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Analyzing QCM Data Using a New Transfer-Matrix Model: Long-Ranged Asymmetric Gradient in Shear Modulus Identified Across Immiscible Glassy–Rubbery Polymer Interface
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-18 DOI: 10.1021/acs.macromol.4c02847
Alexander A. Couturier, Justin C. Burton, Connie B. Roth
{"title":"Analyzing QCM Data Using a New Transfer-Matrix Model: Long-Ranged Asymmetric Gradient in Shear Modulus Identified Across Immiscible Glassy–Rubbery Polymer Interface","authors":"Alexander A. Couturier, Justin C. Burton, Connie B. Roth","doi":"10.1021/acs.macromol.4c02847","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02847","url":null,"abstract":"A new approach to analyzing quartz crystal microbalance (QCM) data using an acoustic transfer-matrix model is presented that enables determining a local depth-dependent shear modulus <i>G̃</i>(<i>z</i>) profile. A strong decrease in dissipation upon annealing is observed for immiscible polymer bilayer films of rubbery polybutadiene (PB) atop glassy polystyrene (PS), reflecting large viscoelastic changes in the sample corresponding to the emergence of a broad gradient in modulus <i>G̃</i>(<i>z</i>) when the ≈5 nm compositional interface is formed. Using a new transfer-matrix form of our continuum mechanics model that matches boundary conditions of shear waves between discrete modeled layers, we computationally fit these changes in frequency Δ<i>f</i>(<i>n</i>) and dissipation ΔΓ(<i>n</i>) shifts over a range of harmonics <i>n</i> to the evolution of a modulus gradient. The <i>G̃</i>(<i>z</i>) gradient across the PS/PB bilayer, treated as a hyperbolic tangent, is observed to be broad (230 nm) and strongly asymmetric (200 nm) toward the glassy PS side, consistent with the general trends of local glass transition <i>T</i><sub>g</sub>(<i>z</i>) previously reported. Surprisingly, the <i>G̃</i>(<i>z</i>) gradient is found to be symmetric on a log <i>G</i> scale, with the value of <i>G</i> at the interface equivalent to the geometric mean that optimizes acoustic energy transmission.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"25 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Competing Effects of Amorphous and Crystalline Networks on the Mechanical Behavior of Poly(vinyl alcohol) Hydrogel
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-18 DOI: 10.1021/acs.macromol.4c02149
Kun Song, Ming-Ke Zhang, Jing-Jing Han, Ming-Ming Chen, Jia-Zhuang Xu, Yue Yin, Zhong-Ming Li, Dong Liu
{"title":"Competing Effects of Amorphous and Crystalline Networks on the Mechanical Behavior of Poly(vinyl alcohol) Hydrogel","authors":"Kun Song, Ming-Ke Zhang, Jing-Jing Han, Ming-Ming Chen, Jia-Zhuang Xu, Yue Yin, Zhong-Ming Li, Dong Liu","doi":"10.1021/acs.macromol.4c02149","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02149","url":null,"abstract":"We investigate the effect of amorphous and crystalline networks on the mechanical behavior of poly(vinyl alcohol) physical hydrogels by comparing the rheological properties and flow-induced structural evolution for samples annealed at different temperatures with rheometers and <i>in situ</i> small-angle X-ray and neutron-scattering measurements. Four strain regions, namely, the linear (I), yielding (II), linear (III), and strain-hardening (IV) regions, are revealed in the tensile response. A critical annealing temperature 74 °C is observed, which corresponds to the structural transition from isolated crystal to crystalline network and the mechanical transition from quasi-linear to nonlinear response. For samples annealed below 74 °C, mechanical response depends on the deformation of the soft amorphous network, and the destruction in network connectivity plays a key role in the slight yielding. For samples annealed above 74 °C, the hard crystal network provides high strength and stiffness to the gels, resulting in loss modulus and Young’s modulus an order of magnitude higher than those annealed below 74 °C. In region II, the rupture of crystalline network leads to the more drastic yielding. For all samples, crystal disaggregation along the flow direction is found to be constrained by the secondary nucleus length. Moreover, the flow-induced recrystallization results in the strain-hardening behavior in region IV. These results reveal the role of soft and hard network structures in determining the mechanical performance of physical hydrogels.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"16 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Clustering and Nanoscale Vitrimeric Behavior in Telechelic Polybutadiene Model Vitrimers
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-18 DOI: 10.1021/acs.macromol.4c03035
Angel Alegría, Arantxa Arbe, Juan Colmenero, Nikolaos Patelis, Saibal Bhaumik, Mingtao Zhou, Nikos Hadjichristidis
{"title":"Clustering and Nanoscale Vitrimeric Behavior in Telechelic Polybutadiene Model Vitrimers","authors":"Angel Alegría, Arantxa Arbe, Juan Colmenero, Nikolaos Patelis, Saibal Bhaumik, Mingtao Zhou, Nikos Hadjichristidis","doi":"10.1021/acs.macromol.4c03035","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03035","url":null,"abstract":"Despite the promise of vitrimeric materials applications, there are many aspects that remain poorly understood. To advance the fundamental knowledge of these materials, model systems of well-controlled composition are needed. Here we report the synthesis of polybutadiene-based model vitrimers, which are further investigated with respect to their structure and dynamic properties. Four vitrimers with different cross-linking concentrations were obtained by modifying the molecular weight of the precursor functionalized polybutadiene precursors. A tetrafunctional aromatic cross-linker was used in all cases. Due to the nature of the cross-linker, the resulting vitrimers exhibit fluorescence indicative of cross-linker association. The structural investigation by small-angle X-ray diffraction showed that the cross-linkers cluster together to form very stable cylindrical structures linked by polybutadiene chains. The dynamic behavior of the vitrimers, as studied by differential scanning calorimetry and broadband dielectric spectroscopy, can be interpreted by the presence of such a cluster structure, where already a few degrees above the glass transition there are significant fluctuations of the dynamic covalent bonds, which remain essentially limited to the intracluster level─i.e., confined in the interphase between the cross-linkers’ clusters and the polymer. This results in rubber-like vitrimeric materials in which the mechanical stability is maintained by the cluster network as long as it is not perturbed by the application of high mechanical stresses, in stark contrast to recently investigated polyisoprene-based model vitrimers with flexible triamine cross-linkers, which also exhibit cluster structure.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"25 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Versatile Anisotropic Coarse-Grained Models for the Structure and Dynamics of Unentangled Poly(tetrafluoroethylene) Melt
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-18 DOI: 10.1021/acs.macromol.4c02413
Yen-Ting Hsu, Hsiu-Yu Yu
{"title":"Versatile Anisotropic Coarse-Grained Models for the Structure and Dynamics of Unentangled Poly(tetrafluoroethylene) Melt","authors":"Yen-Ting Hsu, Hsiu-Yu Yu","doi":"10.1021/acs.macromol.4c02413","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02413","url":null,"abstract":"We develop anisotropic coarse-grained (CG) models for unentangled poly(tetrafluoroethylene) (PTFE) melts to investigate their structural and dynamical properties at two CG levels, corresponding to six and eight CF<sub>2</sub> groups per bead. Higher CG levels improve computational efficiency but face challenges, such as unphysical chain crossing due to reduced steric hindrance and weaker interactions. Additionally, the inherent chain stiffness of PTFE chains is evident. Analyses of the gyration tensor and asphericity indicate that structural anisotropy increases with CG levels. Therefore, we pursue a structure-based, bottom-up coarse-graining approach based on accurate all-atom (AA) simulations. Systematic probing of intermolecular interactions, internal conformations, and global chain dimensions reveals that our models effectively capture structural characteristics. Chain stiffness, such as the Kuhn length, agrees reasonably with AA simulations and experimental data. Furthermore, with appropriate scaling factors introduced, these CG models closely align with the atomistic counterpart in dynamics, including self-diffusivity and zero-shear viscosity. Assessments across molecular weights (48–192 carbons per chain) and temperatures (500 to 650 K) confirm the adaptability of these models. Utilizing the devised CG models, the computational efficiency is approximately accelerated by a factor of <i>N</i><sup>2</sup>, where <i>N</i> is the number of CF<sub>2</sub> groups per CG bead.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"7 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Designing Highly Entangled, Homogeneous, and Low-Defect Networks for High-Performance Rubbers
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-17 DOI: 10.1021/acs.macromol.4c03133
Lingmin Kong, Junqi Zhang, Shaoqi Huang, Rongchun Zhang, Jiaming Li, Zhengtian Xie, Jinrong Wu
{"title":"Designing Highly Entangled, Homogeneous, and Low-Defect Networks for High-Performance Rubbers","authors":"Lingmin Kong, Junqi Zhang, Shaoqi Huang, Rongchun Zhang, Jiaming Li, Zhengtian Xie, Jinrong Wu","doi":"10.1021/acs.macromol.4c03133","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03133","url":null,"abstract":"Rubbers are critical in a wide range of engineering applications; however, conventional processing methods often disrupt the entanglements and introduce defects that compromise their mechanical performance. In this study, we introduce a nondestructive, latex-based processing method for the fabrication of high-performance rubbers with highly entangled, homogeneous, and low-defect networks. As a proof of concept, natural rubber (NR) materials prepared using this novel approach retain their intrinsic entanglements while exhibiting a more homogeneous network structure with fewer defects. This optimized NR network enhances strain-induced crystallization (SIC), achieving a crystallinity of up to 38% and larger crystal sizes. These improvements lead to superior mechanical properties, including a tensile strength of 37.3 MPa, a toughness of 77.3 MJ/m<sup>3</sup>, a modulus of 2.37 MPa, and a fatigue threshold of 258 J/m<sup>2</sup>, outperforming conventional NR materials. Furthermore, this method is versatile and can be applied to other rubbers, demonstrating its broad potential for producing high-performance rubber materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"75 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Mechanical Performance of Polyampholyte Hydrogels Influenced by Ionic Bond Strength under Isochoric Conditions
IF 5.1 1区 化学
Macromolecules Pub Date : 2025-03-17 DOI: 10.1021/acs.macromol.4c0242010.1021/acs.macromol.4c02420
Xueyu Li, Haruna Tsuchibora, Ya Nan Ye, Kunpeng Cui* and Takayuki Kurokawa*, 
{"title":"Mechanical Performance of Polyampholyte Hydrogels Influenced by Ionic Bond Strength under Isochoric Conditions","authors":"Xueyu Li,&nbsp;Haruna Tsuchibora,&nbsp;Ya Nan Ye,&nbsp;Kunpeng Cui* and Takayuki Kurokawa*,&nbsp;","doi":"10.1021/acs.macromol.4c0242010.1021/acs.macromol.4c02420","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02420https://doi.org/10.1021/acs.macromol.4c02420","url":null,"abstract":"<p >Hydrogels composed of hierarchical structures are notable for their exceptional strength and toughness. Understanding the toughening mechanisms associated with these hierarchical structures is essential for the application and design of tough soft materials. Using polyampholyte hydrogels as a model system, this study introduces a novel approach that combines electrolyte-induced ionic bond dissociation with PEG-induced osmotic stress to systematically investigate how ionic bond strength and phase separation influence mechanical properties under isochoric conditions. We reveal that increasing electrolyte concentrations induces a structural transition from strong bicontinuous phase-separated networks to a homogeneous structure and eventually to weak bicontinuous phase-separated networks, accompanied by characteristic relaxation times that initially decrease and subsequently increase. This transition leads to abnormal nonmonotonic changes in mechanical properties. We further elucidate that the nonmonotonic behavior in fracture stress and work of extension to fracture, along with self-recovery dynamics, is governed by the phase-separated structural transition, while variations in fracture energy are primarily related to the dynamics of ionic bonds. This work provides valuable insights into the design of tough soft materials through the modulation of the strengths of physical associations.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 6","pages":"2984–2995 2984–2995"},"PeriodicalIF":5.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Mechanical Performance of Polyampholyte Hydrogels Influenced by Ionic Bond Strength under Isochoric Conditions
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-17 DOI: 10.1021/acs.macromol.4c02420
Xueyu Li, Haruna Tsuchibora, Ya Nan Ye, Kunpeng Cui, Takayuki Kurokawa
{"title":"Mechanical Performance of Polyampholyte Hydrogels Influenced by Ionic Bond Strength under Isochoric Conditions","authors":"Xueyu Li, Haruna Tsuchibora, Ya Nan Ye, Kunpeng Cui, Takayuki Kurokawa","doi":"10.1021/acs.macromol.4c02420","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02420","url":null,"abstract":"Hydrogels composed of hierarchical structures are notable for their exceptional strength and toughness. Understanding the toughening mechanisms associated with these hierarchical structures is essential for the application and design of tough soft materials. Using polyampholyte hydrogels as a model system, this study introduces a novel approach that combines electrolyte-induced ionic bond dissociation with PEG-induced osmotic stress to systematically investigate how ionic bond strength and phase separation influence mechanical properties under isochoric conditions. We reveal that increasing electrolyte concentrations induces a structural transition from strong bicontinuous phase-separated networks to a homogeneous structure and eventually to weak bicontinuous phase-separated networks, accompanied by characteristic relaxation times that initially decrease and subsequently increase. This transition leads to abnormal nonmonotonic changes in mechanical properties. We further elucidate that the nonmonotonic behavior in fracture stress and work of extension to fracture, along with self-recovery dynamics, is governed by the phase-separated structural transition, while variations in fracture energy are primarily related to the dynamics of ionic bonds. This work provides valuable insights into the design of tough soft materials through the modulation of the strengths of physical associations.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"55 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effect of Homopolymers on Phase Separation Dynamics in Multicompartment Block Copolymer Colloids with Immiscible Liquids
IF 5.1 1区 化学
Macromolecules Pub Date : 2025-03-17 DOI: 10.1021/acs.macromol.5c0006410.1021/acs.macromol.5c00064
Kyuhyung Jo, Juyoung Lee, Jinhyeok Cho and Kang Hee Ku*, 
{"title":"Effect of Homopolymers on Phase Separation Dynamics in Multicompartment Block Copolymer Colloids with Immiscible Liquids","authors":"Kyuhyung Jo,&nbsp;Juyoung Lee,&nbsp;Jinhyeok Cho and Kang Hee Ku*,&nbsp;","doi":"10.1021/acs.macromol.5c0006410.1021/acs.macromol.5c00064","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00064https://doi.org/10.1021/acs.macromol.5c00064","url":null,"abstract":"<p >Multicompartment complex colloids offer novel architectures with anisotropic properties, which arise from the interplay between different components and their spatial organization. Incorporating homopolymers into block copolymer (BCP) particles allows for precise tuning of both shape and phase separation dynamics, particularly in mixed liquid–solid systems. This study presents a comprehensive library of complex colloids composed of symmetric poly(styrene-<i>b</i>-2-vinylpyridine) (PS-<i>b</i>-P2VP) BCPs, their constituent homopolymers, and an immiscible oil. By systematically tuning the volume fraction, molecular weight, and ratio of each homopolymer, we achieve diverse particle morphologies, including liquid-merged elongated bullets, spherical domes, Janus structures, and golf-ball-like multiphase configurations. Strong segregation between oil and polymer, coupled with higher compatibilization within host domains, facilitates the axial stacking of lamellar layers into bullet-shaped particles. A carefully balanced addition of homopolymers enables precise control over the stacked domain sizes, resulting in structural colors that span the entire visible spectrum. In contrast, strong segregation between homopolymers and BCPs driven by increased molecular weight and volume fraction promotes multiphase silicone oils attached to the particle surface. Real-time observations of the particle evolution elucidate the mechanisms underlying these phase separations, paving the way for designing advanced colloidal architectures with tailored optical and structural properties.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 6","pages":"3038–3047 3038–3047"},"PeriodicalIF":5.1,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Degradable Polydithioacetals with Adjustable Mechanical Properties and Insights into Entropy-Driven Ring-Opening Polymerization
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-17 DOI: 10.1021/acs.macromol.4c03237
Abdulwarith O. Kassim, Lasith S. Kariyawasam, Ying Yang
{"title":"Degradable Polydithioacetals with Adjustable Mechanical Properties and Insights into Entropy-Driven Ring-Opening Polymerization","authors":"Abdulwarith O. Kassim, Lasith S. Kariyawasam, Ying Yang","doi":"10.1021/acs.macromol.4c03237","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03237","url":null,"abstract":"The environmental challenges posed by the persistence of synthetic polymers after disposal underscore the need for sustainable alternatives. Polydithioacetals have shown promise as candidates for ring–chain recycling through ring-closing depolymerization, generating a mixture of macrocycles and entropy-driven ring-opening polymerization back to the polymers. A major limitation of previously synthesized polydithioacetals has been their poor thermomechanical properties. In this study, we demonstrated that incorporating varying ratios of alkyl and aryl dithiol monomers into the linear polydithioacetal backbone significantly enhanced the mechanical properties compared with the homopolymers. The modified copolymers exhibited glass transition temperatures ranging from −2 to 90 °C and improved mechanical properties, including an increase in tensile strain up to 387%, making them comparable to some commodity polymers. These polymers are thermally stable up to 297 °C. High molecular weight polymers were achieved by introducing additional benzaldehyde and adjusting the ratios of monomer, catalyst, and initiator, providing insights into the ring-opening polymerization mechanism of macrocyclic dithioacetals.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"13 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effect of Homopolymers on Phase Separation Dynamics in Multicompartment Block Copolymer Colloids with Immiscible Liquids
IF 5.5 1区 化学
Macromolecules Pub Date : 2025-03-17 DOI: 10.1021/acs.macromol.5c00064
Kyuhyung Jo, Juyoung Lee, Jinhyeok Cho, Kang Hee Ku
{"title":"Effect of Homopolymers on Phase Separation Dynamics in Multicompartment Block Copolymer Colloids with Immiscible Liquids","authors":"Kyuhyung Jo, Juyoung Lee, Jinhyeok Cho, Kang Hee Ku","doi":"10.1021/acs.macromol.5c00064","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00064","url":null,"abstract":"Multicompartment complex colloids offer novel architectures with anisotropic properties, which arise from the interplay between different components and their spatial organization. Incorporating homopolymers into block copolymer (BCP) particles allows for precise tuning of both shape and phase separation dynamics, particularly in mixed liquid–solid systems. This study presents a comprehensive library of complex colloids composed of symmetric poly(styrene-<i>b</i>-2-vinylpyridine) (PS-<i>b</i>-P2VP) BCPs, their constituent homopolymers, and an immiscible oil. By systematically tuning the volume fraction, molecular weight, and ratio of each homopolymer, we achieve diverse particle morphologies, including liquid-merged elongated bullets, spherical domes, Janus structures, and golf-ball-like multiphase configurations. Strong segregation between oil and polymer, coupled with higher compatibilization within host domains, facilitates the axial stacking of lamellar layers into bullet-shaped particles. A carefully balanced addition of homopolymers enables precise control over the stacked domain sizes, resulting in structural colors that span the entire visible spectrum. In contrast, strong segregation between homopolymers and BCPs driven by increased molecular weight and volume fraction promotes multiphase silicone oils attached to the particle surface. Real-time observations of the particle evolution elucidate the mechanisms underlying these phase separations, paving the way for designing advanced colloidal architectures with tailored optical and structural properties.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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