Article

3D‐printed PLA/PMMA polymer composites: A consolidated feasible characteristic investigation for dental applications

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Abstract

This research article focused on the blending of poly(lactic acid)/poly(methyl methacrylate) (PLA/PMMA) polymer materials to overcome PLA's inherent weaknesses, such as low glass transition temperature, brittleness, and lack of melt strength. Consolidated feasible characteristic investigations, such as mechanical, thermal, and aging behavior, were carried out for PLA/PMMA blended polymer materials. Initially, the miscibility of PLA/PMMA blend filaments was prepared at various blend ratios (91/9, 82/18, and 73/27) and samples were printed by fused deposition modeling (FDM). Differential scanning calorimetry (DSC) and Fourier infrared spectroscopy (FTIR) analysis have been utilized to evaluate the glass transition temperature (Tg) and intermolecular interaction, respectively, on blended polymer materials. Experimental tensile, compression, and flexural strength testing were performed on neat polymers and blended polymer composites. Compared to neat PLA materials, blended composites had 13.24% and 19.07% higher flexural and compression strengths. Besides, the interfacial interaction of neat and blended polymers has been done using dynamic mechanical analysis (DMA). Furthermore, Tg, storage modulus, and aging behavior of blended polymer materials have significantly improved over neat PLA materials. Altogether, the development of PMMA/PLA blends as sustainable biomaterials for dental applications aligns with environmental concerns and the need for biocompatible materials in dentistry. Highlights Blending of PLA and PMMA helps mitigate the inherent constraints of PLA. Blended composites exhibited greater compressive and flexural strengths. Better glass transition temperature and intermolecular interaction. Excellent thermal stability and water aging imply viable dental biomaterials.

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This material is still not enough to achieve the ideal mechanical requirements for dental applications although it is the most commonly used in dentistry for fabrication of denture bases. This problem was attributed mainly to its low plaque accumulation and low fracture resistance [2 and 3]. It was found that nearly 70% of dentures had broken within the first 3 years of their delivery in a survey to compare ten types of denture base resins. In a study [4] evaluating the denture fracture, it was reported that 29% of the repairs were because of midline fractures which were more commonly seen in the upper dentures and the rest were other types of fracture and 33% of the repairs were due to de bonded/detached teeth. Composites are multiphase materials that are chemically dissimilar and artificially made and separated by distinct interface [5]. 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B., added powders such as silver, copper and aluminum with (99.9 %) purity into PMMA acrylic resin denture base material in different volume fraction of (5%, 10%, 15%, 20% and 25%) with average particle size of (10 µm). The addition of these metal fillers showed a decrease in the tensile strength and an increase in the compressive strength as the percentage of metal fillers increases. With the addition of these metal fillers, thermal conductivity increased progressively but did not proportionally as the metal fillers volume fraction increased [8]. Z. A. Mohd Ishak, et al, studied the effect of water absorption and Simulated Body Fluid (SBF) on the flexural properties of PMMA/HA composites for an immersion duration of 2 months. Silane coupling agent [3-methacryloxypropyltrimethoxy silane [(γ-MPS)] was used in order to enhance the interfacial interaction between the PMMA and HA. 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Hanan Abdul, et al., studied the effect of the addition of Siwak powder in three different concentrations (3%, 5% and 7%) by weight with average particle size of 75 micro meters on the Certain Mechanical Properties of Acrylic Resin The results showed that the addition of Siwak powder with (3% and 5%) by weight to the Acrylic Resin did not greatly affect the compressive strength, tensile strength and impact strength of the Acrylic Resin in comparison to the control group, while the addition of (7 %) Siwak powder to the Acrylic Resin revealed a significant decrease in the compressive strength, tensile strength and impact strength [11]. The one recent study mentioned elsewhere, which involved the numerical study by the tensile properties analysis of the prosthetic dentures which prepared from the same of composite material maintained in the reference above, and the numerical analysis results of the finite element method shown the some agreement with the experimental results [12].
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Statement of problem: Biomaterials, including polymethyl methacrylate (PMMA) and bisacrylate, have been widely used as conventional interim materials and may exhibit cytotoxicity or systemic toxicity. Purpose: This study was designed to compare the mechanical properties of polylactic acid (PLA) as an alternative to conventional dental polymers for computer-aided design and manufacturing (CAD/CAM). Material and methods: Four groups (n = 20 per group) of CAD/CAM polymers were assessed. Specimens of PLA (PLA Mill) and PMMA (PMMA Mill) for subtractive manufacturing, PLA for fused deposition modeling (PLA FDM), and bisphenol for additive manufacturing by stereolithography (Bisphenol SLA) were fabricated into 2-mm-wide, 2-mm-thick and 25-mm-long specimens using a milling machine, an FDM printer, and an SLA printer, respectively.The flexural strength (FS) and elastic modulus (EM) were calculated. The surface roughness and Shore D hardness were analyzed with a 3D optical surface roughness analyzer and a Shore durometer, respectively. Results: PLA Mill showed the lowest FS (64.9 ± 8.28), followed by PLA FDM (104.27 ± 4.42 MPa), PMMA Mill (139.2 ± 20.95 MPa), and Bisphenol SLA (171.56 ± 15.38 MPa), with statistically significant differences. PLA FDM showed the highest EM, followed by PLA Mill, Bisphenol SLA, and PMMA Mill. Significant differences were observed not only between PMMA Mill and Bisphenol SLA but also between PLA FDM and PLA Mill. The lowest Shore D hardness was observed for PLA FDM, followed by PLA Mill, PMMA Mill, and Bisphenol SLA, which showed the highest value among the 4 groups, with significance. The highest values for the surface roughness parameters were observed for PLA Mill, and the lowest were observed for Bisphenol SLA. Conclusions: Among the tested CAD/CAM polymers, Bisphenol SLA was the most durable material, and the mechanical properties of PLA FDM were within the clinically acceptable range.
Article
Poly(methyl methacrylate) (PMMA) was incorporated as compatibilizer in immiscible poly(vinylidene fluoride) (PVDF)/poly(lactic acid) (PLA) blends at different ratios. Scanning electron microscopy results revealed that, after adding PMMA, the phase morphology of PVDF/PLA blends evidently changed and the boundary became diffused, indicating improved interaction between PVDF and PLA. The sea-island biphasic morphology of PVDF/PLA (1:1) blend transferred to pseudo co-continuous morphology with the incorporation of PMMA. Differential scanning calorimetry and polarized light microscopy results showed that the presence of pre-crystallized PVDF facilitated the crystallization of PLA on cooling from the melt, but the molten PLA slightly retarded the crystallization of PVDF. With the inclusion of PMMA in the blends, PVDF crystal growth was further inhibited due to its miscibility with PMMA, and its crystallinity was also decreased. The elongation at break (ductility) of PLA and PVDF/PLA blends increased drastically by up to 27.8 and 11.1 times respectively, after formation of ternary PVDF/PLA/PMMA blends. Dynamic mechanical analysis results showed that the individual glass transition temperatures of PVDF and PLA in the blends shifted to higher temperatures after adding PMMA. PMMA showed more affinity to PVDF than to PLA. Rheological property measurements confirmed the increase in complex viscosity and storage modulus of the blends with increasing PMMA loading.
Article
Polymer blends have been intensively studied because of their theoretical and practical importance in different variety application field. In the present work, the development on hybrid gel polymer based poly(methylmethacrylate) (PMMA) blended with biodegradable polymer namely poly(lactic acid) (PLA) as a host polymer in polymer electrolytes application have been successfully prepared. The effect of PLA in PMMA as hybrid polymer was investigated for their structural properties via fourier transform infrared (FTIR), x-ray diffraction (XRD) and differential scanning calorimetry (DSC). FTIR analysis shown that the interaction between PMMA and PLA has occurred via dipole-dipole forces. XRD analysis revealed the increment of amorphous phase when PLA was added into PMMA. Decreased in Tg value upon addition of PLA into PMMA indicate that the flexibility of the polymer backbone, thus enhanced the amorphous behaviour of hybrid gel polymer. These findings shown that the present hybrid polymer shown favourable properties to be used as host polymer for polymer electrolytes application.
Article
The incorporation of PMMA into phosphorus-containing flame retarded PLA was assessed as a possible strategy to reduce the sensitivity of the material to ageing in water at 70 °C. PLA and PMMA are miscible and the unique glass transition temperature can be easily controlled by a proper amount of PMMA according to Gordon-Taylor equation. Water penetration as well as phosphorus release was reduced when incorporated PMMA amount increased. Consequently, the ability to form char and the fire performances measured in cone calorimeter were further preserved. Nevertheless, an efficient protective effect was only observed when PMMA incorporation allows the glass transition temperature in the blend to increase above the ageing temperature. This is achieved for a weight ratio PMMA/PLA no lower than 1.
Chapter
Poly(methyl methacrylate) (PMMA) is widely used worldwide for artificial teeth and the fabrication of denture bases. Compared to metallic denture base materials, PMMA exhibits beneficial properties, such as aesthetic value, lighter weight, ease of manipulation, and cost-effectiveness. On the other hand, prostheses based on PMMA are susceptible to fracture due to poor mechanical properties (flexural and impact strengths) and tend to degrade over time due to water sorption. To improve the mechanical attributes of the PMMA resins for dental applications, various techniques have been investigated and varying results have been obtained. One method is to fabricate PMMA based biocomposites (e.g., polyamides, epoxy resins) or adding a rubber based copolymer (e.g., butadiene styrene) to PMMA to enhance its impact strength. Alternative methods include the use of metal wires or different types of fibers to strengthen PMMA based dentures. However, metal incorporation negatively affects the aesthetics, and tends to generate stress concentration zones which weaken the dentures instead of strengthening them. The addition of carbon/graphite fibers (CFs) into PMMA resins has been shown to substantially enhance the flexural and impact strengths of acrylic resin-based dentures. However, their gray color negatively affects their esthetic value. Therefore, they are not commonly used as a means of reinforcing dentures. Ultra-high molecular weight polyethylene (UHMWPE) fibers have a naturally white appearance and they have been shown to strengthen PMMA based dentures by increasing the impact strength and Young’s modulus. However, in order to create a bond between the fibers and PMMA resin, these fibers need to undergo special pretreatment (e.g., plasma treatment) before they can be used. Despite substantially enhancing the tensile strength and toughness of PMMA based dentures, aramid fibers (AFs) are not commonly used for denture reinforcement as they possess a yellow color and are difficult to incorporate into PMMA resins. Encouraging results have been achieved by the incorporation of glass fibers (GFs) into PMMA resins for denture strengthening. The beneficial effect of the addition of GFs on the mechanical properties of acrylic resins has been documented in several research studies. GFs possess excellent esthetics, in addition to having excellent mechanical properties. As a result, they are currently the prime focus of research aimed at reinforcing acrylic dentures. Additionally, GFs easily bond with PMMA resins after treatment with a suitable silane coupling agent, such as trimethoxysilylpropylmethacrylate silane. Apart from the obvious benefits of fiber reinforcement on PMMA dentures, their clinical use is still limited due to their high cost and the difficult technique necessary for their incorporation into PMMA, especially when short and randomly oriented GFs are used which tend to “clump” within the denture and negatively affect the strength of the prosthesis. This issue can be overcome by using woven or multidirectional fibers in the form of a mesh or network. The aim of this chapter is to highlight the benefits of PMMA and the advancements in PMMA based materials for dental application.
Article
Three flame-retarded systems based on PLA, PMMA and PLA/PMMA blend have undergone hydrothermal ageing. The miscibility of the blend as well as the crystallization behaviour of PLA were studied by DSC. The impact of ageing in terms of weight variations, melt viscosity, molecular weight distribution, morphology, and thermal degradation was investigated. Results showed that crystallization of PLA and significant hydrolysis phenomenon occurred during ageing. Flame retardant content determined by EDX and ICP revealed a loss of phosphorus during ageing, especially for flame-retarded PLA (91 wt% phosphorus loss after ageing). Incorporation of 50 wt% PMMA moderated the negative impacts observed. Fire properties evaluated using cone calorimeter revealed almost no impact of ageing on flame-retarded PMMA, contrary to flame-retarded PLA (increase of pHRR from 291 to 487 kW/m²). Flame-retarded blend shows intermediate properties. It revealed the positive effect of incorporation of PMMA in PLA, by limiting the water diffusion and by reducing the loss of phosphorus.
Article
The inherent shortcomings of polylactide (PLA) including brittleness, low glass transition temperature, and melt strength during processing were addressed through a facile melt blending of PLA with polybutadiene-g-poly(styrene-co-acrylonitrile) (PB-g-SAN) core–shell impact modifier and poly(methyl methacrylate) (PMMA). Highly tough PLA-based ternary blends with drastically enhanced glass transition temperature (≈ 21 °C) and melt strength were successfully prepared. The effect of PMMA content (ranging from 0 to 30 wt %) on the phase miscibility, morphology, mechanical properties, thermal behavior, rheological properties, and toughening mechanisms of PLA/PB-g-SAN/PMMA blends with 30% PB-g-SAN was systematically investigated. It was found that PMMA can effectively tune the interfacial interactions, phase morphology and performance of incompatible PLA/PB-g-SAN blend owing to its partial miscibility with PLA matrix and miscibility with SAN shell of PB-g-SAN, as evidenced by DMTA analysis. Increase in PMMA content promoted the phase adhesion and dispersion state of PB-g-SAN terpolymer in the blends and highly toughened blends were achieved which showed incomplete break of impact specimen. The significant effect of phase morphology on imparting tremendous improvement in impact toughness was clarified. The maximum impact strength (about 500 J/m), elongation-at-break and glass transition were obtained for ternary blend with 25% PMMA. The PLA crystallinity was gradually suppressed in ternary blends upon progressive increase in PMMA content. Rheological studies showed solid-like behavior with enhanced viscosities for ternary blends. Micromechanical deformations and toughening mechanisms were studied by post-mortem fractography. Massive matrix shear yielding was found as the main source of energy dissipation triggered by suitable interfacial adhesion and microvoid formation.
Article
The effect of UV light on polylactide/poly(methyl methacrylate) (PLA/PMMA) blends produced by melt-extrusion with a special emphasis on the peculiar influence of PLA stereocomplexes on the photochemical behavior of the blends is the focus of this paper. Stereocomplexable PLA have been prepared by melt-blending of high-molecular-weight poly(l-lactide) (PLLA), poly(d-lactide) (PDLA) and PMMA. The photochemical behavior of resulting PLA/PMMA blends was studied by irradiation under photooxidative conditions (λ > 300 nm, temperature of 70 °C and in the presence of oxygen). The chemical modifications induced by UV light irradiation were analyzed using infrared spectroscopy (IR) and size exclusion chromatography (SEC). Morphological changes were studied by differential scanning calorimetry (DSC) and atomic force microscopy (AFM). It was shown that PDLA and PMMA don't affect the rate of photooxidation of PLLA. However, PLA stereocomplexes have a strong impact on the morphology of the blends during photochemical ageing.
Article
This study examines the rheological, mechanical and thermal behavior of Poly(lactic acid)/Poly(methyl methacrylate) (PLA/PMMA) blends and takes a look at the phase structure evolution during their melt processing. Semi-crystalline or amorphous PLA grades were combined with PMMA of different molecular weight to prepare the blends. The rheological properties and phase structure was first assessed using small-amplitude oscillatory shear experiments. The blends were injection molded into bars and characterized in terms of their tensile properties and of their dynamic mechanical behavior. Differential scanning calorimetry was also used to study the miscibility and crystallization behavior of prepared blends. Tensile properties of the blends nearly followed a linear mixing rule with no detrimental effect that could have been associated with an uncompatibilized interface. However, dynamic mechanical analysis and calorimetric experiments showed that some phase separation was present in the molded parts. Nevertheless, a single Tg was found if sufficient time was given in quiescent conditions to achieve miscibility. The Gordon-Taylor equation was used to assess the polymer interactions, suggesting that miscibility is the thermodynamically stable state. The ability of PLA to crystallize was strongly restricted by the presence of PMMA and little or no crystallinity development was possible in the blends with more than 30% of PMMA. Results showed an interesting potential of these blends from an application point of view, whether they are phase separated or not.
Article
Poly(lactic acid)/poly(methyl methacrylate) (PLA/PMMA) blends were prepared by melt compounding technique. The miscibility of PLA/PMMA blends at various blending ratios (i.e. 80/20, 60/40, 40/60, and 20/80) was investigated using a dynamic mechanical analyzer (DMA) and solvent uptake experiment. The solvent uptake experiment was conducted to estimate the interaction of PLA/PMMA blends based on the calculation of Flory–Huggins interaction parameter (χ12). DMA results revealed that only single glass transition temperature (Tg) existed along the PLA/PMMA blends. Smallest χ12 (i.e. −0.03) was found on the PLA/PMMA20 blend, suggesting interaction between PLA and PMMA at this composition. The incorporation of PMMA slightly improved the UV protection properties of the PLA/PMMA blend, while maintaining their optical transparency.
Article
Recent advances in 3D printing technologies have led to a rapid expansion of applications from the creation of anatomical training models for complex surgical procedures to the printing of tissue engineering constructs. In addition to achieving the macroscale geometry of organs and tissues, a print layer thickness as small as 20 µm allows for reproduction of the microarchitectures of bone and other tissues. Techniques with even higher precision are currently being investigated to enable reproduction of smaller tissue features such as hepatic lobules. Current research in tissue engineering focuses on the development of compatible methods (printers) and materials (bioinks) that are capable of producing biomimetic scaffolds. In this review, an overview of current 3D printing techniques used in tissue engineering is provided with an emphasis on the printing mechanism and the resultant scaffold characteristics. Current practical challenges and technical limitations are emphasized and future trends of bioprinting are discussed.
Article
In order to improve the toughness of poly(lactic acid) (PLA), the incorporation of natural rubber (NR), which has a high elasticity and flexibility, can be used. However, the phase incompatibility between PLA and NR can cause poor mechanical properties of the final product in the absence of a compatibilizer because of their different polarities. In this research, epoxidized NR (ENR) and poly(methyl methacrylate) (PMMA) were used as co-compatibilizers for linking PLA/NR blends (PLA 100: NR 15 parts by weight per hundred parts of resin (phr)). Therefore, the aim of this research was to study the effect of the ENR/PMMA co-compatibilizer contents on the mechanical, thermal and morphological properties of the 100:15 phr PLA/NR blend. With 3 phr of ENR and 1 phr of PMMA, the elongation at break and impact strength of the 100:15 phr PLA/NR blend was significantly improved up to 1,813% and 362%, respectively. The thermal stability of the PLA/NR blend was also increased when using the co-compatibilizers. Interestingly, the PLA/NR blend containing the co-compatibilizer showed a high ultimate tensile strength after thermal aging at 100 °C for 1 h with good mechanical properties. However, the percentage of crystallinity and glass transition temperature were decreased by the added co-compatibilizer. Finally, a good compatibility between the PLA and NR matrices could be clearly observed by scanning electron microscopy in the presence of the co-compatibilizer.
Article
In this paper, we report a simple approach for the fabrication of bone-like composite materials (BCMs) by blending chitosan (CTS), a natural polysaccharide, nano-hydroxyapatite as bone mineral, and polymethylmethacrylate-co-polyhydroxyethylmethacrylate (PMMA-co-PHEMA) as bone cement. Fourier transform infrared spectroscopy and X-ray diffraction (XRD) studies were performed to determine the components of composites. Scanning electron microscopy study of composites revealed a well-dispersed flake-like structure with increasing content of PMMA-co-PHEMA. The water-uptake ability of the BCMs was also found to increase with increasing the PMMA-co-PHEMA content. Study of mechanical properties revealed that the Young's modulus and stiffness increased significantly after the addition of PMMA-co-PHEMA in BCMs compared with CTS–HAP blend. © 2013 Wiley Periodicals, Inc. Adv Polym Technol 2014, 33, 21391; View this article online at wileyonlinelibrary.com. DOI 10.1002/adv.21391
Article
The miscibility of polylactic acid (PLA) and atactic poly(methyl methacrylate) (PMMA) blends is investigated as a function of composition. The blends quenched from the melt show the presence of a single glass transition temperature dependent on the composition. The equilibrium melting temperature is determined using the Hoffman-Weeks method and a depression is observed with increasing content of the PMMA component. The PLA spherulite growth rate and the overall isothermal crystallization rates decrease with increasing the amount of the amorphous component. The increase of the long period value as a function of the PMMA content in the blend is due to the segregation of PMMA component in the amorphous PLA interlamellar regions. The Lauritzen-Hoffman secondary nucleation theory analysis shows that the segregation of the PMMA in the interlamellar region induces an increase in the surface entropy of folding. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014
Article
The reactive block copolymers were introduced as chain extenders to eliminate thermo-hydrolysis, transesterification or depolymerization of polylactic acid (PLA) during the thermal processing. A novel modified living anionic polymerization was employed to conquer the tough conditions of traditional anionic polymerization to synthesis the reactive block copolymers. In the first step, polystyrene capped with thiol end-group which can act as initiators for mercaptan/ε-caprolactam living polymerization was synthesized by anionic polymerization at room temperature. Then, the reactive block copolymers poly(styrene-b-methyl methacrylate-b-glycidyl methacrylate) (PS-b-PMMA-b-PGMA, PSMG) and poly(styrene-b-glycidyl methacrylate) (PS-b-PGMA, PSG), were synthesized via the mercaptan/ε-caprolactam living polymerization as proposed by our previous studied. FT-IR, 1H NMR, DSC, and POM analyses were used to confirm the structure, characteristics and thermal behavior of the PSMG, PSG and the processed PLAs. Analysis of the processed PLAs showed that their crystallization behaviors were strongly influenced by the segment content of the chain extenders, PSMG and PSG. The GMA segment contains epoxide moieties, which can increase the molecular weight and melt strength of PLA, while the MMA and styrene segments enhance miscibility with PLA and act as nucleating agents to promote crystallization, respectively. Compared to PSMG, PSG did not show a good reactivity and nucleation ability in PLA melt-blending because of lacking MMA segments. This result reveals the MMA segments are the key structure of the chain extender and the optimum ratio of styrene to MMA is at 1.0–1.2. The crystallinity of PLA could increase from 12.29% to 47.54% when these chain extenders, PSMG, were added in PLA melt-blending. By controlling the structure and segment length of PSMG via a novel modified living anionic polymerization route, we can obtain a quickly crystallinization and good mechanical properties of PLA resins.
Article
Effects of thermal aging on electric properties of polymethyl methacrylate (PMMA) polymer are reported in this paper. PMMA samples are submitted to successive heat-cooling cycles (Tmax=45°C and Tmin=20°C) in the ambient air. Different complementary techniques are thus employed to investigate structural modifications, conduction processes and dielectric relaxations. These are the Fourier Transform Infra Red (FTIR) spectroscopy, impedance spectroscopy and current–voltage technique. Results are discussed in terms of FTIR bands intensities, relaxation frequencies and electrical conductivity. We demonstrated that thermal aging favors oxidation phenomenon. This causes an increase of free radicals leading to space charge amount increasing. PMMA polymer presents therefore a less insulating character.
Article
Low molecular weight poly(lactic acid) was synthesized by direct polycondensation of lactic acid. The oligomers were characterized by viscometry, light scattering, and gel permeation chromatography (GPC). The swelling behaviour of tablets made of the above polymer immersed in buffer solutions at 37°C was studied. In the same experiments, the hydrolytic stability of d,l-PLA was assessed by measuring the weight loss after drying the tablets. In order to inhibit any degradation due to bacteria, formaldehyde was added in the solution as biostatic factor. The effect of an incorporated drug on the swelling behaviour of d,l-PLA tablets was also considered. It was found that the incorporation of drug in d,l-PLA tablets increases their swelling index, probably due to the creation of additional porosity in the specimens or other interaction between drug and polymeric matrix.
Article
Poly(L-lactide) (PLLA) films having different crystallinities (Xc's) and crystalline thicknesses (Lc's) were prepared by annealing at different temperatures (Ta's) from the melt and their high-temperature hydrolysis was investigated at 97°C in phosphate-buffered solution. The changes in remaining weight, molecular weight distribution, and surface morphology of the PLLA films during hydrolysis revealed that their hydrolysis at the high temperature in phosphate-buffered solution proceeds homogeneously along the film cross-section mainly via the bulk erosion mechanism and that the hydrolysis takes place predominantly and randomly at the chains in the amorphous region. The remaining weight was higher for the PLLA films having high initial Xc when compared at the same hydrolysis time above 30 h. However, the difference in the hydrolysis rate between the initially amorphous and crystallized PLLA films at 97°C was smaller than that at 37°C, due to rapid crystallization of the initially amorphous PLLA film by exposure to crystallizable high temperature in phosphate-buffered solution. The hydrolysis constant (k) values of the films at 97°C for the period of 0–8 h, 0.059–0.085 h–1 (1.4–2.0 d–1), were three orders of magnitude higher than those at 37°C for the period of 0–12 months, 2.2–3.4×10–3 d–1. The melting temperature (Tm) and Xc of the PLLA films decreased and increased, respectively, monotonously with hydrolysis time, excluding the initial increase in Tm for the PLLA films prepared at Ta = 100, 120, and 140°C in the first 8, 16, and 16 h, respectively. A specific peak that appeared at a low molecular weight around 1×104 in the GPC spectra was ascribed to the component of one fold in the crystalline region. The relationship between Tm and Lc was found to be Tm (K) = 467·[1–1.61/Lc (nm)] for the PLLA films hydrolyzed at 97°C for 40 h.
Article
This paper reports which are the possibilities of quantification by time of flight secondary ion mass spectrometry (ToF-SIMS) for some polymer blends. In order to assess the composition of the mixtures, we studied first different poly(l-lactide)/polymethylmethacrylate (PLA/PMMA) blends by X-ray photoelectron spectroscopy (XPS), this technique being quantitative. By XPS fitting of the C 1s level, we found a very good agreement of the measured concentrations with the initial compositions. Concerning ToF-SIMS data treatment, we used principal component analysis (PCA) on negative spectra allowing to discriminate one polymer from the other one. By partial least square regression (PLS), we found also a good agreement between the ToF-SIMS predicted and initial compositions. This shows that ToF-SIMS, in a similar way to XPS, can lead to quantitative results. In addition, the observed agreement between XPS (60–100 Å depth analyzed) and ToF-SIMS (10 Å depth analyzed) measurements show that there is no segregation of one of the two polymers onto the surface.
Article
A thick film of aniline-formaldehyde copolymer and PMMA is synthesized via dispersion of aniline-formaldehyde copolymer powder as filler particles in PMMA with two different concentrations. Variation of the complex elastic modulus and mechanical loss factor (tanδ) with temperature is studied. It is observed that the complex elastic modulus decreases with temperature owing to thermal expansion of films. On the other hand, tanδ increases up to a characteristic temperature beyond which it shows a decreasing trend toward melting. Transition temperature T g of sample S1 (pure PMMA) is found to be 80°C. In sample S2 (1 wt % aniline formaldehyde copolymer), the peak of tanδ at a lower temperature (66°C) corresponds to glass transition temperature T g of the PMMA matrix, while the peak of tanδ at a higher temperature (107.8°C) corresponds to T g of a polymer chain restricted by filler particles of aniline-formaldehyde copolymer. A further increase (10 wt % aniline-formaldehyde copolymer) in the concentration of filler particles of aniline-formaldehyde copolymer results in a more compact structure and a shift of T g to a higher temperature, 122.2°C. This shift in the glass transition temperature of thick films of aniline-formaldehyde copolymer and PMMA is dependent upon the concentration of filler particles in the sample.
Article
Methyl methacrylate (MMA), a monomer of acrylic resin, has a wide variety of dental, medical and industrial applications. Concerns have been raised regarding its potential toxicity in dental use, both for the patient and also in the workplace. Dental patients are also exposed to MMA leached from some dental appliances and the effects, at least in vitro, appear toxic to cells and may cause local mucosal irritation or even an allergic reaction. When exposed to MMA in the dental clinic, dentists and other dental staff appear to occasionally suffer hypersensitivity, asthmatic reactions, local neurological symptoms, irritant and local dermatological reactions. The integrity of latex gloves may also be compromised after exposure to MMA during dental procedures. MMA is not thought to be carcinogenic to humans under normal conditions of use. Techniques should be employed to reduce patients' exposure to MMA during dental procedures in order to reduce the risks of possible complications. Dental staff should avoid direct contact with MMA and room ventilation should be optimised.
Article
The first use of polymethyl methacrylate (PMMA) as a dental device was for the fabrication of complete denture bases. Its qualities of biocompatibility, reliability, relative ease of manipulation, and low toxicity were soon seized upon and incorporated by many different medical specialties. PMMA has been used for (a) bone cements; (b) contact and intraocular lens; (c) screw fixation in bone; (d) filler for bone cavities and skull defects; and (e) vertebrae stabilization in osteoporotic patients. The many uses of PMMA in the field of medicine will be the focus of this review, with particular attention paid to assessing its physical properties, advantages, disadvantages, and complications. Although numerous new alloplastic materials show promise, the versatility and reliability of PMMA cause it to remain a popular and frequently used material.
A review of three-dimensional printing in tissue engineering
  • N A Sears
  • D R Seshadri
  • P S Dhavalikar
  • E Cosgriff-Hernandez
Sears NA, Seshadri DR, Dhavalikar PS, Cosgriff-Hernandez E. A review of three-dimensional printing in tissue engineering. Tissue Eng Part B-Rev. 2016;22(4):298-310. doi:10.1089/ten.teb.2015.0464
  • M K Subramaniyan
  • S Thanigainathan
  • V Elumalai
Subramaniyan MK, Thanigainathan S, Elumalai V. Proc Inst Mech Eng E. 2023. doi:10.1177/09544089231205791