Modulating crystal polymorphism via membrane-regulated supersaturation: an experimental and molecular dynamics simulation study.

Polymers have been widely used to physically stabilize amorphous drugs by forming amorphous solid dispersions (ASDs), resulting in commercial and clinical success as a pharmaceutical technique to improve the bioavailability of a poorly water-soluble drug. However, the role of polymers in maintaining the physical stability of ASDs has not been fully understood. Herein, we investigated how poly(methyl methacrylates) (PMMAs) with different tacticities impact the liquid dynamics and crystallization kinetics of amorphous griseofulvin (GSF). PMMAs with similar chain lengths and identical monomer structures were selected, aiming to exclude effects arising from differences in monomer structure and end groups. The syndiotactic form of PMMA (s-PMMA) exhibited a stronger inhibitory effect on the crystal growth of amorphous GSF in comparison with isotactic (i-PMMA) and atactic (a-PMMA) forms. Effects of the isotactic atactic forms of PMMA on the crystal growth of GSF can be mainly attributed to their molecular mobility, as shown by the overlapping of the logarithm growth rate curves versus viscosity and α-relaxation time. However, the crystal growth rate curves of GSF in the system containing 10 wt% s-PMMA did not overlap with those of the pure GSF system. These results suggest that liquid dynamics is not a main contributor to the inhibitory effect of s-PMMA during drug crystallization.

Non-thermal crystallization kinetics of ammonium hydrogen phosphate in stirred systems: Metastable zone characterization, moment-based modeling, and size-dependent growth dynamics

Understanding the rheological evolution of solidifying magma during its migration through the crust and the subsequent emplacement as lava is critical for assessing volcanic hazards. Crystallization plays a primary role in governing the rheology of low-viscosity basaltic magmas, thereby controlling lava inundation potential. While several studies have addressed this behavior under faster cooling conditions, experimental data bridging the gap toward the quasi-equilibrium regime remain scarce due to the technical challenges of long-duration high-temperature rheometry experiments. This highlights the critical need for new datasets designed to quantify the rheological evolution pertinent to lava flow emplacement conditions. Here, we present a rheological dataset carried out on an Etnean trachybasalt, focusing on low cooling rates (0.1 and 0.5 °C/min) under variable shear strain rates (1-10 s-1). Within the range of cooling and shear rates applied, results indicate that the cooling rate exerts a first-order control on crystallization kinetics, whereas the shear rate plays a secondary role, consistent with previous literature data. The technical validation is provided through instrument calibration and the verification of the chemical integrity of the pre- and post-run sample. Interestingly, the dataset captures the non-linear dependence of the crystallization onset temperature, which asymptotically approaches the thermodynamic liquidus (~1210 °C) as the cooling rate decreases. Beyond improving our understanding of magma crystallization kinetics, this dataset provides critical constraints for parameterizing the rheological evolution of lava flows during their emplacement in numerical models under varying thermal and dynamic regimes.

Precise control over orientation and crystallinity in additive manufacturing (AM) of organic semiconductor arrays is critical for achieving high-performance organic integrated electronics. However, achieving such control in conventional AM remains particularly challenging without engineered spatial constraints due to the complex crystallization kinetics of small-molecule organic semiconductors under nonequilibrium ink deposition conditions. Here, we report a simple yet effective mask-free, pattern-free printing of high-resolution organic single-crystal arrays with controlled location, orientation, and aspect ratio. Central to this method is the establishment of a dynamic liquid-crystal area (DLCA) beneath the nozzle, which governs the kinetically coupled interplay of solute transport, solvent evaporation, and nucleation. By tuning DLCA geometry via applied voltage and speed, the random nucleation and anisotropic crystal growth is suppressed. This mechanism, supported by classical theory and transition region theory, is universally applicable to most solution-processable high-performance small-molecule organic semiconductors. The organic single crystal array exhibits highly uniform mobility, with around 12 to 15% variation, representing the most uniform organic single-crystal arrays achieved by electrohydrodynamic printing so far. In addition, the printed organic single-crystal patterns can be successfully integrated into a functional 96 organic field-effect transistor photodetector array, demonstrating their potential for information recognition and organic integrated electronics.

The integration of crystallographic control into solution-processed perovskite films remains a challenge for efficient light emission, as disordered optical dipoles fundamentally limit photon extraction, a bottleneck constraining both classical and quantum planar optoelectronic devices. Here, we address this by developing an in situ formation strategy for oriented quasi-2D perovskite nanosheets within films via ligand-engineered crystallization. By designing and orchestrating steric hindrance and π-π interactions of ligands, we direct the crystallization kinetics to yield regular face-on nanosheets exhibiting enhanced horizontal transition dipole moment orientation compared to conventional isotropic films. The in situ architectural control also elevates both the photoluminescence quantum yield beyond 90% and carrier mobility comparable to 3D perovskite levels. These synergies enable perovskite light-emitting diodes (PeLEDs) with an external quantum efficiency (EQE) of 31.2% for pure-red emission at 635 nm, comparing favorably to other pure-red PeLEDs. Concurrently, the peak luminance and operational stability of the in situ nanosheet PeLEDs exhibit significant improvements.

Perovskite solar cells (PSCs), recognized for their high efficiency and scalable manufacturing potential, face significant challenges in achieving uniform, high-quality large-area films via ambient doctor-blading techniques, particularly due to limitations in conventional solvent systems. This study addresses the critical need for solvent systems capable of serving as viable alternatives to conventional solvent, while simultaneously optimizing crystallization kinetics and film morphology under ambient conditions. We demonstrate a N, N-dimethylformamide (DMF)-free co-solvent strategy utilizing 2-methoxyethanol (2-ME) and N-methyl-2-pyrrolidone (NMP) to precisely modulate solvent evaporation dynamics and perovskite nucleation. The weak coordination of Pb2+ by 2-ME promotes rapid volatilization, while the strong coordination by NMP stabilizes the intermediates and delays surface nucleation, enabling uniform crystallization and dense films formation. The optimized NMP improved crystallinity, reduced non-radiative recombination, and boosted charge transport, enhancing power conversion efficiency (PCE) from 20.18% to 23.43%. Furthermore, a mini-module (10.3 cm2) fabricated under the same conditions achieved a PCE of 19.08%, underscoring the scalability and applicability of the proposed approach. These findings suggest that the DMF-free co-solvent strategy is highly effective for the scalable fabrication of large-area PSC modules and offers a promising pathway toward their commercialization.

ABSTRACT Mullite‐type Al 4 B 2 O 9 glass ceramics (GCs) activated by transition metal ions such as Cr 3 + and Ni 2 + represent a promising class of solid‐state photo‐conversion materials for near‐infrared (NIR) luminescence devices. However, their optical efficiency is often limited by a series of quenching defects that are generated during crystallization. Here, we introduce a partial cation substitution engineering by replacing Al 3 + with Ga 3 + to regulate crystallization kinetics and defect formation. Structural and thermodynamic analyses reveal that Ga 3 + incorporation increases the crystallization activation energy, suppressing grain growth rate and promoting dominant Cr 3 + emission from [AlO 6 ] sites. Consequently, the Ga 3+ ‐induced (Al 4 ‐ x Ga x )B 2 O 9 phase evolution yields significantly enhanced NIR intensity, quantum efficiency (EQE = 34%, IQE = 46%), and thermal stability (I 140°C /I 25°C = 69.2%). The NIR LEDs integrated with the GCs deliver a NIR output power of 464 mW with 9.2% photoelectric conversion efficiency. This work establishes a generalizable approach for defect‐controlled crystallization and luminescence engineering in glass ceramics, opening a pathway toward high‐power, thermally robust NIR LEDs for next‐generation photonic and optoelectronic devices.

To develop smart materials with tailored functional response, the combination of poly-(vinylidene fluoride) (PVDF) and advanced ionic additives such as ionic liquids (ILs) is increasingly being investigated. Depending on the processing conditions, the incorporation of these additives into PVDF, together with their functional response, promotes the nucleation of specific electroactive phases. This work explores the effect of incorporating sodium tetra-(2-thenoyltrifluoroacetonate) europate-(III), Na-[Eu-(tta)4] and 1-butyl-3-methylimidazolium tetra-(2-thenoyltrifluoroacetonate) europate-(III), [Bmim]-[Eu-(tta)4], into PVDF matrices through a comprehensive analysis of isothermal crystallization behavior, morphological features, crystalline phase development, and dielectric behavior. Field-emission scanning electron microscopy (FESEM) was used to analyze the microstructure, while Fourier transform infrared (FTIR) spectroscopy was used to assess the development of PVDF crystalline phases during its isothermal crystallization at various temperatures. All samples exhibited α, β, and γ crystalline phases, although their relative proportions differed significantly depending on the type of filler used. This suggests that [Bmim]-[Eu-(tta)4] is a strong promoter of the electroactive (EA) phases of PVDF. The results are attributed to the interaction between the IL charges and the PVDF dipoles of the EA structures, which are promoted by higher crystallization temperatures, as supported by both FTIR and DSC data. Thus, the addition of Na-[Eu-(tta)4] and [Bmim]-[Eu-(tta)4] strongly influences the crystallization kinetics of PVDF and allows nucleation of specific phases of PVDF. Additionally, dielectric spectroscopy revealed that the nature of the cation strongly influences conductivity behavior, as demonstrated by the dielectric results. Overall, the incorporation of Na-[Eu-(tta)4] and [Bmim]-[Eu-(tta)4] not only influences the crystallization kinetics of PVDF but also provides PVDF with intrinsic functional properties such as luminescent behavior and improved electrical performance, offering a simple and efficient strategy of nucleating specific PVDF phases.

The intrinsic phase instability of CsPbI3 perovskites necessitates stringent fabrication conditions, significantly hindering the practical deployment. In the DMA-mediated CsPbI3 nucleation system, the Cs+/DMA+ ion exchange critically governs the resulting film quality. Here, we employ a moisture-responsive crystallization strategy utilizing propyltriethoxysilane (PTES) to deposite CsPbI3 under ambient air with high humidity (55%). We demonstrate that the siloxane groups can capture DMA+ in the intermediate DMAPbI3, facilitating DMA+ extraction and Cs+ incorporation, thereby accelerating crystallization kinetics. This approach enables CsPbI3 PSCs to achieve a power conversion efficiency (PCE) of 21.00% with an impressive fill factor (FF) of 86.1% while processing perovskite under relative humidity (RH) of 55%. Higher PCEs of 21.85% and 22.60% (certified 22.02%) were achieved for devices fabricated at a lower RH of 25% and for films spin-coated under an N2 atmosphere followed by annealing in ambient air, respectively. Furthermore, PTES-treated devices exhibit excellent operational stability under ambient conditions.

Gap-Filling and Crystallization Kinetics Regulation in VTD/Spray Hybrid Perovskite Solar Cells

The crystallization kinetics of picromerite play a crucial role in optimizing the fertilizer quality. This study developed a crystallization kinetics model of picromerite. Results show that increasing temperature mainly leads to higher supersaturation, which, in turn, enhances both nucleation and growth rates, with significant improvements in crystal size and uniformity. Higher stirring speed was found to have positive effects on crystal nucleation and growth rate. The decrease in supersaturation leads to the diminution of the driving force for crystallization and the gradual decline in crystallization. The study provides a comprehensive analysis of the relationships between these crystallization conditions and the resultant crystal properties.

Benchmarking PA12 and PA12CF35 for selective laser sintering of patient-specific implants: a thermo-mechanical analysis.

Kinetics of lactose crystallization in milk powders – Preconditioning to preserve functionality during storage

Wide-bandgap (WBG) perovskite solar cells (PSCs) have promising applications in tandem cells, offering a viable pathway to surpass the theoretical efficiency limits of single-junction photovoltaic devices. However, WBG perovskite with increasing bromide content suffers from inhomogeneous phase distribution and bulk defects, owing to the mismatched crystallization kinetics between halogen phases. Herein, we propose a synchronous halogen crystallization strategy utilizing a multifunctional additive, 4,4',4″-tricarboxyl triphenylamine (TTA), to modulate the bromine/iodine phase competitive crystallization. TTA preferentially coordinates with bromine-rich components and reduces its rapid crystallization, while simultaneously accelerating the crystallization of the iodine-rich phase, resulting in their synchronous crystallization. This approach also improves composition uniformity and film quality, which effectively suppresses non-radiative recombination and enhances phase stability under light irradiation and voltage bias. As a result, the TTA-modified device achieves a remarkable power conversion efficiency (PCE) of 20.55% with an open-circuit voltage (VOC) of 1.339V. Moreover, the unencapsulated device retains 90% of its initial efficiency after 1050 h of storage in the ambient environment and exhibits an extended T90 lifetime of 750 h under ISOS-L-1 conditions. This work offers a new perspective for addressing inhomogeneous crystallization in mixed-halide perovskite and facilitates their integrated into tandem photovoltaics.

Formamidinium lead triiodide (FAPbI3) perovskite solar cells (PSCs) demonstrate exceptional photovoltaic performance but face critical stability challenges impeding commercialization. Herein, we integrate polypropylene glycol (PPG) into an inverse temperature crystallization process to synthesize highly stable α-FAPbI3 microcrystals, which retain phase purity for over six months in air. Our approach enables large-scale production (nearly 50g) of PPG-coated α-FAPbI3 (target) microcrystals from low-cost PbI2, with over 95% yield-sufficient to manufacture 23 m2 of perovskite solar modules. Redissolving the target α-FAPbI3 microcrystals, followed by spin-coating and annealing, yields target perovskite films with reduced defect density, minimized residual strain, and enhanced carrier transport. Mechanistic investigations reveal that colloidal species form upon the redissolution of target microcrystals which modulate the film crystallization kinetics, i.e. accelerating (100)-oriented nucleation and growth. Employing this integrated strategy, a champion PSC with a power conversion efficiency (PCE) of 26.50% (certified 26.22%) was obtained at a laboratory scale (0.06 cm2) and 22.66% for a module with an aperture area of 28.99 cm2, together with prolonged operational stability. This work opens new avenues for the industrial-scale fabrication of efficient and stable large-area perovskite photovoltaics.

Insights into the crystallization kinetics of lithium 12-hydroxystearate in lubricating oil from differential scanning calorimetry

Effect of cross-linked silicone networks on the non-isothermal crystallization kinetics of shape-stable phase change materials

ABSTRACT The realization of bifunctional perovskite devices integrating photovoltaic (PV) and light‐emitting diode (LED) capabilities requires precisely controlled grain architectures to facilitate dual carrier transport pathways. In this work, sulfaguanidine (SG) molecules were introduced into the perovskite solution to reconstruct the crystallization kinetics and further form vertically oriented single‐layer grains in FAPbI 3 films. The guanidinium group (−NH‐C (=NH)‐NH 2 ‐) and the sulfonamide group (−SO 2 ‐NH‐) synergistically create continuous carrier channels: The former bridges adjacent grains through Pb 2+ coordination, whereas the latter establishes hydrogen‐bonding networks with FA + cations. This through‐thickness transport structure simultaneously enhances out‐of‐plane charge transport and enables bidirectional functionality, resulting in an increase of approximately one order of magnitude in the carrier mobility. Consequently, the external quantum efficiency (EQE) of the device increased from 14.4% to 25.8%, with a record‐ultralow turn‐on voltage of 1.10 V and < 20% EQE roll‐off at a current of 500 mA cm −2 , while maintaining 12.58% PV efficiency. This work establishes through‐thickness transport structure engineering as a critical strategy for developing monolithic optoelectronic systems.

Manipulation of kinetic pathways is essential to self-assemble nanoparticle building blocks into complex ordered structures, as the emergence of intermediate metastable states could either facilitate or hinder crystallization of the target lattice. Molecular simulations and Markovian and transition state theory are used to validate our conjecture that intermediary mesophases, with partial but long-range translational or orientational structural ordering, accelerate crystallization kinetics from the disordered structure. Using four representative models, two lyotropic single-component and two thermotropic binary mixture systems, we demonstrate that mesophases with intermediate entropies, such as nematic fluid, rotator solid, and microsegregated mesophases, speed up the overall crystallization rate. This enhancement occurs by effectively splitting a larger isotropic-to-crystal free energy barrier into two smaller barriers corresponding to isotropic-to-mesophase and mesophase-to-crystal transitions, with mesophase "bulk" macrostates being kinetically more favorable than microscopic fluctuations. The single-step isotropic-to-crystal transition occurs through a composite-cluster pathway that includes mesophase microdomains; an isotropic-crystal interfacial energy greater than or comparable to the sum of the isotropic-mesophase and mesophase-crystal interfacial energies is associated with enhanced two-step crystallization rate. Overall, our findings validate the conjecture, which offers additional guidance for selecting nanoparticle designs and conditions that promote efficient crystallization pathways.