Search Results (228)

This study conducts a detailed viscoelastic simulation of the side-by-side PA6/PA66 bicomponent melt spinning process to investigate the mechanisms behind reduced fiber elasticity. A two-dimensional (2D) axisymmetric finite element model was developed using ANSYS Polyflow, incorporating the Phan–Thien–Tanner (PTT) constitutive equation and a non-isothermal crystallization model. Simulation outcomes were validated with experimental and published data, showing close agreement in fiber radius, velocity, and temperature profiles (within 8% deviation). Results indicate that the dominance of the higher-viscosity PA66 phase induces uneven stress distributions and localized crystallization, leading to decreased elastic recovery. Higher winding speeds amplify this effect. This work offers a predictive framework for optimizing industrial melt spinning conditions to improve elasticity in bicomponent fibers. Key results indicate that the dominance of the PA66 component—due to its higher melt viscosity—leads to uneven stress distribution, elevated tensile stress, and localized crystallinity peaks along the spin line. These factors collectively contribute to reduced elastic recovery in the fiber. Moreover, increased winding speeds amplify axial stress and crystallinity disparities, further exacerbating the stiffness of the final product. In contrast, better elasticity was associated with lower pressure drop, balanced crystallinity, and minimized axial velocity differences between the two polymer phases. The findings offer valuable insights into optimizing industrial melt spinning processes to enhance fiber elasticity. This research not only improves fundamental understanding of viscoelastic flow behavior in bicomponent spinning but also provides a predictive framework for tailoring mechanical properties of fibers through process and material parameter adjustments. Full article

Poly(trimethylene terephthalate) (PTT) is a thermoplastic polyester with a unique structure due to having three methylene groups in the glycol unit. PTT competes with poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) in carpets, textiles, and thermoplastic materials, primarily due to the development of economically efficient synthesis methods. PTT is widely utilized in textiles, carpets, and engineering plastics because of its advantageous properties, including quick-drying capabilities and wrinkle resistance. However, its low melting point, resistance to chemicals, and brittleness compared to PET, have limited its applications. To address some of these limitations for targeted applications, PTT nanocomposites incorporating clay, carbon nanotube, silica, and ZnO have been developed. The distribution of nanoparticles within the PTT matrix remains a significant challenge for its potential applications. Several techniques, including sol–gel blending, melt blending, in situ polymerization, and in situ forming methods have been developed to obtain better dispersion. This review discusses advancements in the synthesis of various PTT nanocomposites and the effects of nanoparticles on the isothermal and nonisothermal crystallization of PTT. Full article

Thermokinetic characterization of amorphous carbamazepine was performed utilizing non-isothermal differential scanning calorimetry (DSC) and thermogravimetry (TGA). Structural relaxation of the amorphous matrix was described in terms of the Tool–Narayanaswamy–Moynihan model with the following parameters: Δh* ≈ 200–300 kJ·mol⁻¹, β = 0.57, x = 0.44. The crystallization of the amorphous phase was modeled using complex Šesták–Berggren kinetics, which incorporates temperature-dependent activation energy and degree of autocatalysis. The activation energy of the crystal growth was determined to be >320 kJ·mol⁻¹ at the glass transition temperature (T_g). Owing to such a high value, the amorphous carbamazepine is stable at T_g, allowing for extensive processing of the amorphous phase (e.g., self-healing of the quench-induced mechanical defects or internal stress). A discussion was conducted regarding the converse relation between the activation energies of relaxation and crystal growth, which is possibly responsible for the absence of sub-T_g crystal growth modes. The high-temperature thermal decomposition of carbamazepine proceeds via multistep kinetics, identically in both an inert and an oxidizing atmosphere. A complex reaction mechanism, consisting of a series of consecutive and competing reactions, was proposed to explain the second decomposition step, which exhibited a temporary mass increase. Whereas a negligible degree of carbamazepine degradation was predicted for the temperature characteristic of the pharmaceutical hot-melt extrusion (~150 °C), the degradation risk during the pharmaceutical 3D printing was calculated to be considerably higher (1–2% mass loss at temperatures 190–200 °C). Full article

During the thermal treatment of kaolinite, the main mineral phase in kaolin rock, dehydroxylation occurs, forming metakaolin through a process that has significant industrial applications. This study experimentally analyzed dehydroxylation in two kaolinite samples: a well-crystallized reference sample from the Clay Mineral Society and a locally sourced, industrial kaolin sample. The mechanism and kinetic parameters were evaluated from a series of thermogravimetric measurements. Non-isothermal kinetic analysis revealed that dehydroxylation followed a third-order (F3) reaction mechanism, with activation energies ($E_a$) ranging from 35 to 60 kcal/mol. Additionally, theoretical calculations based on Density Functional Theory were performed on four systems in which a water molecule was removed by combining OH group and H atom vacancies in the kaolinite unit cell. These models represented the onset of dehydroxylation and provided values for the reaction energy Q from first-principles calculations, which served as reference values for $E_a$. The results confirm that water molecule formation involving both OH at the kaolinite outer surface and inner surface are energetically competitive and highlight the crucial role of structural relaxations following water removal to determine Q values in the range of 30–50 kcal/mol, in very good agreement with the experiments. Full article

This study investigates the impact of hydrolysis on the crystallization behavior of poly(butylene succinate-co-adipate) (PBSA), a biodegradable polyester. Hydrolysis was conducted in a controlled environment using phosphate-buffered saline at 70 °C to isolate the impact of hydrolytic degradation on the polymer’s properties. The consequent changes in molecular weight characteristics were tracked using gel permeation chromatography (GPC), revealing a decrease in both weight average molecular weight (M_w) and an increase in polydispersity index (PDI) as hydrolysis progressed. The thermal behavior of PBSA during hydrolysis was thoroughly investigated using differential scanning calorimetry (DSC), which demonstrated significant changes in melting temperature (T_m), glass transition temperature (T_g), and crystallinity (X). These changes in T_m and T_g suggest a change in copolymer composition, likely due to the greater susceptibility of the adipic acid unit to hydrolysis compared to the succinic acid unit. Furthermore, polarized optical microscopy (POM) was employed to observe the morphological evolution of PBSA, showing a transition from spherulitic structures in the early stages of hydrolysis to dendritic structures with prolonged hydrolysis time. The decrease in nucleation activity led to a reduction in the number of spherulites, which in turn allowed the remaining spherulites to grow larger. Full article

This work reports a study on the structural characterization, evaluation of thermal stability, and non-isothermal decomposition kinetics of urea–formaldehyde (UF) resin modified with hydrochar (obtained by the hydrothermal carbonization of spent mushroom substrate (SMS)) (UF-HC). The structural characterization of UF-HC, performed by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and X-ray diffraction analyses, showed that UF-HC consists of a large number of spheroidal particles, which are joined, thus forming clusters. It constitutes agglomerates, which are composed of crystals that have curved plate-like forms, including crystalline UF structure and graphite lattices with an oxidized face (graphene oxide, GO). The measurement of inherent thermal stability and non-isothermal decomposition kinetic analysis was carried out using simultaneous thermogravimetric–differential thermal analyses (TGA-DTA) at various heating rates. Parameters that are obtained from thermal stability assessment have indicated the significant thermal stability of UF-HC. Substantial variation in activation energy and the pre-exponential factor with the advancement of decomposition process verifies the multi-step reaction pathway. The decomposition process takes place through three independent single-step reactions and one consecutive reactions step. The consecutive stage represents a path to the industrial production of valuable heterocyclic organic compounds (furan) and N-heterocyclic compounds (pyrroles), building a green-protocol trail. It was found that a high heating rate stimulates a high production of furan from cellulose degradation via the ring opening step, while a low heating rate favors the production of urea compounds (methylolurea hemiformal (HFn)) by means of methylene ether bridges breaking. Full article

Reducing the environmental impact is a key reason for developing recyclable insulation materials for high-voltage industries. In this study, polypropylene (PP) blends were prepared via melt mixing with styrene–ethylene–butylene–styrene (SEBS), a thermoplastic elastomer, to improve breakdown strengths at various cooling speeds. A systematic investigation was conducted to evaluate the influence of crystal size, degree of crystallinity, and nucleation growth rate on the breakdown strength. Crystallization behavior was analyzed using isothermal and non-isothermal methods based on the Avrami model. Increasing SEBS content reduced crystallinity, with the lowest nucleation growth rate observed at 35% SEBS. Breakdown strength correlated with crystallization behavior and was further validated by Weibull distribution method. Notably, PP/SEBS blends containing 35% SEBS exhibited the highest breakdown strength of 66.4 kV/mm at a cooling speed of 10 °C/mm. This improvement reflected a reduction in the degree of crystallinity from 36.0% to 22.9% and the lowest growth rate constant (k) at 35% SEBS. Furthermore, the predicted lifetime of PP/SEBS blend containing 35% SEBS, calculated using the oxidation induction time and the Arrhenius equation, was 42 years. These findings demonstrate that SEBS content and cooling rate effectively modulate crystallization and breakdown strength, enabling recyclable PP/SEBS with XLPE-comparable performance for sustainable high-voltage insulation. Full article

The impact of adding 1%, 3%, and 5% by mass of kaolin residue (KR) was investigated regarding the mechanical, thermomechanical, and morphological properties, as well as the non-isothermal crystallization and melting kinetics of poly(ε-caprolactone) (PCL). The processing to obtain the PCL/KR composites was carried out through extrusion in a twin-screw extruder, followed by injection molding. This study investigated the events of first melting, fusion crystallization, and second melting using differential scanning calorimetry (DSC), with heating rates ranging from 5 to 25 °C/min. Additionally, models for the expanded Prout–Tompkins equation (BNA), the nth-order reaction with m-power autocatalysis by product (Cnm), and the Sestak and Berggren equation (SB) were tested. The PCL/KR composites exhibited an increase in the elastic modulus and the heat deflection temperature (HDT) compared to the pure PCL. Furthermore, high ductility was observed, as evidenced by the impact strength and elongation at break. The good distribution of KR in the PCL matrix was confirmed by scanning electron microscopy (SEM), which contributed to a more efficient crystallization process. The increase in KR content in the PCL matrix shifted the crystallization sigmoids to higher temperatures, acting as a nucleating agent, which reduced the energy barriers and increased the crystallization temperature by up to 5 °C. The melting events did not show significant changes with the addition of the KR. The results are important for the plastics processing industry, mainly due to the opportunity to add value to the waste and use it as an additive. Full article

The ability of biochars derived from fallen (F-BC) and non-fallen (NF-BC) maple leaves to adsorb Cu²⁺ ions from aqueous solutions was examined. Biochars were produced at pyrolysis temperatures of 350, 550, and 750 °C. Higher pyrolysis temperatures resulted in enhanced specific surface areas and promoted CaCO₃ crystallization while limiting MgCO₃ formation. The Cu²⁺ adsorption capacity depended on the biochar type and pyrolysis conditions. Although the Cu²⁺ adsorption efficiency of NF-BCs decreased with increasing pyrolysis temperature, F-BC550 exhibited a higher Cu²⁺ adsorption capacity than F-BC750. Additionally, the Cu²⁺ adsorption performance of both NF-BC350 and F-BC550 improved with increasing solution pH. Cu²⁺ adsorption onto NF-BC350 and F-BC550 followed the two-compartment first-order (involving fast and slow adsorption compartments) and Langmuir (meaning homogeneous monolayer adsorption) models, respectively. The maximum Cu²⁺ adsorption capacity of F-BC550 (147.3 mg Cu/g BC) was 7.8-fold higher than that of NF-BC350 (18.8 mg Cu/g BC), as determined by isotherm studies. The enhanced adsorption performance of F-BC550 may be attributable to physical adsorption facilitated by increased surface area and multiple mechanisms, including cationic attraction via functional groups, ion exchange (Ca and Mg), and van der Waals interaction facilitated by increased surface area. These findings suggest that F-BC550, derived from waste biomass, exhibits superior Cu²⁺ adsorption performance compared to NF-BCs, making it a promising adsorbent for wastewater treatment applications. Full article

Non-isothermal differential scanning calorimetry (DSC) and Raman microscopy were used to study the crystallization behavior of the 20–50 μm amorphous nifedipine (NIF) powder. In particular, the study was focused on the diffusionless glass-crystal (GC) growth mode occurring below the glass transition temperature (T_g). The exothermic signal associated with the GC growth was indeed directly and reproducibly recorded at heating rates q⁺ ≤ 0.5 °C·min⁻¹. During the GC growth, the α_p polymorphic phase was exclusively formed, as confirmed via Raman microscopy. In addition to the freshly prepared NIF samples, the crystallization of the powders annealed for 7 h at 20 °C was also monitored—approx. 50–60% crystallinity was achieved. For the annealed NIF powders, the confocal Raman microscopy verified a proportional absence of the crystalline phase on the sample surface (indicating its dominant formation along the internal micro-cracks, which is characteristic of the GC growth). All DSC data were modeled in terms of the solid-state kinetic equation paired with the autocatalytic model; the kinetic complexity was described via reaction mechanism based on the overlap of 3–4 independent processes. The kinetic trends associated with decreasing q⁺ were identified, confirming the temperature-dependent kinetic behavior, and used to calculate a theoretical kinetic prediction conformable to the experimentally performed 7 h annealing at 20 °C. The theoretical model slightly underestimated the true extent of the GC growth, predicting the crystallinity to be 35–40% after 7 h (such accuracy is still extremely good in comparison with the standard kinetic approaches nowadays). Further research in the field of kinetic analysis should thus focus on the methodological ways of increasing the accuracy of considerably extrapolated kinetic predictions. Full article

Changes in microRNA (miRNA) levels are closely associated with the pathological processes of many diseases. The sensitive and fast detection of miRNAs is critical for diagnosis and prognosis. Here, we report a platform employing CRISPR/Cas12a to recognize and report changes in miRNA levels while avoiding complex multi-thermal cycling procedures. A non-enzyme-dependent hybridization chain reaction (HCR) was used to convert the miRNA signal into double-stranded DNA, which contained a Cas12a activation sequence. The target sequence was amplified simply and isothermally, enabling the test to be executed at a constant temperature of 37 °C. The detection platform had the capacity to measure concentrations down to the picomolar level, and the target miRNA could be distinguished at the nanomolar level. By using photonic crystal microarrays with a stopband-matched emission spectrum of the fluorescent-quencher modified reporter, the fluorescence signal was moderately enhanced to increase the sensitivity. With this enhancement, analyzable fluorescence results were obtained in 15 min. The HCR and Cas12a cleavage processes could be conducted in a single tube by separating the two procedures into the bottom and the cap. We verified the sensitivity and specificity of this one-pot system, and both were comparable to those of the two-step method. Overall, our study produced a fast and sensitive miRNA detection platform based on a CRISPR/Cas12a system and enzyme-free HCR amplification. This platform may serve as a potential solution for miRNA detection in clinical practice. Full article

Zr₄₈Cu_47.5Al₄Co_0.5 bulk amorphous alloy composites were prepared by selective laser melting (SLM) technology under different processing conditions and their non-isothermal crystallization behaviors were systematically investigated. The results show that the crystallization phases are Cu₁₀Zr₇ and CuZr₂ for both gas-atomized powder and SLMed samples. The dependence of volume fraction of Cu₁₀Zr₇ and CuZr₂ on laser energy density can be fitted by an exponential function. The crystalline sizes of Cu₁₀Zr₇ and CuZr₂ linearly increase with increasing energy density. The thermal stability is larger for the gas-atomized powders than for the SLMed bulk samples. It is interestingly found that there is an exponential relationship between the crystallization enthalpy ΔH_x and the amorphous content. In addition, the glass transition is more difficult for the gas-atomized powders than for the SLMed bulk samples. The crystallization procedure is more difficult for the SLMed bulk samples than for the gas-atomized powders. The local activation energy E_α decreases with increasing α for the gas-atomized powder and the SLMed bulk samples. In addition, the E_α is larger for the SLMed bulk samples than for the gas-atomized powder at the corresponding crystallization fraction α. The dependence of the local Avrami exponent n(α) on the α is similar for both the gas-atomized powders and the SLMed bulk samples at studied heating rates. The crystallization mechanism is also discussed. Full article

The isothermal oxidation behavior of single crystal DD6 film-cooling blades was investigated. The isothermal oxidation tests were conducted at 1050 °C, and the phase analysis was performed by XRD, while SEM (EDS) was employed to observe the material. In addition to experimental studies, a numerical simulation using three-dimensional finite element analysis based on Abaqus software (Version 6.13) was implemented to model the growth stress in specimens during the isothermal test. The obtained results showed that the average oxidation rate of specimens rose with increments in film hole spacing, up to a maximum value at a film hole spacing of 0.75 mm, and then fell, which could be interpreted with the concepts of the oxidation-affected zone and the growth stress. The results obtained from the numerical simulation of the growth stress agreed with the experimental results of the average oxidation rate. The oxide scale of film-cooling specimens mainly consisted of three layers, the NiO outer layer, the spinel sublayer containing cracks, and the non-continuous thin Al₂O₃ inner layer. The surface of the oxide scale commonly underwent spallation of the NiO outer layer, and the exposed sublayer could grow new NiO particles. The size of the NiO particles on the edge of the film holes was larger than those on the walls of the film holes. SEM images clearly showed that electro-hydraulic beam drilling on DD6 superalloy specimens could erode the γ phase in the γ/γ′ two-phase matrix, thereby inducing damages in regions near film holes. Full article

The non-isothermal melt crystallization process of poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoateate] (PHBHx) was monitored using attenuated total reflection infrared (ATR IR) measurement. The resulting time- and temperature-dependent spectra were subjected to the two-dimensional correlation spectroscopy (2D-COS) analysis. The C=O stretching region of the PHBHx sample consisted of several distinct IR contributions attributable to the population of amorphous component, well-ordered type I lamellar crystal, and less ordered inter-lamellar type II crystal. The spectral intensity change in type I crystal occurs in the earlier stage of the crystallization at a higher temperature range compared to the overall intensity decrease in the amorphous component occurring throughout the crystallization process. The growth of the type II crystal started in a later stage at a lower temperature than the creation of the type I crystal. An early decrease in a small but distinct portion of the amorphous component may be related to a crystallization precursor species with some level of molecular order. Hetero-mode correlation analyses revealed that the crystalline band intensity changes in the C-H stretching and fingerprint regions all occur later than the population changes in crystalline species reflected by the carbonyl stretching bands. This observation suggests that the spectral intensity changes in the C-H stretching and fingerprint regions do not directly represent the population dynamics of the crystalline and amorphous species but probe instead the molecular state of the crystalline entities still undergoing the evolutionary changes. Full article

The utilization of form-stable phase change materials (PCMs) represents a reliable technology for achieving energy conversion. In this study, starch was impregnated into the layers of expanded vermiculite (EVM) and subsequently carbonized at high temperatures to produce in situ carbon layers modified materials (EVMC), which enhance heat storage efficiency. The EVMC, characterized by its carbon network, acted as encapsulated material, leading to the development of paraffin (P)/EVCM-based shape-stable composite PCM (EVMCP). The latent heat of the EVMCP was measured at 179 J/g, surpassing that of EVMP at 144.8 J/g. This finding suggested that in situ porous carbon significantly improves the heat storage ability. Furthermore, non-isothermal crystallization curves indicated that EVMC markedly accelerated the nucleation and simultaneously restricted the non-isothermal crystal growth. Full article