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Unsaturated Polyester Resins: Fundamentals, Design, Fabrication, and Applications
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Unsaturated Polyester Resins: Fundamentals, Design, Fabrication, and Applications explains the preparation, techniques and applications relating to the use of unsaturated polyester resin systems for blends, interpenetrating polymer networks (IPNs), gels, composites and nanocomposites, enabling readers to understand and utilize the improved material properties that UPRs facilitate. Chapters cover unsaturated polyester resins and their interaction at the macro, micro and nano levels, in-depth studies on the properties and analysis of UPR based materials, and the applications of UPR based composites, blends, IPNs and gels across a range of advanced commercial and industrial fields.
This is a highly detailed source of information on unsaturated polyester resins, supporting academics, researchers and postgraduate students working with UPRs, polyesters, polymeric or composite materials, polymer chemistry, polymer physics, and materials science, as well as scientists, R&D professionals and engineers in industry.
Covers the use of unsaturated polyester resin systems for blends, IPNs, gels, composites and nanocomposites Presents cutting-edge techniques for the analysis and improvement of properties of advanced UPR-based materials Unlocks the potential of unsaturated polyester resins in high-performance materials for a range of advanced applicationsAções de livro
Comece a lerDados do livro
Unsaturated Polyester Resins: Fundamentals, Design, Fabrication, and Applications
Descrição
Unsaturated Polyester Resins: Fundamentals, Design, Fabrication, and Applications explains the preparation, techniques and applications relating to the use of unsaturated polyester resin systems for blends, interpenetrating polymer networks (IPNs), gels, composites and nanocomposites, enabling readers to understand and utilize the improved material properties that UPRs facilitate. Chapters cover unsaturated polyester resins and their interaction at the macro, micro and nano levels, in-depth studies on the properties and analysis of UPR based materials, and the applications of UPR based composites, blends, IPNs and gels across a range of advanced commercial and industrial fields.
This is a highly detailed source of information on unsaturated polyester resins, supporting academics, researchers and postgraduate students working with UPRs, polyesters, polymeric or composite materials, polymer chemistry, polymer physics, and materials science, as well as scientists, R&D professionals and engineers in industry.
Covers the use of unsaturated polyester resin systems for blends, IPNs, gels, composites and nanocomposites Presents cutting-edge techniques for the analysis and improvement of properties of advanced UPR-based materials Unlocks the potential of unsaturated polyester resins in high-performance materials for a range of advanced applicationsAmostra do livro
Unsaturated Polyester Resins
China
Chapter 1
Unsaturated Polyester Resins, Blends, Interpenetrating Polymer Networks, Composites, and Nanocomposites: State of the Art and New Challenges
Anjali A. Athawale¹ and Jyoti A. Pandit², ¹Department of Chemistry, Savitribai Phule Pune University, Pune, India, ²School of Chemistry, Dr. Vishwanath Karad MIT World Peace University, Pune, India
Abstract
Unsaturated polyesters resins (UPRs) comprise an important class of thermoset polymers. They are used extensively due to their low cost, easy processability, good corrosion resistance, and availability in a variety of grades. During their curing process they do not emit any volatile by-products; this feature makes them more attractive. They are classified into five different types based on structure. The properties of UPRs can be tailored by varying the type and ratio of monomers and curing agents used. Generally, aromatic groups improve hardness and stiffness while aliphatic chain components increase flexibility. However, as they contain polyester linkages, they are susceptible to water, have high glass transition temperatures (Tg), and have poor fire resistance. Although they have stable structures and good mechanical and thermal properties compared to other thermosets, they are not suitable for advanced applications. Hence, they have been modified as blends, interpenetrating polymer network (IPNs), composites, nanocomposites, and others. The blending of polymers results in the formation of new materials which combine the useful properties of each constituent polymer. UPRs have been blended with elastomers (e.g., nitrile butadiene rubber, maleated nitrile rubber, carboxyl-terminated butadiene acrylonitrile rubber, etc.,) to improve their impact strength and other mechanical properties. Usually, fire properties are enhanced by blending with phenol formaldehyde resins. UPR blends with epoxy resin show improved toughness and impact properties. In some blends, superior thermal and damping properties are observed. IPNs are blends of two or more polymers in a network form, with one of the polymers synthesized and/or cross-linked in the immediate presence of the other(s). Although they are not bonded covalently with each other, they have partial or total physical interlocking between them. Semi-IPNs and full IPNs of UPR with other polymers such as polyurethanes, epoxy, nylons, phenol formaldehyde resin, and polyacrylates are discussed. Composites are made by combining two dissimilar materials at a macroscopic level in such a way that the resultant material is conferred with properties superior to those of any of its components. Of the two, one is the continuous phase, known as the matrix, and the other is the reinforcement. These components neither take part in any chemical reaction nor do they dissolve or completely merge into each other, yet they still remain strongly bonded and maintain an interphase between them. The reinforcement and matrix are complimentary to each other. They make use of each other’s properties in such a way that the composite exhibits enhanced properties. The reinforcing material may be in the form of fibers, particles, or flakes, and the polymer constitutes the matrix. Glass-reinforced composites are most popular, but apart from these, natural fibers such as sugar palm fibers, coconut fibers, henequen fibers, cotton fibers, hemp fibers, kenaf fibers, etc., have been used. Composites with metals, metal oxides, carbon fibers, and graphite have also been investigated. They have superior mechanical, chemical, thermal, and electrical properties. Nanocomposites consist of nanofillers dispersed in a polymer matrix with the reinforcement having a nanoscale structure (at least one dimension less than 100 nm) with a high aspect ratio (surface to volume ratio). A smaller size of filler leads to an exceptionally large interfacial area between the matrix and reinforcement compared to conventional composites. Polymer nanocomposites show significantly enhanced properties at much lower filler loading rates, which ultimately results in lower component weight and can simplify processing. In general, nanofillers are broadly classified on the basis of their geometries as particles, layered, or fibrous materials. Examples of particle-type nanofillers are carbon black, metal oxides (ZnO, Al2O3, and TiO2), silica nanoparticles, and polyhedral oligomeric silsesquioxanes. Carbon nanotubes (CNTs) and cellulose nanofibrils are examples of fibrous materials, while nanoclays and montmorillonite are layered materials. UPR nanocomposites show improved thermal, mechanical, electrical, water absorption, solvent resistance, flame retardancy, and volume shrinkage properties. Modification or functionalization of polymers and/or fillers leads to further enhancements in the properties of these materials. They are widely used in several industrial applications such as the automotive, construction, marine, and electrical fields, as well as in coatings, among others. Major challenges faced by the composite industry include reducing dependency on petroleum sources for the synthesis of UPRs by recycling polymer waste and making use of sustainable sources, the elimination of halogens in order to achieve fire retardancy, and the replacement of styrene to overcome environmental and health hazards.
Keywords
Unsaturated polyesters; blends; IPNs; composites; nanocomposites; mechanical properties; thermal properties; fire retardancy; challenges
1.1 Introduction
Unsaturated polyesters (UPs) are synthetic copolymers having applications as fibers, plastics, composites, and coatings. Depending on the choice of monomers, initiators, curing agents, additives, and modifiers used, different varieties of products can be produced exhibiting a wide range of chemical and mechanical properties. The low cost involved in their production makes them attractive. Their main application is as matrices in the composite industry. Among the composites, fiber glass–reinforced composites are of prime importance.
1.2 Types of Unsaturated Polyester Resins
Based on their structure, unsaturated polyesters resins (UPR) can be classified as: (1) ortho resins; (2) iso resins; (3) bisphenol A fumarates; (4) chlorendics; or (5) vinyl ester (VE) resins.
1.2.1 Ortho Resins
Ortho resins are also referred to as general-purpose polyester resins and are based on orthophthalic acid, namely, phthalic anhydride (PA), maleic anhydride (MA)/fumaric acid, and glycols. PA is relatively cheap and provides rigidity to the backbone. However, it has limited thermal and chemical resistance and processability. Among the glycols, resins formed using 1,2-propylene glycol (PG) are more important in comparison to other glycols. The pendant methyl group in PG lowers the crystallinity of resin and improves its compatibility with commonly used reactive diluents (such as styrene). Neopentyl glycol or hydrogenated bisphenol A yields resins with high heat and chemical resistance.
1.2.2 Iso Resins
Iso resins are prepared using isophthalic acid, MA/fumaric acid, and glycol. They are relatively expensive and have considerably high viscosities. Hence, they require a large proportion of reactive diluent, which also imparts improved water and alkali resistance to cured resins. They find applications as gel barrier coats in marine environments since they have better thermal and chemical resistance and mechanical properties.
1.2.3 Bisphenol A Fumarates
These are synthesized using ethoxy-based bisphenol A and fumaric acid. Though expensive, they exhibit superior chemical properties as well as corrosion resistance as compared to ortho and iso resins. The presence of bisphenol A in the backbone renders a higher degree of hardness and rigidity and improved thermal performance. Due to the reduced number of interior chain ester groups, their hydrolysis resistance is best among commercial unsaturated resins.
1.2.4 Chlorendics
Chlorine/bromine-containing anhydrides or phenols are used for preparing chlorendics. They exhibit flame resistance along with good chemical and corrosion resistance. For example, the reaction between chlorendic anhydride/chlorendic acid and MA/fumaric acid and glycol yields resin with better flame retardancy than general-purpose UPR. Other monomers used include tetrachloro- or tetrabromophthalic anhydride. The bromine content must be at least 12% in order to obtain a self-extinguishing polyester.
1.2.5 Vinyl Ester Resins
VE resins contain unsaturated sites only at the terminal position as bisacryloxy or bismethacryloxy derivatives of epoxy resins. They are prepared through the reaction of acrylic acid or methacrylic acid with epoxy resin (e.g., diglycidyl ether of bisphenol A (DGEBA), epoxy of the phenol novolac type, or epoxy based on tetrabromobisphenol A). These resins were first commercialized in 1965 by Shell Chemical Company under the trade name Epocryl [1]. In 1966 Dow Chemical Company introduced a similar series of resins for molding purposes under the trade name Derakane resins [1]. The viscosity of neat resins is high; hence, reactive diluents (e.g., styrene) are added to obtain solutions with lower viscosities (100–500 poise). Notable advances in VE resin formulations include low-styrene-emission resins, automotive grades with high tensile strength and heat deflection temperature, hybrid grades that balance performance and economy, and materials for corrosion resistance.
1.3 Synthesis of Unsaturated Polyester Resins
UP is often synthesized as a viscous liquid through the melt condensation of an aromatic dicarboxylic acid such as phthalic acid or anhydride with polyhydric alcohol and unsaturated dicarboxylic acid or anhydride. The viscosity of the reaction product/oligoester (OER) is reduced using a reactive diluent such as a vinyl monomer, usually styrene. Free radical copolymerization between styrene and the double bonds of UP results in a rigid three-dimensional cross-linked structure, which is a heterochain thermoset type of polymer. Methyl ethyl ketone peroxide (MEKP) is a standard catalyst that initiates the curing reaction in combination with a cobalt or cobalt-amine activator system/accelerator at room temperature. Other free radicals used for curing UPRs include benzoyl peroxide (BPO) or cumene hydroperoxide [2]. After synthesis, an inhibitor is added to the resin to provide a long storage life, fast cure, and to minimize catalyzed or uncatalyzed drift, undesirable colors, odors, or side effects. Hydroquinone, 4,4-dihydroxybiphenyl, and substituted catechols are some examples of inhibitors [3].
Attempts have been made by various researchers to tailor the mechanical, thermal, corrosion, and fire resistance properties of UPRs for various applications. Parker et al. suggested the use of isophthalic acid for improved mechanical properties and corrosion resistance 
~480–477,000 and glass transition temperature (Tg) of between −30.1°C and −16.6°C with solubilities differing based on the starting monomers used [8]. Yoon et al. regenerated UPR after recycling cured UPR. The recycled UPR exhibited a faster curing rate than that of neat resin. A comparison of the mechanical properties of the neat resin and the mixtures (neat resin and recycled) revealed that although the properties of neat resin were superior, those of the mixtures were dependent on composition and were found to be suitable for many applications [9].
Different proportions of cobalt (Co) curing agent were used (0.05%–1%). An increase in the concentration of Co from 0% to 1% led to a decrease in curing time. This was reduced to half in the presence of 0.05% Co [10]. The effect of volume ratios of curing agents, viz., cobalt octoate as an accelerator and MEKP as an initiator, on gelation time and exotherm behavior of a UPR has also been studied. The gelation of the resin was found to correspond with the onset of an increase in temperature during resin curing. The gelation time was found to vary inversely with the concentrations of accelerator and initiator [11]. The viscosity of the liquid system was found to decrease with increasing temperature, but increased at the curing temperature. The quality of the cured UPR was predicted on the basis of its fragility parameter (Mc). In the UPR–MEKP system, the smaller the Mc the larger the Tg and the better the heat resistance [12].
The curing behavior of UPR was studied using an experimental and theoretical model by Kosar and Gomzi [13]. The kinetic behavior of the curing system was investigated using both dynamic and isothermal measurements and a good agreement was established between the two (in terms of presented kinetic parameters and reaction heat). Heat generated from the cure reaction was measured in molds of cylindrical shape. The difference in heat conductivity between glass and copper was the main reason for the greater heat generated in the glass mold.
Control over resin shrinkage of residual monomers is an important concern in low-temperature molding processes. The presence of low-profile additives (LPAs) can reduce the shrinkage of UPR/styrene resins under proper processing conditions, but may increase the residual styrene content. A systematic study was carried out to investigate the effect of the initiator system and reaction temperature on the sample morphology, final resin conversion, and resin shrinkage of UPR with LPA. The results showed that the final conversion of the resin system could be improved by dual initiators, with the effect being prominent at low temperatures. The study on shrinkage control reported that good LPA performances were achieved at low (35°C) and high (100°C) temperatures, but worse performances were observed in the intermediate temperature range (e.g., 60°C–75°C) (Fig. 1.1). The final shrinkage is influenced by the effect of temperature on the morphology, the relative reaction rate in the LPA-rich and UPR-rich phases, and microvoid formation [14]. The sample morphology shows a two-phase cocontinuous structure at 35°C (Fig. 1.2). One is a particulate phase (LPA-rich) having loosely packed spherical particles with diameters ranging from 1 to 5 mm. The other phase is a flake-like region (UPR-rich) with domain sizes ranging from 10 to 20 mm. At a curing temperature of 60°C, a similar two-phase structure is observed, but it is no longer cocontinuous. The particulate region is smaller and becomes the dispersed phase with a domain size of less than 20 mm, while the flake-like region forms the continuous phase. On increasing the temperature to 75°C and 100°C, the size of the particulate region is further reduced. The various morphological structures result in different interface areas, strongly affecting the shrinkage control.
Figure 1.1 Volume shrinkage of UP/St/LPA systems cured at different temperatures (3.5% LPA, 0.5% Co Oct., 1.3% MEKP, 0.4% TBPB, 300 ppm BQ).
Figure 1.2 Morphology of St/UP/LPA samples cured at different temperatures (3.5% LPA, 0.5% Co Oct., 1.3% MEKP, 0.4% TBPB, 300 ppm BQ).
Commercial UPRs contain 30%–40% styrene by mass. The miscibility of resin and styrene depends on the resin composition. Phase separation is reported with an increase in styrene concentration. Thermal stability and mechanical properties are governed by the phase behavior of the mixture and can, therefore, be controlled by styrene content [15]. Dynamic mechanical analysis (DMA) tests have shown phase separation in cured resin with high styrene concentrations. Tg is also dependent on styrene concentration together with thermal stability and mechanical behavior [16].
1.3.1 Low-Styrene-Emission Unsaturated Polyester Resin
Styrene has remained a preferred reactive diluent for adding to UP due to its cost and availability. It controls the viscosity and facilitates the curing of polyesters at room temperature. However, the use of styrene is associated with serious health problems such as respiratory diseases and skin irritation. It is carcinogenic and also attacks the central nervous system on exposure over a long period of time, leading to possible headaches and depression. The minimization of styrene volatilization or its elimination using alternative monomers is being attempted to overcome these problems.
The volatilization of styrene is reduced by paraffinic waxes which act as a barrier. However, the wax layer needs prior removal to avoid problems of adhesion to other parts. The ambient concentration of styrene vapor can be reduced using spray guns that can monitor the amount of resin sprayed. Since alternatives such as vinyl toluene, alpha-methylstyrene, and diallyl phthalate suggested for styrene also involve health hazards, Poillucci and Hansen proposed the use of bio-derived limonene oil and petroleum-derived vinyl neodecanoate and vinyl laurates as other substitutes for styrene, but they exhibit limited chemical compatibility. The styrene content was reduced by 50% using trimethylolpropane diallyl ether [17]. Mariani used various cross-linking agents such as 2-hydroxyethyl acrylates (HEA) or a mixture constituted of diurethane diacrylate and styrene or HEA for frontal curing of UPR derived from the reaction of MA and 1,2 propanediol [18]. Zang et al. reported a benzyl end-cap-UP resin with low styrene emission using benzyl alcohol as the end-capper [19].
For nonhalogenated resins, a marked restriction in styrene emission is achieved by including long-chain alpha-olefins with 18–40 carbon (C) atoms without the addition of wax. These olefins on their own will not usually provide such a marked restriction in styrene emission, but will allow for the incorporation of a waxy compound in an amount sufficiently large to achieve the desired styrene emission restriction without incurring the expected disadvantages associated with the incorporation of such large amounts of waxy compound [20].
1.3.2 Styrene-Free Compositions for Curable Coatings
When UPRs are used as coatings, styrene-free compositions are favored since volatile emissions by such compositions are expected to be low. An example of such a formulation consists of one comonomer selected from the (meth)acrylates of cycloaliphatic alcohols and optional comonomers could be tetrahydrofurfuryl (meth)acrylate, methoxypolyethylene glycol, mono(meth)acrylate, ethylene glycol dimethacrylate, and di(ethylene glycol) di(meth)acrylate while the curing can be done by radiation and/or through the peroxide or thermal routes. More specifically, curing can be performed by adopting a process comprising at least one step of radiation and/or peroxide curing [21].
Styrene-free UPR coatings cured by infrared radiations are described as containing an unsaturated ether component as well as saturated monohydric alcohol along with dicarboxylic acid and dihydric alcohol [22]. Also, radically curable styrene-free coatings are claimed to be composed of compounds containing a (meth)acryloyl group and/or vinyl ether groups along with paraffin, a plasticizer, and carbamic acid [23]. Styrene-free compositions are reported by using various reactive diluents singly or in combination such as 2-hydroxyethyl methacrylate, 2-hydroxy propyl methacrylate, 2-HEA, 2-hydroxypropyl acrylate, and related compounds [24].
UPR can also be obtained as a reaction product of at least one diol having 2–8 C atoms, one monoalcohol with at least one allylic unsaturation, and at least one saturated aliphatic monoalcohol having 4–10 C atoms or one aromatic monoalcohol having 7–10 C atoms. The coating or molding composition of such a UPR is curable by radiation and/or through the peroxide or thermal routes [25]. McAlvin reported UPR derived from biologically renewable resources and recycled materials, which are styrene-free and ultralow volatile organic compound (VOC) resins that provide matrix materials to produce more ecologically friendly composites [26]. A styrene-free UPR forming a stable dispersion in water has been reported. The modification was done by introducing polar hydrophilic groups such as carboxylic and sulfonic groups (sodium 5-sulfonatoisophthalic acid) into the resin molecule, which ensure good tolerance to water. Styrene has been replaced with the glycerol monoethers of allyl alcohol and unsaturated fatty alcohols as reactive built-in cross-linking monomers for resin modification [27].
1.3.3 Modification of Unsaturated Resin for Viscosity Control
UPRs have replaced sheet metal in many applications such as in the automotive, electric, and home appliance industries as a consequence of their properties such as being light weight, having high strength, and their noncorrosive nature. UPR composite products are manufactured by compression molding in the form of sheet molding compounds (SMCs) or bulk molding compounds (BMCs), through injection molding in the form of BMC, resin transfer molding, casting, and hand layup. Chiu et al. attempted to develop UPR systems exhibiting viscosity profile properties such as rapid increase during maturation/thickening and mold filling so that they can be handled easily, have good fiber carrying characteristics, and long-term stability. For good material flow, a significant reduction in viscosity is required during molding which facilitates the complete filling of the mold as well as the complete wetting of the filler and other ingredients in the system by the UPR [28]. Fig. 1.3 shows the ideal viscosity profiles for SMCs and BMCs during molding.
Figure 1.3 Ideal viscosity profile for SMCs or BMCs during molding: (I) thickening; (II) storage; (III) mold filling; and (IV) curing.
Chemically, thickening or maturation
occurs by linking up various UPR molecules together to form polymer chains of considerably higher molecular weights. Usually, this is done by adding a di- or multifunctional compound to the system which couples two or more polyester molecules together via their terminal hydroxyl and/or carboxyl groups. As UPR molecules usually contain more than two functional groups, the actual product formed is a complex network of interconnected polymer chains rather than discrete individual chains. Compounds used for thickening UPRs are known as thickening agents
or maturation agents.
Two types of compounds are used as thickening agents. The first type comprises Group IIA metal oxides and hydroxides, for example, MgO [29]. Maturation with this type of agent occurs via the formation of ionic bonds through the reaction of MgO with the carboxylic acid end groups of polyester molecules. The other type of maturation agent is diisocyanate [30]. Diisocyanates operate by forming covalent bonds, specifically urethane linkages, with the terminal hydroxyl groups of polyester molecules. Each type of maturation agent has its own advantages and disadvantages. The maturation process with MgO-type agents is slow. They form ionic bonds which weaken at elevated temperatures encountered during molding. This results in a reduced compound viscosity and hence the desired material flow. Diisocyanate maturation agents exhibit rapid thickening. The covalent bonds formed with isocyanate-type thickeners do not weaken at molding temperatures and hence material flow is more difficult. MgO-type maturation agents are highly sensitive to humidity after maturation, whereas diisocyanates are not. A thermally breakable di-keto group can be introduced onto the UPR molecule before curing through salt formation. This group, along with the salt, may break at elevated temperature in most UPR molding operations and therefore reduce the compound viscosity upon heating; hence the desired amount of material flow is realized. Modified resins are further thickened with MgO or diphenyl diisocyanate. This exhibits a fast viscosity rise during molding and a stable viscosity during room temperature storage [28].
Molded articles made with conventional UPRs often exhibit poor surface finishes. This is probably due to shrinkage of the UPR during the molding operation. LPAs are used to overcome this problem. Along with LPAs, good material flow during molding is also necessary to obtain finishes of the highest quality. The reduced material flow encountered when diisocyanates are used as thickeners reduces the effectiveness of LPA in these systems, which in turn may lead to significant finish problems. One proposal to overcome this limitation is to use a combination of both MgO-type and diisocyanate-type thickeners in the same system [31].
1.4 Unsaturated Polyesters Resin Blends
Polymer blends are made by the physical mixing of two or more different polymers or copolymers to produce a mixture with desirable mechanical and physical properties. Usually, the Tg of cured UPRs are high and their brittleness presents an obstacle for their use in engineering applications [32]. The mechanical, physical, and thermal properties of UPR can be improved by blending with other polymers or by reacting them with different additives or modifiers which generally form a second dispersed phase after the resin is cured. Blends show the demanded performance at low cost.
1.4.1 Unsaturated Polyesters Resin–Elastomer Blends
The addition of elastomeric phases to UPRs usually improves their overall ductility over a wide range of temperatures, toughness, and impact resistances. Elastomers are blended with UPR before curing by physical and chemical methods. When blends are formed by the physical mixing of two or more polymers at least 5% of another polymer is necessary to form a blend. If the component polymers are miscible, a single-phase blend is obtained. If they are immiscible, a multiphase blend is formed. Even if rubber additives are soluble in uncured resin, phase separation during curing is advantageous since these blends are tougher than homogeneous blends [33,34]. The presence of elastomeric domains increases the absorption and dissipation of mechanical energy. Various mechanisms proposed for toughening by blending with rubber include the debonding of the rubber matrix interphase, energy absorption by rubber particles, matrix crazing, shear yielding, and combining shear yielding and crazing [32,33].
Essential characteristics of elastomers for toughening are [35]:
1. The presence of a sufficient number of polar groups to enhance solubility in the resin.
2. The elastomer should have a slow rate of cross-linking compared to the UPR used to facilitate the distribution of discrete elastomeric particles during cross-linking.
3. The weight of the elastomer should be relatively high.
4. The major part of the elastomer should be thermodynamically incompatible with resin.
1.4.1.1 Unsaturated polyesters resin–natural rubber blends
Natural rubber is an elastic material present in latex from rubber trees. Its easy availability, low cost, and excellent physical properties such as good resilience, high tensile strength, superior resistance to tear and abrasion, good tack, and self-adhesion have led to its use in preparing blends. On the other hand, it has poor age resistance and oil resistance.
Blends based on UPR from recycled poly(ethylene terephthalate) (PET) wastes with varying percentages (0%–7.5 wt.%) of liquid natural rubber (LNR) have been prepared by Hisham et al. They are found to exhibit good compatibility compared to commercial resins, but show higher Tg. A blend with 2.5 wt.% LNR rendered the highest strength and best dispersion of elastomer particles while commercial resin required 5% of LNR to achieve optimum properties [36]. Studies on the influence of the source of water and immersion time on the mechanical properties of UPR–natural rubber blends have revealed increases in the impact strength and strain rates and decreases in the Young’s modulus of polymer blends under identical conditions [33]. Hybrid proton exchange membranes as an alternative for Nafion in polymer electrolyte membrane fuel cell (PEMFC) were developed by Jimenez et al. UPR–natural rubber blends were prepared and subjected to the process of vulcanization and TiO2 was added as an inorganic load. The blends exhibited higher Young’s moduli and strains compared to commercial Nafion membranes. The water uptake as well as ion exchange capabilities of the vulcanized membrane was found to be superior [37]. Natural rubber latex (NRL) when blended with UPR in the presence of dispersion aids such as sodium lauryl sulfate (SLS), toluene, and ammonia led to an improvement in impact strength. However, the flexural strength decreased with NRL content in the blend (Fig. 1.4). The impact strength was highest when NRL and toluene were 15 phr and 20 wt.%, respectively [38].
Figure 1.4 Impact strength of pure UPR and UPR/NRL blends using different dispersion aids: (A) using SLS as a dispersion aid; (B) using toluene as a dispersion aid; and (C) using liquid ammonia as a dispersion aid.
1.4.1.2 Unsaturated polyesters resin-synthetic rubber blends
Synthetic rubbers have also been used for blending with UPRs. Binary polymer blends of UPR and different weight ratios (0%, 5%, 10%, and 15%) of nitrile butadiene rubber (NBR) have been prepared by mechanical mixing using toluene as a solvent. However, they showed poor mechanical properties, except for their strain rates which were higher. The wear rates of the blends were found to decrease with increasing NBR content [39]. Cherian and Thachil prepared blends of UPR with elastomers bearing reactive functional groups such as hydroxy-terminated polybutadiene, epoxidized natural rubber, hydroxy-terminated natural rubber, and maleated nitrile rubber. These elastomers show better compatibility with resin and impart superior toughness, fracture resistance, and impact resistance as compared to unmodified elastomers [34]. The authors also synthesized UPR blends using two different strategies for incorporating rubber. The first method involves the dissolution of masticated elastomers such as natural rubber (NR), styrene butadiene rubber (SBR), NBR, butyl rubber (IIR), and chloroprene rubber (CR) in styrene followed by blending with UPR, while in the second method, elastomers are modified with MA and then dissolved in styrene and blended with UPR to get maleated elastomers. Blends having elastomers modified with MA show improved mechanical properties (toughness, impact resistance, and tensile strength) compared to unmodified rubbers (Tables 1.1 and 1.2). The performance of nitrile rubber is found to be far superior in comparison to all other rubbers [32]. Toughening agents like carboxyl and vinyl terminated nitrile rubbers as well as urethane rubbers have also been used for preparing blends. The incorporation of flexible polyorganosiloxane segments in the UPR network enhances its flexibility [34]. The thermal stability of toughened UPR–NBR improved on reinforcing it with slag powder. The sample modified with stearic acid showed better mechanical properties. A fire resistance test showed reduced mass loss when exposed to direct open flame [40].
Table 1.1
Table 1.2
Suspene et al. observed an improvement in the compatibility of a UPR–carboxyl-terminated butadiene-acrylonitrile rubber (CTBN)blend by exchanging 10% CTBN for epoxy-terminated nitrile rubber (ETBN) in a blend with 5 phr of rubber. In the resulting triblock copolymer a decrease in particle size of the dispersed rubbery phase from 12 to 5 µm was observed and the interfacial tension between UPR and CTBN is also reduced. The impact behavior of the triblock copolymer was enhanced due to a reduction in failures caused by the presence of large particles [41].
1.4.2 Unsaturated Polyesters Resin–Phenol Formaldehyde Resin Blends
UPRs are highly flammable and produce large quantities of smoke and toxic gases on burning. The flame resistance of UPR can be improved by adding flame-retardant additives or by blending it with other polymers such as phenolic formaldehyde resins (PF). The addition of additives usually leads to unfavorable reactions between the polymer and additives resulting in the deterioration of the mechanical properties of polymers to some extent. Blends of UPR and PF show good fire retardant abilities due to the high charring tendency of PF. PF is known to generate less toxic gases and smoke and leave a large amount of carbon residue [42].
Among phenolic resins, resoles and novolacs are important; on curing, they produce highly cross-linked thermally stable network structures, which on exposure to high heat or fire, char, thus producing relatively low levels of combustible volatiles [43]. Kandola et al. used ethanol-soluble epoxy and allyl-functionalized phenolic resoles to overcome the incompatibility of UPR and PF resins resulting from their chemical structures and curing mechanisms. They demonstrated an increase in compatibility with functionalization. Allyl-functionalized resole exhibited the best compatibility with UPR. A mechanism has been proposed for their decomposition and interactions and their effects on flammability based on thermal behavior and infrared spectroscopic analysis of volatile degradation products [44]. Mahadar et al. blended UPR with resole to produce materials with good flame retardancy. The blends showed good compatibility when compounded with kenaf fiber, which is a natural fiber. Although the thermal stability of the blends was improved, the mechanical properties were found to be slightly inferior [42]. Novolac resin was modified with free-radically curable methacrylate groups (M-Nov) with styrene to give a material with a higher Tg, better thermal and thermo-oxidative stabilities, and better flame retardancy than cured UPR, with an approximately 20% lower modulus at room temperature (RT) [43]. An alternative modification of novolac with the vinylbenzyl group to obtain a homogeneous, free-radically cocured phenolic/UPR blend with better flame retardancy than those made using M-Nov has also been attempted. The cured vinylbenzylated novolac and its cocured blends with UPR exhibited superior flame retardancy in comparison to cured UPR and have potential applications as matrix resins in glass-reinforced composite laminates, especially for marine structures [45].
1.4.3 Unsaturated Polyesters Resin–Epoxy Resin Blends
UPR and epoxy resin are miscible with each other and show good compatibility. Hybrid polymer networks (HPNs) based on UPR and epoxidized phenolic novolacs (EPNs) have been prepared through reactive blending. EPN shows good miscibility and compatibility with UPR. The blend shows substantially improved toughness and impact resistance along with better thermal stability. Blends with 5 wt.% of EPN exhibit the highest tensile strength [46,47]. HPNs were also synthesized by coreacting UPR with epoxidized cresol novolac and DGEBA. Cocured blended resins showed substantial improvements in toughness and impact resistance along with thermal stability and damping properties. The performance of the blends with EPN was found to be superior [47].
A new bioresin was produced by Mustapha et al. by blending UPR with epoxidized palm oil (EPO) in 10, 20, and 30 wt.%. The addition of EPO in UPR resin lowered the Tg at 20 wt.% loading of EPO, Tg decreased by ±5°C, and the storage modulus decreased by about 20% in comparison to UPR. However, the impact properties increased with the amount of EPO added. EPO provides a rubbery phase and absorbs the energy applied by the impact loadings. Bio-based thermoset UPR blended with EPO may reduce the dependency on conventional composite matrix systems made from petrochemicals [48].
UPRs were prepared by reacting bisphenol A epoxy resin with various glutaconic acids using a base catalyst. They were functionalized by treatment with acryloyl chloride to yield acrylated polyesters (APEs). Blending of these APEs were carried out with styrene monomers. In comparison to APEs, these blends exhibited high curing temperatures, slow degradation of products (i.e., low weight loss), good chemical resistances, and good mechanical and electrical strengths [49].
1.4.4 Unsaturated Polyesters Resin–Esters Blends
Ardhyananta blended VE and UPR containing aromatic benzene rings (10%–80 wt.%). The UPR/VE blends were prepared by mechanical blending and cured at room temperature using 4% of MEPK in the absence of an accelerator. The mechanical and thermal properties of the blends were found to be superior [50]. Polymer blends of unsaturated polyether ester resins and dicyclopentadiene polyester resins yield cured thermoset resins having high tensile and flexural strengths. The coaction resulting from blended polymers provides an economic way to improve both the stiffness and strength of cured polyether ester resins [51].
Styrenated polyester resins were blended with poly(vinyl acetate) (PVAc). A cocontinuous phase morphology was observed in blends containing PVAc with concentrations ≥6% and styrene levels ≥40%. An increase in the styrene content from 20% to 80% resulted in the sharpening of the principal dynamic loss peak, and the peak temperature reached a maximum at a concentration of 40%. The change from particulate PVAc to cocontinuous structure was associated with a sharp drop in G~c and K~c. Parallel studies have shown this transition to be important in low-profile
behavior [52].
1.4.5 Unsaturated Polyesters Resin–Polysaccharide Blends
Modified UP was blended with cellulose and ethyl cellulose (5%–25%) at ambient conditions in the presence of MEKP as a curing agent. The blends showed compatibility with modified UP as a result of the polar –OH groups in their structure. The results indicate that cellulose increases the impact strength, hardness, and dielectric constant and decreases the bending of the blends, while ethyl cellulose causes an increase in the impact strength, hardness, and bending but a decrease in the dielectric constant of the blends [53]. The work done by Salih et al. involves the blending of UPR with starch powder (0–3 wt.% fraction) with particle sizes less than 45 µm. The blends were further irradiated by UV acceleration. The UV irradiations had a noticeable effect on most of the mechanical properties of the blends. The mechanical properties were found to be a function of particle size and the dispersion of starch powder in the UP matrix. A significant decrease was observed in the ultimate tensile strength and elongation percentage with increasing weight fractions of starch powder, while the modulus of elasticity of the blend showed a significant increase. Other mechanical properties of the blends such as hardness, impact strength, fracture toughness, and flexural strength also increased with increasing weight fractions of starch powder (1%), except the flexural modulus at 1.5%, followed by a decrease at higher percentages of starch [54].
1.4.6 Thermoplastic Blends
Xanthos and Wan reported the melt blending of polypropylene (PP) with a nonconventional low molecular weight UPR (5:3 PP/UPR wt. ratio) in the presence of organic peroxide by reactive processing. The reacted blend exhibited a finer and more uniform morphology and different properties. The results indicate the possibility of the formation of block and/or graft PP/UPR compatibilizing copolymers [55]. UPR blends of different compositions were prepared with two different thermoplastics, polystyrene (PS) and polycarbonate (PC), by mixing solutions of the polymers in chloroform. A miscibility study of these solution blends was carried out using simple and inexpensive techniques. The UPR/PS blend was found to be miscible while the UPR/PC blend was immiscible [56].
Hydrogen bonding interactions between the two components in poly(ethylene oxide) (PEO)/OER blends and PEO/cross-linked UPR blends were understood by Fourier transform infrared spectroscopy (FTIR) study. These hydrogen bonding interactions are responsible for the miscibility of the blends. The crystallization kinetics and morphology of PEO in the PEO/UPR blend was found to be dependent on cross-linking. At the crystallization temperature, the overall crystallization rate of PEO in the PEO/UPR blend was larger than that in PEO/OER blend [57]. Li et al. used an improved nuclear magnetic resonance (NMR) method to measure the interphase thickness and to interpret the phase behavior, miscibility, heterogeneous dynamics, and microdomain structure of a thermoset blend of UPR with a cotriblock polymer of PEO-block-poly(propylene oxide)-block-PEO (PEO-PPO-PEO). The results indicated that thermodynamic interaction between the block copolymer and the cross-linked thermoset resin is a key factor in controlling the phase behavior, domain size, and interphase thickness of these blends [58]. Although poly(ε-caprolactone) (PCL) was found to be miscible with uncured polyester/OER, it is partially miscible with crosslinked polyester resin (PER). The miscibility of PCL and OER/PER was found to be a consequence of intermolecular hydrogen bonding between the components of the blend. The importance of the contribution of entropy to the miscibility of thermosetting polymer blends is also shown from FTIR results. The spherulitic morphology of the blends was remarkably affected by cross-linking. Birefringent spherulites were observed in uncured PCL/OER blends, whereas a distinct pattern of extinction rings, which was absent both in the pure PCL or in the uncured PCL/OER blends, was apparent in the cross-linked PCL/PER blends [59].
1.4.7 Simulation Studies on Blends
Ruffier et al. performed a simulation to show the connection between voids scattered inside the UPR–polyvinyl acetate blend and the blend phase separation mechanism [60]. The effect of curing temperature on the morphology of UPR/styrene/PVAc blends with 5% and 10% PVAc cured between 75°C and 150°C was studied. A cocontinuous phase separated structure resulted for 10% PVAc. An insignificant change in morphology with curing temperature was observed for this composition [61].
A computer simulation model to analyze the reaction injection molding process of polyurethane and UP blends has also been proposed [62]. Mezzenga et al. modeled the free energy of mixing during polymerization in blends of UPR, styrene, and allyl ether functionalized hyperbranched polyesters. They combined the Flory–Huggins theory and gel permeation chromatography (GPC) molecular weight measurements during modeling. The cure behaviors of UPR, phenol, and UPR/phenol blends were detected and simulated using differential scanning calorimetry (DSC) and DMA. Cure behavior was used to calculate and predict the cure rate, cure temperature, conversion, and changes in the Tg along with various cure orders in order to obtain the optimum parameters for processing [63]. With dynamic scanning, isothermal DSC procedures, and Borchardt–Daniels dynamic software, cure data for the UP resin were obtained; 90% of the conversion rate at 100°C being achieved after 15 minutes. However, for the phenol and UPR/phenol blends, gradually increasing the temperature was found to be the best for curing according to the DSC and DMA test results [64].
1.5 Interpenetrating Networks of Unsaturated Polyester Resin
These are a relatively new type of polymer blends which consists of two or more cross-linked polymers in which at least one network is synthesized in the presence of the other. Although different modification processes are reported, the formation of interpenetrating polymer networks (IPNs) is a promising method.
1.5.1 Unsaturated Polyesters Resin–Polyurethane Interpenetrating Polymer Networks
Mutually permeable semi-IPN-type networks consisting of UPR and polyurethane resin (PUR) (semi-IPN UPR/PUR) have been prepared using a new method of adding PUR to styrene. Both resins form dispersed phases with heterogeneous microstructures. PUR seems to affect the mechanical properties significantly, but the effect ceases on increasing the PUR content above 10%. The dynamic elasticity modulus depends only on composition [65]. IPNs with four different types of UPRs (commercially available unsaturated polyester (UPE), partially end capped UPE, OH-free, and having acetate linkages at the end) and PU were cured with UV. The reaction sequence was found to be an important factor in determining the phase mixing, phase morphology, and hence, the mechanical properties of the IPNs. The simultaneous reaction of the two reacting systems resulted in a cocontinuous structure that provided enhanced tensile properties and impact strengths [66].
A series of BaTiO3 fiber and nanopowder unfilled and filled IPNs composed of polyurethane (PU) and UPR were prepared using a simultaneous polymerization process. The damping behaviors and degree of phase separation of the unfilled and filled IPNs were strongly dependent on the PU/UP component ratios, types of filler, and the amount of nanopowder added. The filled IPNs exhibited synergistic effects on damping properties. Performing a polarizing process enhanced the properties. The temperature ranges exhibited excellent consistency of maximum dielectric loss and dielectric constant with damping loss factor [67].
1.5.2 Unsaturated Polyesters Resin–Acrylate Interpenetrating Polymer Networks
Polyester–poly(ethyl acrylate-co-styrene) IPNs were synthesized using a two-step in situ sequential technique. Both semi- and full IPNs were synthesized. Poly(ethyl acrylate-co-styrene) acts as the rubbery phase and polyester as a hard phase. With increasing proportions of ethyl acrylate in the IPN, the elongation at break, toughness, and molecular weight between cross-links was higher, but tensile strength, modulus, tear strength, and density were lower. The full IPNs showed higher tensile strength, modulus, tear strength, density, and hardness, but lower elongation at break and toughness compared to semi-IPNs. The semi-IPNs showed higher toughness and elongation. The extent of cross-linking of the elastomer had a determining role in the mechanical property profile. The diameter of the domain depended on the amount of elastomer added [68]. Acrylate-modified PUR resin was first prepared and then added to UPR to obtain an IPN that could be cured at RT. An improvement in miscibility led to higher degree of penetration and entanglement, thus resulting in improved mechanical properties [69]. A series of semi-IPNs based on different compositions of an acyclic PET oligomer and UPR were prepared with styrene as a cross-linker, MEKP as a catalyst, and cobalt naphthenate as a promoter. The mixture was cured at RT. The tensile strength of the IPNs decreased, whereas the elongation at break increased with the concentration of PET oligomer [70].
1.5.3 Unsaturated Polyesters Resin–Epoxy Resins Interpenetrating Polymer Networks
Simultaneous IPNs based on epoxy (DGEBA) and UP were prepared using m-xylene diamine and BPO as curing agents. Single Tg suggested good compatibility of epoxy and UP. Interlock between the two growing networks led to a retarded viscosity increase. The hydroxyl end groups in the UP catalyzed the curing reaction of epoxy; leading to rapid increase in viscosity. Entanglement affected the cracking energy absorption and was reflected in an improvement in toughness [71]. The Tg of simultaneous IPNs was found to increase with the EP (epoxy polyester) content (10%–90 wt.%). IPNs containing higher EP contents exhibited higher values of tan δ(max.) (Fig. 1.5) and lower cross-linking densities in the rubbery state probably due to the plasticization effect of the EP component along with the heterogeneous network structure [2]. Studies on the curing kinetics of simultaneous UP/DGEBA IPNs showed lower total heat of reaction compared to that observed while curing pure resins. This could be an effect of network interlock that could not be compensated completely by an increase in curing temperature. Incomplete curing in isothermal mode is caused by both network interlock and the vitrification of DGEBA. The rate constant for 50/50 of UP/DGEBA was higher while the activation energy was lower presumably due to the catalytic environment provided by the hydroxyl end group of UP in the IPN [72,73].
Figure 1.5 tan δ versus temperature of BPO/THPA-cured IPNs, BPO-cured UPR, and THPA-cured EP.
A series of IPNs with excellent flame-retardant and damping properties were developed. The flexibility and range of thermal transition increased as the content of UPR increased in the IPNs while the homogeneity decreased. The heat resistance, damping, and mechanical properties were all improved simultaneously with the addition of plate-shaped carbon black (CB) into the UPR/epoxy IPNs [74]. Shin and Jeng also prepared UPR/epoxy IPNs. A series of IPNs based on UP/epoxy were developed. Phase separation was observed when the UPR content was higher than 30%. The best miscibility for IPN was obtained for a composition with similar amounts of hydrogen donors and carbonyl group [75]. From a kinetic study of EP/UPR it was found that the heat resistance of UP was enhanced with the addition of a flame-retardant or epoxy resin [76].
A series of translucent, compatible IPNs were prepared by Shaker et al. using an elastomeric amine-cured epoxy and UPR. A 45% increase in toughness was observed for one of the compositions. This was a reflection of the homogeneous distribution of the rubber component [77]. Semi-IPNs of epoxy and UPR have been synthesized with different proportions of UPR (0%–50%). Trimethylenetetramine was used as a room temperature curing agent. IPNs with 11.1% of UPR exhibited improved mechanical properties. The blends were further modified by aromatic amines such as benzidine and diphenyl amine. The mechanical properties of the blend modified with diphenyl amine were found to be superior [78].
1.5.4 Unsaturated Polyesters Resin–Phenol and Unsaturated Polyesters Resin–Nylon Interpenetrating Polymer Networks
IPNs of UPR and several phenolic resoles have been reported by Avendano et al. These IPNs were found to show both physical and chemical compatibility as they cocure such that they result in cocontinuous IPNs. The participation of the allyl groups of resole in the cross-linking process of IPNs could be confirmed from the solid-state ¹³C-NMR spectra [79].
Novel semi-IPNs of UPR and nylon have been produced by mixing different amounts of Nylon 66 oligomers (residues of industrial Nylon 66 polymerization) into UPR and heating followed by cross-linking. Nylon 66 was obtained from industrial waste. Three important aspects of this work include (1) the possibility of producing new materials with improved impact strengths, (2) the plastifying effect of Nylon 66 oligomers on the UP resin, and (3) ecologically more important, the feasibility of reutilizing waste materials for producing engineering materials with tailored properties [80].
1.6 Unsaturated Polyesters Resin Composites
Composites are heterogenous materials made up of two or more chemically distinct constituents. The basic components are a reinforcement and a matrix. Each of these should have appropriate characteristics and function both individually and collectively so that composites attain the desired superior properties. The reinforcement contributes to the strength and modulus to the composite, while the main role of the matrix is to transmit and distribute stresses in the reinforcement. Reinforcements are of two types, namely particulate and fibers. Commercially, glass fiber (GF)-reinforced polyester composites are important due to their high strength-to-weight ratio, low cost, and easy manufacturing methods. In comparison to particulate-filled composites, many fiber-filled composites are anisotropic with tremendous strength in one direction; although uniaxially oriented fiber composites have very high moduli in one direction, the other moduli are low. Therefore to get good properties in atleast two or three directions, fibers can be randomly oriented such that composites are nearly isotropic in a plane. In the case of fibers as a reinforcement, it also provides protection against both fiber aberration and fiber exposure to moisture or other environmental conditions.
1.6.1 Unsaturated Polyesters Resin–Synthetic/Glass Fiber Composites
Commercial interest in GF-reinforced UPR composites is due to their high strength-to-weight ratio, and low cost.
E-GF composites prepared using a hand layup technique with concentrations varying between 15 and 60 wt.% rendered excellent mechanical properties. Table 1.3 shows the improvement in the mechanical properties as a function of filler content [81].
Table 1.3
Belaid et al. carried out thermal ageing studies on polyester fiberglass composites and reported a strong effect on mechanical properties. The Young’s modulus decreased with aging time; from 6% after 30 days to 55% after 120 days [82]. Pedroso et al. achieved significant improvements in the texture, flexural strength, and impact resistance of sheets of UPR GF composites by pressing and heating the sheets at 40°C and 50°C during curing [83]. Studies on the immersion of GF-reinforced composites (GFRP) in seawater revealed significant water absorption initially, while soluble material extraction was higher later. The tensile and bending strengths showed decrease with prolonged immersion. Serious corrosion of the interface was observed in micrographs [84]. Mechanical properties such as density, ultrasonic velocity, shear modulus, except Poison’s ratio and elasticity modulus were reported to increase with increasing concentrations of GF (5%–25%) after ultrasonic treatment at 26 KHz [85].
Ferreira et al. reported a higher char yield for an aluminized E-GF composite compared to that of an unmetallized E-GF composite [86]. Surface functionalized chopped cellulose fibers (CFs) when added in small amounts (1%–3 wt.%) further enhanced the strength of composites [87]. The incorporation of methylene spacers in the backbone of UPR enhanced the strength of oil palm empty fruit bunch (OPEBF) as well as fiberglass–UPR composites. Composites based on six methylene spacers showed the highest strength as compared to UP composites based on two methylene spacers [88].
Dagwa and Ohaeri prepared composites of UPR together with banana empty fruit bunch fibers, GFs, and OPEBF particles, which showed a decrease in flexural strength with increases in banana fiber content, while with GFs it increased. A ternary composite with 5 wt.% OPEBF and 10 wt.% banana fiber/10 wt.% GF showed a high impact strength, that is, 55.556 J/m², representing a 1568.67% improvement over virgin UP. A binary composite with 15 wt.% banana fiber and 5 wt.% GF showed the highest hardness (3.55 HV), representing a 136.67% improvement. Hardness is seen to be influenced by increase in banana fiber content; therefore, banana fiber could be considered for applications requiring high impact strengths such as some parts of automobile vehicles (Fig. 1.6) [89].
Figure 1.6 Hardness test values for banana and glass fiber polyester composites.
TiO2 particulate-filled GF-reinforced polymer composites were prepared by Moorthy and Manonmani with two different fiber lengths, 3 and 5 cm, by hand layup method. The TiO2 content was varied from 10 to 40 wt.%. The combined reinforcement yielded better mechanical properties with increased fiber length and particulate material. Chemical resistance was more pronounced in the 5 cm fiber length composites [90].
The toughness of GF/UPR composites was improved by adding low-molecular-weight polyisobutylene (1–12 wt.%), which was grafted onto MA and glycidyl methacrylate through the novel solvothermal method to improve compatibility [91]. GF/URP exhibited considerable chromatic changes upon UV exposure. Although the mechanical properties were slightly poor, especially in the immersion and condensation chambers, the durability tests proved the generally good behavior of this material under aggressive conditions [92].
Microfibril cellulose (0.3 wt.%) when added to GF–UPR composites improved its mechanical properties. The composites were prepared by hand layup and vacuum bagging method. The impact strength was increased by 19.6% and flexural strength increased from 192.40 Mpa to 208.63 Mpa by hand layup method. The tensile strength increased from 10.24% to 19.62% for samples prepared by hand layup and vacuum bagging, respectively as reported by Vu et al. [93].
Jiang et al. modified carbon fibers with two different functional polyhedral oligomeric silsesquioxanes (POSS) monofunctional (methacrylolsobutyl) and multifunctional (methacryl) POSS and mixed these with UPR to form composites. They showed significantly increased lamellar strength (62 and 67 MPa, increase of 31.9% and 42.6%, respectively) and interfacial shear strength (IFSS). The impact energy was also higher for modified CF composites in comparison with CF/UPR composites [94].
1.6.2 Unsaturated Polyesters Resin–Natural Fiber/Particle Composites
1.6.2.1 Fibers
The use of natural fibers in composites is increasing due to their light weight, nonabrasive, combustible, nontoxic, low cost, and biodegradable properties. The only limitation is their poor mechanical properties, and to overcome this synthetic fibers are used.
Osman et al. observed that alkali treatment and the length of kenaf fibers affect the mechanical properties of composites [95]. The effect of water absorption on the flexural properties of kenaf fiber composites significantly reduced with the incorporation of recycled jute fibers [96]. In the case of natural fibers, it is commonly observed that alkali-treated fibers render superior properties in composites. The structural features of sugar palm fibers were found to be affected by alkali treatment using NaOH and an enhancement in IFSS was observed due to the internal morphological changes of the sugar palm fibers. Also, the effect of sugar palm fiber for both untreated and that treated with NaOH on single fiber strength and IFSS has been studied
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This book is great for a beginner looking to master the technology of polyester composite.