Structuration of lipid bases zero-trans and palm oil-free for food applications.

This work evaluated structured lipids (SLs) through chemical and enzymatic interesterification (CSLs and ESLs). Blends of soybean oil and peanut oil 1:1 wt% were used, with gradual addition of fully hydrogenated crambe to obtain a final behenic acid concentration of 6, 12, 18, and 24 %. Chemical catalysis used sodium methoxide (0.4 wt%) at 100 °C for 30 min, while enzymatic catalysis used Lipozyme TL IM (5 wt%) at 60 °C for 6 h. Major fatty acids identified were C16:0, C18:0, and C22:0. It was observed that with gradual increase of hard fat, the CSLs showed high concentrations of reaction intermediates, indicating further a steric hindrance, unlike ESLs. Increased hard fat also altered crystallization profile and triacylglycerols composition and ESLs showed lower solid fat, unlike CSLs. Both methods effectively produced SLs as an alternative to trans and palm fats, view to potential future applications in food products.

Lattice Matching and Microstructure of the Aromatic Amide Fatty Acid Salts Nucleating Agent on the Crystallization Behavior of Recycled Polyethylene Terephthalate.

To solve the decrease in the crystallization, mechanical and thermal properties of recycled polyethylene terephthalate (rPET) during mechanical recycling, the aromatic amide fatty acid salt nucleating agents Na-4-ClBeAmBe, Na-4-ClBeAmGl and Na-4-ClAcAmBe were synthesized and the rPET/nucleating agent blend was prepared by melting blending. The molecular structure, the thermal stability, the microstructure and the crystal structure of the nucleating agent were characterized in detail. The differential scanning calorimetry (DSC) result indicated that the addition of the nucleating agent improved the crystallization temperature and accelerated the crystallization rate of the rPET. The nucleation efficiencies (NE) of the Na-4-ClBeAmBe, Na-4-ClBeAmGl and Na-4-ClAcAmBe were increased by 87.2%, 87.3% and 41.7% compared with rPET which indicated that Na-4-ClBeAmBe and Na-4-ClBeAmGl, with their long-strip microstructures, were more conducive to promoting the nucleation of rPET. The equilibrium melting points (Tm0) of rPET/Na-4-ClBeAmBe, rPET/Na-4-ClBeAmGl and rPET/Na-4-ClAcAmBe were increased by 11.7 °C, 18.6 °C and 1.9 °C compared with rPET, which illustrated that the lower mismatch rate between rPET and Na-4-ClBeAmGl (0.8% in b-axis) caused Na-4-ClBeAmGl to be the most capable in inducing the epitaxial crystallization and orient growth along the b-axis direction of the rPET. The small angle X-ray diffraction (SAXS) result proved this conclusion. Meanwhile, the addition of Na-4-ClBeAmGl caused the clearest increase in the rPET of its flexural strength and heat-distortion temperature (HDT) at 20.4% and 46.7%.

The Effect of SiO2 Particle Size on Crystallization Behavior and Space Charge Properties for SiO2/MMT/LDPE Composites.

The matrix material used in this paper was low-density polyethene (LDPE), and the added particles selected were silicon oxide (SiO2) particles and montmorillonite (MMT) particles. The sizes of the SiO2 particles were 1 µm, 30 nm, and 100 nm, respectively; three kinds of SiO2/MMT/LDPE multi-component composites were prepared based on MMT/LDPE composites doped with MMT particles. The effect of the SiO2 particle size on the crystallization behavior and space charge properties of SiO2/MMT/LDPE composites was studied. The crystalline behaviors and crystallinity of the materials were analyzed. At the same time, the changes in the relative dielectric constant εr and loss factor tanδ for each material with the influence of frequency were studied, and the space charge accumulation, residual characteristics, and apparent charge mobility of each material were explored. The results show that the smaller the size of the added particles, the smaller the grain size and the clearer the grain outline for the multi-composite material. After adding 30 nm SiO2 particles, the crystallinity of the material increases significantly. The microstructure formed by the addition of 100 nm SiO2 particles effectively restricts molecular chain movement and makes it difficult to establish the polarization of the composite. The incorporation of large-size particles can reduce the proportion of the crystalline structure for the material as a whole, resulting in the formation of a new structure to promote charge transfer. Among the three kinds of SiO2 particles, the addition of 30 nm SiO2 particles can effectively suppress the space charge, and the composite material has the lowest residual space charge after depolarization. The addition of 100 nm SiO2 particles can cause the accumulation of many homopolar charges near the anode.

Improvement of Multilevel Memory Performance of MnTe Thin Films by Ta Doping.

The pressing need for data storage in the era of big data has driven the development of new storage technologies. As a prominent contender for next-generation memory, phase-change memory can effectively increase storage density through multilevel cell operation and can be applied to neuromorphic and in-memory computing. Herein, the structure and properties of Ta-doped MnTe thin films and their inherent correlations are systematically investigated. Amorphous MnTe thin films sequentially precipitated cubic MnTe2 and hexagonal Te phases with increasing temperature, causing resistance changes. Ta doping inhibited phase segregation in the films and improved their thermal stability in the amorphous state. A phase-change memory cell based on a Ta2.8%-MnTe thin film exhibited three stable resistive states with low resistive drift coefficients. The study findings reveal the possibility of regulating the two-step phase-change process in Ta-MnTe thin films, providing insight into the design of multilevel phase-change memory.

Crystallization of Polylactic Acid with Organic Nucleating Agents under Quiescent Conditions.

Polylactic acid (PLA) is a versatile and sustainable polymer used in various applications. This research explores the use of orotic acid (OA) and ethylene bis-stearamide (EBS) as nucleating agents to enhance the quiescent crystallization of PLA within the temperature range of 80 °C to 140 °C. Different blends were produced via melt processing before analyzing via DSC, XRD, and SEM. Our results show that both nucleating agents significantly accelerated the crystallization process and reduced the incubation time and the crystallization half-time. The most promising results were obtained with 1% EBS at 110 °C, achieving the fastest crystallization. The XRD analysis showed that at 80 °C, the disordered α'phase predominated, while more stable α phases formed at 110 °C and 140 °C. Combining the 1% nucleating agent and 110 °C promotes densely packed crystalline lamellae. The nucleated PLA exhibited a well-organized spherulitic morphology in agreement with the Avrami modeling of DSC data. Higher nucleating agent concentrations yielded smaller, more evenly distributed crystalline domains. Utilizing OA or EBS in PLA processing could offer enhanced properties, improved processability, and cost-efficiency, making PLA more competitive in various applications.

Study on the Crystallization Behavior of Neodymium Rare-Earth Butadiene Rubber Blends and Its Effect on Dynamic Mechanical Properties.

Utilizing neodymium-based butadiene rubber as a baseline, this study examines the effect of eco-friendly aromatic TDAE oil, fillers, and crosslinking reactions on neodymium-based rare-earth butadiene rubber (Nd-BR) crystallization behavior. The findings suggest that TDAE oil hinders crystallization, resulting in decreased crystallization temperatures and heightened activation energies (Ea). The crystallization activation energies for 20 parts per hundreds of rubber (PHR) and 37.5 PHR oil stand at -116.8 kJ/mol and -48.1 kJ/mol, respectively, surpassing the -264.3 kJ/mol of the unadulterated rubber. Fillers act as nucleating agents, hastening crystallization, which in turn elevates crystallization temperatures and diminishes Ea. In samples containing 20 PHR and 37.5 PHR oil, the incorporation of carbon black and silica brought the Ea down to -224.9 kJ/mol and -239.1 kJ/mol, respectively. Crosslinking considerably restricts molecular motion and crystallization potential. In the examined conditions, butadiene rubber containing 37.5 PHR oil displayed no crystallization following crosslinking, albeit crystallization was discernible with filler inclusion. Simultaneously, the crystallinity level sharply declined, manifesting cold crystallization behavior. The crosslinking process elevates Ea, while the equilibrium melting point (Tm0) noticeably diminishes. For instance, the Tm0 of pure Nd-BR is approximately -0.135 °C. When blended with carbon black and silica, the Tm0 values are -3.13 °C and -5.23 °C, respectively. After vulcanization, these values decrease to -21.6 °C and -10.16 °C. Evaluating the isothermal crystallization kinetics of diverse materials via the Avrami equation revealed that both the oil and crosslinking process can bring about a decrease in n values, with the Avrami index n for various samples oscillating between 1.5 and 2.5. Assessing the dynamic mechanical attributes of different specimens reveals that Nd-BR crystallization notably curtails its glass transition, marked by a modulus shift in the transition domain and a decrement in loss factor. The modulus in the rubbery state also witnesses a substantial augmentation.

Exploitation of a New Nucleating Agent by Molecular Structure Modification of Aryl Phosphate and Its Effect on Application Properties of the Polypropylene.

In this work, a novel α-nucleating agent (NA) for polypropylene (PP) termed APAl-3C-12Li was prepared and evaluated compared with the commercially available type NA-21. For the synthesis of the organophosphate-type NA (APAl-3C), the -OH group of the acid part of NA-21 was substituted by the isopropoxy group. The structure of APAl-3C was analyzed by spectroscopy and element analysis, the results of which were consistent with the theoretical molecular formula. APAl-3C's thermal stability was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG), which showed only weak mass loss below 230 °C, meaning that it would not decompose during the processing of PP. The APAl-3C-12Li was used as a novel nucleating agent, studying its effects on crystallization, microstructure, mechanical and optical properties. Tests were performed in a PP random copolymer at different contents, in comparison to the commercial NA-21. The composite with 0.5 wt% APAl-3C-12Li has a similar crystallization temperature of 118.8 °C as with the addition of 0.5 wt% NA-21. An advantage is that the composite with the APAl-3C-12Li has a lower haze value of 9.3% than the counterpart with NA-21. This is due to the weaker polarity of APAl-3C-12Li after the introduction of methyl and better uniform dispersion in the PP matrix, resulting in stronger improvement of optical and mechanical properties.

Influence of samarium modification on the phase-change performance and phase structure of tin antimonide.

This work presents the optimization of the crystallization behavior and reliability of Sn15Sb85thin films by doping Sm element. The phase transition behaviors induced by thermal were investigated byin situresistance measurement. With the addition of Sm element, Sn15Sb85film exhibits the superior crystallization temperature (232 °C) and data conservation (172.32 °C for 10 years), larger activation energy of crystallization (4.91 eV) and crystalline resistance (∼103Ω), which contributes to the increased thermal stability of the amorphous state and decrease in the programming energy. The Sm-doping can broaden the energy band gap from 0.55 to 1.07 eV. The amorphous Sm and Sn compositions could retard grain growth and refine grain size from 21.13 to 11.13 nm, combining with x-ray diffraction and x-ray photoelectron spectroscopy. The surface morphology of Sn15Sb85film becomes smoother after Sm doping as determined by atomic force microscopy images, resulting in the improved interfacial reliability. Phase change memory devices based on Sm0.095(Sn15Sb85)0.905films can successfully achieve the complete SET and RESET reversible operation process with high operating speed (200 ns) and low power consumption (1.6 × 10-10J). The results suggest that doping the proper concentration of Sm element will be an effectual solution to adapt and optimize the crystallization properties of Sn15Sb85phase change material.

Effect of Octene Block Copolymer (OBC) and High-Density Polyethylene (HDPE) on Crystalline Morphology, Structure and Mechanical Properties of Octene Random Copolymer.

Blending octene random copolymer (ORC) with other polymers is a promising approach to improving ORC mechanical properties, such as tensile strength and elongation. In this study, octene block copolymer (OBC) with lower density than ORC and high-density polyethylene (HDPE) were used to blend with ORC. The effect of both OBC and HDPE on ORC was analyzed using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and small-angle X-ray scattering (SAXS). For ORC/OBC blends, a small amount of OBC can improve the crystallization ability of ORC. Meanwhile, for ORC/HDPE blends, the crystallization ability of ORC was significantly suppressed, attributed to good compatibility between ORC and HDPE as indicated by the homogeneous morphology and the disappearance of the α transition peak of ORC in ORC/HDPE blends. Therefore, the tensile strength and elongation of ORC/HDPE blends are significantly higher than those of ORC/OBC blends. For ORC/OBC/HDPE ternary blends, we found that when ORC:OBC:HDPE are at a ratio of 70:15:15, cocrystallization is achieved. Although HDPE improves the compatibility of ORC and OBC, the three-phase structure of the ternary blends can be observed through SAXS when HDPE and OBC exceed 30 wt%. Blending HDPE and OBC (≤30 wt%) could improve the mechanical property of ORC.

Structure and Properties of the Xerogels Based on Potassium Silicate Liquid Glass and Urea.

The xerogels based on the aqueous solutions of urea in potassium silicate liquid glass (PSLG) were produced by CO2 bubbling and investigated. The structure and chemical composition of the obtained materials were analyzed. Using the SEM, XRD, IR-FT, DSC, and low energy local EDS analysis, it was recognized that the dried gels (xerogels) contained three forms of urea: oval crystals of regular shape appeared onto the surface of xerogel particles; fibrous crystals were located in the silicate matrix; and molecules/ions were incorporated into the silicate matrix. It was shown that an increase in [(NH2)2CO] in the gel-forming system promoted increased contents in crystalline forms of urea as well as the diameter of the fiber-shaped urea crystals. A rate of the urea release in water from the granulated xerogels containing 5.8, 12.6, and 17.9 wt.% of urea was determined by the photometric method. It was determined that the obtained urea-containing xerogels were characterized with a slow release of urea, which continued up to 120 days, and could be used as controlled release fertilizers containing useful nutrients (N, K).

A New Self-Healing Degradable Copolymer Based on Polylactide and Poly(p-dioxanone).

In this paper, the copolymerization of poly (p-dioxanone) (PPDO) and polylactide (PLA) was carried out via a Diels-Alder reaction to obtain a new biodegradable copolymer with self-healing abilities. By altering the molecular weights of PPDO and PLA precursors, a series of copolymers (DA2300, DA3200, DA4700 and DA5500) with various chain segment lengths were created. After verifying the structure and molecular weight by 1H NMR, FT-IR and GPC, the crystallization behavior, self-healing properties and degradation properties of the copolymers were evaluated by DSC, POM, XRD, rheological measurements and enzymatic degradation. The results show that copolymerization based on the DA reaction effectively avoids the phase separation of PPDO and PLA. Among the products, DA4700 showed a better crystallization performance than PLA, and the half-crystallization time was 2.8 min. Compared to PPDO, the heat resistance of the DA copolymers was improved and the Tm increased from 93 °C to 103 °C. Significantly, the rheological data also confirmed that the copolymer was self-healing and showed obvious self-repairing properties after simple tempering. In addition, an enzyme degradation experiment showed that the DA copolymer can be degraded by a certain amount, with the degradation rate lying between those of PPDO and PLA.

Optimization of Process Parameters for Carbon Fiber Reinforced Polyamide 6 Composites Fabricated by Self-Resistance Electric Heating Technology.

As an energy-saving and efficient composites-forming technology, the properties of carbon fiber self-resistance electric (SRE) heating technology still need to be improved, which is not conducive to the popularization and application of this technology. To deal with this problem, the SRE heating technology was combined with a compression molding process to form carbon-fiber-reinforced polyamide 6 (CF/PA 6) composite laminates in this study. Orthogonal experiments of three factors (temperature, pressure, and impregnation time) were designed to study the effect of process parameters on the impregnation quality and mechanical properties of CF/PA 6 composite laminates and to obtain the optimized set of process parameters. Furthermore, the effect of the cooling rate on crystallization behaviors and mechanical properties of laminates was studied according to the optimized settings. The results show that the laminates possess a good comprehensive forming quality under process parameters using a forming temperature of 270 °C, forming pressure of 2.5 MPa, and an impregnation time of 15 min. The ununiform impregnation rate is due to the ununiform temperature field in the cross-section. When the cooling rate decreases from 29.56 °C/min to 2.64 °C/min, the crystallinity of the PA 6 matrix increases from 25.97% to 37.22%; the α-phase of the matrix crystal phase also increases significantly. The effect of the cooling rate on crystallization properties also further affects the impact properties; laminates with a faster cooling rate have stronger impact resistance.

The Study of Crystallization Behavior, Microcellular Structure and Thermal Properties of Glass-Fiber/Polycarbonate Composites.

Polycarbonate (PC) foam is a versatile material with excellent properties, but its low thermal stability limits its application in high-temperature environments. The aim of this study was to improve the thermal stability of PC foam by adding glass fibers (GF) and to investigate the effect of GF on PC crystallization behavior and PC foam cell morphology. This study was motivated by the need to improve the performance of PC foams in various industries, such as construction, automotive, and medical. To achieve this goal, PC/GF composites were prepared by extrusion, and PC/GF composite foams were produced using a batch foaming process with supercritical carbon dioxide (SC-CO2) as the blowing agent. The results showed that the addition of GF accelerated the SC-CO2-induced crystallization stability of PC and significantly increased the cell density to 4.6 cells/cm3. In addition, the thermal stability of PC/GF foam was improved, with a significant increase in the residual carbon rate at 700 °C and a lower weight loss rate than PC matrix. Overall, this study highlights the potential of GF as a PC foam reinforcement and its effect on thermal and structural properties, providing guidance for industrial production and applications.

Effects of Ethylene-Propylene-Diene Monomers (EPDMs) with Different Moony Viscosity on Crystallization Behavior, Structure, and Mechanical Properties of Thermoplastic Vulcanizates (TPVs).

Moony viscosity of ethylene-propylene-diene monomers (EPDMs) can have effect on the crystallization dynamics, structure, and properties of EPDM/polypropylene (PP)-based thermoplastic vulcanizates (TPVs). TPVs with two different Moony viscosities are prepared via a twin-screw extruder, respectively. Crosslinked EPDM with lower Moony viscosity has a higher crosslinking density and the nucleation effect of its crosslink point improves the crystallization ability of PP in TPV, leading to PP phase crystallization at higher temperatures. For TPV with an EPDM of higher Moony viscosity, it has higher crystallinity and the EPDM phase crystallized earlier. Synchrotron radiation studies show that the EPDM with low Moony viscosity has no obvious crystalline structure, and the prepared TPV has an obvious phase separation structure, while the TPV with higher Mooney viscosity of the EPDM does not exhibit obvious phase separation, indicating that the longer EPDM chains have better compatibility with PP in TPV, also evidenced by the almost disappearance of the PP glass transition peak in TPV, from the dynamic mechanical analysis. The longer EPDM chains in TPV provide more physical entanglement and better interaction with PP molecules, resulting in a stronger strain hardening process, longer elongation at break, and higher tensile stress in TPV.

Crystallization behaviors regulations and mechanical performances enhancement approaches of polylactic acid (PLA) biodegradable materials modified by organic nucleating agents.

Polylactic acid (PLA) has attracted much attention because of its good biocompatibility, biodegradability, and mechanical properties. However, the slow crystallization rate of PLA during molding leads to its poor heat resistance, which limit its diffusion for many industrial applications. In this review, the relationship between PLA crystallization and its molecular structure and processing conditions is summarized. From the perspective of the regulation of PLA crystallization by organic nucleating agents, the research progress of organic micromolecule (e.g., esters, amides, and hydrazides), organic salt, supramolecular, and macromolecule nucleating agents on the crystallization behavior of PLA is mainly introduced. The nucleation mechanism of PLA is expounded by organic nucleating agents, and the effect of the interaction force between organic nucleating agents and PLA molecular chains on the crystallization behavior of PLA is analyzed. The effects of the crystallization behavior of PLA on its mechanical properties and heat resistance are discussed. It will provide a theoretical reference for the development and application of high-efficiency nucleating agents.

Probing into the nucleation and reinforcing effects of poly (vinyl acetate) grafted cellulose nanocrystals in melt-processed poly (lactic acid) nanocomposites.

Blending poly (lactic acid) (PLA) with cellulose nanocrystals (CNCs) to fabricate nanocomposites is a valuable strategy to improve the properties of PLA without sacrificing its biodegradability. However, the nucleation and reinforcing mechanisms of CNCs for semi-crystalline PLA matrix are still elusive in melt-processed PLA/CNC nanocomposites. Herein, poly (vinyl acetate) (PVAc) chains were grafted onto the surface of CNCs via an efficient radical polymerization in an aqueous medium, making CNCs suitable for conventional melting processing techniques. It is found that the dispersion state of CNCs in the PLA matrix and the interface interaction between PLA and CNCs can be tailored by varying the PVAc grafting density. Further studies show that well-dispersed CNCs play a positive role in reinforcing PLA. But unexpectedly, the nucleation effect is suppressed even though the homogeneous dispersion of CNCs is achieved with higher PVAc grafting density because the rich PVAc chains at the interface dilute the PLA chains, thus hindering the nucleation and spherulite growth of PLA. This research sheds light on the nucleation and reinforcing mechanisms of polymer grafted CNCs, and will provide theoretical guidance for the industrialization of high-performance bio-based nanocomposites.

Crystallization and phase behavior in mixture systems of anhydrous milk fat, palm stearin, and palm oil: Formation of eutectic crystals.

The comparison between the crystallization and phase behavior of binary blends of anhydrous milk fat (AMF)/palm stearin (POs) and POs/palm oil (PO) was investigated. POs/POs blends showed good compatibility, while the compatibility of AMF/POs blends showed no ideal and was dominated by eutectic behavior. And the eutectic growth of blends was found to be a phenomenon that the triacylglycerol (TAG) of AMF grew on the peripheral of POs seed crystals. In binary blends, the addition of POs not only increased the liquid phase transition temperature but also induced the formation of ß crystal forms in more than 70% POs. The addition of soybean oil to binary blends could improve the compatibility of the ternary system. It eventually provided potential formulations for the production of non-hydrogenated puff pastry margarine.

Crystallinity, Rheology, and Mechanical Properties of Low-/High-Molecular-Weight PLA Blended Systems.

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.

Non-Isothermal Crystallization Kinetics of Polyether-Ether-Ketone Nanocomposites and Analysis of the Mechanical and Electrical Conductivity Performance.

High-performance polyether-ether-ketone (PEEK) is highly desirable for a plethora of engineering applications. The incorporation of conductive carbon nanotubes (CNTs) into PEEK can impart electrical conductivity to the otherwise non-conductive matrix, which can further expand the application realm for PEEK composites. However, a number of physical properties, which are central to the functionalities of the composite, are affected by the complex interplay of the crystallinity and presence of the nanofillers, such as CNTs. It is therefore of paramount importance to conduct an in-depth investigation to identify the process that optimizes the mechanical and electrical performance. In this work, PEEK/CNTs composites with different carbon nanotubes (CNTs) content ranging from 0.5 to 10.0 wt% are prepared by a parallel twin-screw extruder. The effects of CNTs content and annealing treatment on the crystallization behavior, mechanical properties and electrical conductivity of the PEEK/CNTs composites are investigated in detail. A non-isothermal crystallization kinetics test reveals a substantial loss in the composites' crystallinity with the increased CNTs content. On the other hand, mechanical tests show that with 5.0 wt% CNTs content, the tensile strength reaches a maximum at 118.2 MPa, which amounts to a rise of 30.3% compared with the neat PEEK sample after annealing treatment. However, additional annealing treatment decreases the electrical conductivity as well as EMI shielding performance. Such a decrease is mainly attributed to the relatively small crystal size of PEEK, which excludes the conductive fillers to the boundaries and disrupts the otherwise conductive networks.

Crystallization Behavior of Poly(ε-Caprolactone)-Hollow Glass Microspheres Composites for Rotational Molding Technology.

Composites suitable for rotational molding technology based on poly(ε-caprolactone) (PCL) and filled with hollow glass microspheres (HGM) or functionalized hollow glass microspheres (HGMf) were prepared via melt-compounding. The functionalization of glass microspheres was carried out by a silanization treatment in order to improve the compatibility between the inorganic particles and the polymer matrix and achieve a good dispersion of glass microspheres in the matrix and an enhanced filler-polymer adhesion. The crystallization behavior of materials was studied by DSC under isothermal and non-isothermal conditions and the nucleating effect of the glass microspheres was proven. In particular, the presence of silanized glass microspheres promoted faster crystallization rates and higher nucleation activity, which are enhanced by 75% and 50%, respectively, comparing neat PCL and the composite filled with 20 wt% HGMf. The crystalline and supermolecular structure of PCL and composites crystallized from the melt was evaluated by WAXD and SAXS, highlighting differences in terms of crystallinity index and structural parameters as a function of the adopted crystallization conditions.