Theory of spinodal decomposition assisted crystallization in binary mixtures

Mitra, Mithun K.; Muthukumar, Murugappan

doi:10.1063/1.3425774

Cited by 54 publications

(56 citation statements)

References 24 publications

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“…The occurrence of this nucleation might be due to a low surface tension existing between PLLA lateral crystal surfaces and PBS melt. Nucleation at the interfaces between immiscible polymer components, during or after phase separation, has been predicted theoretically [43] and observed experimentally also in amorphous/semicrystalline polymer pairs [44]. The addition of relatively small quantities of graphene oxide has a large impact on the crystallization behavior of PLLA/PBS (70/30 wt%) blend.…”

Section: Crystallization Of Plla/pbs/go Blend Nanocompositesmentioning

confidence: 89%

Correlating the morphology of poly(L-lactide)/poly(butylene succinate)/graphene oxide blends nanocomposites with their crystallization behavior

Fenni¹,

Monticelli²,

Conzatti³

et al. 2018

Express Polym. Lett.

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Abstract. Bio-based blend nanocomposites of poly(L-lactic acid) (PLLA) and poly(butylene succinate) (PBS), with different concentrations (from 0.1 to 0.5 wt%) of graphene oxide (GO), are prepared via solution dispersion of PBS/GO followed by melt blending with PLLA in a 70/30 PLLA/PBS weight ratio. Scanning and Transmission Electron Microscopy reveals micron-sized droplets of PBS in the PLLA matrix with the GO nanofiller preferentially found in the PBS phase. The GO acts as nucleating agent for both semicrystalline polymers. The nanofiller nucleating effect is compared to the one of own selfnuclei for each polymer, to define a convenient nucleating efficiency (NE) scale. A value of around 80% is determined for GO towards PBS, among the highest NEs ever reported for this polymer. On the other hand, the efficiency in nucleating PLLA is equal to a modest 15%, also due to the uneven distribution of the nanofiller in the two polymers. A close relationship between the nanocomposite morphology and crystallization behavior of the two different polymers is thus established.

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Section: Crystallization Of Plla/pbs/go Blend Nanocompositesmentioning

confidence: 89%

Correlating the morphology of poly(L-lactide)/poly(butylene succinate)/graphene oxide blends nanocomposites with their crystallization behavior

Fenni¹,

Monticelli²,

Conzatti³

et al. 2018

Express Polym. Lett.

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“…Fitting the derived expression for the nucleation rate for specific systems would lead to an understanding of the newly defined transition temperature and the effective dissolution temperature of the heterogeneous melt state. It would be of further interest to extend the present theory to account for additional concomitant mechanisms such as microphase separation, 17 liquid-liquid phase separation, 18,20,33 and entanglement effects.…”

Section: Discussionmentioning

confidence: 99%

Communication: Theory of melt-memory in polymer crystallization

Muthukumar

2016

The Journal of Chemical Physics

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Details of crystallization processes of a polymer at the crystallization temperature T c from its melt kept initially at the melt temperature T m depend profoundly on the nature of the initial melt state and often are accompanied by memory effects. This phenomenon is in contrast to small molecular systems where the supercooling (T 0 m − T c ), with T 0 m being the equilibrium melting temperature, and not (T m − T c ), determines the nature of crystallization. In addressing this five-decade old puzzle of melt-memory in polymer crystallization, we present a theory to describe melt-memory effects, by invoking an intermediate inhomogeneous melt state in the pathway between the melt and crystalline states. Using newly introduced dissolution temperature T

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“…17−21 Another one attributes the static to the heterogeneous nucleation at the interface. 22 In our opinion, both of these factors contribute to the nucleation in dynamically symmetric blends (see Supporting Information, Figure 3). However, for this iPP/PMMA blend, the phaseseparation dynamics is severely suppressed at lower temperatures so that the concentration fluctuation and the interdiffusion at the interface are suppressed and can be neglected in this case, so we can observe the interface-assisted crystallization by the static heterogeneous nucleation at the interface only.…”

mentioning

confidence: 96%

Viscoelastic Phase Separation and Interface Assisted Crystallization in a Highly Immiscible iPP/PMMA Blend

et al. 2012

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Polymer blends with dynamic asymmetry have attracted much interest recently. In this study, we report a more typical case where the dynamically asymmetric system is highly immiscible. We find that there is a transient network growth and phase inversion for the slow minor component. The network structure shows a hierarchical growth behavior, which is the result of competition between a slow relaxationcontrolled concentration growth on local scale and a fast hydrodynamic growth on large scale. When phase separation couples with a subsequent crystallization, the interfacial boundary may assist lateral crystallization and irregular spherulites would grow epitaxially around the amorphous componentrich domains. The interface may play the role of substrates for heterogeneous nucleation. These phenomena may help us with morphological control in material processing.T o meet mutifunctional demand (optics, conductivity, mechanics, and so on) in industrial applications, morphological control is important in polymer mixtures. 1−3 As most polymer pairs are thermodynamically immiscible, the conventional study finds that the minority phase should always disperse in the matrix of the majority phase. 4−7 This leads to less morphological variations and thus less adaptable functional properties. Recently, it has been reported that more variations of morphology can be obtained under the effect of dynamic asymmetry, which comes from the unequal mobility between component molecules. 8−11 A viscoelastic model has been constructed and verified when a mixture is quenched from the miscible state to an unstable state. 11 However, an even more typical case has not been tested: how phase separation proceeds for a highly immiscible polymer blend under the effect of dynamic asymmetry.In addition to phase separation, crystallization is another intriguing phase transition that is usually encountered in polymer blends. 1,12−16 The single process of crystallization has been intensively studied in the miscible condition. But when crystallization couples with phase separation, the case becomes much more complicated. 17−19 One common conclusion up to now is that crystal nucleation becomes less active as phase separation proceeds. 19−21 It has been long predicted and expected that this phenomenon is closely related to the interfacial boundary between different phases. 19,22,23 Although there has been much effort on this topic, some direct macroscopic evidence is still needed. We checked the previous studies and found that conventional studies on the coupled crystallization and phase separation were usually carried out in systems with dynamic symmetry. 19,24,25 There are shortcomings in morphology control: first, the phase transition dynamics cannot be easily controlled; second, there usually lacks clear interfacial boundaries; and also, phase-separated domains can be easily destroyed by crystal growth. But we believe such shortcomings can be delicately avoided in a highly immiscible blend under large dynamic asymmetry. 17,18 To investigate the above tw...

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Theory of spinodal decomposition assisted crystallization in binary mixtures

Cited by 54 publications

References 24 publications

Correlating the morphology of poly(L-lactide)/poly(butylene succinate)/graphene oxide blends nanocomposites with their crystallization behavior

Correlating the morphology of poly(L-lactide)/poly(butylene succinate)/graphene oxide blends nanocomposites with their crystallization behavior

Communication: Theory of melt-memory in polymer crystallization

Viscoelastic Phase Separation and Interface Assisted Crystallization in a Highly Immiscible iPP/PMMA Blend

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