Oriented Microstructures of Crystalline–Crystalline Block Copolymers Induced by Epitaxy and Competitive and Confined Crystallization

Rosa, Claudio De; Girolamo, Rocco Di; Auriemma, Finizia; D'Avino, Maria; Talarico, Giovanni; Cioce, Claudia; Scoti, Miriam; Coates, Geoffrey W.; Lotz, Bernard

doi:10.1021/acs.macromol.6b00705

Cited by 31 publications

(56 citation statements)

References 83 publications

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“…Epitaxial crystallization has been used to control the crystallization and morphology of block copolymers in thin films to acquire the oriented crystals and microdomains. De Rosa and coworkers have done many excellent works in this area [137][138][139][140]. For example, they have achieved the highly-orientated crystals and microdomains from the polyethylene (PE)-b-poly(ethylene-alt-propylene)-b-PE triblock copolymers through epitaxial crystallization, in which the long-range orientation of the crystal unit cell induced the alignment of microdomains [137].…”

Section: Crystalline Morphology Of Polymer Segments Confined In Blockmentioning

confidence: 99%

“…Similarly, they have successfully prepared the epitaxially-crystallized samples of PE-b-syndiotactic polypropylene (sPP) copolymers onto the p-terphenyl crystals to control the crystallizations of both blocks. The epitaxial crystallization generated oriented overgrowths of sPP and PE crystals, with an ordered single orientation of sPP lamellae and a double orientation of PE lamellae [139].…”

Section: Crystalline Morphology Of Polymer Segments Confined In Blockmentioning

confidence: 99%

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Crystalline and Spherulitic Morphology of Polymers Crystallized in Confined Systems

Xie

Bao

et al. 2017

Crystals

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Due to the effects of microphase separation and physical dimensions, confinement widely exists in the multi-component polymer systems (e.g., polymer blends, copolymers) and the polymers having nanoscale dimensions, such as thin films and nanofibers. Semicrystalline polymers usually show different crystallization kinetics, crystalline structure and morphology from the bulk when they are confined in the nanoscale environments; this may dramatically influence the physical performances of the resulting materials. Therefore, investigations on the crystalline and spherulitic morphology of semicrystalline polymers in confined systems are essential from both scientific and technological viewpoints; significant progresses have been achieved in this field in recent years. In this article, we will review the recent research progresses on the crystalline and spherulitic morphology of polymers crystallized in the nanoscale confined environments. According to the types of confined systems, crystalline, spherulitic morphology and morphological evolution of semicrystalline polymers in the ultrathin films, miscible polymer blends and block copolymers will be summarized and reviewed.

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Section: Crystalline Morphology Of Polymer Segments Confined In Blockmentioning

confidence: 99%

Section: Crystalline Morphology Of Polymer Segments Confined In Blockmentioning

confidence: 99%

Crystalline and Spherulitic Morphology of Polymers Crystallized in Confined Systems

Xie

Bao

et al. 2017

Crystals

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“…There have been a couple examples of work done in the past five years on CC copolymers with similar T c s as well. De Rosa et al . synthesized highly controlled, moderate molecular weight syndiotactic PP‐ b ‐PE ( s PP‐ b ‐PE) copolymers with w PE = 0.27 and 0.49.…”

Section: Conventional Crystallizable Diblock Copolymersmentioning

confidence: 99%

“…Following cooling to room temperature, the crystal thickness increased due to PEO crystallization on the basal surfaces of the formed PLLA crystal. De Rosa et al . observed the influence of a nucleating agent, p ‐terphenyl, on thin films of s PP‐ b ‐PE.…”

Section: Conventional Crystallizable Diblock Copolymersmentioning

confidence: 99%

Recent progress in block copolymer crystallization

Horn

Steffen

O'Connor

2018

Polymer Crystallization

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Block copolymers (BCPs) are important for technological advances in numerous industries, including but not limited to, electronics, biomedical, optics, environmental, and infrastructure. Because of their ubiquity, it is important to understand their hierarchical phase behavior to tune their macroscopic properties for efficient use. These macroscopic properties are derived from the microscopic self‐assembled structures. One unique form of hierarchical assembly exists when one or more of the polymeric blocks form lamellar crystals. These crystals are integral to understanding and predicting the macroscopic behavior. This review reports on recent advances in crystallization of BCPs, including bulk and solution assembly. Reports highlighting development in fundamental processes regarding crystallization mechanisms and behavior as well as for the design of practical applications are included.

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“…During the past decades, polymer crystallization under nano‐spatial confinement has attracted a great attention, which is important to guide the exploration of nanomaterials and their applications . The crystallization of many semicrystalline polymers, such as polyethylene oxide (PEO), poly(ɛ‐caprolactone) (PCL), poly(vinylidene fluoride) (PVDF), poly( L ‐lactic acid) (PLLA), polyethylene (PE) and etc., in various confinement environments, including anodic alumina oxide (AAO) template, ultrathin polymer layers fabricated by layer‐multiplying coextrusion process, ultrathin films, microphase‐separated block copolymers, coaxial electrospinning fibers, etc ., has been widely studied. The crystallization behavior of semicrystalline polymers under nano‐spatial confinement may be fundamentally different from that in bulk.…”

Section: Introductionmentioning

confidence: 99%

Effect of interface and confinement size on the crystallization behavior of PLLA confined in coaxial electrospun fibers

Zou

Wang

Fan

et al. 2017

J of Applied Polymer Sci

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Poly(l‐lactide)/polyacrylonitrile (PLLA/PAN) core‐sheath composite fibers were fabricated by coaxial electrospinning. The crystallization behavior of PLLA within the coaxial electrospun fibers was studied by differential scanning calorimetry (DSC). The PLLA/PAN coaxial electrospun fiber with a PLLA diameter of ∼32 nm (C1) exhibits a crystallization temperature (Tc) of 22.5 °C higher but a cold‐crystallization temperature (Tcc) of 10 °C lower than bulk PLLA. The crystallinity of C1 fiber is also higher than bulk PLLA. In both isothermal melt‐ and cold‐crystallization, PLLA in C1 fiber crystallizes faster than the bulk PLLA, as revealed by the smaller half crystallization times (t1/2). The enhanced crystallizability of PLLA in the C1 fiber may be attributed to the increased nuclei number and crystal growth rate induced by the PAN surface, i.e., surface‐induction effect. However, PLLA also suffers a nano‐confinement effect exerted by PAN sheath in the coaxial electrospun fiber, which can suppress PLLA crystallization. When the diameter of PLLA is too small (< 32 nm), the nano‐confinement effect may prevail over the surface‐induction effect, leading to a slower crystallization rate and smaller crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45980.

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Oriented Microstructures of Crystalline–Crystalline Block Copolymers Induced by Epitaxy and Competitive and Confined Crystallization

Cited by 31 publications

References 83 publications

Crystalline and Spherulitic Morphology of Polymers Crystallized in Confined Systems

Crystalline and Spherulitic Morphology of Polymers Crystallized in Confined Systems

Recent progress in block copolymer crystallization

Effect of interface and confinement size on the crystallization behavior of PLLA confined in coaxial electrospun fibers

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