2400 TEX, less than or equal to 2000 TEX, or even less than or equal to 1600 TEX. In some embodiments, the plurality of unidirectional continuous fibers can have an average linear mass density of greater than or equal to 276 TEX, greater than or equal to 400 TEX, greater than or equal to 600 TEX, greater than or equal to 800 TEX, or even greater than or equal to 1000 TEX.In some embodiments, the plurality of unidirectional continuous fibers can have an average linear mass density of 4400 TEX to 276 TEX, 4400 TEX to 400 TEX, 4400 TEX to 600 TEX, 4400 TEX to 800 TEX, 4400 TEX to 1000 TEX, 4000 TEX to 276 TEX, 4000 TEX to 400 TEX, 4000 TEX to 600 TEX, 4000 TEX to 800 TEX, 4000 TEX to 1000 TEX, 3600 TEX to 276 TEX, 3600 TEX to 400 TEX, 3600 TEX to 600 TEX, 3600 TEX to 800 TEX, 3600 TEX to 1000 TEX, 3200 TEX to 276 TEX, 3200 TEX to 400 TEX, 3200 TEX to 600 TEX, 3200 TEX to 800 TEX, 3200 TEX to 1000 TEX, 2800 TEX to 276 TEX, 2800 TEX to 400 TEX, 2800 TEX to 600 TEX, 2800 TEX to 800 TEX, 2800 TEX to 1000 TEX, 2400 TEX to 276 TEX, 2400 TEX to 400 TEX, 2400 TEX to 600 TEX, 2400 TEX to 800 TEX, 2400 TEX to 1000 TEX, 2000 TEX to 276 TEX, 2000 TEX to 400 TEX, 2000 TEX to 600 TEX, 2000 TEX to 800 TEX, 2000 TEX to 1000 TEX, 1600 TEX to 276 TEX, 1600 TEX to 400 TEX, 1600 TEX to 600 TEX, 1600 TEX to 800 TEX, or even 1600 TEX to 1000 TEX, or any and all subranges formed from any of these endpoints.

[0060] In some embodiments, the plurality of unidirectional continuous fibers can be in the form of a tow, a yarn, a roving, or a woven mat.

[0061] In one or more embodiments, the plurality of unidirectional continuous fibers can include a sizing composition to allow for compatibilization between the polyketone component and the fibers, which can help the plurality of unidirectional continuous fibers to interact and bond with the polyketone component, thereby improving the mechanical properties of the CFR tape. In some embodiments, the sizing composition can include at least one of a film former, a lubricant, and a coupling agent. In some embodiments, the sizing composition can include a polyamide.

[0062] CFR tape

[0063] Referring now to Figure 1 , a CFR tape is shown at 100. As described herein, the CFR tape 100 can include a polyketone component and a plurality of unidirectional continuous fibers embedded in the polyketone component, resulting in the CFR tape having retained shear strength at elevated temperatures as well as improved chemical resistance.

[0064] In some embodiments, the CFR tape can retain greater than 65% of its in-plane shear strength at 100°C. For example, the CFR tape can retain shear strength greater than 70%, greater than 75%, or even greater than 80%.

[0065] In some embodiments, the CFR tape can have an in-plane shear strength at 21°C greater than or equal to 35 MPa, greater than or equal to 36 MPa, or even greater than or equal to 37 MPa. In some embodiments, the CFR tape can have an in-plane shear strength at 21°C less than or equal to 40 MPa, or even less than or equal to 39 MPa. In some embodiments, the CFR tape can have an in-plane shear strength at 21°C from 35 MPa to 36 MPa, from 36 MPa to 37 MPa, from 37 MPa to 38 MPa, from 38 MPa to 39 MPa, or even from 39 MPa to 40 MPa, or any and all subranges formed from any of these endpoints.

[0066] In some embodiments, the CFR tape can have an in-plane shear strength at 100°C greater than or equal to 30 MPa, greater than or equal to 31 MPa, or even greater than or equal to 32 MPa. In some embodiments, the CFR tape can have an in-plane shear strength at 100°C less than or equal to 34 MPa, or even less than or equal to 33 MPa. In some embodiments, the CFR tape can have an in-plane shear strength at 100°C from 30 MPa to 31 MPa, from 31 MPa to 32 MPa, from 32 MPa to 33 MPa, or even from 33 MPa to 34 MPa, or any and all subranges formed from any of these endpoints.

[0067] As described herein, in some embodiments, the CFR tape 100 can have a length / , a width w, and a thickness t suitable for its intended application. In some embodiments, the CFR tape 100 can have a thickness t of 0.010 cm to 0.125 cm. For example, the CFR tape can have a thickness of 0.010 cm to 0.100 cm, 0.010 cm to 0.075 cm, 0.010 cm to 0.050 cm, 0.010 cm to 0.025 cm, 0.025 cm to 0.125 cm, 0.025 cm to 0.100 cm, 0.025 cm to 0.075 cm, 0.025 to 0.050 cm, 0.050 cm to 0.125 cm, 0.050 cm to 0.100 cm, 0.050 cm to 0.075 cm, 0.075 cm to 0.125 cm, 0.075 cm to 0.100 cm, 0.100 cm to 0.125 cm, or any and all subranges formed from any of these endpoints.

[0068] In some embodiments, the CFR tape can have a tensile strength greater than or equal to 650 MPa (94 ksi) or even greater than or equal to 700 MPa (102 ksi). In some embodiments, the CFR tape can have a tensile strength less than or equal to 800 MPa (116 ksi) or even less than or equal to 750 MPa (109 ksi). In some embodiments, the CFR tape can have a tensile strength of 650 MPa to 800 MPa, 650 MPa to 750 MPa, 700 MPa to 800 MPa, or even 700 MPa to 750 MPa, or any and all subranges formed from any of these endpoints. In embodiments where the unidirectional continuous fibers are carbon fibers, the CFR tape can have a tensile strength greater than or equal to 1000 MPa, such as greater than or equal to 1250 MPa, or even greater than or equal to 1500 MPa.

[0069] In some embodiments, the tensile modulus of the CFR tape can be greater than or equal to 22,000 MPa (3,191 ksi) or even greater than or equal to 24,000 MPa (3,481 ksi). In some embodiments, the tensile modulus of the CFR tape can be less than or equal to 28,000 MPa (4,061 ksi) or even less than or equal to 26,000 MPa (3,771 ksi). In some embodiments, the tensile modulus of the CFR tape can be from 22,000 MPa to 28,000 MPa, from 22,000 MPa to 26,000 MPa, from 24,000 MPa to 28,000 MPa, or even from 24,000 MPa to 26,000 MPa, or any and all subranges formed by any of these endpoints. In embodiments where the unidirectional continuous fibers are carbon fibers, the tensile modulus of the CFR tape can be greater than or equal to 50,000 MPa, such as greater than or equal to 75,000 MPa, or even greater than or equal to 100,000 MPa.

[0070] In some embodiments, the tensile elongation of the CFR tape can be greater than or equal to 1% or even greater than or equal to 2%. In some embodiments, the tensile elongation of the CFR tape can be less than or equal to 10% or even less than or equal to 5%. In some embodiments, the tensile elongation of the CFR tape can be from 1% to 10%, from 1% to 5%, from 2% to 10%, or even from 2% to 5%, or any and all subranges formed by any of these endpoints.

[0071] In some embodiments, the flexural strength of the CFR tape can be greater than or equal to 300 MPa (43 ksi) or even greater than or equal to 350 MPa (51 ksi). In some embodiments, the flexural strength of the CFR tape can be less than or equal to 900 MPa (131 ksi) or even less than or equal to 850 MPa (123 ksi). In some embodiments, the flexural strength of the CFR tape can be from 300 MPa to 900 MPa, from 350 MPa to 850 MPa, from 400 MPa to 800 MPa, from 450 MPa to 750 MPa, from 500 MPa to 700 MPa, from 550 MPa to 650 MPa, from 600 MPa to 650 MPa, or even from 550 MPa to 600 MPa, or any and all subranges formed by any of these endpoints.

[0072] In some embodiments, the CFR tape can have a flexural modulus greater than or equal to 22,000 MPa (3,191 ksi) or even greater than or equal to 24,000 MPa (3,481 ksi). In some embodiments, the CFR tape can have a flexural modulus less than or equal to 28,000 MPa (4,061 ksi) or even less than or equal to 26,000 MPa (3,771 ksi). In some embodiments, the CFR tape can have a flexural modulus of 22,000 MPa to 28,000 MPa, 22,000 MPa to 26,000 MPa, 24,000 MPa to 28,000 MPa, or even 24,000 MPa to 26,000 MPa, or any and all subranges formed from any of these endpoints.

[0073] In certain applications, it can be desirable for the CFR tape to have resistance to water absorption. Accordingly, in some embodiments, the CFR tape can have a percent change in weight after 1,000 hours of water immersion of less than 1.5 wt.%, based on the total weight of the CFR tape. For example, the CFR tape can have a percent change in weight after 1,000 hours of water immersion of less than 1.25 wt.%, less than 1.0 wt.%, less than 0.75 wt.%, less than 0.5 wt.%, or even less than 0.25 wt.%, based on the total weight of the CFR tape.

[0074] Method of manufacture

[0075] As will be appreciated by one of ordinary skill in the art, the CFR tapes disclosed herein can be produced by a variety of methods. Different form factors of the polymer mat are introduced into the continuous fibers as desired, and then the combination of fibers and polymer can be processed to manufacture the CFR tape. In some embodiments, the CFR tape can be produced during a process in which the fibers are collected before being introduced into the molten polymer. The fibers can then be impregnated with the molten polymer before being processed to form the CFR tape.

[0076] The CFR tapes disclosed herein can be used to manufacture any CFR article that requires strength and / or chemical resistance at elevated temperatures. The CFR tapes disclosed herein are particularly useful for manufacturing CFR articles for use in oil and gas applications, such as but not limited to, laminates and fiber reinforced pipe.

[0077] Referring now to Figure 2The laminate material is shown at 200. The laminate material 200 can include a first layer 210 and a second layer 220. The CFR tape can be the first layer 210 or both the first layer 210 and the second layer 220 in the laminate material 200. The second layer 220 in the laminate material 200 can be a layer other than the CFR tape. For example, the second layer 220 in the laminate material 200 can be a tape having a different composition or a foam layer. In certain embodiments, the second layer 220 in the laminate material 200 can be a foam layer, a balsa wood layer, or a honeycomb layer. Exemplary foam layers include one or more of polyethylene terephthalate (PET), polyurethane (PU), polyvinyl chloride (PVC), and styrene acrylonitrile (SAN). In certain embodiments, the foam layer can be a foam core sandwiched between one or more CFR tape layers on each side. While shown with a first layer 210 and a second layer 220, the laminate material 200 can include 2-12 layers, 3-11 layers, 4-10 layers, 5-9 layers, or 6-8 layers.

[0078] Referring now to Figure 3 In other embodiments, the CFR tape can be used to form a fiber-reinforced pipe 300. In some embodiments, the fiber-reinforced pipe 300 can include an inner pipe 302 having an inner lumen 310 and an outer surface 320 and a CFR tape 100. The CFR tape 100 can be wrapped around the outer surface 320 of the inner pipe 302. In some embodiments, the CFR tape can be wrapped in a helical manner on the outer surface 320 of the pipe 302. In some embodiments, the CFR tape can completely cover the outer surface 320 of the pipe 302. In some embodiments, the inner pipe 302 can include one or more of high-density polyethylene, polyamide, or polyvinylidene.

[0079] Referring now to Figure 4 In some embodiments, the fiber-reinforced pipe 400 can include an inner cylindrical liner 402 having an inner lumen 410 and an outer surface 420. The fiber-reinforced pipe 400 can also include an outer cylindrical sheath 422 having an inner lumen 430 and an outer surface 440. The fiber-reinforced pipe 400 can also include a CFR tape 100. The CFR tape 100 can be located between the inner cylindrical liner 402 and the outer cylindrical sheath 422 and within the inner lumen 430 of the outer cylindrical sheath 424. The CFR tape 100 can be wrapped in a helical manner. In some embodiments, the inner cylindrical liner 402 can include one or more of high-density polyethylene, polyamide, or polyvinylidene.

[0080] In some embodiments, the fiber-reinforced pipe can have flexibility as measured according to the ASTM F2686-14 Standard Specification for Glass-Fiber-Reinforced Thermoplastic Piping.

[0081] In some embodiments, the CFR tape of the fiber-reinforced pipe can be a first CFR tape, and the fiber-reinforced pipe can include a second CFR tape helically wound over the first CFR tape. In some embodiments, the second CFR tape can be helically wound in an opposite direction to the wound first CFR tape.

[0082] In some embodiments, the fiber-reinforced pipe can include 2 to 12 CFR tape windings. As used herein, the term "windings" refers to layers of CFR tape wound around the circumference of the outer surface of the pipe, for example, 2 to 11 CFR tape windings, 2 to 10 windings, 2 to 9 windings, 2 to 8 windings, 2 to 7 windings, 2 to 6 windings, 2 to 5 windings, 2 to 4 windings, 2 to 3 windings, 3 to 12 windings, 3 to 11 windings, 3 to 10 windings, 3 to 9 windings, 3 to 8 windings, 3 to 7 windings, 3 to 6 windings, 3 to 5 windings, 3 to 4 windings, 4 to 12 windings, 4 to 11 windings, 4 to 10 windings, 4 to 9 windings, 4 to 8 windings, 4 to 7 windings, 4 to 6 windings, 4 to 5 windings, 5 to 12 windings, 5 to 11 windings, 5 to 10 windings, 5 to 9 windings, 5 to 8 windings, 5 to 7 windings, 5 to 6 windings, 6 to 12 windings, 6 to 11 windings, 6 to 10 windings, 6 to 9 windings, 6 to 8 windings, 6 to 7 windings, 7 to 12 windings, 7 to 11 windings, 7 to 10 windings, 7 to 9 windings, 7 to 8 windings, 8 to 12 windings, 8 to 11 windings, 8 to 10 windings, 8 to 9 windings, 9 to 12 windings, 9 to 11 windings, 9 to 10 windings, 10 to 12 windings, 10 to 11 windings, 11 to 12 windings, or any and all sub-ranges formed from any of these endpoints.

[0083] Example

[0084] Table 1 below shows the sources of ingredients used to form the control tapes CI and C2 and the exemplary tapes El and E2.

[0085] Table 1

[0086]

[0087] Table 2 below shows the formulations (in weight %, based on the total weight of the CFR tape) and mechanical properties of exemplary tapes E1 and E2 and control tapes C1 and C2. The CFR tapes of the present examples were made by first impregnating the fibers with the polymer matrix before processing the combined fibers and polymer matrix into a CFR tape.

[0088] Table 2

[0089]

[0090] Table 2 (continued)

[0091]

[0092] Table 3 below shows further mechanical properties of exemplary tape E2 at different temperatures.

[0093] Table 3

[0094]

[0095] As shown in Table 3, exemplary tape E2, which is a CFR tape comprising a polyketone component and a plurality of unidirectional continuous fibers, maintained greater than 84% of its in-plane shear strength at 100°C compared to its in-plane shear strength at 21°C. As shown in Table 3, the CFR tapes disclosed herein comprising a polyketone component have maintained shear strength at elevated temperatures.

[0096] Referring now to Figure 5 and Figure 6 Exemplary tape E2, which is a CFR tape comprising a polyketone component, has better in-plane shear strength retention at elevated temperatures compared to control tapes C1 and C2, which lack a polyketone component. At 100°C, both control tapes have less than 60% in-plane shear strength retention. In contrast, exemplary tape E2 has more than 80% in-plane shear strength retention at 100°C. As shown in Figure 5 and Figure 6 the CFR tapes disclosed herein comprising a polyketone component have maintained shear strength at elevated temperatures.

[0097] Referring now to Figure 7 Exemplary tape E2 has less than 1.5% change in dry weight after 1000 hours of water immersion, while control tape C1 has more than 4.0% change in dry weight. In addition, exemplary tape E2 has less reduction in flexural strength compared to control composition C1. As shown in Figure 7 the CFR tapes disclosed herein have relatively low water absorption and high flexural strength retention.

[0098] Referring now toFigures 8-13 Glass fibers containing polyethylene terephthalate / polybutylene terephthalate sizing compositions as shown in Figure 10 and 11 Glass fibers containing polypropylene sizing compositions as shown in Figure 12 and 13 Glass fibers containing polyamide sizing compositions as shown in Figure 8 and 9 resulted in better adhesion of the glass fibers. As shown in Figure 8 and Figure 9 the surface of the glass fiber fragments had residual polymer, indicating better adhesion between the polyamide sized glass and the polyketone component. In addition, Figures 10-13 no residual polymer on the surface of the glass fibers was shown, indicating little to no adhesion between the glass fibers and the polymer matrix.

[0099] Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this document shall control.

[0100] It will be clear to those skilled in the art that various modifications and changes can be made without departing from the scope of the disclosure as set forth in the appended claims. While certain aspects of the disclosure have been determined to be preferred or particularly advantageous, it is contemplated that the disclosure is not necessarily limited to these aspects.

Claims

1. A continuous fiber-reinforced tape comprising, based on the total weight of the continuous fiber-reinforced tape: 20 to 50 weight percent of a polyketone component; and 50 to 80 weight percent of a plurality of unidirectional continuous fibers embedded in the polyketone component.

2. The continuous-fiber reinforced tape of claim 1, wherein, The plurality of unidirectional continuous fibers span all or substantially all dimensions of the continuous fiber-reinforced tape.

3. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The plurality of unidirectional continuous fibers comprises at least one of glass fibers, aramid fibers, basalt fibers, and carbon fibers.

4. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The plurality of unidirectional continuous fibers has an average diameter of 10 to 30 pm.

5. The continuous-fiber reinforced tape of claim 4, wherein, The plurality of unidirectional continuous fibers has an average diameter of 13 to 17 pm.

6. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The plurality of unidirectional continuous fibers has an average linear mass density of 4400 to 276 TEX.

7. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The plurality of unidirectional continuous fibers is in the form of a tow, a yarn, an end, a pic, or a roving.

8. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The plurality of unidirectional continuous fibers is continuous glass fibers.

9. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The plurality of unidirectional continuous fibers comprises a sizing composition comprising a polyamide.

10. The continuous-fiber reinforced tape of any of claims 1 to 8, wherein, The plurality of unidirectional continuous fibers comprises a sizing composition comprising at least one of a film former, a lubricant, and a coupling agent.

11. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The polyketone component comprises a polyketone polymer comprising at least 50 weight percent of polyketone monomer units, based on the total weight of the polyketone polymer.

12. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The polyketone component comprises a polyketone polymer comprising less than or equal to 15 weight percent of propylene monomer units, based on the total weight of the polyketone polymer.

13. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The polyketone component comprises a thermal stabilizer.

14. The continuous-fiber reinforced tape of claim 13, wherein, The thermal stabilizer comprises calcium hydroxyapatite.

15. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The continuous fiber-reinforced tape has a length, a width, and a thickness, the thickness being 0.010 to 0.125 cm.

16. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The continuous fiber-reinforced tape has a weight percent change of less than 1.5 weight percent after 1000 hours of water immersion.

17. The continuous-fiber reinforced tape of any of the preceding claims, wherein, The continuous fiber-reinforced tape is one layer in a laminate.

18. A fiber-reinforced pipe comprising: an inner tube having an inner lumen and an outer surface; and the continuous fiber-reinforced tape of any of the preceding claims; wherein the continuous fiber-reinforced tape is wrapped around the outer surface of the inner tube.

19. The fiber reinforced pipe of claim 18, wherein, The continuous fiber-reinforced tape is wrapped in a helical manner.

20. A fiber-reinforced pipe comprising: an inner cylindrical liner having an inner lumen and an outer surface; an outer cylindrical sheath having an inner lumen and an outer surface; and the continuous fiber-reinforced tape of any of claims 1 to 17; wherein the continuous fiber-reinforced tape is positioned between the inner cylindrical liner and the outer cylindrical sheath.

21. The fiber reinforced pipe of claim 20, wherein, The continuous fiber-reinforced tape is wrapped in a helical manner around the outer surface of the inner cylindrical liner.

22. The fiber reinforced pipe according to claim 20 or 21, wherein, The fiber-reinforced pipe is flexible.

23. The fiber reinforced pipe according to any one of claims 20 to 22, wherein, The continuous fiber-reinforced tape is a first continuous fiber-reinforced tape, and the fiber-reinforced pipe further comprises a second continuous fiber-reinforced tape wrapped in a helical manner around the first continuous fiber-reinforced tape.

24. The fiber reinforced pipe of claim 23, wherein, The second continuous fiber-reinforced tape is helically wrapped in an opposite direction to the wrapped first continuous fiber-reinforced tape.

25. The fiber reinforced pipe according to any one of claims 20 to 24, wherein, The fiber-reinforced pipe includes 2 to 12 turns of continuous fiber-reinforced tape.

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