Confinement Effects in Polymer Crystal Nucleation from the Bulk to Few-Chain Systems

Massa, Michael V.; Carvalho, Jessica L.; Dalnoki-Veress, Kari

doi:10.1103/physrevlett.97.247802

Cited by 73 publications

(79 citation statements)

References 28 publications

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“…2.10c). These low Avrami index values around 1.0 suggested that the low-temperature crystallization should be homogeneously nucleated, similar to the results observed for PEO homogeneous nucleation [29,47]. From this crystallization kinetics study, we concluded that the high-temperature crystallization was heterogeneously nucleated in large PVDF droplets, while the low-temperature crystallization was homogeneously nucleated in PVDF nanodroplets.…”

Section: Fractionated Crystallization In Pvdf Nanodropletssupporting

confidence: 83%

Nanodroplet Formations in Electrospun Fibers of Immiscible Polymer Blends and Their Effects on Fractionated Crystallization

Zhong¹,

Zhu

Fong

2013

Lecture Notes in Nanoscale Science and Technology

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A new and facile method to obtain polymeric nanodroplets was developed by thermally annealing of electrospun fibers of immiscible polymer blends. Through thermally annealing at a temperature slightly above the glass transition temperature of the matrix, the ribbon-or fiber-like dispersed phase broke up into nanodroplet with the diameter mainly in the range of 50-300 nm due to the Plateau-Rayleigh instability. Our study shows that these nanodroplets can be used to study the fractionated crystallization and homogeneous nucleation of almost any semicrystalline polymers, such as poly(ethylene oxide), poly(vinylidene fluoride), polyethylene, and polypropylene. We observed that the homogeneously nucleated crystallization of PVDF took place at 55-60 • C for the first time. Additionally, this method can be utilized to investigate the effect of nanoconfinement on crystalline morphologies of semicrystalline polymers.

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Section: Fractionated Crystallization In Pvdf Nanodropletssupporting

confidence: 83%

Nanodroplet Formations in Electrospun Fibers of Immiscible Polymer Blends and Their Effects on Fractionated Crystallization

Zhong¹,

Zhu

Fong

2013

Lecture Notes in Nanoscale Science and Technology

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“…Later AFM techniques were used for the break-out crystallization as well as the confined crystallization in crystalline-amorphous diblocks. [19][20][21][22] AFM results provide direct information on the crystallization at sampled points, while SAXS and DSC techniques supply average information over the whole systems. In addition, it is necessary for the understanding of crystallization to analyze the crystallization process by using some method developed for homopolymer crystallization.…”

mentioning

confidence: 99%

Dynamic Mechanical Study of Block Copolymer Crystallization Confined within Spherical Nanodomains

Nojima

Inokawa

Kawamura

et al. 2008

Polym J

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We have measured the thermal and dynamic mechanical properties of a crystalline-amorphous diblock copolymer, poly("-caprolactone)-block-polybutadiene (PCL-b-PB), in which the crystallization of PCL blocks was completely confined within spherical domains. DSC results showed that the crystallization behavior of PCL blocks was substantially different from that of crystalline homopolymers, and similar to that usually observed in other spherically confined crystalline blocks. The result of dynamic mechanical measurements clearly showed that the crystallization within each domain occurred independently to immediately yield crystallized rigid domains, indicating that crystal nucleation drives the total crystallization in this system. It is demonstrated that the dynamic mechanical measurement is an alternative method to pursue the spherically confined crystallization.KEY WORDS: Crystalline-amorphous Diblock Copolymer / Spherical Nanodomain / Confined Crystallization / Dynamic Mechanical Measurements /Crystalline-amorphous diblock copolymers show a unique crystallization behavior when they are quenched from a microphase-separated melt into low temperatures. It is well known that two kinds of crystallized morphology are formed in the system depending on the segregation strength of existing microdomain structures, mobility (or glass transition) of amorphous blocks, or crystallization rate (or degree of supercooling).1,2 When the microdomain structure is not stable against the crystallization, it is replaced by a lamellar morphology, an alternating structure consisting of lamellar crystals and amorphous layers, in which the amorphous blocks are sandwiched between lamellar crystals.3,4 When the microdomain structure is enough stable against the crystallization, on the other hand, it is completely preserved through the crystallization process to yield a crystallized microdomain structure. 5,6When crystalline blocks form (strongly segregated) spherical domains surrounded by amorphous blocks in high molecular weight diblocks, they crystallize within it. The crystallization behavior and resulting morphology for this case have extensively been studied so far 5-17 mainly by small-angle X-ray scattering (SAXS) and/or differential scanning calorimetry (DSC) techniques. The crystallization behavior was found to be extremely different from that of crystalline homopolymers; the crystallinity development did not show a sigmoid change usually observed in homopolymer crystallization with increasing crystallization time t c . Alternatively it was reasonably approximated by a first-order kinetics, that is, the crystallization rate was proportional to the volume fraction of uncrystallized blocks existing in the system at t c . These experimental facts lead to a conclusion that the crystallization occurs independently within each domain. Therefore, the nucleation in individual domain drives the total crystallization process, because the crystal growth is considered to be extremely fast.Reiter et al. directly confirmed this conclusion by using...

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“…While previous measurements of nano‐confined crystallization in diblocks has typically been carried out with DSC,14, 15, 17, 19, 21 here we use ellipsometry to probe crystallization 10, 36–38. Ellipsometry exploits the fact that linearly polarized light emerges elliptically polarized when reflected from a film covered substrate to obtain the thickness and index of refraction of a film 36.…”

Section: Methodsmentioning

confidence: 99%

“…For this reason, there is separation of timescales and the overall crystallization rate is a direct probe of the nucleation rate. Measurements of this type have typically been carried out using small crystallizable droplets that were phase‐separated in an amorphous matrix,1–7 droplets dewetted on some substrate,8–12 or using phase separated block copolymers which provide an ideal system for creating isolated nanoscale domains 13–21…”

Section: Introductionmentioning

confidence: 99%

Additional case of minocycline‐induced cutaneous polyarteritis nodosa: Comment on the article by Culver et al

Abad¹,

Kambouchner²,

Nejjari³

et al. 2006

Arthritis & Rheumatism

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Confinement Effects in Polymer Crystal Nucleation from the Bulk to Few-Chain Systems

Cited by 73 publications

References 28 publications

Nanodroplet Formations in Electrospun Fibers of Immiscible Polymer Blends and Their Effects on Fractionated Crystallization

Nanodroplet Formations in Electrospun Fibers of Immiscible Polymer Blends and Their Effects on Fractionated Crystallization

Dynamic Mechanical Study of Block Copolymer Crystallization Confined within Spherical Nanodomains

Additional case of minocycline‐induced cutaneous polyarteritis nodosa: Comment on the article by Culver et al

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