Periodic crystal assembly of Poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid): From surface to interior microstructure

Wu, Chun; Woo, Eamor M.

doi:10.1016/j.polymer.2021.123866

Cited by 11 publications

(9 citation statements)

References 39 publications

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“…This transition between crystal-plate orientations in the dendritic spherulite is an important discovery. According to the results in the literature, ,, flat-on to edge-on crystal transition is detected only under the ridges of ring-banded spherulites. Furthermore, the transition of the composite dendritic spherulites from the nucleus to rim, and the microbeam SAXS data for spots of nos 1 to 9 require detailed discussion.…”

Section: Resultsmentioning

confidence: 87%

“…Common morphologies of crystal aggregates include ringless spherulites, ring-banded spherulites, dendritic spherulites, and many other special morphologies such as feather-like spherulites, seaweed-like spherulites, ring-banded with an eye-like region, dendritic sector-face spherulites, and flower-petal like ring bands,nd so forth. Recently, Wu, et al diluted poly(hydroxybutyrate- co -hydroxyvalerate) (with valerate unit = 8–12%) with low-melting poly(trimethylene adipate), and reported that ring-banded spherulites were observed under a polarized light microscope, with alternate blue/orange-color rings on spherulites. These periodic optical patterns are widely reported in many other semicrystalline polymers.…”

Section: Introductionmentioning

confidence: 99%

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Microscopic and Small-/Wide-Angle Microbeam X-ray Analyses on Dendritic Crystals in Poly(butylene succinate)

Nagarajan

Chuang

et al. 2023

Macromolecules

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A unique composite dendritic spherulite is detected in a specific crystallization temperature range (T c = 60–78 °C), whose assembly is probed using microscopy techniques and powerful synchrotron X-ray microbeam analyses. Composite dendritic spherulites composed of feather-like and fern-like branches in poly(butylene succinate) (PBSu) crystallized with poly(ethylene oxide) diluent are analyzed on top surface morphologies correlating with interior-dissected assembly, concurrently through polarized-light optical microscopy, scanning electron microscopy, and synchrotron-radiation X-ray microbeam analysis. The feather-like branch is composed of fully edge-on crystal plates, while the fern-like branch is composed of flat-on crystal plates. These branches originate from a common nucleus with different growth rates. For the first time, the dendritic PBSu spherulite serves as a convenient model for understanding the mechanisms how edge-on and flat-on crystal orientations can alternate not only in a serial mode to form ring bands but also in a parallel mode to form straight dendrites. Morphology evidence and detailed microbeam techniques collectively prove that these discontinuous lamellar plates discretely and gradually tilt and bend to transform from a vertical to a horizontal crystal plate with a corresponding alteration in birefringence.

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Section: Resultsmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Microscopic and Small-/Wide-Angle Microbeam X-ray Analyses on Dendritic Crystals in Poly(butylene succinate)

Nagarajan

Chuang

et al. 2023

Macromolecules

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“…From several recent literature results on other polymers, such as poly(butylene adipate) (PBA), poly(ε-caprolactone) (PCL), and poly([3-hydroxybutyrate] (PHB), poly(nonamethylene terephthalate) (PNT), high-density polyethylene (PE), etc. [ 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 ], the periodic morphology is certainly not limited to top surfaces. Still, it also distributes in 3D bulks throughout the entire sample volume.…”

Section: Resultsmentioning

confidence: 99%

Unique Periodic Rings Composed of Fractal-Growth Dendritic Branching in Poly(p-dioxanone)

Huang

Nagarajan

2022

Polymers

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Amorphous poly(p-vinyl phenol) (PVPh) was added into semicrystalline poly(p-dioxanone) (PPDO) to induce a uniquely novel dendritic/ringed morphology. Polarized-light optical, atomic-force and scanning electron microscopy (POM, AFM, and SEM) techniques were used to observe the crystal arrangement of a uniquely peculiar cactus-like dendritic PPDO spherulite, with periodic ring bands not continuingly circular such as those conventional types reported in the literature, but discrete and detached to self-assemble on each of the branches of the lobs. Correlations and responsible mechanisms for the formation of this peculiar banded-dendritic structure were analyzed. The periodic bands on the top surface and interior of each of the cactus-like lobs were discussed. The banded pattern was composed of feather-like lamellae in random fractals alternately varying their orientations from the radial direction to the tangential one. The tail ends of lamellae at the growth front spawned nucleation cites for new branches; in cycles, the feather-like lamellae self-divided into multiple branches following the Fibonacci sequence to fill the ever-expanding space with the increase of the radius. The branching fractals in the sequence and the periodic ring-banded assembly on each of the segregated lobs of cactus-like dendrites were the key characteristics leading to the formation of this unique dendritic/ringed PPDO spherulite.

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“…A few notable examples can be cited here: poly(1,4-butylene adipate) (PBA), poly(ε-caprolactone) (PCL), and poly([β-hydroxybutyrate] (PHB), poly(nonamethylene terephthalate) (PNT), high-density polyethylene (PE), etc. [ 36 , 37 , 38 , 39 , 40 , 41 , 42 ]. This is a continuous extension of one of our previous works on PPDO [ 35 ].…”

Section: Introductionmentioning

confidence: 99%

Crystal-by-Crystal Assembly in Two Types of Periodically Banded Aggregates of Poly(p-Dioxanone)

Huang

Huang²,

Lee³

et al. 2023

Polymers

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The exterior and interior lamellar assemblies of poly(p-dioxanone) (PPDO) crystallized at 76 °C yield the most regular ones to interpret the 3D assembly mechanisms and potential for structural coloration iridescence, which are investigated using atomic-force microscopy (AFM), and scanning electron microscopy (SEM). PPDO displays two types of ring-banded spherulites within a range of Tc with dual-type birefringent spherulites (positive and negative-type) only within a narrow range of Tcs = 70–78 °C. At Tc > 80 °C, the inter-band spacing decreases from a maximum and the crystal assembly becomes irregularly corrupted and loses the capacity for light interference. Periodic grating assemblies are probed by in-depth 3D dissection into periodically banded crystal aggregates of poly(p-dioxanone) (PPDO) to disclose such layered gratings possessing iridescence features similar to nature’s structural coloration. This work amply demonstrates that grating assembly by orderly stacked crystal layers is feasible not only for accounting for the periodic birefringent ring bands with polarized light but also the distinct iridescence by interfering with white light.

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Periodic crystal assembly of Poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid): From surface to interior microstructure

Cited by 11 publications

References 39 publications

Microscopic and Small-/Wide-Angle Microbeam X-ray Analyses on Dendritic Crystals in Poly(butylene succinate)

Microscopic and Small-/Wide-Angle Microbeam X-ray Analyses on Dendritic Crystals in Poly(butylene succinate)

Unique Periodic Rings Composed of Fractal-Growth Dendritic Branching in Poly(p-dioxanone)

Crystal-by-Crystal Assembly in Two Types of Periodically Banded Aggregates of Poly(p-Dioxanone)

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