Novolaks are produced by reacting phenol with methanal (formaldehyde). These modifications are made to reduce costs, to improve performance, and to improve processing convenience. Some epoxies are cured by exposure to ultraviolet light. Instead of bisphenol A, other bisphenols (especially bisphenol F) or brominated bisphenols (e. g. tetrabromobisphenol A) can be used for the said epoxidation and prepolymerisation. [9] Claims of discovery of bisphenol-A-based epoxy resins include Pierre Castan[10] in 1943. Important industrial grades are triglycidyl-p-aminophenol (functionality 3) and N,N,N,N-tetraglycidyl-bis-(4-aminophenyl)-methane (functionality 4). Fluorinated epoxy resins have been investigated for some high performance applications, such as the fluorinated diglycidether 5-heptafluoropropyl-1,3-bis[2-(2,3-epoxypropoxy)hexafluoro-2-propyl]benzene. [40] Down investigated various room-temperature-cure epoxy resin adhesives suitable for use in glass conservation, testing their tendency to yellow. Epoxy resins may be reacted (cross-linked) either with themselves through catalytic homopolymerisation, or with a wide range of co-reactants including polyfunctional amines, acids (and acid anhydrides), phenols, alcohols and thiols (usually called mercaptans). ), by adding flexibilizers, viscosity reducers, colorants, thickeners, accelerators, adhesion promoters, etc. Epoxies are typically cured with stoichiometric or near-stoichiometric quantities of hardener to achieve the best physical properties. 30,00070,000 g/mol) form a class known as phenoxy resins and contain virtually no epoxide groups (since the terminal epoxy groups are insignificant compared to the total size of the molecule). An important criterion for epoxy resins is the Epoxy value which is connected to the epoxide group content. Epoxy resins produced from such epoxy monomers are called glycidyl-based epoxy resins. These systems provide a tough, protective coating with excellent hardness. Transformer and inductor hot spots are greatly reduced, giving the component a stable and longer life than unpotted product. Typical fiber reinforcements include glass, carbon, Kevlar, and boron. However, aliphatic epoxy resins polymerize very slowly at room temperature, so higher temperatures and suitable accelerators are usually required. Reaction and subsequent crosslinking occur only after opening of the anhydride ring, e.g. These resins typically display low viscosity at room temperature (10200 mPa.s) and are often referred to as reactive diluents. [43] In addition, for offshore and onshore wind energy installations, epoxy resins are used as protective coatings on steel towers, base struts and concrete foundations. Most of the commercially used epoxy monomers are produced by the reaction of a compound with acidic hydroxy groups and epichlorohydrin. There are hundreds of ways that these formulators can modify epoxiesby adding mineral fillers (talc, silica, alumina, etc. through poor working hygiene or lack of protective equipment) over a long period of time. Increasing the ratio of bisphenol A to epichlorohydrin during manufacture produces higher molecular weight linear polyethers with glycidyl end groups, which are semi-solid to hard crystalline materials at room temperature depending on the molecular weight achieved. [45] The chemical reactions in both cases are exothermic. 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate). [6][7][8], Condensation of epoxides and amines was first reported and patented by Paul Schlack of Germany in 1934. All quantities of mix generate their own heat because the reaction is exothermic. One-component products generally have shorter shelf-lives than standard 2-component systems, and products may require cooled storage and transport. Germany [44] is the largest market for epoxy resins in Europe, followed by Italy, France, the UK, Spain, the Netherlands and Austria. Daniels LJ, PhD thesis Lancaster University 1992, 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, "Electrical Resistance Sensing of Epoxy Curing Using an Embedded Carbon Nanotube Yarn", "The Influence of Mixing Methods of Epoxy Composition Ingredients on Selected Mechanical Properties of Modified Epoxy Construction Materials", "US Patent Application for FIRE-RESISTANT GLAZING Patent Application (Application #20130196091 issued August 1, 2013) - Justia Patents Search", "Epoxy resins thermosetting for mechanical engineering", "Health Effects from Overexposure to Epoxy WEST SYSTEM", "Allergic Contact Dermatitis from a Nonbisphenol A Epoxy in a Graphite Fiber Reinforced Epoxy Laminate", "Occupational Contact Dermatitis Due to Epoxy Resin in a Fiberglass Binder", "Diluting Agent - an overview | ScienceDirect Topics", "Diluents and viscosity modifiers for epoxy resins", "Developments in reactive diluents: a review", "Effect of reactive and non-reactive diluents on thermal and mechanical properties of epoxy resin", "The effect of reactive diluent on mechanical properties and microstructure of epoxy resins", "Synthesis and Application of Polyepoxide Cardanol Glycidyl Ether as Biobased Polyepoxide Reactive Diluent for Epoxy Resin", "The application of differential scanning calorimetry (DSC) to the study of epoxy resin curing reactions", "Epoxy Resin - an overview | ScienceDirect Topics", "Benefits and Applications of BTDA and Other Dianhydrides in Polyimide and Epoxy Resins", "Structural Adhesives - Improvements in Vehicle Crash Performance", "Effects of CNBR Modification on Mode I Fracture of Epoxy Adhesives for Automotive Application", "Preparation and Research of Solvent-Free Epoxy Coating for Drinking Water Tank", "Mechanism of Yellowing: Carbonyl Formation during Hygrothermal Aging in a Common Amine Epoxy", Preliminary Study on Epoxy-Based Polymer for Water Shut-Off Application, "Mechanical Properties and Microstructure of Epoxy Mortars Made with Polyethylene and Poly(Ethylene Terephthalate) Waste", "A new embedding technique for electron microscopy, combining a water-soluble epoxy resin (Durcupan) with water-insoluble Araldite", "A Modification of the Water-miscible Epoxy Resin "Durcupan" Embedding Method for Ultrathin Sectioning", "Improvements in epoxy resin embedding methods", "The Yellowing of Epoxy Resin Adhesives: Report on Natural Dark Aging", "The Application of Epoxy Resins for the Restoration of Historic Structures", "The Use of Epoxy Resins for the Stabilization of Deteriorated Masonry", "Epoxy Resin Market- By Application (Paints & Coatings, Wind Energy, Composites, Construction, and Electrical & Electronics): Global Industry Perspective, Comprehensive Analysis, and Forecast, 20222028", "Synthesis and characterization of bio-based epoxy blends from renewable resource based epoxidized soybean oil as reactive diluent", "Synthesis and Properties of Organosilicon-Grafted Cardanol Novolac Epoxy Resin as a Novel Biobased Reactive Diluent and Toughening Agent", https://en.wikipedia.org/w/index.php?title=Epoxy&oldid=1101140406, Short description is different from Wikidata, Articles with unsourced statements from March 2021, Creative Commons Attribution-ShareAlike License 3.0, This page was last edited on 29 July 2022, at 14:20. These resins do however contain hydroxyl groups throughout the backbone, which may also undergo other cross-linking reactions, e.g. While some epoxy resin/ hardener combinations will cure at ambient temperature, many require heat, with temperatures up to 150C (302F) being common, and up to 200C (392F) for some specialist systems. Epoxy materials tend to harden somewhat more gradually, while polyester materials tend to harden quickly, particularly if a lot of catalyst is used. Epoxies generally out-perform most other resin types in terms of mechanical properties and resistance to environmental degradation. Epoxy resins diluents are typically formed by glycidylation of aliphatic alcohols or polyols and also aromatic alcohols. Homopolymerization may also occur between epoxide and hydroxyl groups. However, reactivity is rather low compared to other classes of epoxy resin, and high temperature curing using suitable accelerators is normally required. One of the best examples was a system of using solvent free epoxies for priming ships during construction, this used a system of hot airless spray with premixing at the head. They can be made flexible or rigid, transparent or opaque/colored, fast setting or slow setting. In this case, the peracids can also be formed in situ by reacting carboxylic acids with hydrogen peroxide. [61] Exposure to epoxy resins can, over time, induce an allergic reaction. Aliphatic polyurethane top coats are applied on top to ensure full UV protection, prolong operational lifetimes and lowering maintenance costs. plant derived glycerol used to make epichlorohydrin). [34] In general, epoxies are known for their excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties and very good electrical insulating properties. These highly viscous to solid resins typically carry 2 to 6 epoxy groups per molecule. However, polyester resins are much cheaper. Bisphenol F may undergo epoxy resin formation in a similar fashion to bisphenol A. [52], Epoxy resin, mixed with pigment, may be used as a painting medium, by pouring layers on top of each other to form a complete picture. Variations offering high thermal insulation, or thermal conductivity combined with high electrical resistance for electronics applications, are available.[35]. Polyfunctional primary amines form an important class of epoxy hardeners. They can be used as adhesives for wood, metal, glass, stone, and some plastics. Polyester resins are typically low strength unless used with a reinforcing material like glass fibre, are relatively brittle unless reinforced, and have low adhesion. The epoxide functional group is also collectively called epoxy. While it is common to associate polyester resins and epoxy resins, their properties are sufficiently different that they are properly treated as distinct materials. Allergic reaction is often visible in the form of dermatitis, particularly in areas where the exposure has been highest (commonly hands and forearms). The rate of cure of polyesters can therefore be controlled by the amount and type of catalyst as well as by the temperature. Allergic reaction sometimes occurs at a time which is delayed several days from the exposure. Its reactivity to hardeners is comparable to that of bisphenol A. The reaction is carried out in the presence of a base such as sodium hydroxide, analogous to the formation of bisphenol A-diglycidyl ether. Amine type hardeners will alter both the processing properties (viscosity, reactivity) and the final properties (mechanical, temperature and heat resistance) of the cured copolymer network. A fundamental molecular understanding of epoxy yellowing was achieved, when Krauklis and Echtermeyer discovered the mechanistic origin of yellowing in a commonly used amine epoxy resin, published in 2018. Cycloaliphatic epoxides are therefore usually homopolymerized thermally or UV-initiated in an electrophilic or cationic reaction. Primary amines undergo an addition reaction with the epoxide group to form a hydroxyl group and a secondary amine. Relative reactivity (lowest first) is approximately in the order: phenol < anhydride < aromatic amine < cycloaliphatic amine < aliphatic amine < thiol. Compared with LERs (liquid epoxy resins) they have very low viscosities. Significant advances in understanding yellowing of epoxies were achieved by Down first in 1984 (natural dark aging) [39] and later in 1986 (high-intensity light aging). As adhesives, epoxies bond in three ways: a) Mechanically, because the bonding surfaces are roughened; b) by proximity, because the cured resins are physically so close to the bonding surfaces that they are hard to separate; c) ionically, because the epoxy resins form ionic bonds at an atomic level with the bonding surfaces. German Patent 676117. Epoxy resin may be reacted with itself in the presence of an anionic catalyst (a Lewis base such as tertiary amines or imidazoles) or a cationic catalyst (a Lewis acid such as a boron trifluoride complex) to form a cured network. In principle, any molecule containing a reactive hydrogen may react with the epoxide groups of the epoxy resin. Curing with phenolics to make drum linings, curing esters with amine resins and pre-curing epoxies with amino resins to make resistant top coats. The formulation may then be reacted in the same way as pure bisphenol A. [16] Cycloaliphatic epoxides are characterised by their aliphatic structure, high oxirane content and the absence of chlorine, which results in low viscosity and (once cured) good weather resistance, low dielectric constants and high Tg. They are produced by the reaction of a cyclic alkene with a peracid (see above). Epoxy adhesives are better in heat and chemical resistance than other common adhesives. These commodity epoxy manufacturers mentioned above typically do not sell epoxy resins in a form usable to smaller end users, so there is another group of companies that purchases epoxy raw materials from the major producers and then compounds (blends, modifies, or otherwise customizes) epoxy systems from these raw materials. [58][59], Liquid epoxy resins in their uncured state are mostly classed as irritant to the eyes and skin, as well as toxic to aquatic organisms. This process is known as catalytic homopolymerisation. Epoxy use is a main source of occupational asthma among users of plastics. In 1946, Sylvan Greenlee, working for the Devoe&Raynolds Company, patented resin derived from bisphenol-A and epichlorohydrin. for chips on board ), LEDs, high-tension electrical insulators, paint brush manufacturing, fiber-reinforced plastic materials, and adhesives for structural[3] and other purposes. The epoxy curing reaction may be accelerated by addition of small quantities of accelerators. [63], This article is about the thermoset plastic materials. Temperature is sometimes increased in a step-wise fashion to control the rate of curing and prevent excessive heat build-up from the exothermic reaction. This process is commonly referred to as curing or gelation process. The reaction of epichlorohydrin and novolaks produces novolaks with glycidyl residues, such as epoxyphenol novolak (EPN) or epoxycresol novolak (ECN). These resins typically have lower viscosity and a higher mean epoxy content per gram than bisphenol A resins, which (once cured) gives them increased chemical resistance. These high-performance adhesives are used in the construction of aircraft, automobiles, bicycles, boats, golf clubs, skis, snowboards, and other applications where high strength bonds are required. Bisphenol A is a highly effective and widely used accelerator, but is now increasingly replaced due to health concerns with this substance. Bisphenol A-based resins are the most widely commercialised resins but also other bisphenols are analogously reacted with epichlorohydrin, for example Bisphenol F. In this two-stage reaction, epichlorohydrin is first added to bisphenol A (bis(3-chloro-2-hydroxy-propoxy)bisphenol A is formed), then a bisepoxide is formed in a condensation reaction with a stoichiometric amount of sodium hydroxide. Large scale epoxidized vegetable oils such as epoxidized soy and lens oils are used to a large extent as secondary plasticizers and cost stabilizers for PVC.[13]. As it has a low surface tension, it is added as a wetting agent (surfactant) for contact with glass fibres. [11] Devoe&Raynolds, which was active in the early days of the epoxy resin industry, was sold to Shell Chemical; the division involved in this work was eventually sold, and via a series of other corporate transactions is now part of Hexion Inc.[12]. Cure temperature should typically attain the glass transition temperature (Tg) of the fully cured network in order to achieve maximum properties. Epoxy resins are also used for decorative flooring applications such as terrazzo flooring, chip flooring, and colored aggregate flooring. The chlorine atom is released as sodium chloride (NaCl) and the hydrogen atom as water. Epoxy resins are excellent electrical insulators and protect electrical components from short circuiting, dust and moisture. Use of blending, additives and fillers is often referred to as formulating. First a hydroxy group reacts in a coupling reaction with epichlorohydrin, followed by dehydrohalogenation. [15] As the molecular weight of the resin increases, the epoxide content reduces and the material behaves more and more like a thermoplastic. They are often used during boat repair and assembly, and then over-coated with conventional or two-part polyurethane paint or marine-varnishes that provide UV protection. Because of the better mechanical properties relative to the more common polyester resins, epoxies are used for commercial manufacture of components where a high strength/weight ratio is required. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. In Europe, about 323,000 tonnes of epoxy resin were manufactured in 2017 generating some 1,055 million in sales. These co-reactants are often referred to as hardeners or curatives, and the cross-linking reaction is commonly referred to as curing. with aminoplasts, phenoplasts and isocyanates. Common classes of hardeners for epoxy resins include amines, acids, acid anhydrides, phenols, alcohols and thiols. Normal gelcoat formulated for use with polyester resins and vinylester resins does not adhere to epoxy surfaces, though epoxy adheres very well if applied to polyester resin surfaces. The global epoxy resin market was valued at approximately 9.1 (USD Billion) in 2021 and is predicted to gain revenue of about 14.7 (USD Billion) by 2028, is set to record a CAGR of nearly 6.8% over the period from 2022 to 2028. While the resulting network does not typically display high temperature or chemical resistance, the high reactivity of the thiol group makes it useful for applications where heated curing is not possible, or very fast cure is required e.g. The tetrabrominated bisphenol A (TBBPA, 2,2-bis(3,5-dibromophenyl)propane) or its diglycidyl ether, 2,2-bis[3,5-dibromo-4-(2,3-epoxypropoxy)phenyl]propane, can be added to the epoxy formulation. Thiols have a characteristic odour, which can be detected in many two-component household adhesives. The raw materials for epoxy resin production are today largely petroleum derived, although some plant derived sources are now becoming commercially available (e.g. If, however, they are used in larger proportions as reactive diluents, this often leads to reduced chemical and thermal resistance and to poorer mechanical properties of the cured epoxides. [31] The applications include coatings, adhesives[32][33] and composite materials such as those using carbon fiber and fiberglass reinforcements (although polyester, vinyl ester, and other thermosetting resins are also used for glass-reinforced plastic). [62] Safe disposal also needs considering but usually involves deliberate curing to produce solid rather than liquid waste. The other production route for epoxy resins is the conversion of aliphatic or cycloaliphatic alkenes with peracids:[13][14] In contrast to glycidyl-based epoxy resins, this production of such epoxy monomers does not require an acidic hydrogen atom but an aliphatic double bond. Aliphatic glycidyl epoxy resins of low molar mass (mono-, bi- or polyfunctional) are formed by the reaction of epichlorohydrin with aliphatic alcohols or polyols (glycidyl ethers are formed) or with aliphatic carboxylic acids (glycidyl esters are formed). Aromatic amines were widely used as epoxy resin hardeners, due to the excellent end properties when mixed with a parent resin. Epoxies were modified in a variety of ways, Reacted with fatty acids derived from oils to yield epoxy esters, which were cured the same way as alkyds. For dianhydrides, and to a lesser extent, monoanhydrides, non-stoichiometric, empirical determinations are often used to optimize dosing levels. Epoxy systems are used in industrial tooling applications to produce molds, master models, laminates, castings, fixtures, and other industrial production aids. [4][5], The health risks associated with exposure to epoxy resin compounds include contact dermatitis and allergic reactions, as well as respiratory problems from breathing vapor and sanding dust, especially when not fully cured. There are two common types of aliphatic epoxy resins: those obtained by epoxidation of double bonds (cycloaliphatic epoxides and epoxidized vegetable oils) and those formed by reaction with epichlorohydrin (glycidyl ethers and esters). Epoxy resin formulations are important in the electronics industry, and are employed in motors, generators, transformers, switchgear, bushings, insulators, printed wiring boards (PWB), and semiconductor encapsulants. This route of synthesis is known as the "taffy" process. Epoxy resins are polymeric or semi-polymeric materials or an oligomer, and as such rarely exist as pure substances, since variable chain length results from the polymerisation reaction used to produce them. Insufficient heat during cure will result in a network with incomplete polymerisation, and thus reduced mechanical, chemical and heat resistance. Use of a difunctional or polyfunctional amine forms a three-dimensional cross-linked network. The cured epoxy is an electrical insulator and a much better conductor of heat than air. One part epoxy coatings are formulated as an emulsion in water, and can be cleaned up without solvents. They are therefore added to other epoxy resins as reactive diluents or as adhesion promoters. [22] Mechanical properties of epoxy resins are generally not improved by use of diluents. printed circuit boards). Dicarboxylic acids such as hexahydrophthalic acid are used for diglycide ester resins. They are also used for radiation-cured paints and varnishes. by secondary hydroxyl groups in the epoxy resin. A product comprising more repeating units (n = 2 to 30) is at room temperature a colourless solid, which is correspondingly referred to as solid epoxy resin. Fusion Bonded Epoxy Powder Coatings (FBE) are extensively used for corrosion protection of steel pipes and fittings used in the oil and gas industry, potable water transmission pipelines (steel), and concrete reinforcing rebar. Kinetic studies have shown the reactivity of the primary amine to be approximately double that of the secondary amine. The high latency of anhydride hardeners makes them suitable for processing systems which require addition of mineral fillers prior to curing, e.g. Phenols can be compounds such as bisphenol A and novolak. They are also sold in boat shops as repair resins for marine applications. China is the major producer and consumer globally, consuming almost 35% of the global resin production. "Flocoat" that is normally used to coat the interior of polyester fibreglass yachts is also compatible with epoxies. Epoxy coatings are also widely used as primers to improve the adhesion of automotive and marine paints especially on metal surfaces where corrosion (rusting) resistance is important. A related class is cycloaliphatic epoxy resin, which contains one or more cycloaliphatic rings in the molecule (e.g. The risk has been shown to be more pronounced in epoxy resins containing low molecular weight epoxy diluents. This process is known as "advancement". Epoxies, by contrast, are inherently strong, somewhat flexible and have excellent adhesion. The resulting network contains only ether bridges, and exhibits high thermal and chemical resistance, but is brittle and often requires elevated temperature for the curing process, so finds only niche applications industrially. The presence of the catalyst in the final product actually detracts from the desirable properties, so that small amounts of catalyst are preferable, so long as the hardening proceeds at an acceptable pace. Epoxy paints tend to deteriorate, known as "chalking out", due to UV exposure. Higher molecular weight diglycidyl ethers (n 1) are formed by the reaction of the bisphenol A diglycidyl ether formed with further bisphenol A, this is called prepolymerization: A product comprising a few repeat units (n = 1 to 2) is a viscous, clear liquid; this is called a liquid epoxy resin. They are more expensive than polyester resins and vinyl ester resins, but usually produce stronger and more temperature-resistant thermoset polymer matrix composite parts. Hakiki, F., Nuraeni, N., Salam, D.D., Aditya, W., Akbari, A., Mazrad, Z.A.I. They have been extensively used with concrete and cementitious systems. These companies are known as "formulators". Also aliphatic glycidyl epoxy resins usually have a low viscosity compared to aromatic epoxy resins. [20] This has led to the term modified epoxy resin to denote those containing viscosity-lowering reactive diluents. Epoxy resins are applied using the technology of resin dispensing. The applications for epoxy-based materials are extensive and they are considered very versatile. The largest volume type of circuit boardan "FR-4 board"is a sandwich of layers of glass cloth bonded into a composite by an epoxy resin. Very high molecular weight polycondensates (ca. Epoxy resins yellow with time, even when not exposed to UV radiation. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate). The usual route to higher molecular weight epoxy resins is to start with liquid epoxy resin (LER) and add a calculated amount of bisphenol A and then a catalyst is added and the reaction heated to circa 160C (320F). This means that conventional nucleophilic hardeners such as amines are hardly suitable for crosslinking. For the chemical group, see. As there is a general trend to renewable and "green" sources and greater use of biobased materials, research is ongoing in the epoxy arena too. [49], Water-soluble epoxies such as Durcupan[50][51] are commonly used for embedding electron microscope samples in plastic so they may be sectioned (sliced thin) with a microtome and then imaged. Because aliphatic epoxies have a lower electron density than aromatics, cycloaliphatic epoxies react less readily with nucleophiles than bisphenol A-based epoxy resins (which have aromatic ether groups). As a result, a typical formulator sells dozens or even thousands of formulationseach tailored to the requirements of a particular application or market. This obviated the problem of solvent retention under the film, which caused adhesion problems later on. Materials like wood, and others that are 'low-tech' are glued with epoxy resin. Epoxy coatings are often used in industrial and automotive applications since they are more heat resistant than latex-based and alkyd-based paints. By using vacuum impregnation on uncured epoxy, winding-to-winding, winding-to-core, and winding-to-insulator air voids are eliminated. Polyester epoxies are used as powder coatings for washers, driers and other "white goods". Thus amine structure is normally selected according to the application. [60] Solid epoxy resins are generally safer than liquid epoxy resins, and many are classified non-hazardous materials. The secondary amine can further react with an epoxide to form a tertiary amine and an additional hydroxyl group. One downside of high purity liquid grades is their tendency to form crystalline solids due to their highly regular structure, which then require melting to enable processing. Epoxy adhesives can be developed to suit almost any application. In the electronics industry epoxy resins are the primary resin used in overmolding integrated circuits, transistors and hybrid circuits, and making printed circuit boards. Electric generators, connected via the drivetrain with the rotor blades, convert mechanical wind energy in usable electric energy, and rely on epoxies electrical insulation and high thermal resistance properties. Amines are also blended, adducted and reacted to alter properties and these amine resins are more often used to cure epoxy resins than a pure amine such as TETA. trimethylolpropane triglycidyl ether). Metal cans and containers are often coated with epoxy to prevent rusting, especially for foods like tomatoes that are acidic. Over the past few decades concern about the possible adverse health effects of many aromatic amines has led to increased use of aliphatic or cycloaliphatic amine alternatives. There are two main areas of marine use. The technique is named "water shut-off treatment".[28]. Large quantities will generate more heat and thus greatly increase the rate of the reaction and so reduce working time (pot-life). Some (non-crosslinked) epoxy resins with very high molar mass are added to engineering thermoplastics, again to achieve flame retardant properties.
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