The Semicrystalline Morphology of Polybutylene Succinate Supports a General Scheme Based on Intracrystalline Dynamics

Yu, Qiang; Anuar, Afiq; Petzold, Albrecht; Balko, Jens; Saalwächter, Kay; Thurn‐Albrecht, Thomas

doi:10.1002/macp.202200459

Cited by 6 publications

(4 citation statements)

References 49 publications

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“…Fitted crystal parameters based on IDF analysis for the PCL200/PCL2 mixtures are illustrated in Figure in detail. From that, we could obtain not only the average value of the thicknesses of crystalline and amorphous regions but also their distributions represented as the error bars. ,− Clearly, we observed very similar morphologies compared to crystallization at 35 °C. With the decrease of long polymer fraction ϕ p , the average thickness of the amorphous layer decreases while the lamellar thickness stays constant.…”

Section: Resultsmentioning

confidence: 99%

Origin of Lamellar Stack Structures in Dilute Semicrystalline Polymers: Role of Entanglements and Tie-Molecules

Wang,

Schaller,

Petzold

et al. 2024

Macromolecules

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To achieve better performance and processability of semicrystalline polymers [especially with ultrahigh molecular weight (MW)], miscible oligomers or solvents are usually involved to disentangle polymer melt and reduce its viscosity. Entanglements, crystallization temperature, and possible phase segregation behavior make it complicated to predict the morphologies of polymer crystals containing low MW fractions. In our recent work [Proc. Natl. Acad. Sci. U. S. A. 2023, 120 (27), e2217363120], by blending high-MW polycaprolactone with its unentangled oligomers, we elucidated that at a relatively low crystallization temperature (T c ), the thickness of amorphous regions is controlled by entanglement strand density, while the lamellar thickness remains nearly identical. The present work further investigates the morphology of semicrystalline polymers containing a certain amount of molten short oligomer chains at higher T c (53 °C) as determined by solid-state nuclear magnetic resonance freeinduction decay and double quantum measurements. The amorphous layer thickness detected from small-angle X-ray scattering experiments is found following a similar trend as that crystallized at 35 °C even with a strong molecular segregation effect. The inner part fraction of an amorphous region obeys a similar power law for polymer concentration regardless of the value of T c , which is the same as the plateau modulus from the melt rheological measurements. On the other hand, the thickness of the boundary part of the amorphous region at the vicinity of crystals increases with the increase of T c . Our results strongly suggest that long polymer chains tend to form crystalline lamellar stacks, which are connected by intercrystalline links (e.g., tie chains and entanglements), while oligomer chains are expelled into larger spaces in between.

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Section: Resultsmentioning

confidence: 99%

Origin of Lamellar Stack Structures in Dilute Semicrystalline Polymers: Role of Entanglements and Tie-Molecules

Wang,

Schaller,

Petzold

et al. 2024

Macromolecules

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“…On the contrary, other types of semi-crystalline polymers lack intracrystalline chain mobility and are called "crystal-fixed" polymers such as polyamides, poly (ethylene terephthalate), and isotactic polystyrene. Thurn-Albrecht and Saalwächter [72][73][74][75][76][77][78][79] proposed that crystal-mobile polymers usually exhibit relatively high crystallinity (around 80%) due to prominent lamellar thickening behaviors during the isothermal crystallization process, whereas the crystallinity of most crystal-fixed polymers is below 50%.…”

Section: Achieving Drawability: the Importance Of Intracrystalline Ch...mentioning

confidence: 99%

Polymer Physics behind the Gel‐Spinning of UHMWPE Fibers

Wang,

Sangroniz,

et al. 2024

Macromol. Rapid Commun.

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Gel‐spinning of ultra‐high molecular weight polyethylene (UHMWPE) fibers has attracted great interest in academia and industry since its birth and commercialization in the 1980s, due to unique properties such as high modulus, low density, and excellent chemical resistance. However, the high viscosity and long relaxation time greatly complicate processing. In industry, solvents like decalin, paraffin oil, etc., usually disentangle the physical networks and promote final drawability. From extruding the polymer solution to post‐solid‐stretching, many polymer physics problems that accompany high‐modulus fiber gel‐spinning should be understood and addressed. In this review, by detailed discussions about the effect of entanglements and intracrystalline chain dynamics on the mechanical properties of UHMWPE, we provide theoretical descriptions of the structure formation of disentangled UHMWPE crystals and the origin of high modulus and strength of final fibers. Several physical intrinsic key factors are also discussed, revealing why UHMWPE is an ideal material for producing high‐performance fibers.This article is protected by copyright. All rights reserved

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“…The same effect on the lamellar thickness can also be observed in other semicrystalline crystal-fixed polymers such as sPP, 52 PCL, 34 and polybutylene succinate. 70 Despite a small range of lamellar thicknesses for iPB-1/C2 with form I′ crystals, the apparent linearity of the data points in Figure 7 could be used for the extrapolation of the T m dependence to the imaginary infinite lamellar thickness and obtained T m ∞ is still relevant for determining differences in the stability of form I and I′ crystals.…”

Section: Crystallization and Melting Behavior Of Ipb-1 And Ipb-1/c2 I...mentioning

confidence: 99%

Equilibrium Melting Temperature of the Hexagonal Crystals of Polybutene-1 and Its Copolymer

Qin

Litvinov

et al. 2023

Macromolecules

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TheLamellar structures of form I in polymorphic isotactic polybutene-1 (iPB-1) and forms I and I′ in butene-1/ ethylene random copolymer (iPB-1/C2) were investigated by studying their melting behavior using the combination of smallangle X-ray scattering (SAXS) and fast scanning chip calorimetry (FSC) techniques. Hexagonal form I was transformed from tetragonal form II obtained by crystallization of a homogeneous melt of iPB-1 and iPB-1/C2. Hexagonal form I′ was crystallized directly from a heterogeneous melt of iPB-1/C2. Despite the same hexagonal crystallographic structure, forms I and I′ have obviously distinct melting behaviors due to different ways of crystal formation. Well-defined linear dependences of the melting temperature against the reciprocal lamellar thickness were observed for forms I and I′ with frozen chain mobility in crystals. The slopes of the thus obtained melting lines for forms I and I′ are different. Their extrapolations to imaginary infinitely large lamellar thickness provide the equilibrium melting temperature T m ∞ for forms I and I′, which is associated with the stability of the lamellar crystals. In spite of crystal defects in form I′, a higher T m ∞ is observed for this form in iPB-1/C2 than T m ∞ for form I in both iPB-1 and iPB-1/C2. The difference in T m ∞ indicates a less perfect structure of form I crystal lamellae that is caused by the fragmentation of form II crystal lamellae during the polymorphic phase transition from form II to I. The lamellae broke into crystal blocks along the lamellar direction. The smaller lateral sizes of the fragmented lamellae clearly induce a decrease in the stability of crystals, as expressed in a lower T m ∞ for form I.

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The Semicrystalline Morphology of Polybutylene Succinate Supports a General Scheme Based on Intracrystalline Dynamics

Cited by 6 publications

References 49 publications

Origin of Lamellar Stack Structures in Dilute Semicrystalline Polymers: Role of Entanglements and Tie-Molecules

Origin of Lamellar Stack Structures in Dilute Semicrystalline Polymers: Role of Entanglements and Tie-Molecules

Polymer Physics behind the Gel‐Spinning of UHMWPE Fibers

Equilibrium Melting Temperature of the Hexagonal Crystals of Polybutene-1 and Its Copolymer

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