Characterization and Application of Nanomaterials (2023) Volume 6 Issue 1 doi:10.24294/can.v6i1.2537 1 Review Article A review study of the structure, properties and general application of poly(methyl methacrylate) Shaymaa Sansul, Emad Yousif*, Khalid Zainulabdeen Department of Chemistry, College of Science, Al-Nahrain University, Baghdad 10071, Iraq. E-mail: emad_yousif@hot- mail.com ABSTRACT Poly(methyl methacrylate) (PMMA) is a versatile and widely used polymer that has gained significant attention in various industries due to its unique combination of properties and ease of processing. PMMA, also known as acrylic or plexiglass, is a transparent thermoplastic with exceptional optical clarity, high-impact resistance, and excellent weather- ability. This scholarly article endeavors to offer an exhaustive examination of the composition, characteristics, and broad utilization of poly(methyl methacrylate) (PMMA). This study aims to conduct an in-depth analysis of the molecular com- position and chemical attributes inherent to PMMA. Furthermore, it intends to examine the mechanical and physical attributes exhibited by PMMA meticulously. Additionally, an exploration of varied methodologies employed in the pro- cessing and fabrication of PMMA will be undertaken. The extensive array of applications of PMMA spanning multiple industries will be underscored, followed by a comprehensive discourse on its merits, constraints, contemporary advance- ments, and prospective avenues. Understanding the properties and applications of PMMA is crucial for engineers, scien- tists, and professionals working in fields such as automotive, aerospace, medical, and signage, where PMMA finds ex- tensive use. Keywords: Poly(methyl methacrylate); Structure; Properties; Application; Polymer 1. Introduction 1.1 Poly(methyl methacrylate) (PMMA) The discovery of poly(methyl methacrylate) (PMMA) was at- tributed to two British chemists, both Rowland Hill and John Craw- ford, in the 1930s. However, its maiden implementation was in 1934 by German chemist Otto Rohm[1]. PMMA, commonly referred to as acrylic resin, is typically produced through the radical polymerization of methyl methacrylate (MMA), although anionic and coordination polymerization methods are also viable alternatives. PMMA is a trans- parent thermoplastic material that exhibits desirable properties such as impact resistance, weather resistance, and chemical resistance. It is often utilized as a substitute for inorganic glass due to its optical clarity and durability[2]. PMMA is recognized for its exceptional optical prop- erties, rendering it an excellent polymer for optical applications. It exhibits a remarkable visible light transmittance of 92%, surpassing that of glass. Additionally, PMMA possesses the ability to withstand ultraviolet (UV) radiation and harsh outdoor conditions, making it an ideal glass substitute (see Figure 1). PMMA further demonstrates advantageous attributes as a low-cost, non-toxic, environmentally friendly, recyclable, and highly biocompatible polymer. These remark- able characteristics have propelled PMMA’s extensive utilization in ARTICLE INFO Received: 9 March 2023 Accepted: 24 April 2023 Available online: 6 May 2023 COPYRIGHT Copyright © 2023 by author(s). Characterization and Application of Nano- materials is published by EnPress Publisher LLC. This work is licensed under the Creative Commons Attribution-NonCommercial 4.0 In- ternational License (CC BY-NC 4.0). https://creativecommons.org/licenses/by- nc/4.0/ 2 diverse fields such as aviation, construction, automo- tive, advertising, medicine, and the electronics in- dustry[3]. High tensile strength and roughness, high resistance to chemicals, and low-cost production as a result of its properties [R6]. PMMA, also known as plexi-glass or acrylic glass, is a polymer whose mon- omer structures are demonstrated in Figures 1 and 2, respectively[4,5]. Figure 1. The chemical structures of PMMA and its monomer MMA. Figure 2. PMMA crystalline fashion. 1.2 Distinct structural forms of PMMA: Iso- tactic, syndiotactic, and atactic In an academic context, polymer tacticity refers to the spatial arrangement of neighboring chiral cen- ters within a polymer, with particular emphasis on vinyl polymers. The physical characteristics and properties of a polymer are significantly influenced by the composition of its monomer and its overall molecular structure[6]. The isotactic state occurs upon the addition of adjacent monomer groups in a meso diad mode, with the ester groups located on the suc- cessive asymmetrical carbons on the same side of the polymeric chain[7]. In contrast, the syndiotactic state occurs when the addition of the monomer groups is in a racemic diad mode and the ester groups on suc- cessive asymmetric carbons are projected in a regu- lar alternation method on both sides of the plane of a polymeric chain. Similarly, the atactic state repre- sents another racemic diad mode, but it differs in the distribution of the ester groups located on the succes- sive asymmetrical carbons, which are showcased in a random method on either of the plane sides of a polymeric chain, as illustrated in Figure 3[8,9]. Through the employment of radical polymeri- zation (control/living), anionic polymerization, and reversible addition-fragmentation chain transfer techniques, PMMA can be synthesized in its pure form, exhibiting isotactic, syndiotactic, and atactic configurations, contingent upon the specific initiator, monomer feed, and solvent utilized[8,10]. Figure 3. The different tacticities of PMMA[11]. 55C ̊ Isotac�c 120C ̊ atactic 130C ̊ Syndiotactic Tg 3 1.3 Lifetime and degradation science: Ap- plicability to polymers In the pursuit of understanding the degradation mechanisms arising from weathering of PMMA, data-driven techniques from the interdisciplinary area of data science were employed. Specifically, Lifetime and Degradation Science (L & DS) were utilized, employing a stressor, mechanism, and re- sponse framework, to quantify the correlation be- tween environmental stresses and the resulting deg- radation accumulation caused by distinct degrada- tion mechanisms during the weathering process (Figure 4). The weathering data encompassed the monitoring of physical and chemical alterations in PMMA under varying exposure conditions, such as irradiation, temperature, and moisture. To gauge the physical and chemical degradation of PMMA, non- destructive measurements like Fourier-transform in- frared spectroscopy (FTIR), colorimetry, and UV- Vis spectroscopy were employed[11]. Figure 4. weathering process. Depolymerization reaction of PAAM The transformative procedure of depolymeriza- tion involves disassembling a polymer into constitu- ent monomers or smaller molecular units[12]. The de- polymerization phenomenon concerning PMMA holds considerable research interest, primarily due to its extensive spectrum of industrial applications and the potential it harbors for chemical recycling en- deavors[13]. PMMA embodies a polymer character- ized by an aliphatic foundational structure, contrib- uting to its robust chemical and thermal stability[14]. The deliberate disintegration of PMMA can be insti- gated through thermal or chemical methodologies[13]. Thermal pathways for PMMA depolymeriza- tion encompass diverse postulations[15]. One articu- lated mechanism, as proposed by Kashiwagi et al.[16], involves cleavages occurring within the principal PMMA chain. Another theoretical framework put forth by Manring contemplates homolytic cleavages of adjoining methoxycarbonyl groups nestled within the PMMA structure[17]. Notably, the rate constants and activation energies associated with the thermal deterioration of PMMA exhibit variance, thereby en- gendering distinctions in the effectiveness of the de- polymerization process[18]. Nonetheless, consensus aligns with the notion that PMMA’s thermal decomposition transpires via a biphasic sequence[19]. In the primary stage, there emerges a stochastic degradation of polymer chains, culminating in the generation of diminutive frag- ments[12]. Subsequently, the secondary stage heralds depolymerization, wherein both the initial chains and the fragments undergo rupture, culminating in the formation of monomers[12]. The trajectory of PMMA’s depolymerization is intrinsically molded by an amalgamation of factors, encompassing tem- perature, bond cleavage proclivities, and the pres- ence of inhibitory agents[19]. 1.4 Applications of PMMA PMMA found its initial significant application during World War II, where it was employed as air- craft windows and bubble canopies for gun turrets[20]. The suitability of PMMA for these applications hinged on achieving the appropriate weight, compo- sition, and thickness tailored to its intended purposes. Some other studies highlight the essential character- istics of PMMA, with the representative values cor- responding to new and unexposed material. Further- more, Figure 5 illustrates the various applications contributing to the global demand for PMMA[21,22]. Figure 5. Some application of glass replacement. 4 Figure 6 shows the applications for global PMMA demand. Figure 6. Applications for global PMMA demand since 2014– 2024. 1.4.1 Applications of solar technology In the quest for developing a quasi-solid-state dye-sensitized solar cell (DSSC) with a high-con- ductivity polymer gel electrolyte, the selection of a suitable polymeric material as a host matrix within the composite was crucial[23]. Consequently, PMMA emerged as a favorable and compatible choice for this application[24]. This selection was attributed to PMMA’s advantageous mechanical strength, com- patibility, and optical clarity properties[23]. Recently, Shen et al.[22] presented a pioneering study reporting the hydrothermal synthesis of europium ion (Eu+3)- doped sodium gadolinium fluoride (NaGdF4: Eu) nanocrystals (NCs). For the first time, a down-con- version (DC) layer comprising PMMA doped with luminescent NaGdF4: Eu was prepared and affixed to the rear of TiO2 anodes to enhance the efficiency of dye-sensitized solar cells (DSSCs)[23]. The evalu- ation of the impact of doped and undoped NaGdF4 nanocrystal layers on the photovoltaic device, with incident-photon-to-current efficiency (IPCE) as the parameter of comparison, revealed that the DSSC in- corporating a doped NaGdF4: Eu DC-PMMA layer exhibited an improved photoelectric conversion effi- ciency by 4.5%[23]. In another study, Yan et al.[25] conducted successful preparations of a polymer gel electrolyte employing a blend of PMMA, ethylene carbonate, 1,2-propanediol carbonate, dimethyl car- bonate, and sodium iodide/iodine as the source of I- /I-3[26]. This specific polymer electrolyte, denoted as PMMA-EC/PC/DMC-NaI/I2, exhibited a remarka- ble ionic conductivity of 6.89 mS cm–1. The re- searchers further utilized this high-conductivity elec- trolyte to fabricate a quasi-solid-state dye-sensitized solar cell (DSSC), which displayed impressive long- term stability and achieved a notable light-to-electri- cal energy conversion efficiency of 4.78%[27]. More- over, Hammam et al.[24] fabricated a fluorescent PMMA film incorporating a commercial coumarin dyestuff (MACROLEX Fluorescent Red G) via a flow-spin coating technique. The dye concentration within the film was adjusted to achieve the maxi- mum intensity, and its emission characteristics were optimized to align with the absorption bands of chlo- rophyll (650–680 nm) for greenhouse applica- tions[28]. Remarkably weather-resistant, this fluores- cent film proves suitable for deployment in growing rooms dedicated to commercial plant cultivation[29]. 1.4.2 Applications in optics Optical science plays a vital role across various disciplines, including engineering, medicine, pure science, and astronomy[29]. Its practical applications encompass a wide range of technologies, such as lenses, microscopes, lasers, fibers, and polymers[30]. In particular, the optical activity of materials is an outcome observed when they interact with light, and this activity can be quantified through the refractive index[31]. In the case of PMMA, its optical applications are primarily attributed to its favorable refractive in- dex, excellent resistance to UV light, chemical dura- bility, and commendable mechanical properties[32]. Moreover, organic polymers offer advantages like cost-effectiveness, lightweight nature, and ease of processing, rendering them well-suited for immobi- lizing semiconductors in heterogeneous photocata- lytic applications[33]. Recently, Camara et al.[34] conducted an inves- tigation involving eleven synthetic polymers capable of being coated with TiO2. These coated polymers were exposed to solar radiation for 150 days, both with and without the TiO2 layer, to study the weath- ering effects[28]. Such studies contribute to a better understanding of how polymers respond to environ- mental exposure and play a crucial role in advancing practical applications and innovations in the field of optical materials[31]. Upon careful observation, it was found that among the studied materials, only PMMA exhibited excellent retention of both the optical and mechani- cal properties of titania after undergoing natural weathering[32]. Consequently, PMMA emerges as the 5 most promising candidate for effectively immobiliz- ing TiO2 in applications related to photocatalytic treatment[33]. 1.4.3 Application in dentistry Thermoplastic resins have a long-standing his- tory of utilization in dentistry, characterized by their ability to undergo multiple cycles of softening through heating and hardening via cooling without undergoing chemical alterations[35]. These resins consist of polymer chains, composed of diverse lengths and molecular weights, organized into bun- dles. Four broad classifications of thermoplastic res- ins include thermoplastic acetal, thermoplastic poly- carbonates, thermoplastic acrylic, and thermoplastic nylon[36]. In particular, thermoplastic acetal exists in both homo-polymer and copolymer forms, with the latter exhibiting superior long-term stability compared to its homopolymer counterpart[37]. Its resistance to oc- clusal wear makes it highly suitable for preserving the vertical dimension during provisional restorative therapy[37]. However, when compared to thermo- plastic acrylic and polycarbonate, thermoplastic ace- tal lacks the natural translucency and vitality, making it more suitable for short-term temporary restora- tions[38]. Thermoplastic polycarbonates, composed of bi- sphenol-A carbonate polymer chains, find ideal ap- plications in provisional crowns and bridges, yet are not well-suited for partial denture frameworks[39]. However, dentists have long been using thermo- plastic acrylic, which is shown in Figure 7, for tem- porary crowns and as a base plate material for partial and complete dentures[39]. Nevertheless, thermally polymerized PMMA does exhibit certain drawbacks, such as high porosity, water absorption, volumetric changes, and residual monomer[40]. Figure 7. Temporary crowns. Due to their limited impact resistance, tensile strength, and flexural strength in various applications, the use of traditional thermoplastic resins faces chal- lenges[41]. Consequently, for specific circumstances that demand enhanced flexibility, improved re- sistance to flexural fatigue, and superior impact strength, the adoption of improvised thermoplastic nylon can present a valuable alternative to polymethylmethacrylate[42]. 1.4.4 Applications of the viscosity In the realm of fluid dynamics, viscosity repre- sents the extent of a fluid’s resistance to flow when subjected to applied shear stress[43]. When consider- ing polymeric melts or solutions, they exhibit non- Newtonian behavior, meaning that the shear stress is not directly proportional to the shear rate[44]. How- ever, polymers possess an intrinsic viscosity, serving as an indicator of their capacity to enhance the vis- cosity of another fluid[45]. As a result, a high-molec- ular-weight polymer can effectively modify or influ- ence the viscosity of low molecular weight polymers. PMMA, due to its compatibility and ease of pro- cessing, proves valuable for developing viscosifier copolymers in conjunction with natural polymers[46]. In a study conducted by Mishra and Sen, the grafting of PMMA onto guar gum was accomplished using a microwave-initiated method. The investiga- tion focused on the correlation between the percent- age of grafting and the intrinsic viscosity of the re- sulting product. The findings demonstrated that the modified product could serve as a superior viscosi- fier compared to guar gum in its pristine form[47]. 1.4.5 Nanotechnology applications The interplay between polymers and nano- materials has revolutionized the field of nanotech- nology, leading to the development of polymer nano- composites[48]. These composites exhibit significant enhancements in material properties despite incorpo- rating only minute amounts of nanoparticles. The im- provements encompass a wide range of characteris- tics, including mechanical strength, solubility, elec- trical conductivity, optical properties, scratch re- sistance, thermal stability, and flame retardation, among others. The extensive application potential of nanocomposites in nanotechnology has attracted considerable research attention towards their fabri- cation and diverse applications[49]. Perween et al.[31] explored the utilization of 6 PMMA and graphite in the production of plastic chip electrodes (PCEs) using a straightforward solution casting technique. The resulting electrodes were cost-effective, versatile, and dispensable for various applications. Microscopy (SEM and AFM), thermal properties (TGA), and mechanical and electrical analyses were conducted to characterize the fabri- cated electrode. In a novel approach for preparing nanocompo- sites involving nanoparticles, the combination of co- valent and noncovalent interactions was found to be highly beneficial. Wang et al.[32] investigated the ef- fect of SiO2 nanoparticles on SiO2/PMMA compo- sites. The fabrication involved a two-step process: noncovalent modification of SiO2 nanoparticles with tetraoctylammonium bromide to facilitate their dis- persion in the solvent, and covalent process through radical suspension polymerization with MMA mon- omer, leading to the formation of silicon ox- ide/PMMA nanocomposite. This method aimed at enhancing the mechanical properties of PMMA for broader applications. The study revealed remarkable improvements in tensile strength and flexural strength, with enhancements of up to 80.6% and 127.3% compared to pure PMMA, respectively. Surface functionalization of nanoparticles through polymer grafting holds significant im- portance in the design of both organic and inorganic nanocomposites. Atom Transfer Radical Polymeri- zation (ATRP) has emerged as a leading method due to its superior control over molecular weight and low polydispersity. The surface-initiated ATRP technique is widely adopted for grafting homopolymers, di- block copolymers, graft copolymers, star polymers, and branched polymers from various nanoparticles, such as nanotubes, nanowires, and nanoclays[26]. PMMA has been successfully grafted into carbon nanotubes (CNTs) to improve the solubility and pro- cessability of CNTs. This is significant considering the exceptionally low density, mechanical, electrical, and thermal properties of CNTs, which are hindered by limited solubility due to π-π bond interactions. 1.4.6 Applying thick PMMA layers onto con- ductive metal substrates Three distinct methods are available for the ap- plication of thick PMMA layers onto a conducting metal substrate: multilayer coating, casting, and sheet adhesion. Among these, casting and commer- cial sheet adhesion are the most frequently employed techniques[50]. 1.4.7 Application of PMMA in the construc- tion of microanalytical separation apparatus PMMA possesses several advantageous charac- teristics that render it a suitable substrate for the fab- rication of microanalytical separation devices. Its ease of machinability using various methods, such as laser ablation, injection molding, imprinting, and hot embossing, allows for efficient device production. Additionally, molds produced through the LIGA pro- cess, which is a German acronym for lithography, electroplating, and moulding (Lithographie, Gal- vanik und Abformung), have been effectively em- ployed to create PMMA microanalytical separation devices. The material’s optical properties enable an- alyte detection using fluorescence and visible spec- troscopies[46]. Furthermore, PMMA demonstrates the ability to withstand high electric fields and effectively dis- sipate heat, making it a desirable choice for applica- tions in the microanalytical separation device indus- try. With a glass transition temperature (Tg) of –100 ℃ in commercially available PMMA sheets, microde- vices fabricated from PMMA can be thermally sealed using a PMMA top plate via thermal bonding procedures. Notably, PMMA exhibits solubility in various organic solvents while remaining insoluble in polar solvents like water and alcohols, which are commonly employed in conventional CE and CEC solvent systems. Likewise, it remains insoluble in nonpolar solvents such as hexanes and cyclohex- ane[42,43]. 1.4.8 PMMA as a significant resist material in microelectronic applications PMMA has garnered considerable significance as a pivotal resist material within the realm of micro- electronic applications. Its prominence arises from its capability to form ultra-thin, coherent films and its susceptibility to etching processes in lithographic operations due to its notable depolymerization profi- ciency[28–35]. Notably, PMMA demonstrates a distinct characteristic in facilitating controlled solvent mo- bility over its polymeric matrices, owing to the facile 7 manipulability of its dissolution kinetics. This attrib- ute has enabled the achievement of highly defined edges with desired slopes in the imagery of the resist material when employing a PMMA matrix[28,36]. The rate of PMMA dissolution during photoresist devel- opment is notably contingent upon parameters such as molecular weight and molecular weight distribu- tion, both of which significantly impact the fabrica- tion of diverse optical elements[45]. Consequently, PMMA serves as a benchmark against which the ef- ficacy of resistive materials can be measured. While numerous alternative polymers have been unveiled, many surpass PMMA in terms of sensitivity. None- theless, the amalgamation of attributes encompass- ing stability, sensitivity, contrast, adhesion, and sol- ubility has perpetuated PMMA’s preeminence[28,47–49]. Consequently, renewed interest has arisen in the in- novative synthesis of PMMA. Photoresists founded on photoinduced free-radical chemistry have gar- nered escalating attention within the sphere of micro- electronic applications[50]. Researchers have success- fully used the solution casting technique to synthe- size PMMA and Rhodamine-B fluorescent dye- doped PMMA[51]. The researchers meticulously rec- orded the UV-visible spectra of these films[52]. They then utilized the spectral data to derive various opti- cal properties, including band gap, refractive index, and metallization criterion[52]. Notably, the investiga- tion revealed that while the band gap generally di- minishes with increasing dopant concentration, the direct band gap exhibited a gradual reduction, whereas the indirect band gap displayed an initial moderate decline that transitioned into a more pro- nounced reduction beyond a dopant concentration of 10 wt%[51]. This discernment underscores the poten- tial for precise modulation of PMMA’s optical char- acteristics through judicious doping with Rhodamine B dye[53]. 1.5 Further positive sides of PMMA The commendable attributes of poly(methyl methacrylate) (PMMA) find significant relevance within diverse academic and industrial spheres, sub- stantiated by empirical evidence: 1) Exceptional Transparency: PMMA’s excep- tional transparency, allowing the transmission of up to 92% of visible light, is well docu- mented[54]. This unique property positions PMMA as a preferred choice for applications necessitating unimpeded clarity and visibility, such as optical lenses, display panels, and win- dows[54]. 2) Resilience to Weather Elements: PMMA’s re- markable resistance to UV radiation is exten- sively recognized[55]. This characteristic en- dows PMMA with suitability for outdoor de- ployment, as it resists yellowing or degradation under prolonged sunlight exposure, thereby maintaining optical integrity over time[55]. 3) Vigorous Impact Endurance: Studies affirm PMMA’s superior impact resistance compared to glass[56]. This intrinsic property fosters its adoption in scenarios demanding shatterproof or impact-resistant attributes, ensuring safety in contexts predisposed to high winds or unin- tended collisions[57]. 4) Featherweight Composition: The lightweight nature of PMMA has been acknowledged in both academic and industrial realms[58]. This feature enhances its handling ease, transporta- tion convenience, and capacity to contribute to weight reduction in diverse structures, thereby exemplifying its pertinence in industries like automotive and aerospace[58]. 5) Adaptability and Dexterity: PMMA’s adaptabil- ity, facilitated shaping, and facile fabrication processes are well-documented[59]. This versa- tility translates into various forms, including sheets, rods, and intricate designs, thereby span- ning applications in architecture, medical equipment, and consumer goods[59]. 6) Chemical Endurance: Extensive research un- derscores PMMA’s commendable chemical re- sistance to acids, alkalis, and solvents[60]. This property positions it favorably in settings in- volving chemical exposure, such as laboratory equipment and chemical storage containers[60]. 7) Simplicity in Upkeep: Scholarly work corrobo- rates the ease of maintenance of PMMA[57]. Its potential for polishing to mitigate surface im- perfections and reduced susceptibility to stain- ing compared to other materials support its lon- gevity and cost-effectiveness[60]. The confluence of these positive attributes un- derscores PMMA’s indispensability within a myriad 8 of industries and applications. A dynamic equilib- rium between optical performance, resilience, and adaptability substantiates PMMA’s continued prom- inence. 2. Conclusions In conclusion, poly(methyl methacrylate) (PMMA) is a remarkable polymer with a wide range of applications and unique properties. Its transparent nature, excellent mechanical strength, and ease of processing make it highly valuable in industries such as automotive, aerospace, medical, and signage. While PMMA offers numerous advantages, it also has certain limitations that need to be considered in specific applications. Ongoing research and develop- ment efforts continue to explore new manufacturing processes and expand the potential applications of PMMA. Further research should focus on enhancing its properties, improving its sustainability, and ex- ploring novel applications in emerging fields. With its versatility and promising future prospects, PMMA remains an important material in the polymer industry. Author contributions Conceptualization, SS and EY; methodology, SS; software, SS; validation, SS, EY and KZ; formal analysis, SS; investigation, SS; resources, SS; data curation, EY; writing—original draft preparation, SS and KZ; writing—review and editing, KZ; visualiza- tion, EY and KZ; supervision, EY; project admin- istration, SS and EY. All authors have read and agreed to the published version of the manuscript. Conflict of interest The authors declare no conflict of interest. References 1. Lacroix HL, Van der Tempel L. Thermohygroelastic properties of polymethylmethacrylate. 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