Composite parts with improved modulus

Abstract

A high modulus composite part is disclosed comprising a polymeric resin and a plurality of high performance unidirectional glass fibers. The high performance unidirectional glass fibers have an elastic modulus of at least 89 GPa and a tensile strength of at least 4000 MPa according to ASTM D2343-09. The composite part comprises a fiber weight fraction (FWF) of no more than 88% and an elastic modulus of at least 60 GPa according to ASTM D7205.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to and all the benefits of U.S. Provisional Patent Application No. 62 / 981,760, filed February 26, 2020, the disclosure of which is incorporated herein in its entirety by reference. TECHNICAL FIELD

[0003] The present invention relates generally to composite parts, and more particularly to high modulus composite parts composed of high performance glass fibers, such as reinforcing bars for concrete (“rebar”). BACKGROUND

[0004] Concrete is one of the most common building materials. It is used in a variety of structures, such as bridges, walls, floors, building supports, roads, and runways, among others. Concrete has excellent compressive strength, but has very poor tensile strength. Thus, if a concrete structure will be subjected to tensile stresses, such as those resulting from bending loads, it is almost always necessary to reinforce the concrete structure. Traditionally, this reinforcement has been provided by incorporating metal, usually in the form of rebar, into the concrete in order to improve the tensile strength of the concrete structure.

[0005] Steel rebar in concrete structures presents a number of disadvantages, at least in certain applications. For example, when exposed to water and salt, steel rebar corrodes over time. As the steel corrodes, it tends to expand due to the formation of rust layers, which causes the concrete to crack and the concrete structure to deteriorate. Thus, attempts have been made to replace steel rebar with bars made at least partially of non-metallic materials. For example, pultruded composite reinforcing materials comprising a thermoset resin embedded with continuous fibers have been developed.

[0006] Fiber-reinforced composites, such as composite rebar, typically include a fiber reinforcement material (e.g., glass fibers, polymer fibers, or carbon fibers) embedded in a resin matrix (e.g., a polymer such as unsaturated polyester or epoxy vinyl ester). The fiber reinforcement material typically includes yarns or tows (each of which includes a plurality of fibers or filaments) as well as one or more fiber mats or webs.

[0007] Such fiber-reinforced composites are typically produced by a pultrusion process and have a linear or uniform profile. A conventional pultrusion process involves drawing a bundle of reinforcement material from a source of reinforcement material, wetting and impregnating the fibers (preferably with a thermoset polymer resin) by passing the reinforcement material through a resin bath in an open trough, pulling the resin-wetted and impregnated fiber bundle through a shaping die in order to align the fiber bundle and manipulate it into an appropriate cross-sectional configuration, and curing the resin in the die while maintaining tension on the filaments.

[0008] Some fiber-reinforced composites, such as rebars, require corrosion resistance and are traditionally manufactured using corrosion-resistant glass fibers (or E-CR glass fibers). E-CR glass fibers are a type of aluminosilicate glass that exhibits high water, acid, and alkali resistance. E-CR glass is known to be a boron-free modified E-glass composition with high acid corrosion resistance, containing calcium aluminosilicate and approximately 1% alkali metal oxides. E-CR glass is typically used in applications requiring strength, electrical conductivity, and acid corrosion resistance.

[0009] An example of boron-free E-CR glass fiber is shown in the trademark. (Owens Coming, Toledo, Ohio, USA) for sale. Such boron-free fibers (disclosed in U.S. Patent 5,789,329, which is incorporated herein by reference in its entirety) offer a significant improvement in operating temperature compared to boron-containing E-glass. E-CR glass fiber falls under the ASTM definition of E-glass fiber for general purpose use.

[0010] For composite components to be a viable alternative to current steel solutions, they must exhibit improved modulus and excellent resistance to alkali corrosion.

[0011] Recently, a new class of glass fibers, known as high-performance glass fibers, has been developed, focusing on improving the mechanical properties of glass. Compared to traditional E-glass fibers, high-performance glass fibers exhibit higher strength and stiffness. The modulus of elasticity (interchangeable with "Young's modulus") is a measure of fiber stiffness, defining the relationship between the stress applied to a material and the strain produced by that material. Rigid materials have a high modulus of elasticity and undergo only slight changes in shape under elastic loads. Flexible materials have a low modulus of elasticity and significantly alter their shape. In particular, for some products, stiffness is critical to molding and performance.

[0012] While high-performance glasses are well-known, this performance improvement comes at the cost of corrosion resistance. Conventional high-performance glasses use fluxes to lower the melting point and improve their forming window, or delta T (“ΔT”). These fluxes (such as lithium, boron, and fluorine) are known to negatively impact alkaline corrosion resistance. Therefore, the use of conventional high-performance glasses in reinforcing applications is limited. In fact, there are currently no high-performance glass types available for use in fiber-reinforced composites requiring corrosion resistance. Therefore, it is desirable to develop fiber-reinforced composites utilizing high-performance glasses while maintaining alkali corrosion resistance, thereby improving the physical properties of composite components such as reinforcing ribs and balustrades. Summary of the Invention

[0013] The above and other objects, features and advantages of the invention will be more fully set forth below in consideration of the following detailed description.

[0014] Various aspects of the inventive concept are directed to a high modulus composite part comprising a polymeric resin and a plurality of high performance unidirectional glass fibers. The high performance unidirectional glass fibers have an elastic modulus of at least 89 GPa and a tensile strength of at least 4500 MPa, according to ASTM D2343-09. The composite part has a fiber weight fraction (FWF) of no more than 88% and an elastic modulus of at least 60 GPa, measured according to ASTM D7205.

[0015] In some example embodiments, the polymeric resin is selected from the group consisting of polyurethane, acrylic, polyester, vinyl ester, and epoxy.

[0016] The high modulus composite part can include a reinforcing bar, a railing, a utility pole, a pipe, a cross arm, an infrastructure, a cable, a telecommunication application, a ladder rail, or the like.

[0017] In some example embodiments, the high modulus composite comprises glass fibers formed from a composition that is substantially free of B2O3and fluorine. In these or other embodiments, the composition is free of Li2O.

[0018] The high performance glass fibers have a tensile strength of at least 4800 MPa and an elastic modulus of at least 90 GPa. In some example embodiments, the high performance glass fibers have a specific modulus (i.e., modulus normalized with density) of about 32.0 MJ / kg to about 37.0 MJ / kg.

[0019] High modulus composite parts formed using such high performance glass fibers include an elastic modulus of at least 60 GPa (according to ASTM D7205) and can include one or more of a flexural modulus of at least 50 GPa and a tensile modulus of at least 50 GPa (according to ASTM D7205), depending on fiber content and density.

[0020] Various aspects of the inventive concept are also directed to a method for forming a high modulus composite part, the method comprising drawing a bundle of high performance unidirectional glass fibers from an input source. The fibers comprise an elastic modulus of at least 89 GPa and a tensile strength of at least 4500 MPa, according to ASTM D2343-09. The method further comprises passing the bundle through a bath of polymeric resin material, forming a resin-coated bundle; drawing the resin-coated bundle through a forming die; and curing the resin-coated bundle, thereby forming a high modulus composite part comprising a fiber weight fraction (FWF) of no more than 88% and an elastic modulus of at least 60 GPa, according to ASTM D7205.

[0021] In some example embodiments, the polymeric resin is selected from the group consisting of polyester, vinyl ester, and epoxy.

[0022] In some example embodiments, the high performance glass fiber is formed from a composition that is substantially free of B2O3and fluorine. In these or other embodiments, the composition can be free of Li2O.

[0023] In some example embodiments, the high performance glass fiber has a tensile strength of at least 4800 MPa and an elastic modulus of at least 90 GPa.

[0024] In some example embodiments, the high performance glass fiber has a specific modulus of about 32.0 MJ / kg to about 37.0 MJ / kg.

[0025] High modulus composite parts formed using such high performance glass fibers include an elastic modulus of at least 60 GPa, and can include one or more of a flexural modulus of at least 50 GPa and a tensile modulus of at least 50 GPa. BRIEF DESCRIPTION OF DRAWINGS

[0026] The general inventive concept, embodiments thereof, and advantages thereof are described in greater detail below, by way of example, with reference to the drawings in which:

[0027] Figure 1A and 1B is a graphical representation of a pultrusion line for manufacturing composite rods in accordance with example embodiments.

[0028] Figure 2 Graphically illustrates the effective elastic modulus of the reinforcement bar versus fiber weight fraction for composites formed with conventional E-CR glass and high performance glass.

[0029] Figure 3A and 3B illustrates the flexural modulus of composite parts formed with conventional E-CR glass and high performance glass in unsaturated polyester and polyurethane resins.

[0030] Figure 4A and 4B illustrates the flexural strength of composite parts formed with conventional E-CR glass and high performance glass in unsaturated polyester and polyurethane resins.

[0031] Figure 5A and 5B illustrates the tensile modulus of composite parts formed with conventional E-CR glass and high performance glass in unsaturated polyester and polyurethane resins.

[0032] Figure 6A and 6B illustrates the interlaminar shear strength of composite parts formed with conventional E-CR glass and high performance glass in unsaturated polyester and polyurethane resins. Detailed Implementation

[0033] Although the general inventive concept allows for many different embodiments shown in the accompanying drawings and described in detail herein, it should be understood that this disclosure should be considered as an illustrative representation of the principles of the general inventive concept.

[0034] 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 these exemplary embodiments pertain. The terminology used in the description herein is for descriptive purposes only and is not intended to limit the exemplary embodiments. Therefore, the general inventive concept is not intended to be limited to the specific embodiments shown herein. Although other methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of the invention, preferred methods and materials are described herein.

[0035] As used in the specification and appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0036] Unless otherwise stated, all figures used in the specification and claims to represent amounts of components, chemical and molecular properties, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the specification and appended claims are approximate values ​​that may vary depending on the desired characteristics sought to be obtained through the present exemplary embodiments. Each numerical parameter should at least be interpreted according to significant digits and common rounding methods.

[0037] While the numerical ranges and parameters illustrating the broad range of example embodiments are approximate, the values ​​described in the specific examples are reported as precisely as possible. However, any numerical value inherently contains some error, which is necessarily due to the standard deviation present in their respective test measurements. Each numerical range given in this specification and claims will include every narrower numerical range falling within that broader range, as these narrower ranges are explicitly stated herein. Furthermore, any values ​​reported in the embodiments may be used to define the upper or lower endpoints of the broader compositional range disclosed herein.

[0038] This disclosure relates to a high-modulus fiber-reinforced composite component (“high-modulus composite”) comprising a polymer matrix and a corrosion-resistant, high-performance glass for improved performance and cost efficiency, and systems and methods for producing such high-modulus composites. The high-modulus composite achieves a modulus of at least 60 GPa, measured according to ASTM D7205, and has a glass loading of no more than 85% fiber weight fraction (“FWF”).

[0039] The high modulus composite material is formed by a pultrusion process (described below), in which continuous high performance glass fibers are fed through a die to form a rod, bar, or other linear reinforcing member having a desired cross-section. The high modulus composite material can include any type of pultruded composite known in the art, including but not limited to reinforcing bars, railings, utility poles, pipes, cross-arms, infrastructure, cables, telecommunication applications, ladder rungs, and the like.

[0040] Typically, the reinforcing members are in the form of rods having a circular cross-section. These rods can be cut to any desired length. In some exemplary embodiments, the rods can be shaped (e.g., bent) and / or connected to other rods to form more complex shapes and structures.

[0041] The high modulus composite material includes an input of continuous high performance glass fibers. By "high performance glass fibers" is meant that the glass fibers are corrosion resistant, have a tensile strength of at least 4000 MPa (in some cases, at least 4500 MPa), and an elastic modulus of at least 89 GPa, according to ASTM D2343-09. The elastic modulus of the glass fibers can be determined by averaging the measurements of five individual glass fibers measured according to the sonic measurement procedure outlined in "Glass Fiber and Measuring Facilities at the U.S. Naval Ordnance Laboratory," Report No. NOLTR 65-87, June 23, 1965.

[0042] Traditional high performance glasses use fluxing agents, such as lithium, boron, and fluorine, which are known to have a negative impact on corrosion resistance. In contrast, the high performance glass compositions of the present invention include low levels or at least substantially no B2O3, Li2O, and fluorine. As used herein, substantially no B2O3, Li2O, and fluorine means that the total amount of B2O3, Li2O, and fluorine present can be less than 1.0 wt.% of the composition. The total amount of B2O3, Li2O, and fluorine present can be less than about 0.5 wt.%, including less than about 0.2 wt.%, less than about 0.1 wt.%, and less than about 0.05 wt.% of the composition. However, in some exemplary embodiments, low levels of lithium can be included, such as 0.1 to 2.0 wt.%.

[0043] It has been surprisingly discovered that a high performance glass fiber input can be developed that has an elastic modulus of at least 89 GPa and corrosion resistance (exhibiting less than 12% weight loss after 24 hours of immersion in a corrosive medium, or having greater than 75% strength retention after 32 days of immersion in a corrosive medium) sufficient for use in applications traditionally utilizing lower performing traditional E-CR glass fibers, such as composite reinforcing bars.

[0044] Fiber tensile strength is also referred to herein simply as "strength." In some example embodiments, tensile strength is measured on raw fiber (i.e., laboratory produced fiber that has not been sized and contacted) according to ASTM D2343-09 using an Instron tensile testing apparatus. The fiber tensile strength of example glass fibers can be at least 4500 MPa, at least 4800 MPa, at least 4900 MPa, at least 4950 MPa, at least 5000 MPa, at least 5100 MPa, at least 5150 MPa, and at least 5200 MPa. In some example embodiments, the fiber tensile strength of glass fibers formed from the above-described compositions is from about 3500 to about 5500 MPa, including from about 4000 to about 5300 MPa, from about 4600 to about 5250 MPa. Advantageously, the tensile strength of high performance glass fibers is at least 4800 MPa, including at least 4900 MPa and at least 5000 MPa.

[0045] The modulus of elasticity of the high performance glass fibers can be at least about 85 GPa, including at least about 88 GPa, at least about 88.5 GPa, at least about 89 GPa, and at least about 89.5 GPa. In some example embodiments, the modulus of elasticity of example glass fibers is from about 85 GPa to about 95 GPa, including from about 87 GPa to about 92 GPa, and from about 88 GPa to about 91 GPa. The modulus of elasticity of a glass fiber can be determined by averaging the measurements of five individual glass fibers measured according to the sonic measurement procedure outlined in the report "Glass Fiber and Measuring Facilities at the U.S. Naval Ordnance Laboratory," Report No. NOLTR 65-87, June 23, 1965.

[0046] In one or more example embodiments, the high performance glass fibers have a mid-high modulus of elasticity of from about 90 GPa to about 92 GPa. In some example embodiments, the high performance glass fibers have a modulus of elasticity of at least 90.5 GPa, such as at least 90.6 GPa, at least 90.8 GPa, at least 91.0 GPa, at least 91.2 GPa. In some example embodiments, the high performance glass fibers have a modulus of elasticity of from about 90.2 GPa to about 92 GPa, including from about 90.5 GPa to about 91.9 GPa, and from about 90.7 GPa to about 91.8 GPa.

[0047] The modulus can then be used to determine the specific modulus. It is desirable to have as high a specific modulus as possible to obtain lightweight composites that increase the stiffness of the final article. The specific modulus is important in applications where product stiffness is an important parameter, such as reinforcement for concrete. As used herein, the specific modulus is calculated by the following equation:

[0048] Specific Modulus (MJ / kg) = Modulus (GPa) / Density (kg / m 3 )

[0049] The specific modulus of the high performance glass fiber can be from about 32.0 MJ / kg to about 37.0 MJ / kg, including from about 33 MJ / kg to about 36 MJ / kg, and from about 33.5 MJ / kg to about 35.5 MJ / kg.

[0050] Density can be measured by any method known in the art and generally accepted, such as the Archimedes method (ASTM C693-93 (2008)), performed on unannealed bulk glass. The density of the glass fiber is from about 2.0 to about 3.0 g / cc. In other exemplary embodiments, the density of the glass fiber is from about 2.3 to about 2.8 g / cc, including from about 2.4 to about 2.7 g / cc and from about 2.5 to about 2.65 g / cc.

[0051] Further, the high performance glass fiber has improved resistance to alkali corrosion. Corrosion resistance can be quantified by any method known in the art and generally accepted, such as by measuring the weight loss (%) of the glass fiber after immersion in one of the following for 24 hours: pH 12.8 NaOH, 10% HC1, or 10% H2SO4. Glass fiber with a weight loss of less than 12% after 24 hours of immersion is considered to have improved corrosion resistance. Corrosion resistance can also be quantified in terms of the percent (%) strength retention after immersion in one of the following for 32 days: pH 12.8 NaOH, 10% HC1, or 10% H2SO4. Glass fiber that retains at least 75% of the strength of the dry fiber bundle after 32 days of immersion is considered to be corrosion resistant.

[0052] In some exemplary embodiments, the input high performance glass fiber has a diameter in the range of 13 μιη to 35 μιη. In some exemplary embodiments, the input high performance glass fiber has a diameter in the range of 17 μιη to 32 μιη. The input material (e.g., glass fiber, carbon fiber) will typically have sizing applied thereto that is compatible with the resin matrix used to form the composite rod.

[0053] In some example embodiments, the glass content will be no greater than 88 wt% of the pultruded rod. In some example embodiments, the glass or hybrid fiber content will be in the range of 50 wt% to 88 wt% of the pultruded rod. In some example embodiments, the glass content will be in the range of 55 wt% to 86 wt%, including 58 wt% to 85 wt%, and 60 wt% to 80 wt%. In some example embodiments, the glass content will be in the range of 80 wt% to 86 wt% of the pultruded part.

[0054] Glass composition

[0055] Example glass composition I

[0056] The high performance glass composition can include about 55.0 to about 65.0 wt% Si02, about 17.0 to 27.0 wt% Al203, about 8.0 to 15.0 wt% MgO, about 7.0 to 12.0 wt% CaO, about 0.0 to about 1.0 wt% Na20, 0 to about 2.0 wt% Ti02, 0 to about 2.0 wt% Fe203, and no greater than 0.5 wt% Li20.

[0057] In some example embodiments, the glass composition can include about 57.0 to about 62.0 wt% Si02, about 19.0 to about 25.0 wt% Al203, about 10.5 to about 14.0 wt% MgO, about 7.5 to about 10.0 wt% CaO, about 0.0 to about 0.5 wt% Na20, 0.2 to about 1.5 wt% Ti02, 0 to about 1.0 wt% Fe203, and no greater than 0.1 wt% Li20. In some example embodiments, the glass composition includes an Al203 / MgO ratio of less than 2 and a MgO / CaO ratio of at least 1.25.

[0058] In some example embodiments, the glass composition can include about 57.5 to about 60.0 wt% Si02, about 19.5 to about 21.0 wt% Al203, about 11.0 to about 13.0 wt% MgO, about 8.0 to about 9.5 wt% CaO, about 0.02 to about 0.25 wt% Na20, 0.5 to about 1.2 wt% Ti02, 0 to about 0.5 wt% Fe203, and no greater than 0.05 wt% Li20. In some example embodiments, the glass composition includes an Al203 / MgO ratio of no greater than 1.8 and a MgO / CaO ratio of at least 1.25.

[0059] The glass composition includes at least 55 percent by weight, but no greater than 65 percent by weight, of Si02. Inclusion of greater than 65 percent by weight of Si02results in an increase in viscosity of the glass composition to an unfavorable level. Further, inclusion of less than 55 percent by weight of Si02increases the liquidus temperature and the tendency to crystallize. In some exemplary embodiments, the glass composition includes at least 57 percent by weight of Si02, including at least 57.5 percent by weight, at least 58 percent by weight, at least 58.5 percent by weight, and at least 59 percent by weight. In some exemplary embodiments, the glass composition includes no greater than 60.5 percent by weight of Si02, including no greater than 60.3 percent by weight, no greater than 60.2 percent by weight, no greater than 60 percent by weight, no greater than 59.8 percent by weight, and no greater than 59.5 percent by weight.

[0060] To achieve both desirable mechanical properties and fiberization properties, one important aspect of the glass composition is to have a concentration of AI2O3 of at least 19.0 percent by weight and no greater than 27 percent by weight. Inclusion of greater than 27 percent by weight of AI2O3 results in an increase in the glass liquidus to a level above the fiberization temperature, which results in a negative ΔΤ. Inclusion of less than 19 percent by weight of AI2O3 results in glass fibers having an unacceptably low modulus. In some exemplary embodiments, the glass composition includes at least 19.5 percent by weight of AI2O3, including at least 19.7 percent by weight, at least 20 percent by weight, at least 20.25 percent by weight, and at least 20.5 percent by weight.

[0061] The glass composition desirably includes at least 8.0 percent by weight and no greater than 15 percent by weight of MgO. Inclusion of greater than 15 percent by weight of MgO results in an increase in the liquidus temperature, which also increases the tendency of the glass to crystallize. If replaced with CaO, inclusion of less than 8.0 percent by weight results in glass fibers having an unacceptably low modulus, and if replaced with Si02, the viscosity is undesirably increased. In some exemplary embodiments, the glass composition includes at least 9.5 percent by weight of MgO, including at least 10 percent by weight, at least 10.5 percent by weight, at least 11 percent by weight, at least 11.10 percent by weight, at least 11.25 percent by weight, at least 12.5 percent by weight, and at least 13 percent by weight of MgO.

[0062] Another important aspect of the present subject glass compositions that enable desirable mechanical and fiberization properties is having an AI2O3 / MgO ratio of no greater than 2.0. It has been found that glass fibers having similar compositional ranges in other respects but an AI2O3 / MgO ratio greater than 2.0 are not able to achieve a tensile strength of at least 4800 MPa, according to ASTM D2343-09. In certain exemplary aspects, the combination of an AI2O3 concentration of at least 19 wt% and an AI2O3 / MgO ratio of no greater than 2 (e.g., no greater than 1.9 and no greater than 1.85) enables glass fibers having desirable fiberization properties and a tensile strength of at least 4800 MPa, according to ASTM D2343-09.

[0063] The glass compositions advantageously include at least 7.0 wt% and no greater than 12 wt% CaO. Including greater than 12 wt% CaO forms a glass having a low modulus of elasticity. Including less than 7 wt% calcium oxide will disadvantageously increase the liquidus temperature or viscosity, depending on what the CaO is replaced with. In some exemplary embodiments, the glass compositions include at least 8.0 wt% CaO, including at least 8.3 wt%, at least 8.5 wt%, at least 8.7 wt%, and at least 9.0 wt%.

[0064] In some exemplary embodiments, the total amount of SiO2, AI2O3, MgO, and CaO is at least 98 wt%, or at least 99 wt%, and no greater than 99.5 wt%. In some exemplary embodiments, the total amount of SiO2, AI2O3, MgO, and CaO is 98.3 wt% to 99.5 wt%, including 98.5 wt% to 99.4 wt% and 98.7 wt% to 99.3 wt%.

[0065] In some exemplary embodiments, the total concentration of MgO and CaO is at least 10 wt% and no greater than 22 wt%, including 13 wt% to 21.8 wt% and 14 wt% to 21.5 wt%. In some exemplary embodiments, the total concentration of MgO and CaO is at least 20 wt%.

[0066] The glass compositions can include up to about 2.0 wt% TiO2. In some exemplary embodiments, the glass compositions include about 0.01 wt% to about 1.0 wt% TiO2, including about 0.1 wt% to about 0.8 wt% and about 0.2 wt% to about 0.7 wt%.

[0067] The glass compositions can include up to about 2.0 wt% Fe2O3. In some exemplary embodiments, the glass compositions include about 0.01 wt% to about 1.0 wt% Fe2O3, including about 0.05 wt% to about 0.6 wt% and about 0.1 wt% to about 0.5 wt%.

[0068] In some example embodiments, the glass composition includes less than 2.0 wt.% of alkali metal oxides Na20 and K20, including 0 to 1.5 wt.%. The glass composition can advantageously include both Na20 and K20, with the amount of each oxide greater than 0.01 wt.%. In some example embodiments, the glass composition includes about 0 to about 1 wt.% of Na20, including about 0.01 to about 0.5 wt.%, about 0.03 to about 0.3 wt.% and 0.04 to about 0.1 wt.%. In some example embodiments, the glass composition includes about 0 to about 1 wt.% of K20, including about 0.01 to about 0.5 wt.%, about 0.03 to about 0.3 wt.% and 0.04 to about 0.1 wt.%.

[0069] Example Glass Composition II

[0070] In some example embodiments, the high performance glass fiber is formed from a glass composition including at least 57 wt.% but not greater than 62 wt.% of Si02. In some example embodiments, the glass composition includes at least or greater than 57.25 wt.% of Si02, including at least or greater than 57.5 wt.%, at least or greater than 58 wt.% and at least or greater than 58.25 wt.%. In some example embodiments, the glass composition includes not greater than 60.5 wt.% of Si02, including not greater than 60.3 wt.%, not greater than 60.2 wt.%, not greater than 60 wt.%, not greater than 59.8 wt.% and not greater than 59.5 wt.%. In some example embodiments, the glass composition includes 57.5 wt.% to less than 59 wt.% of Si02.

[0071] In these or other example embodiments, to achieve the desired mechanical and fiberization properties, one important aspect of the glass composition is that the Al203concentration is at least 19.0 wt.% and not greater than 25.0 wt.%. Including less than 19.0 wt.% of Al203can result in the formation of glass fibers having an undesirably low modulus. In some example embodiments, the glass composition includes at least 19.5 wt.% of Al203, including at least 19.7 wt.%, at least 20.0 wt.%, at least 20.05 wt.% and at least 20.10 wt.%. In some example embodiments, the glass composition includes not greater than 22.0 wt.% of Al203, including not greater than 21.8 wt.%, not greater than 21.6 wt.%, not greater than 21.2 wt.%, not greater than 21.1 wt.% and not greater than 21 wt.%. In some example embodiments, the glass composition includes 20.0 wt.% to less than 21 wt.% of Al203. Including higher levels of Al203can increase the tendency to crystallize.

[0072] The glass composition advantageously includes at least 8.0 wt.% and no greater than 15 wt.% MgO. Including greater than 15 wt.% MgO will result in an elevated liquidus temperature, which also increases the glass' crystallization tendency. If replaced with CaO, including less than 8.0 wt.% will result in a glass fiber with an undesirably low modulus, and if replaced with Si02, the viscosity is undesirably increased. In some example embodiments, the glass composition includes at least 9.5 wt.% MgO, including at least 10 wt.%, at least 10.5 wt.%, at least 11 wt.%, at least 11.10 wt.%, and at least 11.20 wt.% MgO. In some example embodiments, the glass composition includes no greater than 12.5 wt.% MgO, such as no greater than 12.0 wt.%, no greater than 11.9 wt.%, or no greater than 11.8 wt.%. In various example embodiments, the glass composition has a MgO concentration of 10.5 wt.% to less than 12.0 wt.%.

[0073] The glass composition advantageously includes at least 7.0 wt.% and no greater than 12 wt.% CaO. Including greater than 12 wt.% CaO will result in a glass with a low elastic modulus. Including less than 7 wt.% will undesirably increase the liquidus temperature or viscosity, depending on what oxide the CaO is replaced with. In some example embodiments, the glass composition includes at least 8.0 wt.% CaO, including at least 8.1 wt.% and at least 8.2 wt.%. In some example embodiments, the glass composition includes no greater than 11.5 wt.% CaO, such as no greater than 10.0 wt.%, no greater than 9.8 wt.%, no greater than 9.5 wt.%, and no greater than 9.0 wt.%. In various example embodiments, the glass composition has a CaO concentration of 7.9 wt.% to less than 9.0 wt.%.

[0074] In some example embodiments, the total amount of Si02, AI2O3, MgO, and CaO is at least 98 wt.%, or at least 99 wt.%, and no greater than 99.5 wt.%. In some example embodiments, the total amount of Si02, AI2O3, MgO, and CaO is 97.5 wt.% to less than 99.5 wt.%, including 98.0 wt.% to less than 99.0 wt.%, and 98.05 wt.% to 98.8 wt.%.

[0075] The glass composition can include from 0 to about 2.0 wt.% Li20. The presence of Li20 decreases the fiberizing temperature of the glass composition and increases the modulus of elasticity of the glass fibers formed therefrom. In some exemplary embodiments, the glass composition includes from about 0.2 wt.% to about 1.0 wt.% Li20, including from about 0.4 wt.% to 0.8 wt.% and from about 0.5 wt.% to about 0.7 wt.%. In some exemplary embodiments, the glass composition includes greater than 0.45 wt.% and less than 0.8 wt.% Li20.

[0076] The glass composition can include up to about 2.0 wt.% Ti02. In some exemplary embodiments, the glass composition includes from about 0.05 wt.% to about 1.5 wt.% Ti02, including from about 0.4 wt.% to about 1.0 wt.% and from about 0.5 wt.% to about 0.7 wt.%.

[0077] The glass composition can include up to about 2.0 wt.% Fe203. In some exemplary embodiments, the glass composition includes from about 0.05 wt.% to about 1.0 wt.% Fe203, including from about 0.2 wt.% to about 0.8 wt.% and from about 0.3 wt.% to about 0.6 wt.%.

[0078] In some exemplary embodiments, the glass composition includes less than 2.0 wt.% of the alkali oxides Na20 and K20, including from 0 to 1.5 wt.%. The glass composition can advantageously include both Na20 and K20, and the amount of each oxide is greater than 0.01 wt.%. In some exemplary embodiments, the glass composition includes from about 0 to about 1 wt.% Na20, including from about 0.01 to about 0.5 wt.%, from about 0.03 to about 0.3 wt.% and from 0.04 to about 0.1 wt.%. In some exemplary embodiments, the glass composition includes from about 0 to about 1 wt.% K20, including from about 0.01 to about 0.5 wt.%, from about 0.03 to about 0.3 wt.% and from 0.04 to about 0.2 wt.%.

[0079] Optional Additives

[0080] In some example embodiments, the glass composition forming high- performance glass fibers can also include impurities and / or trace materials without adversely affecting the glass or fiber. These impurities can enter the glass as raw material impurities or can also be products of chemical reactions of the molten glass with the furnace composition. Non-limiting examples of trace materials include zinc, strontium, barium, and combinations thereof. The trace materials can be present as their oxides and can also include fluorine and / or chlorine. In some example embodiments, the glass composition of the present disclosure includes less than 1.0 wt. % of each of BaO, SrO, ZnO, Zr02, P205, and SO3, including less than 0.5 wt. %, less than 0.2 wt. %, and less than 0.1 wt. %. In particular, the glass composition can include less than about 5.0 wt. % of a combination of BaO, SrO, ZnO, Zr02, P205, and / or SO3, wherein each of BaO, SrO, ZnO, Zr02, P205, and SO3, if present, is present in an amount less than 1.0 wt. %.

[0081] In some example embodiments, the glass composition forming high- performance glass fibers includes less than 2.0 wt. % of the following modifying components (collectively): Ce02, Li20, Fe203, Ti02, W03, and Bi203. In some example embodiments, the glass composition includes less than 1.5 wt. % of the modifying components.

[0082] In some example embodiments, the glass composition forming high- performance glass fibers includes less than 1.0 wt. % of rare earth oxides: Y203, Ga203, Sm203, Nd203, La203, Ce203, and Sc203 (“R203”) and Ta205, Nb205, or V205 (“R205”), including 0 to 0.9 wt. %, or 0 to 0.5 wt. %. In some example embodiments, the glass composition is free of rare earth oxides.

[0083] As used herein, the terms “percent by weight,” “wt. %,” “wt. %,” and “percent by weight” can be used interchangeably and are intended to mean percent by weight (or weight percent) based on the total composition.

[0084] Resin binder

[0085] High performance input glass fibers are held together by a resinous binder, also referred to as a matrix resin, which when cured (as described below) fixes the fibers relative to one another and forms a high modulus composite material. In some example embodiments, the resinous binder includes one or more of polyester (PE) resin, vinyl ester (VE) resin, acrylic resin, polyurethane resin, and epoxy (EP) resin, which are common matrix resins or binders used to form polymer composites. In some example embodiments, the resinous binder includes one of a vinyl ester and an epoxy resin. Since the composite material is often used as a reinforcement in harsh or otherwise corrosive environments, such as near seawater, it is an important design consideration to select a resin that can withstand such environments.

[0086] It has been found that proper formulation or modification of the vinyl ester resin is important. For example, a small amount of added polyurethane or phenol-formaldehyde resin or acrylic interpenetrating network or other reactive monomer modification for styrene can further enhance corrosion resistance. High corrosion resistance can be further improved by removing resin from the resin-rich surface of the tendon and / or applying hydration inhibitors such as acrylate, vinyl chloride, octylsilane, and / or silylated polyazamide. Such additives work in conjunction with the concrete, for example, as a barrier to the composite material at the interface with the concrete to achieve further corrosion resistance.

[0087] Other additives can also be further included, such as octanoate salts of n,n-dimethylethanolamine or morpholine-related amines, which are effective surface corrosion inhibitors, can be applied as a coating to the reinforcing tendon to provide an improved concrete bonding interface. Other migrating agents can also be applied at the reinforcing tendon interface during concrete crack initiation to block further corrosion. In addition, certain glass fiber interface sizing components, such as one or more of acrylic acid, salts, sodium or ammonium tetrafluoroborate, or cross-linking agents pentaerythritol or itaconic acid, or highly cross-linked silane / silanol (such as octylsilane) form a stable passivation layer or can work with the glass polycondensed silicate surface together as an interface metamict layer to block or inhibit water and alkali intrusion. The glass / metamict layer interface is more effective than the glass itself in preventing water intrusion. Water mobility in both pristine and metamict glasses is strongly affected by chemical interactions with the solid phase. Under silica-saturated conditions, the reorganized metamict layer achieves equilibrium with bulk and pore solutions, and due to transport limitation effects near the glass surface, the residual corrosion rate is significantly reduced. For stable passivation layers, ideal conditions are typically below 90 °C and 7 < pH < 9.5, silica-saturated solutions, which are optimal for concrete hydration at the adhesive interface with the reinforcing tendon.

[0088] Other additives can include multifunctional fillers for various purposes, such as color and surface aesthetics, adhesion / cohesion properties for strength and toughness, reduced shrinkage, UV resistance, corrosion resistance, and consolidation uniformity with consistent part tolerances. Exemplary fillers can include carbon black, iron black, aluminum trihydrate, calcium carbonate, metal salts of fatty acids (including zinc stearate and calcium stearate), and clays (e.g., kaolin). The specific physical properties and functional properties of the fillers, as well as the amount of filler in the composite part, can be adjusted to achieve the desired attributes or functional purposes.

[0089] The amount of filler that can be included in the high modulus composite parts is about 0 to 20 phr, including about 3 to about 16 phr, about 5 to about 13 phr, and about 6 to about 10 phr. In some exemplary embodiments, the filler is included in the high modulus composite parts in an amount of 10 to 16 phr.

[0090] In some exemplary embodiments, the inclusion of about 5-10 phr of clay filler in a high modulus vinyl ester composite part having a glass content of 71% by volume improves consolidation uniformity and reduces shrinkage while maintaining a tensile strength greater than 1000 MPa, and in some cases greater than 1200 MPa, according to ASTM-D7205.

[0091] Pultrusion process

[0092] The high modulus composites of the present disclosure are formed by a pultrusion process. The pultrusion process is performed by a pultrusion line, system, or the like. In some exemplary embodiments, the pultrusion process is used to form a composite reinforcement bar. As shown in FIGS. 1-2, a pultrusion line 100 can be used to form a composite reinforcement bar 190 according to exemplary embodiments. The pultrusion line 100 includes a feed module 110, a resin bath 120, an optional in-line winder 130, one or more preform machines 140, one or more dies 150, a control station 160, a pull section 170, and a cutting section 180. As further described below, a surface treatment station (not shown) can also be provided. The surface treatment can be performed before and / or after the pultruded rod is cut at the cutting section 180. Figure 1A and 1B As shown in FIGS. 4-5, a pultrusion line 400 can be used to form a composite reinforcement bar 490 according to exemplary embodiments. The pultrusion line 400 includes a feed module 410, a resin bath 420, an optional in-line winder 430, one or more preform machines 440, one or more dies 450, a control station 460, a pull section 470, and a cutting section 480. As further described below, a surface treatment station (not shown) can also be provided. The surface treatment can be performed before and / or after the pultruded rod is cut at the cutting section 480.

[0093] The pultrusion line 400 ensures careful control of the input materials (e.g., glass fibers) and their associated processing in the fiber feed, resin formulation, resin impregnation, fiber structure, alignment through the preform machines, drying and heating, wetting, wet-out, consolidation, and curing to form a continuous rod.

[0094] The feed module 410 organizes the input materials, for example, a batch of roving 402 of glass fibers 404 (e.g., 406) located on a creel 408, and the like. Rovings, which can be obtained from Owens Corning, Toledo, Ohio, are used in the pultrusion process. The rovings 402 can be single-end rovings and / or multi-end rovings.

[0095] In one exemplary embodiment of the feed module 410, as shown in FIG. 4, the rovings 402 are fed in a pultrusion direction 408 toward a resin bath 420. The rovings 402 are fed through a cage 412, which is a structure that holds the rovings 402 in place and positions the ends of the rovings 402 close to each other. The cage 412 is used to position the ends of the rovings 402 close to each other before the ends of the rovings 402 are fed through a guide 416. The guide 416 is used to position the ends of the rovings 402 in a parallel orientation with respect to each other. The guide 416 is also used to position the ends of the rovings 402 close to each other. The guide 416 is used to position the ends of the rovings 402 close to each other and in a parallel orientation with respect to each other before the ends of the rovings 402 are fed through a resin bath 420. The resin bath 420 is used to impregnate the rovings 402 with resin. The impregnated rovings 402 are then fed through a die 424, which is used to form the final product 426. Figure 1A 1B As shown, multiple rovings 402 are used depending on the desired rod diameter. One end of each roving 402 is fed in the pultrusion direction 408 toward the resin bath 420.

[0096] In this embodiment, the fibers 404 are fed through the cage 412 or other structure so that the fibers 404 engage the mandrel 414 disposed therein. The mandrel 414 imparts an initial tension to the fibers 404 as the fibers 404 are drawn through the cage 412. The cage 412 is also used to begin positioning the ends of the fibers 404 close to each other before the ends of the fibers 404 are fed through the guide 416.

[0097] The guide 416 includes multiple holes. One end of each fiber 404 is fed through one of the holes in the guide 416. In this way, as the fibers 404 are drawn in the processing direction 408, the fibers 404 are positioned closer to each other and in a parallel orientation with respect to each other. Thus, as the fibers 404 exit the guide 416, they have begun to form a rope-like member 418 (hereinafter referred to as a “rope”).

[0098] The rope 418 is then drawn through the resin bath 420 so that the resin in the resin bath 420 surrounds the rope 418 and infiltrates the spaces between the fibers 404 that form the rope 418. The rope 418 exits the resin bath 420 as an impregnated rope 422.

[0099] ​The resin bath 420 contains a vinyl ester or modified thermoset resin with an elongation at break greater than 4%. Importantly, the resin has a low cure shrinkage (e.g., 3-7%, depending on formulation) without significant residual stresses that cause voids, chipping, or splitting, leading to premature failure or durability issues due to the loading environment. In one exemplary embodiment, the resin composition is a modified resin based on an Ashland 1398 vinyl ester resin matrix (provided by Ashland Inc. of Covington, KY) or Interplastic 692 or 433 (provided by Interplastic Corporation of St. Paul, MN) with a crosslink density set by the ratio of added styrene monomer for free radical autocatalytic cure to achieve a Tgin the range of 100°C to 130°C. Substitution of acrylic, phenolic, or dicyclopentadiene (DCPD) monomers for a portion (e.g., 10% to 30%) of the styrene can improve toughness, moisture resistance, and meet fire smoke toxicity (FST) standards. The design choices for these resin compositions should be balanced with their cost and impact on the following properties: Tg, modulus, and chipping / cracking in a rod cross section greater than 0.8 mm due to too high a cure rate.

[0100] Vinyl ester resin FFU Test standard Performance Durability - no polyester ASTM D7957 5.2 Meets physical and durability requirements Glass transition (or HDT) ASTM E1356 T g >120°C Tensile elongation or break ASTM D638 >4.5％ Tensile modulus ASTM D638 >3200 MPa Volume shrinkage <7％

[0101] As described above, the glass fibers 404 from the feed module 410 pass through the resin bath 420 such that the glass fibers 404 are coated (i.e., wetted) with resin and the spaces between adjacent fibers are sufficiently filled (i.e., wet through or saturated) with resin. More specifically, the pultrusion production line 400 uses a multi-stage preform in which the glass fibers 404 are aligned vertically and horizontally so as to be positioned in a preform machine 440 after they pass through the resin bath 420. In this way, each discrete stage of the pultrusion production line 400 merges the respective fiber bundles into a glass content of 70% or greater by weight, 80% or greater, or 83% or greater by weight, or a glass content of 68% or greater by volume as the fibers 404 pass through the die 450.

[0102] The preform machine 440 facilitates the positioning and alignment of the input materials, including the resin. The preform machine 440 also facilitates the stacking of the fibers together in a manner that avoids bunching, tangling, and other undesirable issues with the input materials.

[0103] The use of multi-stage preforming also enables the selective placement of different types of fibers (e.g., glass and carbon fibers, combinations of different glass types, combinations of different fiber diameters) so as to produce hybrid rods, improving the elastic modulus or other properties. The use of different fiber diameters in the input materials can also facilitate an increase in the input material content.

[0104] In the pultrusion line 400, an in-line winder 430 (e.g., one or more idler rollers) can be used as a tension adjustment device. For example, the winder 430 can be used if greater tension is needed early in the pultrusion process (e.g., to pull the glass fibers 404 through the resin bath 420). Additionally, the ability to adjust the tension on the glass fibers 404 can facilitate the consolidation / stacking of the glass fibers 404 prior to entering the preformer 440.

[0105] The pultrusion line 400 employs preforming, preheating, and prewetting of the continuous collimated roving to consolidate to greater than 85% by weight glass content and with high alignment (i.e., less than 5 degrees of misalignment, uniformly through the cross-section).

[0106] In some example embodiments, one or more stripper dies 450 are used prior to the pultrusion die 452. In some example embodiments, the stripper dies 450 and the pultrusion die 452 are the same set of dies. When multiple stripper dies 450 are used, the holes in each stripper die 450 will typically be smaller than the holes in the previous stripper die 450. The stripper dies 450 remove excess resin from the impregnated fibers and further consolidate the fibers 404 as the rod 454 is formed.

[0107] Preheating of the glass can drive off residual moisture and can lower the resin viscosity at the glass surface to improve wetting and permeation. Any suitable means of applying heat to the glass can be utilized. Such preheating can occur at multiple locations along the pultrusion line 400.

[0108] Prewetting of the glass fibers is facilitated by direct heating of the resin or otherwise controlling the viscosity of the resin in the impregnation bath 420, or by application at a location in the preformer 440 to better achieve resin wetting to achieve more consolidated consolidation by restriction and / or tension prior to the vinyl ester resin gelling. Alternatively, heating can be achieved by indirect (e.g., radio frequency) heating, which can allow more uniform heating from the inside out. Different glass tex and filament diameter combinations can be used to further improve uniform glass stacking to achieve higher glass fiber volume.

[0109] Once into the die 450, 452 as the final consolidation point, heat from the die 450 and / or 452 causes the thermoset resin to crosslink, resulting in an exotherm within the consolidated fibers 422 to form a rod-like member 454 (herein referred to as a "rod"). In some example embodiments, a helical wrap (e.g., of glass fibers) is applied to the rod 454 to maintain the consolidation and arrangement of the fibers 404 within it.

[0110] The pultrusion line 400 typically includes a control station 460 either as part of the pultrusion line 400 or located nearby (e.g., on site). The control station 460, which can be a distributed control system (DCS), allows for computerized and / or manual control and management of the pultrusion line 400 and related process variables and conditions.

[0111] The rod 454 exits the pultrusion die 452 and advances toward the puller system 470. The rod 454 cools as it reaches the puller system 470 so that it does not deform at the puller contact point. The puller section 470 helps to apply the pulling force required for the pultrusion process, i.e., to maintain the necessary tension on the rod 454 as it is formed.

[0112] Finally, the rod 454 advances to the cutting section 480, where it is cut to length and collected for further processing, such as surface treatment operations. The rod 454 can be cut to any suitable length, which is typically determined by the intended application. In some example embodiments, the rod 454 is cut to a length of 10 feet to 75 feet. In some example embodiments, the rod 454 is cut to a length of 20 feet to 60 feet. Once cut, the rod 454, with or without any further processing, is considered a composite reinforcement 490.

[0113] Thus, the pultrusion line 400 employs pre-forming, pre-heating, and pre-wetting of continuous collimated roving to consolidate to greater than 85 wt% glass content and with high alignment (less than 5 degrees of misalignment, uniformly through the cross-section) in combination with high performance glass fibers to achieve high modulus composites with increased modulus of at least 60 GPa.

[0114] In some example embodiments, at least a portion of the rod cross-section can be hollow or foam cored rather than solid, such as by using suitable mold structures and / or configurations or other processing techniques.

[0115] High modulus composite components

[0116] High modulus composites can be formed that include fiber reinforcement at various fiber weight fractions ("FWF"). While the FWF can vary anywhere between greater than 1% to about 90%, certain example embodiments include an FWF of at least 70%, including at least 72%, at least 75%, at least 77%, and at least 80%. In any example embodiment, the high modulus composite can have an FWF of 75% to 90%, including 77% to 88%, and 80% to 86%.

[0117] High modulus composite materials formed in accordance with the inventive concept have improved physical properties and corrosion resistance compared to reinforced composites formed using conventional ECR-type glass fibers. As noted above, high modulus composite parts include an improved modulus of elasticity of at least 60 GPa, including at least 64 GPa, at least 65 GPa, at least 66 GPa, and at least 68 GPa. In some exemplary embodiments, high modulus composite parts include a modulus of elasticity of 60 GPa to 75 GPa, including 64 GPa to 73 GPa, and 65 GPa to 70 GPa. The modulus of elasticity of the composite parts is measured in accordance with ASTM D7205.

[0118] In some exemplary embodiments, high modulus composites formed in accordance with the inventive concept include a flexural modulus of at least 50 GPa, including at least 52 GPa, at least 55 GPa, and at least 56 GPa. High modulus composites formed in accordance with the inventive concept include an improved flexural strength of at least 1220 MPa, including at least 1250 MPa, at least 1285 MPa, at least 1300 MPa, at least 1350 MPa, at least 1400 MPa, at least 1450 MPa, at least 1500 MPa, and at least 1550 MPa. Both flexural modulus and flexural strength are measured in accordance with ASTM D790.

[0119] In some exemplary embodiments, high modulus composites formed in accordance with the inventive concept include a tensile modulus of at least 50 GPa, including at least 62 GPa, at least 65 GPa, at least 67 GPa, and at least 70 GPa. In some exemplary embodiments, the high modulus composites have a tensile modulus of about 60 to about 75 GPa. The tensile modulus of the composite parts is measured in accordance with ASTM D7205.

[0120] In some exemplary embodiments, high modulus composites formed in accordance with the inventive concept have high corrosion resistance, which extends the life of the composite parts.

[0121] Example

[0122] It is understood that the scope of the general inventive concept is not intended to be limited to the particular exemplary embodiments shown and described herein. From the given disclosure, one skilled in the art will not only understand the general inventive concept and its attendant advantages, but will also find apparent various

[0123] Example 1

[0124] Exemplary fiber-reinforced pultruded reinforcement members were prepared that included fiber reinforcements at various fiber weight fractions ("FWF"). Samples were prepared with high performance glass ("HP glass") having an elastic modulus of 89.5 GPa and conventional E-CR glass having an elastic modulus of 82 GPa. Figure 2 The elastic modulus of the reinforcement samples at different fiber loading levels was shown. As shown, the reinforcement samples including HP glass achieved higher elastic modulus than the reinforcement samples including E-CR glass at the same loading level. For example, an E-CR glass reinforced reinforcement having a fiber weight fraction of 0.843 achieved an elastic modulus of 64.6 GPa (No. 6 reinforcement having a cross-sectional area of 283.9 mm 2 at the same fiber loading level.

[0125] Example 2

[0126] Exemplary fiber-reinforced pultruded plaques were prepared that included both: 1) HP glass fibers and 2) conventional E-CR glass fibers. The pultruded plaques included unidirectional fibers at a loading level of 80% FWF. Two different resins were used in the testing, polyester and polyurethane. The pultruded parts were then tested for performance, including flexural modulus and flexural strength, in accordance with ASTM-D790; tensile modulus in accordance with ASTM D7205, and interlaminar shear strength ("ILSS") in accordance with ASTM D2344. The test results are shown in Figures 3-6.

[0127] Figure 3A and 3B The flexural modulus of pultruded plaques including E-CR unidirectional fibers was shown in comparison to pultruded plaques including HP fibers, in both unsaturated polyester and polyurethane resins. As shown, the HP reinforced plaques exhibited an 14% increase in flexural modulus in polyester resin and a 10% increase in polyurethane resin compared to the E-CR reinforced plaques. The exemplary HP reinforced plaques achieved a flexural modulus of 56 GPa in unsaturated polyester and 59 GPa in polyurethane.

[0128] Figure 4A and 4B The flexural strength of pultruded plaques including E-CR unidirectional fibers was shown in comparison to pultruded plaques including HP fibers, in both unsaturated polyester and polyurethane resins. As shown, the HP reinforced plaques exhibited an 8% increase in flexural strength in polyester resin and a 4% increase in polyurethane resin compared to the E-CR reinforced plaques. The exemplary HP reinforced plaques achieved a flexural strength of 1296 MPa in unsaturated polyester and 1572 MPa in polyurethane.

[0129] Figure 5A and 5B Tensile modulus of pultruded plaques containing E-CR unidirectional fibers is shown in comparison to pultruded plaques containing HP fibers in unsaturated polyester and polyurethane resins. As shown, HP reinforced plaques exhibit a 13% increase in tensile modulus in polyester resin and an 8% increase in polyurethane resin compared to E-CR reinforced plaques. Exemplary HP reinforced plaques achieve a tensile modulus of 70 GPa in unsaturated polyester and 62 GPa in polyurethane.

[0130] Figure 6A and 6B Interlaminar shear strength (ILSS) of pultruded plaques containing E-CR unidirectional fibers is shown in comparison to pultruded plaques containing HP fibers in unsaturated polyester and polyurethane resins. Since ILSS is mainly dependent on the resin, the results indicate compatibility at the glass / resin interface. Exemplary HP reinforced plaques achieve an ILSS of 50 MPa in unsaturated polyester and 81 MPa in polyurethane, which is consistent with (and actually slightly improved from) plaques formed using E-CR glass.

[0131] The application of the present application is described generally above and with respect to specific embodiments. Although the present application has been set forth in what is believed to be the preferred embodiments, a wide variety of alternatives known to those of skill in the art can be selected within the general disclosure. The application is not otherwise limited as set forth in the following claims.

Claims

1. A high-modulus composite material component, comprising: Polymer resins; and Multiple high-performance unidirectional glass fibers having an elastic modulus of at least 89 GPa and a tensile strength of at least 4800 MPa, according to ASTM D2343-09; the composite component having a fiber weight fraction of no more than 88% and an elastic modulus of at least 60 GPa, according to ASTM D7205; The high-performance unidirectional glass fiber is formed from a composition comprising: 55.0 to 65.0 wt% SiO2, 19.0 to 27.0 wt% Al2O3, 10.5 to 15.0 wt% MgO, 7.0 to 12.0 wt% CaO, 0.0 to 1.0 wt% Na2O, 0 to 2.0 wt% TiO2, and 0 to 2.0 wt% Fe2O3; wherein the composition has an Al2O3 / MgO ratio of not more than 2.

0. The high-modulus composite component described herein has a flexural modulus of at least 50 GPa, according to ASTM D790; and The high-modulus composite component described therein has a tensile modulus of at least 50 GPa, according to ASTM D7205.

2. The high modulus composite material component according to claim 1, wherein the polymer resin is selected from one or more of the following: polyurethane resin, acrylic resin, polyester resin, vinyl ester resin, and epoxy resin.

3. The high-modulus composite material component of claim 1, wherein the high-modulus composite material component is used in infrastructure.

4. The high modulus composite material component of claim 1, wherein the high modulus composite material component is used in telecommunications applications.

5. The high modulus composite material component according to claim 1, wherein the high modulus composite material component is selected from any one of the following: reinforcing ribs, railings, utility poles, pipes, crossarms, cables, and ladder railings.

6. The high-modulus composite material component according to claim 1, wherein the elastic modulus of the high-performance glass fiber is at least 90 GPa.

7. The high-modulus composite material component according to claim 1, wherein the specific modulus of the high-performance glass fiber is from 32.0 MJ / kg to 37.0 MJ / kg.

8. The high modulus composite component of claim 1, wherein the high modulus composite component has an elastic modulus of at least 60 GPa, according to ASTM D7205.

9. A method for forming a high-modulus composite material component, comprising: A bundle of high-performance unidirectional glass fibers is drawn from an input source, the fibers having an elastic modulus of at least 89 GPa and a tensile strength of at least 4800 MPa, according to ASTM D2343-09; The bundle is passed through a polymer resin material bath to form a resin-coated bundle; The resin-coated bundle is pulled through the molding die; and The resin-coated bundles are cured to form a high-modulus composite component having a fiber weight fraction of no more than 88% and an elastic modulus of at least 60 GPa, according to ASTM D7205; The high-performance unidirectional glass fiber is formed from a composition comprising: 55.0 to 65.0 wt% SiO2, 19.0 to 27.0 wt% Al2O3, 10.5 to 15.0 wt% MgO, 7.0 to 12.0 wt% CaO, 0.0 to 1.0 wt% Na2O, 0 to 2.0 wt% TiO2, and 0 to 2.0 wt% Fe2O3; wherein the composition has an Al2O3 / MgO ratio of not more than 2.

0. The high-modulus composite component described herein has a flexural modulus of at least 50 GPa, according to ASTM D790; and The high-modulus composite component described therein has a tensile modulus of at least 50 GPa, according to ASTM D7205.

10. The method according to claim 9, wherein the polymer resin is selected from one or more of the following: polyester resin, vinyl ester resin, and epoxy resin.

11. The method of claim 9, wherein the high-modulus composite component is used in infrastructure.

12. The method of claim 9, wherein the high-modulus composite material component is used in telecommunications applications.

13. The method according to claim 9, wherein the high modulus composite material component is selected from any of the following: reinforcing ribs, railings, utility poles, pipes, crossarms, cables, and ladder railings.

14. The method of claim 9, wherein the high-performance glass fiber has an elastic modulus of at least 90 GPa.

15. The method of claim 9, wherein the high-performance glass fiber has a specific modulus of 32.0 MJ / kg to 37.0 MJ / kg.

16. The method of claim 9, wherein the high modulus composite component has an elastic modulus of at least 60 GPa, according to ASTM D7205.

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