Article
Polymer Science
Maryam Safari, Itziar Otaegi, Nora Aramburu, Gonzalo Guerrica-Echevarria, Antxon Martinez de Ilarduya, Haritz Sardon, Alejandro J. Mueller
Summary: Isodimorphic behavior is determined by partial inclusion of comonomer segments within the crystalline structure, with isodimorphic random copolymers able to crystallize regardless of composition and exhibiting coexistence of two crystalline phases in the pseudo-eutectic region. The crystallization conditions determine the crystalline phase of the copolymer in the pseudo-eutectic region where both crystalline phases can coexist.
Article
Polymer Science
Agostino Pietrangelo, Carlos R. Lopez-Barron, Matthew T. DeRocco, Shuhui Kang, Sarah J. Mattler, Pamela J. Wright
Summary: Mapping copolymer properties to composition and microstructure provides insights into their correlation and allows for tuning the material's structure to meet performance demands. In this study, racemic & beta;-butyrolactone (B) and & beta;-valerolactone (V) were polymerized to create syndio-enriched (co)polymers across the entire compositional range. The effect of copolymer composition on thermal and mechanical properties as well as crystallinity and morphology was investigated. Results showed a decrease in elastic modulus and sharp transitions in tensile properties at a V content of 36%, corresponding to changes in crystallinity and crystal structure. C-13 NMR spectroscopy was used to analyze the copolymer microstructure, revealing the presence of syndiotactic tetrads with different B and V units at different compositions.
Article
Polymer Science
Lu-Lu Yang, Xue-Wei Wei, Tianyu Wu, Xiaoyu Meng, Hai-Mu Ye
Summary: Isomorphism is a unique co-crystallization behavior of random copolymers that allows regulating crystalline structure and performance without loss of crystallinity. Incorporating butylene adipate (BA) into a model system of poly(butylene succinate-ran-butylene fumarate) (PBSF) forms PBSFA terpolymers, which exhibit different crystallization features. The addition of BA influences the accommodation capacities of butylene succinate (BS) and butylene fumarate (BF) in the isomorphic lattice, leading to a reversal of their preferences. This study provides insight into the differentiation of co-monomeric units in the isomorphic lattice and the manipulation of isomorphism.
Article
Polymer Science
Xue-Wei Wei, Xin-Xin Zhao, Yi Li, Xiao-Yu Meng, Qiong Zhou, Hai-Mu Ye
Summary: The co-crystallization of different monomeric units significantly affects the performance of random copolymers. Currently, the crystallization manners of random binary copolymers have been categorized into three types, each with its own advantages and disadvantages. This study discovers a novel co-crystallization behavior that combines the benefits of two crystallization manners. Furthermore, the crystal structure undergoes a shift when changing the chain composition.
CHINESE JOURNAL OF POLYMER SCIENCE
(2022)
Article
Materials Science, Multidisciplinary
Xuan Sha, Yang Yue, Wenan Tie, Xiaoyan Tian, Jiachun Feng
Summary: Compared to polypropylene homopolymer, the presence of a beta-nucleating agent usually leads to a lower amount of beta-phase in polypropylene random copolymer with comonomer inserted. The insertion of comonomer reduces the formation of beta-nuclei and weakens the growth rate of beta-phase, leading to the decreased content of beta-phase in polypropylene random copolymer. The study provides important insights into the control of polymorphism in polymers.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Multidisciplinary Sciences
Chengjun Kang, Kuiwei Yang, Zhaoqiang Zhang, Adam K. Usadi, David C. Calabro, Lisa Saunders Baugh, Yuxiang Wang, Jianwen Jiang, Xiaodong Zou, Zhehao Huang, Dan Zhao
Summary: Resolving the single-crystal structures of two-dimensional covalent organic frameworks (2D COFs) is a challenging task. In this study, the authors investigate the growth process of 2D COFs by tracing growth intermediates and identify two different growth mechanisms. This enables the growth and structure determination of micron-sized 2D single-crystalline COFs.
NATURE COMMUNICATIONS
(2022)
Article
Polymer Science
Xuekuan Ma, Xuanbo Wang, Chenxuan Sun, Bao Wang, Chengtao Yu, Guorong Shan, Yongzhong Bao, Ying Zheng, Pengju Pan
Summary: This study demonstrates the crucial role of trans and cis units in controlling chain conformation and crystal polymorphism of polymers, through the synthesis of copolymers containing C=C units.
Article
Chemistry, Multidisciplinary
Kentaro Atsukawa, Shuntaro Amari, Hiroshi Takiyama
Summary: The study introduced the original concept of SDMC for dispersing a target material in a matrix, and investigated the effects of cooling, agitation, and aeration on dissolution rate. The experimental results showed that these operations enhanced the dissolution rate by increasing the nucleation rate based on the SDMC concept.
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
(2021)
Article
Polymer Science
Yilong Liao, Li Pan, Zhe Ma, Dario Cavallo, Guoming Liu, Dujin Wang, Alejandro J. Mueller
Summary: The influence of a novel comonomer ODPA on the crystallization and self-nucleation behavior of isotactic polypropylene copolymers was studied. The results showed that ODPA incorporation significantly slowed down the crystallization kinetics and led to a sharp increase in nucleation density, resulting in smaller spherulitic superstructures. Moreover, ODPA induced a strong melt memory effect that persisted even above the equilibrium melting temperature for certain ODPA content ranges.
Article
Chemistry, Multidisciplinary
Mitsuhiko Morisue, Minami Nakamura, Yusuke Miyake, Yukiyasu Kashiwagi, Seiji Watase, Taiki Hoshino, Hiroyasu Masunaga, Shinichi Sakurai, Sono Sasaki
Summary: The antifreezing effect of central metal on porphyrin supercooled liquid and glass is investigated. The central metal enhances intermolecular interactions, increases viscosity, and slows crystallization process. The impact of the central metal on metalloporphyrins with specific chemical structures is discussed.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Polymer Science
Baku Nagendra, Paola Rizzo, Christophe Daniel, Gaetano Guerra
Summary: The transparency of polymer films is influenced by the planar orientations of nanoporous-crystalline (NC) phases of sPS and PPO, with sPS and PPO exhibiting opposite behaviors. Improvements in transparency are observed when the chain axes of the NC phases are oriented parallel or perpendicular to the film plane for sPS and PPO, respectively.
Article
Polymer Science
Ainhoa Fernandez-Tena, Ricardo Arpad Perez-Camargo, Olivier Coulembier, Leire Sangroniz, Nora Aranburu, Gonzalo Guerrica-Echevarria, Guoming Liu, Dujin Wang, Dario Cavallo, Alejandro J. Mueller
Summary: The role of molecular weight in the crystallization and melt memory of PCL was investigated. Different samples with a range of molecular weights were analyzed using various characterization techniques. The results showed that certain parameters, such as melting temperature and equilibrium melting temperature, saturated at a particular molecular weight, while others, such as crystallization temperature and degree of crystallinity, exhibited a bell-shaped behavior. SAXS analysis revealed different chain conformations at different molecular weights, and morphological studies showed different crystalline structures. The melt memory effect of PCL increased with molecular weight due to increased entanglements and chain folding. SSA experiments indicated that molecular weight did not affect intermolecular interactions.
Review
Polymer Science
Leire Sangroniz, Bao Wang, Yunlan Su, Guoming Liu, Dario Cavallo, Dujin Wang, Alejandro J. Muller
Summary: This study investigates fractionated crystallization, where multiple separated crystallization events are observed in semicrystalline polymers when the number of microdomains is significantly higher than the available number of heterogeneities. The origins of fractionated crystallization effects and their impact on nucleation and crystallization kinetics are discussed.
PROGRESS IN POLYMER SCIENCE
(2021)
Article
Polymer Science
Magdalena Gora, Sebastian Coba-Daza, Enrico Carmeli, Davide Tranchida, Andreas Albrecht, Alejandro J. Muller, Dario Cavallo
Summary: In blends of polyethylene (PE) as the minor component dispersed in a polypropylene (PP) matrix, increasing the crystallization temperature of the PP matrix enhances the crystallization rate of PE by promoting epitaxial nucleation at the interface. This study investigates the behavior of different industrially produced PE grades in immiscible blends with PP as the matrix.
Article
Chemistry, Physical
Megan J. Povey, Rammile Ettelaie, Ken Lewtas, Andy Price, Xiaojun Lai, Fei Sheng
Summary: This article outlines techniques for controlling and measuring the nucleation of crystalline materials. It demonstrates the impact of low power ultrasound on the nucleation and crystallization of a wax-n-eicosane dissolved in a heptane/toluene solvent. A mathematical-physical approach based on rectifying heat and mass transport by low power oscillating pressure fields is suggested, and its combination with dissipative particle dynamics computational modeling is proposed as a predictive method for modeling the impact of low power oscillating pressure fields on nucleating systems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Polymer Science
Lourdes Urpi, Abdelilah Alla, Antxon Martinez de Ilarduya
Summary: The study focuses on the use of renewable monomers and green polymerization processes to synthesize new synthetic polymers. High molecular weight copolyesters were obtained from omega-pentadeca-lactone (PDL), dimethyl succinate (DMS), and 1,4-cyclohexanedimethanol (1,4-CHDM) through ring opening polymerization (ROP) and melt polycondensation processes. The copolyesters showed thermal stability up to 350°C, semicrystalline structure, and the melting temperatures decreased with the increased content of the counterpart comonomer. The crystalline structure and thermal transitions of the copolyesters were studied using synchrotron X-ray diffraction. Copolyesters with elastomeric properties can be obtained at intermediate compositions.
Article
Biochemistry & Molecular Biology
A. Martinez Cutillas, D. Sanz-Serrano, S. Oh, F. Ventura, A. Martinez de Ilarduya
Summary: Synthetic and functional grafts, such as the RGD-PEG-PLA-PGl-PLA-PEG-RGD scaffold used in this study, are a great alternative to conventional grafts. This multifunctional polymer provides physical support and precise signaling for cells to heal damaged tissues. The presence of PGl inner block enhances the toughness of the scaffold, while PEGylation improves its hydrophilicity. The functionalized RGD peptides on the scaffold surface significantly enhance cell adhesion and proliferation. These results make it a great candidate for temporary graft preparation.
MACROMOLECULAR BIOSCIENCE
(2023)
Article
Polymer Science
Anna Malafronte, Miriam Scoti, Maria Rosaria Caputo, Bo Li, Rachel K. O' Reilly, Andrew P. Dove, Alejandro J. Mueller, Claudio De Rosa
Summary: The crystal structure of poly-(7-heptalactone) (PHL) is determined using various techniques including X-ray powder diffraction and electron diffraction patterns. PHL is synthesized through ring-opening polymerization of eta-heptalactone and reversible addition-fragmentation chain transfer polymerization with diphenyl phosphate as a catalyst. The refined crystal structure reveals that the chains of PHL adopt a trans planar conformation and are packed in an orthorhombic unit cell with dimensions a = 7.37 Å, b = 5.05 Å, and c = 10.07 Å, symmetry P2(1).
Article
Polymer Science
Nicholas F. Mendez, Deboleena Dhara, Qingteng Zhang, Suresh Narayanan, Linda S. Schadler, Alejandro J. J. Muller, Sanat K. Kumar
Summary: X-ray photon correlation spectroscopy measurements were used to analyze the dynamics of bare and bimodal grafted silica nanoparticles mixed with PEO melts. The results showed diffusive behavior of the nanoparticles in dilute polymer nanocomposite samples, taking into account the adsorbed PEO polymer layer. The dynamics of grafted nanoparticles were found to be influenced by morphology and grafting parameters at larger scales.
Article
Polymer Science
Ruth N. Schmarsow, Ulises Casado, Marcelo Ceolin, Ileana A. Zucchi, Alejandro J. Mueller, Walter F. Schroeder
Summary: There is increasing interest in the study of supramolecular networks formed by self-assembly of amphiphilic molecules due to their responsive behavior to external stimuli. Embedding these networks into polymer matrices can lead to functional polymers with various applications. This study investigates the behavior of supramolecular networks in a rubbery polymer matrix and reveals the influence of diffusional and topological limitations on the dynamics and crystallization within the network. Mechanical tests show that the deformation capacity of these materials can be precisely tuned by programming the temperature within the melting range of the supramolecular network.
Article
Polymer Science
Mario Ivan Penas, Miryam Criado-Gonzalez, Antxon Martinez de Ilarduya, Araceli Flores, Jean-Marie Raquez, Rosica Mincheva, Alejandro J. Mueller, Rebeca Hernandez
Summary: This study presents two strategies to regulate the enzymatic degradation of PBS films. One is to add multilayer coats of polysaccharide alginate and chitosan to the PBS films, and the other is to embed lipase-filled alginate particles in the PBS films. The results show that the number of protective coating layers and the amount of encapsulated enzyme affect the degradation extent of PBS films.
POLYMER DEGRADATION AND STABILITY
(2023)
Article
Materials Science, Characterization & Testing
Jordana K. Palacios, Rose Mary Michell, Alejandro J. Mueller
Summary: This review provides a comprehensive analysis of the crystallization behavior and self-assembly of block copolymers with up to four potentially crystallizable phases. It discusses the factors affecting the development of crystalline structures and highlights recent advances in block copolymer crystallization. The article also explores the influence of different molecular architectures, as well as the role of nanofillers and additives in the crystallization process.
Article
Pharmacology & Pharmacy
Porochista Dorost, Montserrat Garcia-Alvarez, Antxon Martinez de Ilarduya
Summary: The delivery of hydrophobic and poorly water soluble drugs is challenging. Drug encapsulation on biodegradable and biocompatible polymers, such as poly(γ-glutamic acid) (PGGA), can overcome this issue. PGGA derivatives with different hydrophilic-lipophilic balances were synthesized and self-assembled into nanoparticles. The hydrophobic core of these nanoparticles was used for the encapsulation of the anticancer drug, Doxorubicin (DOX). Drug release studies showed that the nanoparticles were effective in releasing DOX, especially at pH 4.2.
Article
Biochemistry & Molecular Biology
Maria Rosaria Caputo, Changxia Shi, Xiaoyan Tang, Haritz Sardon, Eugene Y. -X. Chen, Alejandro J. Muller
Summary: Among the polyester family, poly(3-hydroxybutyrate) (PHB) has the greatest industrial potential. It can be produced biologically or chemically. However, its poor mechanical properties limit its commercial use. This study investigates the properties of copolymers of PHB and poly(epsilon-caprolactone) (PCL), which can improve the mechanical properties of PHB while maintaining its biodegradability. The presence of PCL in the copolymers affects the thermal parameters, crystallization kinetics, and morphology of PHB. The results show that copolymerization can tailor the thermal properties, morphology, and crystallization kinetics of PHB, potentially improving its processing, optical, and mechanical properties.
Article
Polymer Science
Leire Sangroniz, Maryam Safari, Antxon Martinez de Ilarduya, Haritz Sardon, Dario Cavallo, Alejandro J. Mueller
Summary: This study investigates the effect of incorporating a second comonomer unit in the crystalline unit cell on the melt memory effect of a major component in a random isodimorphic copolymer. It is found that even small amounts of the second comonomer unit significantly reduce the melt memory effect of the copolymers. This reduction is attributed to the disruption of intermolecular interactions and the reduction in self-nucleation capacity caused by the incorporation of the second comonomer unit in the polymer chain.
Article
Polymer Science
Yilong Liao, Ricardo A. Perez-Camargo, Haritz Sardon, Antxon Martinez de Ilarduya, Wenxian Hu, Guoming Liu, Dujin Wang, Alejandro J. Muller
Summary: In this study, poly(hexamethylene-ran-octamethylene carbonate) copolycarbonates were synthesized and found to exhibit higher crystallinities than the parent components. A new crystalline phase different from the homopolymers was also discovered. Through experimental and structural characterization, the unique thermal behavior of the copolymers was confirmed. This finding challenges the concept of isodimorphism.
Article
Polymer Science
Magdalena Gora, Sebastian Coba-Daza, Enrico Carmeli, Davide Tranchida, Andreas Albrecht, Alejandro J. Muller, Dario Cavallo
Summary: In blends of polyethylene (PE) as the minor component dispersed in a polypropylene (PP) matrix, increasing the crystallization temperature of the PP matrix enhances the crystallization rate of PE by promoting epitaxial nucleation at the interface. This study investigates the behavior of different industrially produced PE grades in immiscible blends with PP as the matrix.
Article
Polymer Science
Yilong Liao, Li Pan, Zhe Ma, Dario Cavallo, Guoming Liu, Dujin Wang, Alejandro J. Mueller
Summary: The influence of a novel comonomer ODPA on the crystallization and self-nucleation behavior of isotactic polypropylene copolymers was studied. The results showed that ODPA incorporation significantly slowed down the crystallization kinetics and led to a sharp increase in nucleation density, resulting in smaller spherulitic superstructures. Moreover, ODPA induced a strong melt memory effect that persisted even above the equilibrium melting temperature for certain ODPA content ranges.
Article
Polymer Science
I. Razquin, A. Iregui, M. Cobos, J. Latasa, A. Eceiza, K. Gonzales, L. Martin, A. J. Muller, A. Gonzalez, L. Irusta
Summary: Epoxy/polycaprolactone (PCL) blends with cationic photo-initiator were prepared by solution and melt blending, and processed using various techniques including solvent casting, solution electrospinning, melt electrowriting, and Fused Deposition Modeling (FDM) 3D printing. The shape memory properties varied depending on the processing technique, with electrospun fibers showing optimal fixity and recovery ratios. AFM images revealed different morphologies for different processing techniques, with electrospun mats exhibiting Shish-Kebab-type crystalline morphology and superior solvent resistance properties. The electrospun mats also showed high affinity towards chloroform, suggesting potential applications as chloroform sensors.
Article
Polymer Science
Shaofan Li, Weilong Ju, Guoming Liu, Yunlan Su, Alejandro J. Muller, Dujin Wang
Summary: The properties of polymer nanocomposites (PNCs) are dependent on the dispersion of nanoparticles within the polymer matrix. This study investigates the dispersion and crystallization behaviors of PE/HDPE1289-g-SiO2 PNCs in different polyethylene (PE) matrices. The results show that the dispersion of HDPE1289-g-SiO2 nanoparticles is influenced by the P/N parameter and the similarity between the grafted and matrix polymer chain structures.
