Radiation cured composite materials
11485829 · 2022-11-01
Assignee
Inventors
Cpc classification
C08J5/04
CHEMISTRY; METALLURGY
C08J3/28
CHEMISTRY; METALLURGY
International classification
Abstract
Radiation cured composite materials are greatly improved by enhancing the fiber to matrix bond by prewetting the fibers with an interface resin that has a curing agent mixed in with the interface resin. Furthermore, radiation curing the composite material at or near an expected operating temperature of the composite material improves the mechanical properties of the material by reducing thermally induced strains and stresses caused by thermally curing a material and subsequently cooling the material. Adding an interface resin with a curing agent to the fibers allows relatively thick parts, a must faster curing process, a wide variety of inexpensive and easily workable molding materials, the ability to maintain tight tolerances and reduce or eliminate springback, and a radiation cured material that approaches or exceeds the material characteristics of thermally cured composite materials.
Claims
1. A process, comprising: wetting a reinforcing fiber with a first liquid polymer material, the first liquid polymer material having a first curing agent mixed therein; forming the reinforcing fiber into a desired shape; applying a second liquid polymer material, the second liquid polymer material having a second curing agent mixed therein; and applying radiation to the reinforcing fiber, the first liquid polymer and the second liquid polymer to cause the first liquid polymer and the second liquid polymer to cure into a hardened form.
2. The process of claim 1, wherein the process is performed at ambient temperature.
3. The process of claim 1, wherein the step of applying radiation is performed at a temperature below ambient temperature.
4. The process of claim 1, further comprising cooling the reinforcing fiber, the first liquid polymer, and the second liquid polymer to a temperature below 10° C. prior to the step of applying radiation.
5. The process of claim 1, wherein the step of applying radiation is performed at a temperature selected to approximate an environmental temperature where the hardened form will be used.
6. The process of claim 1, wherein the first liquid polymer material and the second liquid polymer material are different materials.
7. The process of claim 1, wherein the first curing agent and the second curing agent are different materials.
8. The process of claim 1, wherein the step of applying radiation is performed while the step of forming the reinforcing fiber into the desired shape is being performed.
9. The process of claim 1, wherein the step of applying radiation is repeated two or more times.
10. The process of claim 1, wherein the step of applying radiation to the reinforcing fiber is a first dose of radiation, and further comprising applying a second dose of radiation to the reinforcing fiber, the first liquid polymer and the second liquid polymer.
11. The process of claim 10, wherein the first dose of radiation is at a first intensity, and wherein applying the second dose of radiation is performed at a second intensity different from the first intensity.
12. The process of claim 1, wherein the step of applying radiation to the reinforcing fiber, the first liquid polymer and the second liquid polymer is performed by pulsing a radiation source.
13. The process of claim 1, further comprising the step of storing the reinforcing fiber after the step of wetting the reinforcing fiber with the first liquid polymer material.
14. The process of claim 1, wherein the step of forming the reinforcing fiber into a desired shape is performed by placing the reinforcing fiber in contact with a mold.
15. The process of claim 14, wherein the mold is one or more of a plastic, a foam, or a wood.
16. The process of claim 1, wherein the first liquid polymer material is a thermoset material.
17. The process of claim 1, wherein the step of applying radiation comprises activating an electron beam.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) A better understanding of the features, advantages and principles of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, and the accompanying drawings of which:
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DETAILED DESCRIPTION
(16) The following detailed description and provides a better understanding of the features and advantages of the inventions described in the present disclosure in accordance with the embodiments disclosed herein. Although the detailed description includes many specific embodiments, these are provided by way of example only and should not be construed as limiting the scope of the inventions disclosed herein.
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(19) Thermally cured composite processes may often include the step of wetting the reinforcing fibers 104 with an interface resin material, which is also a resin. However, the interface resin does not have a curing agent added to it. As a result, the fibers 104 can be woven and have substantial shelf life until combined with the matrix material 102 and therefore subject to the curing agent provided in the matrix material 102. When the combination of fiber, interface resin, and matrix are thermally cured, there is time, temperature, and chemically driven potential that drives the curing agent, a constituent of the matrix 102, into the interface resin. Without a curing agent in the interface resin, the interface resin will not cure properly. This manufacturing process works well with thermally cured composites but is not as effective for radiation-cured composites.
(20) In a radiation cured composite, the curing happens in a matter of minutes and the matrix material does not have sufficient time or chemically driven diffusion potential to permeate the interface resin or the fibers and create a strong bond. Consequently, the interface resin on the fibers does not have access to the curing agent provided with the matrix material to cure as expected, thus causing a poor bond between the interface resin and the matrix material. Moreover, in radiation-cured composites, the curing agent is typically on the order of 1% to 3% of the matrix, in contrast to the upwards of 30% in a thermally curable matrix material. Not only is the chemical driving potential lower, the curing time happens in a matter of minutes, and the temperatures are very low in comparison to thermally cured composites. This makes it difficult for the curing agent to reach the interface resin to support an effective cure for the composite. The result is that typical radiation cured composite materials exhibit poor matrix and fiber adhesion, thus resulting in poor material performance.
(21) In one aspect, adding a curing agent directly into the interface resin material would improve its functioning and the overall matrix dominated material properties, such as improvements in compression, in-plane shear, interlaminar shear, and fracture toughness. For example, pre-wetting the fibers with an interface resin that includes a curing agent and then adding the fibers to the resin matrix would provide substantial improvements to the final product after radiation curing.
(22) As used herein, the term “interface resin” is a broad term and is used to describe any resin that has compatibility with the matrix and with the fiber. In other words, the interface resin is able to wet the fiber to provide good adhesion. In many instances, the interface resin material includes a curing agent and is applied to the reinforcing fibers before the fibers are formed into a desired shape during a manufacturing process. The catalyst may be provided in an amount of from about 0.5% to 10% of the matrix material by volume. In some instances, the catalyst comprises between about 1% and 5% of the matrix material by volume. In other instances, the catalyst is provided from about 1.5% to 3% by volume of the matrix material.
(23) In some embodiments, the reinforcing fibers are wetted with a first matrix material, which may also be referred to as an interface resin material. The first matrix material includes a curing agent. The fibers may therefore be considered to be pre-impregnated with the first matrix material and the curing agent. The pre-impregnated fibers can be stored until ready for use. The pre-impregnated fibers may be used in any suitable manufacturing method and may be incorporated into a second matrix material to provide reinforcement to the second matrix material. The first matrix material of the pre-impregnated fibers may be the same or different than the second matrix material. Similarly, a curing agent in the first matrix material may be the same or a different catalyst than in the second matrix material.
(24) Another disadvantage of thermally cured composite materials results from thermal stresses. As a composite material is cured at high temperature (e.g., typically above 350° F. 180° C. for a thermoset resin and about 700° F. 370° C. for thermoplastics), it experiences a significant change in temperature as it cools. Any change in temperature causes strain and stress in the material. These strains and stresses can lead to unwanted deformation (e.g., warping/bowing), or premature fracture when the thermal stresses are summed to the operating stresses. This phenomenon is compounded as the composite material is used in an environment having temperature gradients or extremely low temperatures when compared to the high thermal curing temperature.
(25) For example, a composite material may be used in an environment that is extremely cold, such as, for example, less than −17° C., or less than −28° C., or colder. In these extreme environments, the thermally cured composite material may accumulate a high amount of thermally induced stress which can lead to degraded performance and/or failure of the material. Furthermore, thermal expansion or contraction of the composite material can lead to significant changes in the shape of the composite material, which may also lead to less than ideal performance characteristics.
(26) An advantage of radiation cured composite materials is the ability to cure the composite material at any desired temperature. For example, where a composite material is formed into a part that is designed to be operated in an environment of around −17° C., the composite material may be formed and subjected to a temperature of −17° C. while it is cured. In this way, once the part is used in its intended operating environment, the internal thermal strains and stresses will be significantly lower than if the part had been cured at an ambient temperature of 24° C., or the typical elevated curing temperature of 180° C. This results in the formed part exhibiting improved material characteristics that are tailored for the intended operating environment. Furthermore, the part can be appropriately sized to meet strict tolerances even as the operating environment has a relatively low temperature. That is, when radiation-curing the part at the temperature of the intended operating environment, the part can be appropriately sized during formation without having to consider any change in shape caused by thermal contraction, which can be a significant issue, especially in thermally cured materials.
(27) In typical thermal curing manufacturing processes, the materials used for forming the PMC, such as molds or mandrels, must be formed of a suitable material to withstand the temperatures required to cure the PMC, and are selected to typically exhibit a coefficient of thermal expansion as close as possible to the that of the PMC being cured, which is much smaller than that of aluminum alloys and steels. For that reason, molds are usually made out of invar which is expensive to manufacture and heavy. In some cases, the mold is made out of the same PMC material as the part being made. Therefore, a mold is required to make the mold, thus increasing the manufacturing time and materials. The PMC mold doesn't have the same durability as a metal mold and has a lower duration, increasing the frequency at which molds need to be fabricated when forming multiple PMC parts. In many fabrication processes, such as compression molding, transfer molding, pultrusion, or injection molding, the mold materials must be thermally robust, have good hardness (e.g., in some cases above about 150 BHN), and have the ability to withstand the pressure of the molding process. In many cases, molds are made of a variety of steels and must be machined, which is a time intensive and expensive process.
(28) By contrast, radiation curing does not require elevated temperatures, which allow a wide variety of materials to be used to form the PMC. For instance, molds can be formed from a variety of foams, wood (even softwoods), 3D-printed materials, or other plastics, to name a few. Molds for radiation cured materials can be light, inexpensive, and easily formed.
(29) Radiation curing offers the additional benefit of its fast cure time. In many instances, a radiation-cured PMC can be cured in a matter of minutes rather than hours as thermally-cured PMCs typically require.
(30) A radiation-cured PMC can be cured by application of any suitable radiation source. In some implementations, an electron beam is directed at the PMC at a suitable intensity in order to initiate and sustain the polymerization reaction. For instance, an e-beam gun may consist of a cathode, a grid, and an anode, and is used to generate and accelerate the primary beam of electrons. Electron-beam processing causes cross-linking of the polymers in the PMC, which gives the PMC excellent characteristics such as: thermal resistance, stress crack resistance, tensile strength, modulus of elasticity, abrasion resistance, and creep resistance.
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(32) The radiation source can be any suitable ionizing source, and may include, for example, ultraviolet radiation, visible light radiation, electron radiation, X-ray radiation, gamma ray radiation, or some other type of radiation. In some cases, photoinitiation is established through the use of light emitting diodes (LEDs) that provide a desired wavelength and intensity of light, and one or more photoinitiators are selected and used within the matrix material, the interface resin, or both. The photoinitiators within the matrix material and the interface resin may be different and may be selected to react differently to the applied radiation. In some cases, the interface resin is cured before the matrix material by the selective application of radiation to provide different cure characteristics of the various components within the PMC. In some cases, the photoinitiator is the same in the interface resin and the matrix material.
(33) Radiation curing is initiated when the energy which matches the curing agent is applied, and does not cure otherwise. Therefore, a radiation cured part can be cured at a significant time after the lamination is completed. This cannot be done with thermally cured systems, which need to be cured shortly after lamination and fiber impregnation is done. This can pose problems for thermally cured material systems, such as where the part is large and the resin infusion process is done too slowly, curing can occur before the injection is completed resulting in a faulty process.
(34) This process of following the layup process with curing is equally applicable to other forming techniques, such as mandrel wrapping, in which a sheet of prepreg material is wrapped around a mandrel. The e-beam gun can follow the wrapping process to cure the prepreg sheet material shortly after it is wrapped around the mandrel.
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(36) It should be appreciated that while
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(38) In some instances, the fibers are pre-impregnated with a resin and a curing agent. The fibers may have a long shelf life since the resin and curing agent will not react to initiate polymerization in the absence of applied radiation. Similarly, even where the fibers are incorporated into a matrix resin, the resin will not begin to polymerize in the absence of applied radiation. Consequently, pre-impregnated fibers may be stored for indefinite periods of time.
(39) This allows for thermosets the effective ability to have a relatively long shelf life and can then be radiation cured at a later time. In some cases, thermosets that have been sitting for an extended period of time may be treated to become workable prior to radiation curing. The treatment may be any suitable treatment and may be a thermal treatment, liquid treatment, radiation treatment, or some other form of treatment to improve the workability of the thermoplastic.
(40) By providing pre-impregnated reinforcing fibers that have a curing agent, a chemical bond between the reinforcing fibers and a matrix material used for forming components is greatly improved over current techniques. Furthermore, by curing at any desired temperature, the formed PMC part can be made nearly absent of thermal stress. Consequently, parts having a thinner cross-section than is possible with thermally-cured composite materials can exhibit similar material properties, such as strength, stiffness, fatigue, and shear properties. In some cases, the material properties of a radiation cured composite material may well far exceed the characteristics of a similar thermally cured composite material, while allowing for thinner and lighter parts thus using less material.
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(42) The variables illustrate effects of thermal curing of typical thermoset advanced composite material system used in aerospace in which DT=390° F.; curing temperature=350° F., operational temperature=−40° F. (which is representative of typical environments of in-flight conditions of commercial airplanes.
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(44) At step 604, the fiber is wetted with a matrix material, through any suitable process now known or later developed. The matrix material has a curing agent that may be the same or different to the curing agent provided in the interface resin.
(45) At step 606, the fiber is shaped through any suitable shaping process, such as, for example, winding the fiber around a mandrel, molding the fiber with a mold, or some other shaping process. Step 606 may be performed before or after step 604, that is, the fiber may be shaped, such as by a preform, and then the matrix material is infused.
(46) At step 608, the interface resin and the matrix material are cured by application of suitable radiation. In some cases, the radiation is a single source of radiation, which may be applied at a constant intensity. In some cases, the radiation is pulsed. In some cases, the radiation intensity is varied over time. In some cases, more than one type of radiation is applied.
(47) Once the PMC is cured to a satisfactory degree, the PMC may be removed from the mold or mandrel and the process may be repeated for subsequent PMC parts.
(48) According to some embodiments, additives may be provided in the interface resin, the matrix material, or both. Examples of additives include, without limitation, stabilizers, color pigments or dyes, defoamers, adhesion promoters, flattening agents, wetting agents, and slip aids.
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(53) A person of ordinary skill in the art will recognize that embodiments described herein provide a reduction in thermal strains and stresses. Conventional thermoset and thermoplastic polymeric matrix composite manufacturing processes require curing temperatures above 250° F. and 700° F., respectively, which creates thermally induced strains and stresses in the cured part once it cools. Radiation curing at room temperature minimizes the thermally induced strains and stresses caused by thermal curing. Radiation curing at operating temperature further minimized the thermally induced stress when a part is in operation. Due to the low temperature curing, expensive thermally robust molds are not required, neither are ovens or autoclaves. Many of the radiation curable thermoset resins do not have a shelf live and do not require refrigeration to maintain shelf life. Irradiation curing requires minutes to complete as opposed to typically hours for thermally cured composites. There is also a significant benefit in terms of manufacturing and repairs, as radiation cured composites can be used for bonding. Exothermic curing limits the thickness of the composite, requiring multiple layers to increase thickness. However, this is not the case with radiation cured composites as radiation can permeate through the composite to cure at greater depths than is possible with thermal curing.
(54) A person of ordinary skill in the art will recognize that any process or method disclosed herein can be modified in many ways. The process parameters and sequence of the steps described and/or illustrated herein are given by way of example only and can be varied as desired. For example, while the steps illustrated and/or described herein may be shown or discussed in a particular order, these steps do not necessarily need to be performed in the order illustrated or discussed.
(55) The various exemplary methods described and/or illustrated herein may also omit one or more of the steps described or illustrated herein or comprise additional steps in addition to those disclosed. Further, a step of any method as disclosed herein can be combined with any one or more steps of any other method as disclosed herein.
(56) Unless otherwise noted, the terms “connected to” and “coupled to” (and their derivatives), as used in the specification and claims, are to be construed as permitting both direct and indirect (i.e., via other elements or components) connection. In addition, the terms “a” or “an,” as used in the specification and claims, are to be construed as meaning “at least one of.” Finally, for ease of use, the terms “including” and “having” (and their derivatives), as used in the specification and claims, are interchangeable with and shall have the same meaning as the word “comprising.
(57) As used herein, the term “or” is used inclusively to refer items in the alternative and in combination. As used herein, characters such as numerals refer to like elements.
(58) Embodiments of the present disclosure have been shown and described as set forth herein and are provided by way of example only. One of ordinary skill in the art will recognize numerous adaptations, changes, variations and substitutions without departing from the scope of the present disclosure. Several alternatives and combinations of the embodiments disclosed herein may be utilized without departing from the scope of the present disclosure and the inventions disclosed herein. Therefore, the scope of the presently disclosed inventions shall be defined solely by the scope of the appended claims and the equivalents thereof.