Structure, Surface Topography, and Glass Transition Temperature of Dental Poly (Methyl Methacrylate) Resin Conjugated with 3,9-bisethenyl-2,4,8,10-tetraoxaspiro [5,5] Undecane as Cross-linker: An In Vitro Research.

AIM AND OBJECTIVES: To characterize and analyze the structural presentation of a new denture base copolymer with a spiro-acetal cross-linker at 10 and 20 wt.% concentrations by nuclear magnetic resonance (NMR) and field emission scanning electron microscopy-energy-dispersive X-ray (FESEM-EDX) spectroscopies. Also, to evaluate the glass transition temperature (TG) of the new copolymer. MATERIALS AND METHODS: The investigational groups G10 and G20 were heat-cured with the new spiro-acetal cross-linker at the above-mentioned concentrations, respectively. The control group G0 was heat-cured without the new cross-linker. Nuclear magnetic resonance and EDX spectroscopies determined the copolymerization along with elemental composition. The surface characteristics were discerned by FESEM. Differential scanning calorimetry was employed to evaluate the TG of the resultant copolymer. Appropriate statistical operations were performed to compare the mean TG of the groups. RESULTS: The new copolymer's structure with the spiro-acetal cross-linker was configured with protons, carbons, aluminum, zirconium, yttrium, and silicon atoms. The TG of the resultant copolymer was high when compared with the G0. The 20 wt.% spiro-acetal cross-linker in the copolymer exhibited the highest TG. CONCLUSION: The spiro-acetal cross-linking comonomer incorporated in the heat-cure denture polymer produced a new denture base copolymer with elevated TG. The resultant configuration of the new copolymer was characterized, structurally presented, and confirmed. CLINICAL SIGNIFICANCE: The new copolymer might exhibit augmented strength due to the copolymerized spiro-acetal cross-linker. Moreover, the smooth and regular surface of the copolymer would have minimum or negligible microbial adhesion due to the hydrophobicity of the spiro-acetal comonomer incorporated in the denture base composition. How to cite this article: Ravivarman C, Ajay R, Saatwika L, et al. Structure, Surface Topography, and Glass Transition Temperature of Dental Poly (Methyl Methacrylate) Resin Conjugated with 3,9-bisethenyl-2,4,8,10-tetraoxaspiro [5,5] Undecane as Cross-linker: An In Vitro Research. J Contemp Dent Pract 2024;25(5):486-493.

Complexity of confined water vitrification and its glass transition temperature.

The ability of vitrification when crossing the glass transition temperature (Tg) of confined and bulk water is crucial for myriad phenomena in diverse fields, ranging from the cryopreservation of organs and food to the development of cryoenzymatic reactions, frost damage to buildings, and atmospheric water. However, determining water's Tg remains a major challenge. Here, we elucidate the glass transition of water by analyzing the calorimetric behavior of nano-confined water across various pore topologies (diameters: 0.3 to 2.5 nm). Our approach involves subjecting confined water to annealing protocols to identify the temperature and time evolution of nonequilibrium glass kinetics. Furthermore, we complement this calorimetric approach with the dynamics of confined water, as seen by broadband dielectric spectroscopy and linear calorimetric measurements, including the fast scanning technique. This study demonstrated that confined water undergoes a glass transition in the temperature range of 170 to 200 K, depending on the confinement size and the interaction with the confinement walls. Moreover, we also show that the thermal event observed at ~136 K must be interpreted as an annealing prepeak, also referred to as the "shadow glass transition." Calorimetric measurements also allow the detection of a specific heat step above 200 K, which is insensitive to annealing and, thereby, interpreted as a true thermodynamic transition. Finally, by connecting our results to bulk water behavior, we offer a comprehensive understanding of confined water vitrification with potential implications for numerous applications.

Size Effects in Climatic Aging of Epoxy Basalt Fiber Reinforcement Bar.

The purpose of this study was to obtain information on the influence of the size factor on the climatic aging of circular fiber plastics produced by pultrusion. The kinetics of moisture transfer was obtained in humidification and drying modes at 60 °C in samples of epoxy basalt fiber reinforcement bars: after 28 months of exposure in the extremely cold climate of Yakutsk and 30 months of exposure in the moderately warm climate of Gelendzhik. It was shown that the 2D Langmuir model adequately describes the kinetics. The diffusion coefficients in the reinforcement direction for bars with diameters of 6, 8, 10, 16 and 20 mm turned out to be significantly higher than in the radial direction. To clarify the aging mechanism of the bars and the tensile, compressive and bending strength, the coefficient of linear thermal expansion and the glass transition temperature of the epoxy matrix of the bars with a diameter of 6, 8 and 10 mm after 51 months of exposure in Yakutsk and 54 months of exposure in Gelendzhik were measured. It was shown that after climatic exposure, the deformability of the bars decreased with increasing diameter of the bar; the glass transition temperature increased more significantly in the bar with a smaller diameter. In 6 mm diameter bars, the compressive and bending strength limits decreased by 10-25 % due to the plasticizing effect of moisture. With the same depth of moisture penetration into the volume of the samples, its effect on the strength of thin bars was significant, and for thick bars, it was insignificant. An increase in the glass transition temperature by 6 °C, associated with the additional curing of the polymer matrix, occurred in the surface layer of the epoxy basalt fiber reinforcement bars and was revealed in bars with a smaller diameter.

Characterization of Thermal Expansion Coefficient of 3D Printing Polymeric Materials Using Fiber Bragg Grating Sensors.

This work aims at the determination of the coefficient of thermal expansion (CTE) of parts manufactured through the Fused Deposition Modeling process, employing fiber Bragg grating (FBG) sensors. Pure thermoplastic and composite specimens were built using different commercially available filament materials, including acrylonitrile butadiene styrene, polylactic acid, polyamide, polyether-block-amide (PEBA) and chopped carbon fiber-reinforced polyamide (CF-PA) composite. During the building process, the FBGs were embedded into the middle-plane of the test specimens, featuring 0° and 90° raster printing orientations. The samples were then subjected to thermal loading for measuring the thermally induced strains as a function of applied temperature and, consequently, the test samples' CTE and glass transition temperature (Tg) based on the recorded FBG wavelengths. Additionally, the integrated FBGs were used for the characterization of the residual strain magnitudes both at the end of the 3D printing process and at the end of each of the two consecutively applied thermal cycles. The results indicate that, among all tested materials, the CF-PA/0° specimens exhibited the lowest CTE value of 14 × 10-6/°C. The PEBA material was proven to have the most isotropic thermal response for both examined raster orientations, 0° and 90°, with CTE values of 117 × 10-6/°C and 108 × 10-6/°C, respectively, while similar residual strains were also calculated in both printing orientations. It is presented that the followed FBG-based methodology is proven to be an excellent alternative experimental technique for the CTE characterization of materials used in 3D printing.

Prediction of Glass Transition Temperature of Polymers Using Simple Machine Learning.

Polymer materials have garnered significant attention due to their exceptional mechanical properties and diverse industrial applications. Understanding the glass transition temperature (Tg) of polymers is critical to prevent operational failures at specific temperatures. Traditional methods for measuring Tg, such as differential scanning calorimetry (DSC) and dynamic mechanical analysis, while accurate, are often time-consuming, costly, and susceptible to inaccuracies due to random and uncertain factors. To address these limitations, the aim of the present study is to investigate the potential of Simplified Molecular Input Line Entry System (SMILES) as descriptors in simple machine learning models to predict Tg efficiently and reliably. Five models were utilized: k-nearest neighbors (KNNs), support vector regression (SVR), extreme gradient boosting (XGBoost), artificial neural network (ANN), and recurrent neural network (RNN). SMILES descriptors were converted into numerical data using either One Hot Encoding (OHE) or Natural Language Processing (NLP). The study found that SMILES inputs with fewer than 200 characters were inadequate for accurately describing compound structures, while inputs exceeding 200 characters diminished model performance due to the curse of dimensionality. The ANN model achieved the highest R2 value of 0.79; however, the XGB model, with an R2 value of 0.774, exhibited the highest stability and shorter training times compared to other models, making it the preferred choice for Tg prediction. The efficiency of the OHE method over NLP was demonstrated by faster training times across the KNN, SVR, XGB, and ANN models. Validation of new polymer data showed the XGB model's robustness, with an average prediction deviation of 9.76 from actual Tg values. These findings underscore the importance of optimizing SMILES conversion methods and model parameters to enhance prediction reliability. Future research should focus on improving model accuracy and generalizability by incorporating additional features and advanced techniques. This study contributes to the development of efficient and reliable predictive models for polymer properties, facilitating the design and application of new polymer materials.

Thermal and structural changes of a starch flexible film and cellulosic semi-rigid tray during the biodegradation process under controlled composting conditions.

Biopolymers used to mitigate the environmental impact needed establish biodegradation percentage. The thermal and structural changes of two plastic materials, a flexible film based on cassava starch - Poly(lactic acid) (PLA) and a semi-rigid cassava flour-stay cellulose fique fiber, were evaluated biodegradation under ISO 4855-1 standard. The tests were carried out for four weeks at constant temperature and flow of 58 °C ±â€¯2 °C and 250 mL/h, using a mature compost as inoculum. The percentages of CO2, thermal, morphological, and structural changes, variation of degradation temperatures, glass transition temperatures (Tg), Melting temperatures (Tm) and enthalpies of fusion (Hm), were properly evaluated as indicators of the materials biodegradation of two materials. Scanning electron microscopy (SEM), showed the microorganisms colonization on the materials surface, evidencing the appearance of cracks and microbial population. The flexible film showed a biodegradation percentage of 98.24 %, the semi-rigid tray 89.06 %, and the microcrystalline cellulose, 81.37 %.

Polyfluoride Acceptor with Limited Molecular Diffusion Enables Efficient and Stable Ternary Organic Solar Cells.

Due to the slow diffusion of photovoltaic molecules, in particular, small-molecule acceptors (SMAs), under light and heating, the morphology of the active layer in organic solar cells (OSCs) prefers to deviate from the favorably metastable status, leading to the challenge of stability during long-term operation. Employing materials with a high glass transition temperature (Tg) as the third component to suppress molecular diffusion is an efficient method to achieve the balance of efficiency and stability of OSCs. Herein, a dimerized small-molecule acceptor denoted as F6D is synthesized by introducing a polyfluoride moiety as the linker to enhance the Tg. Benefitting from a rational molecular design, F6D not only exhibits a higher Tg, complementary absorption, and cascade energy levels with the host materials of the polymer donor PM6 and the SMA Y6 but also has excellent miscibility and multiple intermolecular interactions with Y6. As a result, a champion power conversion efficiency of 17.52% is achieved in the optimal PM6:Y6:F6D-based device. More importantly, the ternary device exhibits superior stability under continuous heating and lighting compared with the binary device.

Utilization of Polycyclic Aromatic Solid Additives for Morphology and Thermal Stability Enhancement in Photoactive Layers of Organic Solar Cells.

Volatile solid additives have emerged as a promising strategy for enhancing film morphology and promoting the power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, a series of novel polycyclic aromatic additives with analogous chemical structures, including fluorene (FL), dibenzothiophene (DBT), and dibenzofuran (DBF) derived from crude oils, are presented and incorporated into OSCs. All these additives exhibit strong interactions with the electron-deficient terminal groups of L8-BO within the bulk-heterojunction OSCs. Moreover, they demonstrate significant sublimation during thermal annealing, leading to increase free volumes for the rearrangement and recrystallization of L8-BO. This phenomenon leads to an improved film morphology and an elevated glass-transition temperature of the photoactive layers. Consequently, the PCE of the PM6:L8-BO blend has been boosted from 16.60% to 18.60% with 40 wt% DBF additives, with a champion PCE of 19.11% achieved for ternary PM6:L8-BO:BTP-eC9 OSCs. Furthermore, the prolonged shelf and thermal stability have been observed in OSCs with these additives. This study emphasizes the synergic effect of volatile solid additives on the performance and thermal stability of OSCs, highlighting their potential for advancing the field of photovoltaics.

Correlating the Segmental Relaxation Time of Polystyrene.

A previous related paper dealing with the density relaxation of polystyrene (PS) has shown that the equilibrium relaxation time (τeq) has a purely exponential temperature dependence (ETD) below ≈100 °C. Such an ETD is now also confirmed based upon available dielectric spectra data for PS. By combining the ETD behavior of τeq (or aT) at low temperatures with a VFTH behavior at higher temperatures (based mainly on available recoverable shear compliance data), a composite correlation for τeq (or aT) is developed, which is continuous with continuous slope at a crossover temperature that is found to be 99.22 °C, where τeq = 92.15 s. This composite representation is shown to describe (without any adjustable parameters) available independent data for the segmental relaxation time over a finite range both above and below Tcrossover (i.e., the glass transition temperature).

Nucleation, Development and Healing of Micro-Cracks in Shape Memory Polyurethane Subjected to Subsequent Tension Cycles.

Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature Tg leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a Tg of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above Tg enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at Tg + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over Tg, occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over Tg. Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material's surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.

Specific intermolecular interaction with sodium glycocholate generates the co-amorphous system showing higher physical stability and aqueous solubility of Y5 receptor antagonist of neuropeptide Y, a brick dust molecule.

Drugs with poor water and lipid solubility are termed "brick dust." We previously successfully developed a co-amorphous system of a novel neuropeptide Y5 receptor antagonist (AntiY5R), a brick dust molecule, using sodium taurocholate (NaTC) as a co-former. However, the maximum improvement in AntiY5R dissolution by the co-amorphous system was only approximately 10 times greater than that of the crystals. Therefore, in the current study, other bile salts, including sodium cholate (NaC), sodium chenodeoxycholate (NaCC), and sodium glycocholate (NaGC), were examined as co-formers to further improve AntiY5R dissolution. NaC, NaCC, and NaGC have glass transition temperatures above 150°C. All three co-amorphous systems prepared successfully retained the amorphous form of AntiY5R for 3 months at 40°C, but the co-amorphous system with NaGC (AntiY5R-NaGC; 1:9 molar ratio) provided the highest improvement in AntiY5R dissolution, which was approximately 50 times greater than that of the crystals. Possible intermolecular interactions via the glycine moiety of NaGC more than the other bile salts would contribute to the highest dissolution enhancement with AntiY5R-NaGC. Thus, NaGC would be a promising co-former for formulating stable co-amorphous systems to enhance the dissolution behavior of brick dust molecules.

Different or the same? exploring the physicochemical properties and molecular mobility of celecoxib amorphous forms.

The influence of different preparation methods on the physicochemical properties of amorphous solid forms have gained considerable attention, especially with recent publications on pharmaceutical polyamorphism. In the present study, we have investigated the possible occurrence of polyamorphism in the drug celecoxib (CEL) by investigating the thermal behavior, morphology, structure, molecular mobility and physical stability of amorphous CEL obtained by quench-cooling (QC), ball milling (BM) and spray drying (SD). Similar glass transition temperatures but different recrystallization behaviors were observed for CEL-QC, CEL-BM and CEL-SD using modulated differential scanning calorimetry analysis. A correlation between the different recrystallization behaviors of the three CEL amorphous forms and the respective distinct powder morphologies, was also found. Molecular dynamics simulations however, reveal that CEL presents similar molecular conformational distributions when subjected to QC and SD. Moreover, the obtained molecular conformational distributions of CEL are different from the ones found in its crystal structure and also from the ones found in the lowest-energy structure obtained by quantum mechanical calculations. The type and strength of CEL hydrogen bond interactions found in CEL-QC and CEL-SD systems are almost identical, though different from the ones presented in the crystal structure. Pair distribution function analyses and isothermal microcalorimetry show similar local structures and structural relaxation times, respectively, for CEL-QC, CEL-BM and CEL-SD. The present work shows that not only similar physicochemical properties (glass transition temperature, and structural relaxation time), but also similar molecular conformational distributions were observed for all prepared CEL amorphous systems. Hence, despite their different recrystallization behaviors, the three amorphous forms of CEL did not show any signs of polyamorphism.

Thermo-Mechanical Properties and Phase-Separated Morphology of Warm-Mix Epoxy Asphalt Binders with Different Epoxy Resin Concentrations.

The performance and phase-separated microstructures of epoxy asphalt binders greatly depend on the concentration of epoxy resin or bitumen. In this paper, the effect of the epoxy resin (ER) concentration (10-90%) on the viscosity, thermo-mechanical properties, and phase-separated morphology of warm-mix epoxy asphalt binders (WEABs) was investigated using the Brookfield rotational viscometer, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and laser scanning confocal microscopy (LSCM). Due to the high reactivity of epoxy resin, the viscosity of WEABs increases with time. Furthermore, the initial viscosity of WEABs decreases with the ER concentration. Depending on the ER concentration, the viscosity-time behavior of WEABs is divided into three stages: slow (10-40%), fast (50-80%), and extremely slow (90%). In the slow stage, the viscosity slightly increases with the ER concentration, while the fast stage shows an opposite trend. DSC and DMA results reveal that WEABs with 10-80% ER exhibit two glass transition temperatures (Tgs) for cured epoxy resin and bitumen. Moreover, the Tgs of epoxy resin and bitumen increase with the ER concentration. However, WEAB with 90 % ER has only one Tg. LSCM observation shows that phase separation occurs in all WEABs. For WEABs containing 10-40% ER, spherical epoxy particles act as the discontinuous phase and disperse in the continuous bitumen phase. However, in WEABs with 50-90% ER, phase inversion takes place. Contrarily, bitumen particles disperse in the continuous epoxy phase. The damping properties of WEABs with the continuous epoxy phases increase with the ER concentration, while the crosslinking density shows an opposite trend. The occurrence of phase inversion results in a sharp increase in the tensile strength of WEABs. For WEABs with the continuous epoxy phases, the elongation at break increases with the ER concentration. The toughness first increases and then decreases with the ER concentration. A maximum toughness value shows at 70% ER.

Influence of FexOy and Al2O3 Contents on the Thermal Stability of Iron Ore-Waste Fibers: Key Mechanisms and Control.

Traditional rock wool fibres are susceptible to crystallization and pulverization. To mitigate this, glass fibres were produced from iron ore waste (IOW). When the ratio of Fe2+ and Fe3+ is 1:3 and the Al2O3 content is 10 wt.%, increasing the FexOy content enhances the thermal stability.At an FexOy content of 17-19% and an Al2O3 content of 10-13%, the glass transition temperature (Tg) peaked. Increasing the FexOy content from 10% to 20% enhanced the stability of Si-O and Al-O bonds and increased bridged oxygen, stabilizing the structure. Here, Fe2+ balances structural charges, while Fe3+ replaces some Al atoms in the network. When the Al2O3 content is 10-13% and the FexOy content is 17-19%, the thermal stability of the IOW rock glass reaches its optimal level. At 20% FexOy content, the structure becomes three-dimensional and cyclic, increasing polymerization. Consequently, incorporating FexOy alongside a 10% Al2O3 content improves thermal stability, supporting the development of high-stability rock wool from IOW. This approach also enhances the refractory properties of rock wool fibres within the FexOy-Al2O3-SiO2-MgO-CaO system.

Mechanistic study of the differences in lactic acid bacteria resistance to freeze- or spray-drying and storage.

Lactobacillus delbrueckii subsp. bulgaricus and Lactiplantibacillus plantarum are two lactic acid bacteria (LAB) widely used in the food industry. The objective of this work was to assess the resistance of these bacteria to freeze- and spray-drying and study the mechanisms involved in their loss of activity. The culturability and acidifying activity were measured to determine the specific acidifying activity, while membrane integrity was studied by flow cytometry. The glass transitions temperature and the water activity of the dried bacterial suspensions were also determined. Fourier transform infrared (FTIR) micro-spectroscopy was used to study the biochemical composition of cells in an aqueous environment. All experiments were performed after freezing, drying and storage at 4, 23 and 37 °C. The results showed that Lb. bulgaricus CFL1 was sensitive to osmotic, mechanical, and thermal stresses, while Lpb. plantarum WCFS1 tolerated better the first two types of stress but was more sensitive to thermal stress. Moreover, FTIR results suggested that the sensitivity of Lb. bulgaricus CFL1 to freeze-drying could be attributed to membrane and cell wall degradation, whereas changes in nucleic acids and proteins would be responsible of heat inactivation of both strains associated with spray-drying. According to the activation energy values (47-85 kJ/mol), the functionality loss during storage is a chemically limited reaction. Still, the physical properties of the glassy matrix played a fundamental role in the rates of loss of activity and showed that a glass transition temperature 40 °C above the storage temperature is needed to reach good preservation during storage. KEY POINTS: • Specific FTIR bands are proposed as markers of osmotic, mechanic and thermal stress • Lb. bulgaricus CFL1 was sensitive to all three stresses, Lpb. plantarum WCFS1 to thermal stress only • Activation energy revealed chemically limited reactions ruled the activity loss in storage.

Is a Vitrimer with a High Glass Transition Temperature Available? A Case Study on Rigid Polyimides Cross-Linked with Dynamic Ester Bonds.

Vitrimers, possessing associative covalent adaptable networks, are cross-linked polymers exhibiting malleable (glass-like) feature and recyclable and reprocessable (thermoplastics-like) properties. The dynamic behaviors of vitrimer are dependent on both chain/molecular mobility (glass transition temperature, Tg) and dynamic bond-exchanging reaction rate (topology freezing transition temperature, Tv). This work aims on probing the effect of high Tg on the stress relaxation and physical recyclability of vitrimers, employing a polyimide cross-linked with dynamic ester bonds (Tg: 310 °C) as the example. Due to its high Tg and chain rigidity, the cross-linked polyimide does not exhibit a high extent of stress relaxation behavior at 320 °C (10 °C above its Tg), even though the temperature is much higher than the hypothetical Tv. While raising the processing temperature to 345 °C, the cross-linked polyimide exhibits a stress relaxation time of about 3300 s and physical malleability. Nevertheless, side reactions may occur in the recycling and reprocessing process under the harsh condition (high temperature and high pressure) to alter the thermal properties of the recycled sample. The diffusion control plays a critical role on the topography transition of a vitrimer having a high Tg. The Tg ceiling is noticeable for developments of vitrimers.

The temperature dependence of the Hildebrand solubility parameters of selected hydrocarbon polymers and hydrocarbon solvents: a molecular dynamics investigation.

CONTEXT: To determine the miscibility of liquids at high temperatures using the concept of Hildebrand solubility parameter δ , the current practice is to examine the difference in δ between two liquids at room temperature, assuming that δ is not sensitive to temperature. However, such an assumption may not be valid for certain polymer blends and solutions. Therefore, a knowledge of the δ values of the liquids of interest at high temperatures is desirable. The determination of δ at high temperatures, especially for high-molecular-weight polymers, is impossible, as polymers have vapor pressures of zero. To this end, molecular dynamics (MD) simulations provide a practical means for determining δ over a wide range of temperatures. In this work, we study the temperature dependence of δ of five hydrocarbon polymers: polyethylene (PE), isotactic and atactic polypropylene (i-PP and a-PP), polyisobutylene (PIB), and polyisoprene (PI) in five hydrocarbon solvents: n-pentane, n-hexane, n-dodecane, isobutene, and cyclohexane. The polymers are modeled as monodisperse chains with 100 repeat units. The average δ values of PE, i-PP, a-PP, PIB, and PI at 300 K are determined as 18.6, 14.9, 14.6, 14.3, and 16.4 MPa1/2, respectively, in a good agreement with experimental data. The δ values of these polymers at various temperatures are also determined. The temperature dependence of δ is fitted to two linear equations, one above and the other below the polymer's glass transition temperature Tg. The δ values are more sensitive to temperature at T ≥ Tg. The Tg values of the polymers, determined based upon their specific volumes and δ values agree with the experiment qualitatively. The determination of the temperature dependence of δ has a great potential for industrial applications, such as determining miscibility, developing polymeric organogelators as flocculants and oil spill treating agents, and identifying potential solvents and ideal processing temperatures. METHODS: The MD simulations are performed using the GROMACS 2022.3 package with optimized potential for liquid simulations-all atom (OPLS-AA) force field parameters. All polymers are built as extended chains using CHARMM-GUI Polymer Builder.

Degree of Cure, Microstructures, and Properties of Carbon/Epoxy Composites Processed via Frontal Polymerization.

The frontal polymerization (FP) of carbon/epoxy (C/Ep) composites is investigated, considering FP as a viable route for the additive manufacturing (AM) of thermoset composites. Neat epoxy (Ep) resin-, short carbon fiber (SCF)-, and continuous carbon fiber (CCF)-reinforced composites are considered in this study. The evolution of the exothermic reaction temperature, polymerization frontal velocity, degree of cure, microstructures, effects of fiber concentration, fracture surface, and thermal and mechanical properties are investigated. The results show that exothermic reaction temperatures range between 110 °C and 153 °C, while the initial excitation temperatures range from 150 °C to 270 °C. It is observed that a higher fiber content increases cure time and decreases average frontal velocity, particularly in low SCF concentrations. This occurs because resin content, which predominantly drives the exothermic reaction, decreases with increased fiber content. The FP velocities of neat Ep resin- and SCF-reinforced composites are seen to be 0.58 and 0.50 mm/s, respectively. The maximum FP velocity (0.64 mm/s) is observed in CCF/Ep composites. The degree of cure (αc) is observed to be in the range of 70% to 85% in FP-processed composites. Such a range of αc is significantly low in comparison to traditional composites processed through a long cure cycle. The glass transition temperature (Tg) of neat epoxy resin is seen to be approximately 154 °C, and it reduces slightly to a lower value (149 °C) for SCF-reinforced composites. The microstructures show significantly high void contents (12%) and large internal cracks. These internal cracks are initiated due to high thermal residual stress developed during curing for non-uniform temperature distribution. The tensile properties of FP-cured samples are seen to be inferior in comparison to autoclave-processed neat epoxy. This occurs mostly due to the presence of large void contents, internal cracks, and a poor degree of cure. Finally, a highly efficient and controlled FP method is desirable to achieve a defect-free microstructure with improved mechanical and thermal properties.

Optimizing Epoxy Molding Compound Processing: A Multi-Sensor Approach to Enhance Material Characterization and Process Reliability.

The in-line control of curing during the molding process significantly improves product quality and ensures the reliability of packaging materials with the required thermo-mechanical and adhesion properties. The choice of the morphological and thermo-mechanical properties of the molded material, and the accuracy of their determination through carefully selected thermo-analytical methods, play a crucial role in the qualitative prediction of trends in packaging product properties as process parameters are varied. This work aimed to verify the quality of the models and their validation using a highly filled molding resin with an identical chemical composition but 10 wt% difference in silica particles (SPs). Morphological and mechanical material properties were determined by dielectric analysis (DEA), differential scanning calorimetry (DSC), warpage analysis and dynamic mechanical analysis (DMA). The effects of temperature and injection speed on the morphological properties were analyzed through the design of experiments (DoE) and illustrated by response surface plots. A comprehensive approach to monitor the evolution of ionic viscosity (IV), residual enthalpy (dHrest), glass transition temperature (Tg), and storage modulus (E) as a function of the transfer-mold process parameters and post-mold-cure (PMC) conditions of the material was established. The reliability of Tg estimation was tested using two methods: warpage analysis and DMA. The noticeable deterioration in the quality of the analytical signal for highly filled materials at high cure rates is discussed. Controlling the temperature by increasing the injection speed leads to the formation of a polymer network with a lower Tg and an increased storage modulus, indicating a lower density and a more heterogeneous structure due to the high heating rate and shear heating effect.

Sequence of Monomers and Position of Stereocenters Matter for Thermal Properties of Stereocontrolled Oligourethanes.

Polyurethanes are commodity materials used for multiple applications. In recent years, a new category of polyurethane material has emerged, characterized by the lack of polymer molar mass dispersity, control of the monomer arrangement in the chain, and even full stereocontrol. Various multistep synthesis strategies have been developed to fabricate sequence-defined polyurethanes. However, synthesizing stereocontrolled polyurethanes with a controlled sequence is still a challenge. Polyurethanes with structural precision, as represented by biopolymers, i. e. proteins or nucleic acids, have opened new application directions for these groups of materials. It has been shown that polyurethanes can be used as biomimetics, information carriers, molecular tags, and materials with strictly controlled properties. Precise synthesis of macromolecules allows us to fine-tune the properties of polymers to specific needs. Therefore, it is essential to collect information on the sequence-structure relationship of polymers. In our work, we present synthetic pathways to make sequence and stereo-defined oligourethanes. We demonstrate that structural details, i. e., the monomer sequences and position of the stereocenter, have a tremendous effect on the thermal properties of model oligourethanes. We show that the introduction of chirality by constitutional isomerization can be used to program the thermal characteristics of polymers, which are key features for material applications.