Search Results (93)

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

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

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

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

In this research, fully biobased composites consisting of poly(butylene 2,5-furandicarboxylate) (PBF) and cellulose nanocrystals (CNC) were successfully prepared through a common solution and casting method. The influence of CNC on the crystallization behavior, mechanical property, and hydrophilicity of PBF was systematically investigated. Under different crystallization processes, the crystallization of PBF was obviously promoted by CNC as a biobased nucleating agent. The Ozawa equation was not suitable to fit the nonisothermal melt crystallization kinetics of PBF and PBF/CNC composites. The nucleation activity of CNC was quantitatively calculated by the Dobreva method; moreover, the nucleation efficiency of CNC was further evaluated through the self-nucleation procedure. The isothermal melt crystallization kinetics of PBF and PBF/CNC composites was well described by the Avrami method; moreover, the crystallization mechanism and the crystal structure of PBF remained unchanged despite the presence of CNC. CNC also greatly enhanced both the mechanical property and hydrophilicity of PBF in the composites. In sum, low loadings of CNC simultaneously improved the crystallization, mechanical property, and hydrophilicity of PBF, which should be of significant importance and interest in fully biobased polymer composites from a sustainable viewpoint. Full article

Polylactic acid (PLA) is a widely recognized biodegradable polymer. However, the slow crystallization rate of PLA restricts its practical applications. In this study, camphor leaf biochar decorated with multi-walled carbon nanotubes (C@MWCNTs) was prepared using the strong adhesive properties of polydopamine, and PLA/C@MWCNTs composites were fabricated via the casting solution method. The influence of C@MWCNTs as a novel nucleating agent on the melt behavior and non-isothermal crystallization behavior of PLA was investigated using differential scanning calorimetry (DSC). The crystallization kinetic parameters were obtained through the Jeziorny, Ozawa, and Mo methods, and the crystallization activation energy of the PLA/C@MWCNTs composites was calculated by the Kissinger method. The results show that the PLA/C@MWCNTs composites exhibit higher crystallinity and crystallization temperatures than those of PLA. Non-isothermal crystallization kinetic analysis reveals that the Mo method better describes the non-isothermal crystallization kinetics of both PLA and PLA/C@MWCNTs composites. In addition, it was found that C@MWCNTs, despite increasing the crystallization activation energy, can act as an efficient nucleating agent to increase the crystallization rate of PLA. These experimental results provide valuable insights for enhancing the slow crystallization rates associated with PLA. Full article

The polar sulfonate groups in cationic dyeable polyester (CDP) lead to complex crystallization behavior, affecting CDP production’s stability. In this study, cationic dyeable polyesters (CDP) with different sulfonate group contents were prepared via one-step feeding of sodium isophthalic acid-5-sulfonate (SIPA), terephthalic acid (PTA), and ethylene glycol (EG). The non-isothermal crystallization behavior of these copolyesters was analyzed by differential scanning calorimetry (DSC). Results show that the crystallization temperature of the sample shifts to lower values with the increase in SIPA content. The relaxation behavior of the molecular chain is enhanced due to the ionic aggregation effect of sulfonate groups in CDP. Therefore, at low cooling rates (2.5 °C/min and 5 °C/min), some molecular chain segments in CDP are still too late to orderly stack into the lattice, forming metastable crystals, and melting double peaks appear on the melting curve after crystallization. When the cooling rate increases (10–20 °C/min), the limited region of sulfonate aggregation in CDP increases, resulting in more random chain segments, and a cold crystallization peak appears on the melting curve after crystallization. The non-isothermal crystallization behavior of all samples was fitted and analyzed by the Jeziorny equation, Ozawa equation, and Mo equation. The results indicate that the nucleation density and nucleation growth rate of CDP decrease with the increase in SIPA content. Meanwhile, analysis of the Kissinger equation reveals that the activation energy of non-isothermal crystallization decreases gradually with the increase in SIPA content, and the addition of SIPA makes CDP crystallization more difficult. Full article

This study presents a comprehensive approach for simulating the additive manufacturing process of semi-crystalline composite polymers using Fused Deposition Modeling (FDM). By combining thermomechanical Finite Element Analysis (FEA) with experimental validation, our main objective is to comprehend and model the complex behaviors of 50 wt.% carbon fiber-reinforced Polyphenylene Sulfide (CF PPS) during FDM printing. The simulations of the FDM process encompass various theoretical aspects, including heat transfer, orthotropic thermal properties, thermal dissipation mechanisms, polymer crystallization, anisotropic viscoelasticity, and material shrinkage. We utilize Abaqus user subroutines such as UMATHT for thermal orthotropic constitutive behavior, UEPACTIVATIONVOL for progressive activation of elements, and ORIENT for material orientation. Mechanical behavior is characterized using a Maxwell model for viscoelastic materials, incorporating a dual non-isothermal crystallization kinetics model within the UMAT subroutine. Our approach is validated by comparing nodal temperature distributions obtained from both the Abaqus built-in AM Modeler and our user subroutines, showing close agreement and demonstrating the effectiveness of our simulation methods. Experimental verification further confirms the accuracy of our simulation techniques. The mechanical analysis investigates residual stresses and distortions, with particular emphasis on the critical transverse in-plane stress component. This study offers valuable insights into accurately simulating thermomechanical behaviors in additive manufacturing of composite polymers. Full article

During the secondary thermoforming of carbon fiber-reinforced polyphenylene sulfide (CF/PPS) composites, a vital material for the aerospace field, varied thermal parameters profoundly influence the crystallization behavior of the PPS matrix. Notably, PPS exhibits a distinctive self-nucleation (SN) behavior during repeated thermal cycles. This behavior not only affects its crystallization but also impacts the processing and mechanical properties of PPS and CF/PPS composites. In this article, the effects of various parameters on the SN and non-isothermal crystallization behavior of PPS during two thermal cycles were systematically investigated by differential scanning calorimetry. It was found that the SN behavior was not affected by the cooling rate in the second thermal cycle. Furthermore, the lamellar annealing resulting from the heating process in both thermal cycles affected the temperature range for forming the special SN domain, because of the refined lamellar structure, and expelled various defects. Finally, this study indicated that to control the strong melt memory effect in the first thermal cycle, both the heating rate and processing melt temperature need to be controlled simultaneously. This work reveals that through collaborative control of these parameters, the crystalline morphology, crystallization temperature and crystallization rate in two thermal cycles are controlled. Furthermore, it presents a new perspective for controlling the crystallization behavior of the thermoplastic composite matrix during the secondary thermoforming process. Full article

As semi-crystalline polyester (lactic acid) (PLA) is combined with other reinforcing materials, challenges such as phase separation, environmental pollution, and manufacturing difficulties could hinder the benefits of PLA, including complete biodegradability and strong mechanical properties. In the present investigation, melt blending is utilized to establish a mixture of low- and high-molecular-weight polylactic acids (LPLA and HPLA). The crystallinity, rheology, and mechanical properties of the combination were analyzed using rotational rheometry, differential scanning calorimetry, X-ray diffraction, polarized optical microscopy, scanning electron microscopy, and universal testing equipment. The results demonstrate compatibility between LPLA and HPLA. Moreover, an increase in LPLA concentration leads to a decrease in the crystallization rate, spherulite size, fractional crystallinity, and XRD peak intensity during isothermal crystallization. LPLA acts as a diluent during isothermal crystallization, whereas HPLA functions as a nucleating agent in the non-isothermal crystallization process, promoting the growth of LPLA crystals and leading to co-crystallization. The blended system with a 5% LPLA mass fraction exhibits the highest tensile strength and enhances rheological characteristics. By effectively leveraging the relationship between various molecular weights of PLA’s mechanical, rheological, and crystallization behavior, this scrutiny improves the physical and mechanical characteristics of the material, opening up new opportunities. Full article

A computational framework is developed to understand the transient behavior of isothermal and non-isothermal transformation between liquid and solid phases in a binary alloy using a phase-field method. The non-isothermal condition was achieved by applying a thermal gradient along the computational domain. The bulk solid and liquid phases were treated as regular solutions, along with introducing an order parameter (phase field) as a function of space and time to describe the interfacial region between the two phases. An antitrapping flux term was integrated into the present phase-field model to mitigate the amount of solute trapping, which is characterized by the non-equilibrium partitioning of the solute. The governing equations for the phase field and the solute composition were solved by the cell-centered finite volume method using the open-source computational tool OpenFOAM. Simulations were carried out for the evolution of equiaxed dendrites inside an undercooled melt of a binary alloy, considering the effect of various computational parameters such as interface thickness, strength of crystal anisotropy, stochastic noise amplitude, and initial orientation. The simulated results show that the solidification morphology is sensitive to the magnitude of anisotropy as well as the amplitude of noise. A strong influence of interface thickness on the growth morphology and solute redistribution during solidification was observed. Incorporating antitrapping flux resulted in the solute partitioning close to the equilibrium value. Simulations show that the grain shape is unaffected by changes to crystallographic orientation with respect to the Cartesian computational grid. Thermal gradients exerted discernible effects on the solute distribution and the dendritic growth pattern. Starting with multiple nucleation events the model predicted realistic polycrystalline solidification and as-solidified microstructure. Full article

Thermoplastic resin transfer molding (T-RTM) technology was applied to synthesize graphene nanoplatelets-based nanocomposites via anionic ring-opening polymerization (AROP). Polyamide 6 (PA6) was obtained by AROP and was used as the polymeric matrix of the developed nanocomposites. The non-isothermal crystallization behavior of PA6 and nanocomposites was analyzed by differential scanning calorimetry (DSC). Nanocomposites with 0.5 wt.% of graphene nanoplatelets (GNPs) with two different diameter sizes were prepared. Results have shown that the crystallization temperature shifted to higher values in the presence of GNPs. This behavior is more noticeable for the nanocomposite prepared with smaller GNPs (PA6/GN). The crystallization kinetic behavior of all samples was assessed by Avrami and Liu’s models. It was observed that GNPs increased the crystallization rate, thus revealing a nucleating ability, and also validated the reduction of half-time crystallization values. Such tendency was also supported by the lower activation energy values determined by Friedman’s method. Full article

Crystallinity and rheological behavior are significant for processing semi-crystalline polymers with fine mechanical properties. There is always an economical need to create a less expensive new material with better properties. Non-isothermal crystallization and oscillatory shear rheology of different branch-type polyethylene–polyethylene blends were investigated. Samples of high-density and low-density polyethylene (HDPE/LDPE) (20/80, 40/60, 60/40 and 80/20 weight ratios) and two types of high-density and linear low-density polyethylene (HDPE/LLDPE) (40/60 and 60/40 weight ratios) were prepared via extrusion. The materials were tested by differential scanning calorimetry (DSC) at several cooling rates (5, 10, 20, 30 and 40°/min) and by oscillation rheometry (ARES G2) at low angular frequency range to prove their miscibility or immiscibility. It was found that the one-peak melting endotherm of the 80–20% HDPE-LDPE blend could indicate miscibility in the solid phase, while the other HDPE-LDPE blends with two-peak curves are partially or not miscible. In contrast, all the HDPE-LLDPE blends indicate co-crystallization, but the 40–60% HDPE-LLDPE butylene blend is probably immiscible. It was revealed that complex viscosity decreases with angular frequency: linearly for HD-LD blends and not linearly for HD-LLDPE blends. The complex viscosity shows linear behavior with composition for HD-LLDPE blends, while there is a positive–negative deviation for HD-LD blends. In the liquid phase, according to rheological measurements, the HDPE-LDPE blends are not or partially miscible, while the HDPE-LLDPE blends are probably miscible. Full article

Coamorphous formation in binary systems of valsartan (Val) with 4,4′-bipyridine (Bipy) and trimethoprim (Tri) was investigated for mixtures with a mole fraction of 0.16~0.86 of valsartan and evaluated in terms of the glass transition temperature. The glass transition of the systems had a behavior outside the values predicted by the Gordon–Taylor equation, showing that Val-Bipy (hydrogen bonding between the components) had a lower deviation and Val-Tri (ionic bonding between the components) had a higher deviation. Mixtures of compositions 2:1 Val-Bipy and 1:1 Val-Tri were selected for further investigation and verified to be stable, as no crystallization was observed during subsequent heating and cooling programs. For these systems, the effective activation energy during glass transition was evaluated. Compared to pure valsartan, the system with the lower glass transition temperature (Val-Bipy) presented the highest effective activation energy, and the system with the higher glass transition temperature (Val-Tri) presented a lower effective activation energy. The results presented a good correlation between the data obtained from two different techniques to determine the fragility and effective activation energy: non-isothermal kinetic analysis by DSC and TSDC. Full article

Thermo-chemical conversion via the pyrolysis of cigarette butt (CB) filters was successfully valorized and upcycled in the pre-carbonization and carbonization stages. The pre-carbonization stage (devolatilization) of the precursor material (cellulose acetate filter, r-CAcF) was analyzed by micro-scale experiments under non-isothermal conditions using TG-DTG-DTA and DSC techniques. The results of a detailed kinetic study showed that the decomposition of r-CAcF takes place via complex mechanisms, including consecutive reaction steps and two single-step reactions. Consecutive stages include the α-transition referred to as a cellulose polymorphic transformation (cellulose I → II) through crystallization mechanism changes, where a more thermodynamically ordered system was obtained. It was found that the transformation rate of cellulose I → II (‘cellulose regeneration’) is strongly affected by the presence of alkali metals and the deacetylation process. Two single-step reactions showed significant overlapping behavior, which involves a nucleation-controlled scission mechanism (producing levoglucosan, gaseous products, and abundant radicals) and hydrolytic decomposition of cellulose by catalytic cleavage of glycosidic bonds with the presence of an acidic catalyst. A macro-scale experiment showed that the operating temperature and heating rate had the most notable effects on the total surface area of the manufactured carbon. A substantial degree of mesoporosity with a median pore radius of 3.1695 nm was identified. The presence of macroporosity on the carbon surface and acidic surface functional groups was observed. Full article