LIGNIN AND FE-MN-SI BASED SHAPE MEMORY ALLOY REINFORCED EPOXY MATRIX COMPOSITE MATERIAL AND PRODUCTION METHOD

Abstract

This invention relates to the composite material and production method of an epoxy matrix reinforced with lignin and Fe-Mn-Si based shape memory alloy, and its characteristic is that it involves obtaining Fe-Mn-Si based shape memory alloy powder (6) by subjecting metal powders containing iron, manganese and silicon (1) to a mechanical alloying process, preparing an epoxy matrix system by mixing epoxy resin and hardener (3), adding lignin (5) to the said epoxy matrix system and mixing until a homogeneous distribution is obtained, adding the said Fe-Mn-Si based shape memory alloy powder (6) into the lignin (5) modified epoxy matrix and homogenizing it, pouring the resulting liquid composite mixture into a mold (7) and obtaining the composite sample (8) by curing the composite mixture poured into the mold (7).

Description

1 TARIFF REINFORCED WITH LIGNIN AND FE-MN-SI BASED SHAPE MEMORY ALLOY Epoxy matrix composite material and production method. Technological Field: This invention involves epoxy reinforced with a shape memory alloy based on lignin and Fe-Mn-Si. It relates to matrix composite materials and their production methods. State of the Art: Composite materials are materials that do not dissolve in each other, do not chemically bond, and two or more components with different properties, in separate phases These are engineering materials created by assembling several components. These materials include 15 It consists of two main components: matrix and reinforcement, and the elements located between these two components. It consists of an interface (interphase) which is a critical transition region that is not directly visible to the naked eye. The matrix phase provides structural integrity by holding the reinforcing elements together in the composite. It preserves the geometric form of the material and provides moldability. Matrices 20 Generally, they are polymer, metal, or ceramic based. The reinforcement phase is then added to the composite structure. It is the fundamental component that provides strength and rigidity. Reinforcements are generally particles or fibers. It exists in the form of a matrix or layer. The interface (interphase) is located between the matrix and the reinforcement. It is a microscopic transition zone that enables charge transfer. This zone facilitates charge transfer. through which a critical role is played in the load-carrying capacity and mechanical performance of the composite. 25 It plays a role. A weak interface leads to insufficient charge transfer and premature damage generation. However, an excessively strong interface reduces energy absorption capacity, leading to brittleness. This can promote fracture behavior. Therefore, optimum interface properties are important. Ensuring this is of great importance in terms of composite performance. 2 Composite materials can be classified as particle reinforced or fiber reinforced, depending on the type of reinforcing element. and layered composites; and according to the matrix material, polymer matrix, metal matrix and They are classified as ceramic matrix composites. Epoxy matrix composites are characterized by their low density, ease of production, and application time of 5 years. Because their unique features can be designed, aviation, automotive, defense and It is widely used in many engineering fields, such as energy. In this class Epoxy resins are frequently preferred due to their high rigidity, good mechanical strength, and chemical resistance. Despite offering resistance to environmental influences and strong adhesion properties, high Due to their high cross-linking density, they exhibit an inherently fragile structure. These 10 fragility; low impact resistance, limited fracture toughness and under service conditions This leads to significant technical disadvantages, such as susceptibility to microcrack formation. Microcracks that form within the epoxy matrix progress over time and reach macro-scale levels. This can lead to damage and cause sudden, unpredictable structural collapses. This is possible. This situation means that epoxy-based composites have a long lifespan and high reliability. 15 one of the main technical problems that limits its use in applications requiring it It stands out as such. In recent years, smart materials and technologies have been used to address these technical problems. Functional reinforcement elements have become an important area of ​​research. Smart 20 Shape memory alloys, which belong to the category of materials, are resistant to temperature and / or mechanical stress. their ability to regain their previously deformed structures under stimuli thanks to this, in terms of sealing microcracks or limiting their progression. It offers significant potential. In current applications, Ni-Ti is mostly used for this purpose. Essential shape memory alloys are used. However, these alloys require high raw material content. costs, complex production processes, difficult processability, and chemical composition Their sensitivity makes their widespread and economical use in polymer matrix composites important. It limits it to a certain extent. 30 due to the nature of epoxy-based composite materials in current technology brittle structures; low impact resistance, limited fracture toughness and microcracks Due to technical problems such as susceptibility to formation, various solutions are sought in the sector. 3 Approaches have been developed. These solutions generally involve matrix modification and fiber / fiber. It is evaluated under two main headings: reinforcement integration. The first solution approach aims to improve the mechanical properties of the epoxy matrix. It involves the addition of nanomaterials and various particle additives into the matrix. There are 5 such examples. Additives enhance the impact resistance and fracture toughness of the epoxy matrix to a certain extent. It can increase [the effect]. However, these methods, in most cases, involve the composite system. This leads to a decrease in rigidity, thermal stability, and high-temperature performance. This also occurs. In addition, at high additive ratios, the additives in the epoxy matrix inability to distribute homogeneously within it, agglomeration formation, resin viscosity of 10 increase and serious disadvantages such as processability problems in production processes emerge. For these reasons, particle and nanomaterial-modified systems are emerging in industrial applications. It fails to offer a feasible, long-lasting, and reliable solution at scale. As a second solution approach, fiber / fiber reinforced composite systems are widely used. 15 Fiber reinforcements are used to increase the tensile and flexural strength of composites. along with increasing the activity of microcracks forming within the epoxy matrix It has limited effect in suppressing or closing microcracks. It mostly progresses through fiber-matrix interfaces, causing the damage to worsen. And this situation negatively affects the service life of composite structures. Furthermore, 20 Fiber-reinforced systems do not eliminate the need for post-damage repair; maintenance and This makes repair processes complex, time-consuming, and costly. In recent years, composites of smart materials have been developed to address these problems. Studies have been conducted on the integration of systems. In this context, especially 25 Ni-Ti-based shape memory alloys prevent microcracks thanks to their shape memory effects. It has been used to seal and increase damage tolerance. However, Ni-Ti based. Alloys; high raw material costs, complex production and processing processes, chemical their sensitivity to the composition and during integration into composite production processes An economical and widely used industrial solution due to the additional processes required. 30 It is unable to provide. 4 In addition, bio-based additives in line with sustainability and environmental requirements. Composite systems developed using these materials are also included in the literature. In this context, lignin is used as an environmentally friendly additive for the modification of epoxy matrices. It has been evaluated as a substance. However, in current practices, lignin is mostly used. Used as a passive filler or limited mechanical enhancer; micro 5 crack control, actively increasing damage tolerance, or to the composite system Functional features such as the acquisition of intelligent behavior have not been achieved. Furthermore, lignin... with the integrated use of shape memory alloys, functional and An industrial-scale viable composite solution is not currently available in the sector. In conclusion, a new one that can overcome the disadvantages mentioned above. Composite material is needed. Description of the invention: The primary aim of the invention is to address the common problems encountered in epoxy-based composite materials. fragile structure, low impact resistance, limited fracture toughness, emerges under service conditions. the formation of microcracks and the accumulation of damage due to the progression of these cracks. The aim is to reduce their problems. In addition, it is commonly used to provide a shape memory effect. The high cost, complex production and processing of Ni-Ti based alloys used in this way 20 a more economical solution to the problems of limited applicability on an industrial scale with its difficulties and The aim is to introduce a more accessible alternative. At the same time, the passive effect of lignin... not remaining merely as a filler but being considered as a functional additive component In this way, it is low-cost, sustainable and actively treats microcracks. A functional composite specimen is presented that can be limited in scope. 25 One of the most important advantages of the invention is its cost-effectiveness. Figure Fe-Mn-Si based alloys are used instead of Ni-Ti based alloys to achieve the memory effect. The preference for memory alloy facilitates raw material procurement and overall It reduces material costs. The increased availability of Fe, Mn, and Si elements, 30 Moreover, thanks to the fact that this alloy can be prepared using common production methods, not only not only in material costs, but also in production infrastructure and process costs, there is a significant difference. a reduction is achieved. In this respect, the invention strengthens economic sustainability and It offers a solution that facilitates the transfer to industry. Another important advantage of the invention is in terms of manufacturability, scalability, and time. It is revealed that Fe-Mn-Si based alloy can be produced by mechanical alloying and 5 composite structures can be shaped using established industrial methods such as casting. Thanks to this, the need for specialized equipment, tight process tolerances, and complex control steps This simplifies the production process and reduces process complexity. Repeatability is increasing and a structure suitable for mass production is being obtained. This situation It facilitates the transition from laboratory scale to pilot and mass production, and also 10 In practice, this saves time. In terms of mechanical performance and functionality, the invention is superior to classic epoxy composites. It offers significant advantages in this regard. Lignin reduces the brittle character of the epoxy matrix. By modifying it, it reduces the tendency to initiate cracks, and increases impact resistance and fracture resistance. It improves toughness and increases damage tolerance. Fe-Mn-Si based form Memory alloys exhibit shape recovery, especially under the influence of temperature. Suppression, partial closure, or suppression of microcracks that form within the composite structure. It actively contributes to limiting its progress. These two effects together... As a result of its emergence, it is not only a mechanically reinforced structure, but also the same 20 A functional composite system capable of responding to external stimuli over time is obtained. Service life is extended and the risk of sudden structural damage is reduced. The invention also offers strong advantages in terms of sustainability and environmental impact. Lignin being a bio-based and renewable resource, petrochemical-based additive 25 It reduces dependence on raw materials. This is often the case in the paper and pulp industry. Lignin, which remains as a low value-added byproduct, can be transformed into a high value-added product. Transforming it into a functional engineering material component is both environmentally friendly and beneficial. This creates a significant economic gain. Thus, the invention contributes to the circular economy. consistent with this approach, the understanding of developing environmentally friendly and sustainable composites 30 It combines technical performance with other factors. 6 The invention also has significant advantages in terms of industrial applicability. The epoxy resin used contains lignin, iron, manganese, and silicon. The widespread availability of raw materials in industry ensures continuity of supply. It strengthens production and reduces the risk of supply constraints. The methods are capable of being integrated into existing composite production lines, 5 ensuring quality continuity and materials according to different application areas. This makes it possible to adapt its features. Thanks to this, the invention is suitable for aviation, Lightness, strength, and resistance to damage in fields such as automotive, defense, energy, construction, and marine. It can meet expectations in terms of tolerance, long service life and low maintenance requirements. It is becoming a commercially viable solution. 10 Explaining the Figures: The invention will be described by referring to the attached figures, so that the features of the invention can be explained. will be understood and appreciated more clearly, but the purpose of this invention is this particular 15 It is not about limiting it with regulations. On the contrary, the invention is defined by the accompanying claims. all alternatives, modifications, and options that could be included within the defined area The aim is to cover their equivalences. The details shown are only for the present invention. It is shown to illustrate the preferred arrangements and both the methods shaping, as well as the rules and conceptual features of the invention, in the most useful and 20 It should be understood that these drawings are presented to provide an easily understandable definition. In these drawings; Figure 1 shows the metal powders used in the preparation of shape memory alloy powders. This is a view showing the interaction of the balls. Figure 2 shows the production technique for obtaining the composite sample that is the subject of the invention. 25 This is a schematic view illustrating the phenomenon. Illustrations that will help understand this invention are shown in the attached image. They are numbered and their names are given below. 7 Explanation of References: 1. Metal powders 2. Marbles 3. Epoxy resin and hardener component 5 4. Mechanical mixer 5. Lignin 6. Shape memory alloy powder Mold 7 8. Composite sample 10 Detailed Description of the Invention: The terminology used here is intended solely to describe specific applications. and does not limit the scope of the invention. 15 used here The term "and / or" refers to any of the items listed as related. It includes one and all combinations thereof. Also, the singular "one" used here, "one" The terms "number" and "specified" are used in their plural forms unless the context explicitly indicates otherwise. It is designed to include singular forms such as those mentioned above. Furthermore, the terms used in this specification... The terms "includes" and / or "contains" refer to the specified features, steps, processes, 20 It indicates the presence of elements and / or components, but one or more other features, steps, processes, elements, components and / or groups thereof It will be understood that this does not exclude its existence or addition. Unless otherwise noted, all terms used herein (including technical and scientific terms) are copyrighted under Article 25. in the sense that a person with general knowledge in the field to which this invention belongs would generally understand it They have the same meaning. Furthermore, as defined in commonly used dictionaries... The terms will have a meaning consistent with the context of the relevant field and this explanation. it should be interpreted as idealized unless otherwise explicitly defined here. or it will be understood that it will not be interpreted in an overly formal sense. 30 8 The description of the invention will reveal a series of techniques and steps involved. These are: Each of them provides benefits individually, and at the same time, one or more of them can be used together. In some cases, all of the other techniques described may be used in combination. Accordingly, To ensure clarity, each step in the disclosure of the invention should be presented as accurately as possible. All combinations will be avoided by unnecessarily repeating them. With this 5 Together, the specification and claims, such combinations fully constitute an invention and claims. It should be read with the understanding that it falls within its scope. This section discusses a new composite material and its manufacturing method. Below... The statement outlines several specific measures to ensure a full understanding of the current invention. Details have been provided. However, even without these details, the present invention... Its applicability will be clearly understood by experts in the field. The invention addresses the brittle structure and low impact resistance observed in epoxy-based composite materials. strength, limited fracture toughness and microcracks occurring during service 15 a composite aimed at reducing crack formation and propagation problems This relates to the material and the production method of this composite material. More specifically... The invention is a shape memory alloy based on Fe-Mn-Si with lignin (5) in an epoxy matrix. By using the powder (6) together, both the mechanical performance was improved and 20 This structure ensures that the brittle character of the epoxy matrix is ​​preserved. Damage tolerance is increased and microcracks are suppressed or This contributes to limiting its progress. The subject of the invention is a composite structure, epoxy resin and hardener component (3), composite 25 This constitutes the matrix phase of the system. This matrix phase is a composite structure. It holds the other components together, provides load transfer, and ultimately... It maintains the geometric integrity of the product. Lignin (5) makes the epoxy matrix brittle. as a bio-based and functional additive that modifies its structure It is used. Shape memory alloy powder (6) is active in the composite structure. It acts as a reinforcing element and regains its shape, especially under the influence of temperature. by exhibiting gain behavior, leading to partial closure of microcracks and / or 9 It contributes to limiting its progression. In this way, the shape with lignin (5) memory alloy powder (6) works in a complementary way and into the composite structure It creates a synergistic technical effect. The shape memory alloy powder (6) used in the invention is primarily made of metal powders (1) 5 It is prepared using metal powders, preferably iron, manganese, and silicon-based. (1), in certain proportions to provide Fe-Mn-Si based shape memory alloy composition It is weighed and subjected to mechanical alloying. In one application, the metal powders (1), each of which constitutes approximately one third of the total alloy weight It is being prepared and transferred to a mechanical alloying vessel. 10 as grinding medium. balls (2) are used, and these balls (2) are preferably zirconia based and It is approximately 4-6 mm in diameter. The ratio between metal powders (1) and balls (2) is homogeneous. It is adjusted in such a way as to produce an alloy, for example, metal powder / sphere. The ratio can be selected as 1:10. The mechanical alloying process takes approximately 250- By running the mixture at a rotation speed of 400 rpm for approximately 13-25 hours, a homogenous chemical mixture is obtained. Shape memory alloy with composition and microstructure that may exhibit shape memory effect. powder (6) is obtained. Epoxy resin and hardener in the preparation of the matrix phase of the composite structure. Component (3) is combined in the specified weight ratios. Preferably epoxy 20 The resin and hardener component (3) are weighed in approximately a 2:1 ratio by weight and mechanically It is homogenized with the help of a mixer (4). In one application, mechanical The mixer (4) is operated at a speed of approximately 250-600 rpm and for approximately 100-350 seconds. This process is carried out. As a result of this process, a homogeneous mixture suitable for the addition of reinforcing components is obtained. An epoxy matrix system is obtained. The mechanical mixer (4) mixes the matrix phase 25 by ensuring that the constituent components interact appropriately with each other, the final result It plays an important role in terms of the structural integrity of the composite material. Lignin (5) is then added to the prepared epoxy matrix. Lignin (5), 30 different types such as kraft lignin, lignosulfonate, organosolv lignin or soda lignin It can be selected and is a functional solution aimed at reducing the brittleness of the epoxy matrix. It serves as an additive. Lignin (5) is used to improve composite properties. It is used in specific weight ratios. In one application, lignin (5), epoxy matrix Lignin (5) is added to it in varying amounts between 1% and 15%. then the mixture is mechanically processed until a homogeneous distribution is achieved. is mixed. Thus, lignin (5) is distributed evenly within the matrix phase. to reduce the tendency for crack initiation, to limit crack propagation behavior 5 and contributes to improving the impact resistance and damage tolerance of the composite system. It provides. Shape memory alloy then into epoxy matrix modified with lignin (5) Shape memory alloy powder (6) is added. Shape memory alloy powder (6) has the mechanical properties described above. It is a pre-prepared Fe-Mn-Si based metallic reinforcement phase through an alloying process. The subject is alloy powder (6), lignin (5) in certain proportions into the epoxy matrix containing alloy powder (6) and lignin (5). It is added and stirred until the mixture becomes homogeneous. In practice, shape memory alloy powder (6) is used in proportions ranging from 1% to 15%. It is used. Shape memory alloy powder (6) provides only mechanical 15 to the composite structure. It does not provide reinforcement, and external stimuli, especially the effect of temperature, also... microscopic changes occurring within the composite exhibit shape recovery. Actively contributes to the suppression and / or limitation of crack propagation. Thus, when lignin (5) and shape memory alloy powder (6) are used together, Epoxy matrix composite materials offer 20% superior strength and functionality. An improved structure is obtained. The homogenized liquid composite mixture is then placed into the mold (7). The mold (7) is poured, preferably from a non-stick material, e.g. PTFE It is selected from a basic structure. The mold (7) is the desired geometric shape of the composite mixture. It ensures that the product is shaped in the form and after curing the product is removed from the mold (7) without damage. It allows separation without seeing. In one application, the mold (7) is 0.5 mm to 100 with a thickness range varying between mm and dimensions between 300 x 300 mm and 1200 x 2000 mm. It can be selected in varying sizes. The liquid composite mixture is applied to the mold (7) surface. It is poured in a controlled manner and at this stage the mixture is 30 in the mold (7) cavity This ensures proper spreading. Thus, the geometric continuity of the final product and The desired dimensional characteristics are obtained. 11 The composite mixture taken into the mold (7) is then left to cure. During the curing process, the cross between the epoxy resin and the hardener component (3) Bonding reactions are complete and the composite structure achieves its final mechanical integrity. It is gaining. In one application, the curing process takes approximately 48 hours to 96.5 at room temperature. It is continued between hours. After the curing is completed, it is removed from the mold (7). Composite specimen (8) is obtained. Composite specimen (8) is mechanically removed from the mold (7). It can be separated without the need for force and then cut to the desired dimensions. It can be made ready for use for experimental or application purposes. Composite The mechanical, thermal, morphological, corrosion and shape memory behavior of sample (8) was studied. It can be used in analyses aimed at identification. The working principle of the invention involves metal powders (1), balls (2), epoxy resin and hardener. component (3), mechanical mixer (4), lignin (5), shape memory alloy powder (6), mold (7) and Composite specimen (8) should be evaluated together. First, metal powders (1) and balls 15 (2) Shape memory alloy powder (6) is obtained by mechanical alloying using (2). is made, then epoxy resin and hardener component (3) with mechanical mixer (4) The matrix phase is prepared by mixing. Lignin (5) and figure are added to this matrix phase respectively. memory alloy powder (6) is added, the resulting mixture is poured into the mold (7) and After curing, a composite sample (8) is obtained. The final composite sample (8) 20 lignin (5) modifies the brittle structure of the matrix, shape memory alloy powder (6) as an active reinforcing element contributes to the control of microcracks It is located. The invention is not limited to the preferential use described above, but also includes the technical essence 25 Provided they are protected, different lignin types, different additive ratios, different mold sizes and It can also be applied with different production parameters. However, the essence of the invention is epoxy. lignin (5) and Fe-Mn-Si based shape memory alloy powder (6) together in the matrix Its use and combination have both improved mechanical properties and The goal is to obtain a composite specimen (8) that exhibits functional behavior. 30

Claims

12 REQUESTS 1- The invention is an epoxy reinforced with a shape memory alloy based on lignin (5) and Fe-Mn-Si. It is a matrix composite sample production method (8), and its feature is;  Mechanical alloying of metal powders containing iron, manganese and silicon (1) 5 by subjecting it to processing, Fe-Mn-Si based shape memory alloy powder (6) obtaining,  An epoxy is formed by mixing the epoxy resin and the hardener component (3). Preparation of the matrix system,  By adding lignin (5) to the epoxy matrix system in question, a homogeneous distribution is achieved. 10 Mixing until it is obtained,  Fe-Mn-Si into the epoxy matrix modified with lignin (5) homogenization by adding shape memory alloy powder (6),  pouring the resulting liquid composite mixture into a mold (7) and  By curing the composite mixture poured into the mold (7), the composite 15 The process of obtaining the sample (8) includes the steps. 2- The method mentioned in Claim 1, the characteristic of which is; the metal powders in question are iron (1), manganese and silicon metal powders (1) and the total alloy weight of each It is characterized by constituting approximately one-third. 20 3- The method mentioned in Claim 1, characterized by its grinding in the mechanical alloying process. where balls (2) are used as the medium and the ratio of metal powder to balls is 1:10 It is the characterization of the situation. 4- The method mentioned in Claim 3, its characteristic is that the balls (2) are approximately 4-6 It is characterized by having zirconia balls (2) with a diameter of mm. 5- The method mentioned in any of the above requests is characterized by its mechanical nature. The alloying process takes approximately 13-25 hours at a rotational speed of 250 to 400 rpm. It is characterized by its occurrence over a period of time. 13 6- The method mentioned in any of the above requests, and its characteristic feature is; epoxy by mixing the resin and hardener component (3) in approximately 2:1 ratio by weight It is the characterization of the situation. 7- The method mentioned in any of the above requests, and its characteristic is; epoxy 5 resin and hardener component (3) at approximately 250-600 rpm and approximately 100-350 It is characterized by mixing using a mechanical mixer (4) for a period of seconds. It is done. 8- The method mentioned in any of the above requests, its characteristic is; word 10 The subject of lignin is (5) kraft lignin, lignosulfonate, organosolv lignin or soda lignin. It is characterized by... 9- The method mentioned in claim 8 is characterized by the fact that lignin (5) is incorporated into the epoxy matrix. It is characterized by the addition of 1% to 15% by weight. 15 10- The method mentioned in any of the above requests, and its characteristic is; Fe-Mn- By adding Si alloy (1) to the epoxy matrix in amounts of 1 to 15% by weight. It is the characterization of the situation. 11- The method mentioned in any of the above requests, and its characteristic is; liquid by pouring the composite mixture into a non-stick mold, preferably PTFE based (7) It is the characterization of the situation. 12- The method mentioned in Claim 11, its characteristic is that the mold in question is (7) 0.5 mm to 100 25 in the mm thickness range and varying in dimensions from 300 x 300 mm to 1200 x 2000 mm. It is characterized by being selected in terms of dimensions. 13- The method mentioned in any of the above requests, and its characteristic is; curing. 30 characterized by the process taking place at room temperature for approximately 48 to 96 hours. It is done.

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