Crystal Growth & Design最新文献

{"title":"CdS Nanocrystals Grown on MXene Frameworks for Stable Lithium−Sulfur Batteries","authors":"Chuanliang Wei,&nbsp;Ling Xu,&nbsp;Yunlong Zhou,&nbsp;Bin Li,&nbsp;Ruiyang Wang,&nbsp;Peng Wang,&nbsp;Maofeng Zhang,&nbsp;Shenglin Xiong","doi":"10.1021/acs.cgd.6c01057","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01057","url":null,"abstract":"<p>Lithium−sulfur (Li−S) batteries have been widely studied in recent years due to their high theoretical specific capacity and high energy density. However, the S cathode is plagued by issues of low electrical conductivity, shuttling of lithium polysulfides (LiPSs), and slow transformation kinetics, resulting in low rate performance and rapid capacity fading of Li−S batteries. Here, CdS nanocrystals with ultrafine size are grown in situ on accordion-like and highly conductive Ti₃C₂ MXene frameworks by a simple and low-temperature (60 °C) hydrothermal reaction. The loading of CdS nanocrystals on MXene is controlled by regulating the amount of precursors. The functional groups on MXene can act as nucleation sites to promote the uniform growth of CdS nanocrystals among the MXene frameworks. Besides, the accordion-like structure of MXene can restrict the excessive growth of CdS. The fabricated CdS/MXene composite with sufficient adsorption and catalytic active sites can effectively block the shuttle effect and accelerate the transformation of LiPSs, thus relieving the issues of the S cathode. Under the coordinated regulation of MXene frameworks and in situ-grown CdS nanocrystals, Li−S batteries exhibit superior cycling performance and rate capability.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8931–8939"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Zwitterionic Diazonium Salts and Their Peroxosolvates: Peculiarities of Non-Covalent O:→+N2−Ar Interactions","authors":"Mikhail V. Vener,&nbsp;Andrei V. Churakov","doi":"10.1021/acs.cgd.6c01105","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01105","url":null,"abstract":"<p>Two-component crystals composed of potentially unstable species, namely, zwitterionic diazonium salts and hydrogen peroxide, were obtained and structurally characterized. Very unusual intermolecular bonds were observed, with the highlight being oxygen from the peroxide (often not a strong donor) interacting with the diazonium cation. Similar intramolecular interactions were also observed in the crystals of unsolvated diazonium salts. The existence of these bonds (interactions) was confirmed by the presence of the bond’s critical points (3,-1), found by means of Bader analysis of the calculated crystalline electron density. At the shortest contact, the O···N distance reaches ∼2.68 Å, and the energy is ∼15 kJ/mol. Such specific properties allow us to define these interactions as non-covalent O: →⁺N₂−Ar interactions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8966–8977"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308261","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Achieving Mass Transfer and Saturation Homogeneity in the Acidic Ammonothermal Process for Uniform GaN Growth","authors":"Jianzhi Li,&nbsp;Chengmin Chen,&nbsp;Haolong You,&nbsp;Lei Zhang,&nbsp;Hengyi Fang,&nbsp;Rongkai Kang,&nbsp;Feipeng Cai,&nbsp;Krishnaswamy Nandakumar","doi":"10.1021/acs.cgd.6c01217","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01217","url":null,"abstract":"<p>The ammonothermal method is a promising route for growing large-diameter and high-quality gallium nitride (GaN) bulk single crystals, but the extreme high-temperature, high-pressure environment inside the autoclave renders direct observation of growth processes extremely difficult. Conventional horizontal baffle structures tend to induce flow-field disturbances that limit mass-transport efficiency and growth-rate uniformity. Here, a two-dimensional axisymmetric multiphysics-coupled model is established for an acidic mineralizer system, in which a vertical baffle is introduced and a bottom-heated boundary is applied to systematically investigate the coupled laminar-flow, heat-transfer, and dilute-species transport mechanisms. The radial position of the baffle is found to strongly govern the distribution of circulation resistance. At a baffle radius of 1.1 <em>r</em>_T (reference tube radius) and a bottom temperature of 798.15 K, the central upward and outer return channels are optimally matched, local vortices are suppressed, and the directed precursor transport is markedly enhanced, yielding an average seed-surface growth rate of 1.93 μm/h, a surface nonuniformity of 0.0002, and a relative supersaturation of 0.36 within a suitable metastable regime. These numerical findings provide theoretical guidance for the efficient and uniform growth of large bulk GaN crystals. The uncertainty in the thermochemical properties in the mode necessitates experimental validation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"9023–9036"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ligand-Mediated Modulation of Energy Transfer in a Dy-Based MOF for Ratiometric Discrimination of Tetracyclines and Proton Conduction","authors":"Zeyu Zhu,&nbsp;Zhi-Lin Mu,&nbsp;Siyu Wu,&nbsp;Ziqi Zhou,&nbsp;Haotian Cui,&nbsp;Zhongyan Chen,&nbsp;Hong-Ping Xiao,&nbsp;Jing-Yuan Ge","doi":"10.1021/acs.cgd.6c01219","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01219","url":null,"abstract":"<p>Lanthanide metal−organic frameworks (Ln-MOFs) integrate the characteristic f−f luminescence of rare-earth ions with high chemical stability, structural diversity, and functional tunability, rendering them promising platforms for multifunctional applications including luminescence sensing and proton conduction. Herein, we report the hydrothermal synthesis of a Dy-based MOF, denoted as Dy-TPTZ-MOF, constructed via a dual-ligand strategy employing <em>tris</em>(<em>o</em>-carboxyphenyl)phosphine oxide [tri-(<em>o</em>-H₃BPO)] and 2, 4, 6-tri(2-pyridyl)-1, 3, 5-triazine (TPTZ) as coligands. In contrast to the Dy-MOF assembled solely from Tri-(<em>o</em>-H₃BPO), the Dy-TPTZ-MOF exhibits dual-channel luminescence, which arises from the antenna effect of the TPTZ ligand, enabling efficient ligand-to-metal energy transfer and sensitization of Dy³⁺ centers. Benefiting from the synergistic contributions of the aggregation-caused quenching and absorption enhancement effects, the Dy-TPTZ-MOF enables highly selective and sensitive ratiometric luminescence detection of tetracycline antibiotics. Furthermore, principal component analysis demonstrates that the material can effectively discriminate tetracycline antibiotics from structurally related antibiotics. In addition, the framework and abundant hydrogen-bonding interactions endow the material with excellent proton conductivity, reaching 5.60 × 10⁻³ S·cm⁻¹ at 343 K and 98% relative humidity. This work provides a general strategy for the rational design of multifunctional Ln-MOFs with integrated sensing and proton-transport properties.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"9037–9048"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CF3-Incorporated Tetrazole-Based Cu(II)-Organic Framework for Catalytic Transformation of Flue Gas CO2 under Ambient Conditions","authors":"Ming-Li Huang,&nbsp;Xue-Feng He,&nbsp;Chun-Yang Li,&nbsp;Zi-Yi Wang,&nbsp;Hong-Ling Min,&nbsp;Xiang-Yu Zhang","doi":"10.1021/acs.cgd.6c00964","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00964","url":null,"abstract":"<p>Efficient carboxylative cyclization of propargylic amines with CO₂ is of great significance for the synthesis of value-added oxazolidinones and the sustainable utilization of carbon resources. However, this transformation is generally limited by the use of noble-metal catalysts, high temperatures, and high-purity CO₂ feedstocks. To address these challenges, we constructed a novel tetrazole-based Cu(II) metal−organic framework (MOF), <strong>Cu-CF</strong>_{<strong>3</strong>}, via an in situ ligand synthesis strategy. The resulting <strong>Cu-CF</strong>_{<strong>3</strong>} features exposed CF₃ functional sites, accessible Lewis acidic Cu centers, and excellent structural stability. Notably, <strong>Cu-CF</strong>_{<strong>3</strong>} catalyzes the carboxylative cyclization of a broad range of propargylic amines with pure CO₂ under ambient conditions, affording the corresponding oxazolidinones in good to high yields. More importantly, simulated flue-gas CO₂ containing 13% CO₂ can also be directly employed under ambient conditions, affording the products in moderate to high yields. The catalyst can be readily recovered and reused for 10 consecutive runs without obvious loss of catalytic activity or structural integrity. Mechanistic investigations reveal that the Lewis acidic Cu sites facilitate substrate activation, whereas the exposed CF₃ groups enrich CO₂ molecules in the vicinity of the catalytic centers, thereby promoting the cyclization process. This work provides an attractive structural design strategy for constructing MOF catalysts that integrate exposed CO₂-enriching functional sites with open Lewis acidic centers, enabling efficient carboxylative cyclization under ambient conditions using low-concentration CO₂ sources.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8873–8883"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Morphological Evolution of Self-Catalyzed III−V Ternary Nanowires","authors":"Vladimir G. Dubrovskii","doi":"10.1021/acs.cgd.6c00921","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00921","url":null,"abstract":"<p>Self-catalyzed III−V nanowires (NWs) present an interesting example of a system with one degree of freedom, where the NW radius can either gradually increase or self-equilibrate to a stable size depending on the V/III influx imbalance. This effect is well-known for binary NWs but was never studied for ternary NWs. Herein, we consider the morphological evolution of III−V ternary NWs based on group V intermix using a refined approach that takes into account the initial growth stage with the full collection of group III adatoms from the entire NW length. Due to different incorporation rates of dissimilar group V species, the V/III influx imbalance and the corresponding stable radius become dependent on the NW composition. The self-equilibration effect on the NW radius remains in ternary NWs, but the morphological evolution becomes more complex and composition-dependent. We find three distinct NW growth stages, with the initial shrinkage of the radius, followed by its quasi-linear increase with length, and self-equilibration for lengths exceeding the diffusion length of group III adatoms. These results are in agreement with the data on GaP_<em>x</em>As_{1−<em>x</em>} NWs and InAs/InP NW heterostructures, and should be useful for the morphological design of these complex structures.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8856–8866"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure and Stability Prediction of Binary and Ternary Molecular Mixed Crystals Using Ensemble Free Energies","authors":"Anthony J. R. Payne,&nbsp;Sarah Madeira,&nbsp;Graeme M. Day","doi":"10.1021/acs.cgd.6c00999","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00999","url":null,"abstract":"<p>Mixed crystals provide a route to tune the properties of molecular solids through continuous changes in composition. However, predicting their stability is challenging because it requires determining both substitution energies and configurational entropy across large configuration spaces. Here, we combine crystal structure prediction, force field lattice energy and lattice dynamics calculations, and Δ-machine-learning energy corrections with a scaled partition-function approach to assess structure prediction and evaluate binary and ternary mixed crystals of anthracene (ANT), acridine (ACR), and phenazine (PNZ). The composition-dependent ensemble free energy (Δ<em>G</em>_ensemble) was estimated without exhaustive enumeration of all configurations from representative ensembles of substituted supercell models of mixed crystals. Crystal structure prediction reproduces the known polymorphs as the lowest energy structures and the mixed crystal modelling approach reproduces the main experimental binary trends: ACR incorporation into ANT and the α and β polymorphs of PNZ, ANT incorporation into ACR form II, and the formation of a PNZ β-type ternary phase. Furthermore, we predict additional thermodynamically stable compositions, including PNZ incorporation into ACR form IX, and ternary crystals based on ACR forms II, VI and VII. Stable three-component regions arise from binary trends, with ACR mediating between both ANT and PNZ. These results demonstrate a practical framework for predicting the structure, thermodynamic stability and composition limits of molecular mixed crystals. The mixed crystal modelling methods are available within the mol-CSPy crystal structure prediction package.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8884–8898"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mg- and Bi-Nanoparticle-Mediated Growth of InP Nanowires","authors":"Mariana Zavarize,&nbsp;Douglas S. Oliveira,&nbsp;Maurício M. de Lima, Jr.,&nbsp;Arandi Ginane Bezerra, Jr.,&nbsp;Wido H. Schreiner,&nbsp;Jefferson Bettini,&nbsp;Mônica A. Cotta","doi":"10.1021/acs.cgd.6c00361","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00361","url":null,"abstract":"<p>Replacing Au catalysts in III−V nanowire growth is critical for clean, CMOS-compatible nanophotonics. Here, we explore a gold-free route using magnesium and bismuth nanoparticles as mediators. The nanoparticles were synthesized by laser ablation and deposited on gallium arsenide (100) substrates prior to nanowire growth by chemical beam epitaxy. An untreated reference substrate subjected to the same growth procedure produced no nanowires, whereas both nanoparticle pretreatments promoted nanowire formation within the investigated process window. By systematically varying the trimethylindium flow and growth temperature, we found that both magnesium and bismuth influence nanowire morphology and growth behavior, while their distinct temperature-dependent growth rates indicate different interfacial kinetics. Energy-dispersive X-ray spectroscopy did not resolve localized Mg or Bi signals at the nanowire tips, whereas weak signals from the corresponding pretreatment elements were detected in the larger In-rich particles located along the nanowire sidewalls, indicating a spatially nonuniform post-growth distribution. Low-temperature photoluminescence nevertheless revealed distinct optical responses for the Mg- and Bi-pretreated samples, indicating that the two pretreatments produce different defect and recombination landscapes. Electron microscopy revealed balloon-like InP apex regions capped by In-rich, P-depleted hemispherical particles, particularly at higher temperatures, as well as In-rich particles along the nanowire sidewalls. These features are consistent with the redistribution and dewetting of In near growth termination and during vacuum cooldown. High Resolution Transmission Electron Microscopy and electron diffraction further showed that the nanowires remained predominantly wurtzite throughout both type of mediators. These results support a seed-mediated, In-assisted pathway in which magnesium and bismuth promote nanowire nucleation and establish distinct surface and interfacial conditions. This study demonstrates the potential of group-II and group-V nanoparticle pretreatments for the controlled, gold-free growth of indium phosphide nanowires.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8646–8653"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Voxelotor Polymorphs: Crystalline Diversity of a Highly Potent Sickle Cell Anaemia Drug","authors":"Christy P. George,&nbsp;Akram A. Khan,&nbsp;Parth S. Shaligram,&nbsp;Nagabhushan Shet,&nbsp;Tabrez R. Shaikh,&nbsp;Rinu Pandya,&nbsp;Ganesh More,&nbsp;Ziya Tufail,&nbsp;Kumar Vanka,&nbsp;Ajay Kumar,&nbsp;S. Arulmozhi,&nbsp;D. Srinivasa Reddy,&nbsp;C. V. Ramana,&nbsp;Ashwini K. Nangia,&nbsp;Rajesh G. Gonnade","doi":"10.1021/acs.cgd.6c01031","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01031","url":null,"abstract":"<p>The solid-state landscape of highly flexible organic molecules often presents profound challenges and opportunities in materials chemistry, critically dictating macroscopic, physicochemical, and biopharmaceutical properties. Herein, we report voxelotor, a BCS Class II drug historically developed for sickle cell disease, as a noteworthy model system to elucidate nucleation pathways and a non-classical structure-performance relationship, with bioavailability that is critically dependent on its solid form. We report the preferential crystallization, multigram scale-up, and comprehensive structural elucidation of seven distinct polymorphic forms (Forms <strong>I</strong>-<strong>VII</strong>), including four previously undiscovered solid phases. Single-crystal X-ray diffraction and computational lattice energy calculations, including Hirshfeld surface analysis, show that its rich polymorphic diversity is rooted in extreme torsional adaptability (variations in τ₂ from -160.0° to +110.0°), which drives parallel displaced π···π stacking and hydrogen-bonded assemblies. Thermal and humidity stress profiling discloses a complex relationship between thermodynamic stability and kinetic trapping. Notably, we identified paradoxical stability behavior in which seemingly robust, high lattice energy metastable states (e.g., Forms <strong>III</strong>, <strong>IV</strong>, <strong>V</strong>, and <strong>VI</strong>) undergo temperature- and moisture-promoted structural transformation and solid-state conversion to Form <strong>I</strong> crystals, which exhibit greater stability under ambient conditions. Crucially, biopharmaceutical and pharmacokinetic evaluation showed a divergence between drug solubility and biological efficacy. The kinetically trapped Form <strong>VI</strong> exhibited the highest equilibrium aqueous solubility. Form <strong>II</strong> exhibited superior systemic exposure in rats and the highest <em>ex vivo</em> anti-sickling efficacy (74% inhibition at 200 μM). Collectively, these findings offer fundamental insight into how subtle solid-state energetic balance and specific molecular conformations can influence solubility behavior. By demonstrating how structural nuances dictate superior macroscopic performance, this study provides a robust, predictive framework for rationalizing solid-form selection in highly flexible functional drugs.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8912–8930"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Non-isothermal Cold Crystallization as a Tool for Analysis of Crystal Nucleation: The Example of Polytetrahydrofuran","authors":"René Androsch,&nbsp;Katalee Jariyavidyanont,&nbsp;Jürn W. P. Schmelzer,&nbsp;Timur Mukhametzyanov,&nbsp;Christoph Schick","doi":"10.1021/acs.cgd.6c00919","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00919","url":null,"abstract":"&lt;p&gt;Polytetrahydrofuran (PTHF) was employed for analysis of the effect of heating rate &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;/math&gt;&lt;/span&gt; on the peak temperature of cold crystallization &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;p&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; and enthalpy of cold crystallization &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;h&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; to follow crystal nucleation. The isothermal increase of the number of nuclei in the highly supercooled melt can be analyzed by heating at experimentally realizable rates between &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;mi&gt;min&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;mi&gt;max&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;⁠&lt;/span&gt;, with slower and faster heating yielding maximum and zero cold-crystallization enthalpy, respectively. At intermediate fast heating, with &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;/math&gt;&lt;/span&gt; close to &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;mi&gt;min&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;⁠&lt;/span&gt;, the cold-crystallization enthalpy first increases with the number of nuclei, reaches a plateau, and then decreases since crystals grow already at the nucleation temperature. The observation of a plateau is caused by completion of crystallization during slow heating if the number of nuclei exceeds a specific value. This limits the detection of a further increase of the number of nuclei, which, however, still causes a decrease of &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;p&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;⁠&lt;/span&gt;, being a more sensitive measure of the number of nuclei than &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;mi&gt;h&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;/math&gt;⁠&lt;/span&gt;, with the effect of the number of nuclei and &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;/math&gt;&lt;/span&gt; on &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;p&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; summarized with a continuous heating transformation (CHT) diagram. In contrast, fast heating, with &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;/math&gt;&lt;/span&gt; close to &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;mi&gt;max&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;⁠&lt;/span&gt;, is unable to detect the initial stage of the nucleation process, caused by the limited time for growth to yield measurable crystallinity and the initial formation of nuclei of only sub-critical size at &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;p&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;⁠&lt;/span&gt;. Besides the progress in understanding the interplay between nucleation and non-isothermal cold crystallization, the study also provides quantitative information about the kinetics of hot crystallization of PTHF as well as nucleation-pathway-dependent morphological features, requiring sophisticated experimentation to assess crystallization and melting below ambient temperature. Finally, a previously developed theoretical model of the effects of the heating rate and crystal nucleus density on &lt;span&gt;&lt;span&gt;&lt;/span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;p&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; (Polymer 2026, 358, 130181) has successf","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 21","pages":"8843–8855"},"PeriodicalIF":3.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149308239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}