Competition between crystal growth and intracrystalline chain diffusion determines the lamellar thickness in semicrystalline polymers

The non-equilibrium thickness of lamellar crystals in semicrystalline polymers varies significantly between different polymer systems and depends on the crystallization temperature Tc. There is currently no consensus on the mechanism of thickness selection. Previous work has highlighted the decisive role of intracrystalline chain diffusion (ICD) in special cases, but a systematic dependence of lamellar thickness on relevant timescales such as that of ICD and stem attachment has not yet been established. Studying the morphology by small-angle X-ray scattering and the two timescales by NMR methods and polarization microscopy respectively, we here present data on poly(oxymethylene), a case with relatively slow ICD. It fills the gap between previously studied cases of absent and fast ICD, enabling us to establish a quantitative dependence of lamellar thickness on the competition between the noted timescales.

Addition of Ca2+ to Titanium Plates by a Hydrothermal Method and the Effects on Human Gingival Fibroblasts

Background: Human gingival fibroblasts (hGFs) have key roles in the formation of soft-tissue attachments around dental implants. We added calcium ions (Ca2+) to the surface of titanium plates (TPs) to make it more conducive to the early adhesion and proliferation of hGFs. Methods: Ca2+ was loaded onto the TP surface by a hydrothermal method. The morphology and composition of TP surfaces were determined by scanning electron microscopy and energy-dispersive spectroscopy. Proliferation of hGF-1 cells was measured by the CCK-8 assay. Immunofluorescence staining was done to detect adherent proteins on the TP surface. TPs were divided randomly into two groups: control and Ca.Results: In the Ca group, irregular lamellar crystals were found on the surface of TPs; The percentage of hGF-1 cells adhering to TPs in the Ca group was significantly higher than that in control group (P < 0.01); The fluorescence of integrin-β1 and F-actin in the Ca group was stronger than that in the control group. Conclusions: Our data suggest that Ca2+ can be added to TP surfaces by a hydrothermal method, and can enhance hGF adhesion. This property may be beneficial if Ca2+ is added to titanium surfaces before dental implantation.

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional “hydrophobic amphiphile”, was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a “block-molecule”. According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL’s propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl3 at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

Lamellar thickness in semicrystalline polymers as a result of the competition between crystal growth and intracrystalline chain dynamics

The non-equilibrium thickness of lamellar crystals in semicrystalline polymers varies largely between different polymer systems and depends on the crystallization temperature Tc. There is currently no consensus on the mechanism of thickness selection. Previous work has highlighted the decisive role of intracrystalline chain dynamics (ICD) in special cases, but a systematic dependence of lamellar thickness on relevant timescales such as that of ICD and stem attachment has not yet been established. Studying the morphology by small-angle X-ray scattering and the two timescales by NMR methods and polarization microscopy, we here present data on poly(oxymethylene), a case with comparably slow ICD. It fills the gap between previously studied cases of absent and fast ICD, enabling us to establish for the first time a quantitative dependence of lamellar thickness on the competition between the noted timescales.

Properties of Polyethylene Terephthalate (PET) after Thermo-Oxidative Aging

The influence of the thermo-oxidative aging semi-crystalline polyethylene terephthalate process on the thermal and mechanical properties was analysed in the article. For this purpose, PET was aged at 140 °C for 21, 35 and 56 days. The research showed that as a result of aging, the amount of the crystalline phase increases by about 8%, which translates into the properties of the aged material. The glass transition and melt temperature of lamellar crystals formed during first and second crystallisation increase with aging. The mechanical properties of the material were analysed in the temperature range of 25 to 75 °C. The tests were showing an increase in Young’s modulus and a decrease in elongation at the break as a result of aging. This phenomenon was particularly visible during tests at 75 °C and during the morphological observation of the fracture surface, where the fracture character of the material changes from ductile to brittle. In the case of the material aged for the longest time, the temperature has a negligible influence on the elongation at break.

Self-Seeding Procedure for Obtaining Stacked Block Copolymer Lamellar Crystals in Solution

We examined the formation of self-seeded platelet-like crystals from polystyrene-block-polyethylene oxide (PS-b-PEO) diblock copolymers in toluene as a function of polymer concentration (c), crystallization temperature (TC), and self-seeding temperature (TSS). We showed that the number (N) of platelet-like crystals and their mean lateral size (L) can be controlled through a self-seeding procedure. As (homogeneous) nucleation was circumvented by the self-seeding procedure, N did not depend on TC. N increased linearly with c and decayed exponentially with TSS but was not affected significantly by the time the sample was kept at TSS. The solubility limit of PS-b-PEO in toluene (c*), which was derived from the linear extrapolation of Nc→ 0 and from the total deposited mass of the platelets per area (MCc→0), depended on TC. We have also demonstrated that at low N, stacks consisting of a (large) number (η) of uniquely oriented lamellae can be achieved. At a given TC, L was controlled by N and η as well as by ∆c=c−c∗. Thus, besides being able to predict size and number of platelet-like crystals, the self-seeding procedure also allowed control of the number of stacked lamellae in these crystals.

Detection and characterization of folded-chain clusters in the structured melt of isotactic polypropylene

Despite ceaseless efforts in past decades, the memory effect of semi-crystalline polymers has not been elucidated completely yet. An important reason why is that residual lamellar crystals in the structured melt are difficult to characterize. Recently, we developed a new small-angle X-ray scattering (SAXS) theory [Li et al. (2019). IUCrJ, 6, 968–983] and Fourier transform method [Li et al. (2020). CrystEngComm, 22, 3042–3058] for lamellar crystals that could derive structural information from SAXS readily. In this study, we tried to employ the new theory and method to characterize residual lamellar crystals in the structured melt. It was found that although scattering peaks cannot be observed in raw scattering profiles, they actually exist. Subtracting free-melt scattering and multiplying by q 4 benefit the observation of these weak scattering peaks. With the new Fourier transform method, it was found that indeed as proposed previously, thicker lamellar crystals exist in the structured melt. To determine the lateral size of residual lamellar crystal especially, a new method was developed under the guidance of the new theory. With the new method, it was found that although the crystallinity is very low (∼1% at 174°C), the lateral sizes in the structured melts are still large, e.g. 45.3 nm at 174°C, much greater than the critical nucleation size. This implies that these residual lamellar crystals can act as athermal nuclei after quenching to a lower temperature, as proposed by Ziabicki & Alfonso [(1994). Colloid Polym. Sci. 272, 1027–1042; (2002). Macromol. Symp. 185, 211–231] more than 20 years ago. The methodologies proposed here could also be applied to other polymer lamellar systems.

Concepts of Nucleation in Polymer Crystallization

Nucleation plays a vital role in polymer crystallization, in which chain connectivity and thus the multiple length and time scales make crystal nucleation of polymer chains an interesting but complex subject. Though the topic has been intensively studied in the past decades, there are still many open questions to answer. The final properties of semicrystalline polymer materials are affected by all of the following: the starting melt, paths of nucleation, organization of lamellar crystals and evolution of the final crystalline structures. In this viewpoint, we attempt to discuss some of the remaining open questions and corresponding concepts: non-equilibrated polymers, self-induced nucleation, microscopic kinetics of different processes, metastability of polymer lamellar crystals, hierarchical order and cooperativity involved in nucleation, etc. Addressing these open questions through a combination of novel concepts, new theories and advanced approaches provides a deeper understanding of the multifaceted process of crystal nucleation of polymers.