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.

Effects of Variety and Growing Location on Physicochemical Properties of Starch from Sweet Potato Root Tuber

Three sweet potato varieties with purple-, yellow-, and white-fleshed root tubers were planted in four growing locations. Starches were isolated from their root tubers, their physicochemical properties (size, iodine absorption, amylose content, crystalline structure, ordered degree, lamellar thickness, swelling power, water solubility, and pasting, thermal and digestion properties) were determined to investigate the effects of variety and growing location on starch properties in sweet potato. The results showed that granule size (D[4,3]) ranged from 12.1 to 18.2 μm, the iodine absorption parameters varied from 0.260 to 0.361 for OD620, from 0.243 to 0.326 for OD680 and from 1.128 to 1.252 for OD620/550, and amylose content varied from 16.4% to 21.2% among starches from three varieties and four growing locations. Starches exhibited C-type X-ray diffraction patterns, and had ordered degrees from 0.634 to 0.726 and lamellar thicknesses from 9.72 to 10.21 nm. Starches had significantly different swelling powers, water solubilities, pasting viscosities, and thermal properties. Native starches had rapidly digestible starch (RDS) from 2.2% to 10.9% and resistant starch (RS) from 58.2% to 89.1%, and gelatinized starches had RDS from 70.5% to 81.4% and RS from 10.8% to 23.3%. Two-way ANOVA analysis showed that starch physicochemical properties were affected significantly by variety, growing location, and their interaction in sweet potato.

Differential scanning calorimetry/small-angle X-ray scattering analysis of ultraviolet sensible polypropylene filaments

In this work, ultraviolet (UV) sensible metallocene isotactic polypropylene (miPP) filaments were produced with different drawing ratios and various concentrations of photochromic pigment. The effects of pigment concentration and drawing ratio on the chromatic properties and the structural modification for the miPP filaments were studied extensively by differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering (SAXS/WAXS) measurements. The change in melting temperature and the polymeric structures, such as lamellar thickness, long period and degree of crystallinity of miPP with the addition of a UV sensible pigment into miPP and the drawing process, were evaluated. The results show that the pigment concentration and the drawing ratio influence the inner structure of miPP filaments. Finally, our investigation shows that SAXS and also WAXS are appropriate to determine the lamellar thickness and the degree of crystallinity established by the DSC approach. This work attempts to correlate the results of lamellar thickness, the degree of crystallinity and the higher-order structure of the polymer acquired by DSC as well as X-ray diffraction (XRD) techniques in order to develop an appropriate approach to find the influence of pigment concentration and drawing ratio on miPP filaments.

Composite Films of HDPE with SiO2 and ZrO2 Nanoparticles: The Structure and Interfacial Effects

Herein, we investigated the influence of two types of nanoparticle fillers, i.e., amorphous SiO2 and crystalline ZrO2, on the structural properties of their nanocomposites with high-density polyethylene (HDPE). The composite films were prepared by melt-blending with a filler content that varied from 1% to 20% v/v. The composites were characterized by small- and wide-angle x-ray scattering (SAXS and WAXS), small-angle neutron scattering (SANS), Raman spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). For both fillers, the nanoaggregates were evenly distributed in the polymer matrix and their initial state in the powders determined their surface roughness and fractal character. In the case of the nano-ZrO2 filler, the lamellar thickness and crystallinity degree remain unchanged over a broad range of filler concentrations. SANS and SEM investigation showed poor interfacial adhesion and the presence of voids in the interfacial region. Temperature-programmed SANS investigations showed that at elevated temperatures, these voids become filled due to the flipping motions of polymer chains. The effect was accompanied by a partial aggregation of the filler. For nano-SiO2 filler, the lamellar thickness and the degree of crystallinity increased with increasing the filler loading. SAXS measurements show that the ordering of the lamellae is disrupted even at a filler content of only a few percent. SEM images confirmed good interfacial adhesion and integrity of the SiO2/HDPE composite. This markedly different impact of both fillers on the composite structure is discussed in terms of nanoparticle surface properties and their affinity to the HDPE matrix.

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.

Crystallization of Polymers under the Influence of an External Force Field

We simulated the crystallization and melting behavior of entangled polymer melts using molecular dynamics where each chain is subject to a force dipole acting on its ends. This mimics the deformation of chains in a flow field but represents a well-defined equilibrium system in the melt state. Under weak extension within the linear response of the chains, the mechanical work done on the system is about two orders of magnitude smaller as compared with the heat of fusion. As a consequence, thermodynamic and simple arguments following the secondary nucleation model predict only small changes of the crystalline phase. By contrast, an increase of the stem length up to a factor of two is observed in our simulations. On the other hand, the lamellar thickening induced by the external force is proportional to the increase of the entanglement length in the melt prior to crystallization as measured by the primitive path method. While the mechanical work done on the system is only a small perturbation for thermodynamics of polymer crystallization, the change of the primitive path is large. This suggests that a strong increase in the lamellar thickness induced, by external deformation, a topological rather than a thermodynamic origin.

Protein Charge Neutralization is the Proximate Driver Dynamically Tuning a Nanoscale Bragg Reflector

Reflectin is a cationic, block copolymeric protein that mediates the dynamic fine-tuning of color and brightness of light reflected from nanostructured Bragg reflectors in iridocyte skin cells of squids. In vivo, neuronally activated phosphorylation of reflectin triggers its assembly, driving osmotic dehydration of the membrane-bounded Bragg lamellae containing the protein to simultaneously shrink the lamellar thickness and spacing while increasing its refractive index contrast, thus tuning the wavelength and increasing the brightness of reflectance. In vitro, we show that reduction in repulsive net charge of the purified, recombinant reflectin – either (for the first time) by generalized anionic screening with salt, or by pH titration - drives a finely tuned, precisely calibrated increase in size of the resulting multimeric assemblies. The calculated effects of phosphorylation in vivo are consistent with these effects observed in vitro. X-ray scattering analyses confirm the sphericity, size and low polydispersity of the assemblies. Precise proportionality between assembly size and charge-neutralization is enabled by the demonstrated rapid dynamic arrest of multimer growth. The resulting stability of reflectin assemblies with time ensures reciprocally precise control of the particle number concentration, thereby encoding a precise calibration between the extent of neuronal signaling, osmotic pressure, and the resulting optical changes. The results presented here strongly suggest that it is charge neutralization, rather than any change in aromatic content, that is the proximate driver of assembly, fine-tuning a colligative property-based nanostructured biological machine. A physical mechanism is proposed.

The Role of Panx3 in Age-Associated and Injury-Induced Intervertebral Disc Degeneration

Pannexin 3 (Panx3) is a mechanosensitive, channel-forming glycoprotein implicated in the progression of post-traumatic osteoarthritis. Despite evidence for Panx3 expression in the intervertebral disc (IVD), its function in this cartilaginous joint structure remained unknown. Using Panx3 knockout mice, this study investigated the role of Panx3 in age-associated IVD degeneration and degeneration induced by annulus fibrosus (AF) needle puncture. Loss of Panx3 did not significantly impact the progression of age-associated histopathological IVD degeneration; however, loss of Panx3 was associated with decreased gene expression of Acan, Col1a1, Mmp13 and Runx2 and altered localization of COLX in the IVD at 19 months-of-age. Following IVD injury in the caudal spine, histological analysis of wild-type mice revealed clusters of hypertrophic cells in the AF associated with increased pericellular proteoglycan accumulation, disruptions in lamellar organization and increased lamellar thickness. In Panx3 knockout mice, hypertrophic AF cells were rarely detected and AF structure was largely preserved post-injury. Interestingly, uninjured IVDs adjacent to the site of injury more frequently showed evidence of early nucleus pulposus degeneration in Panx3 knockout mice but remained healthy in wild-type mice. These findings suggest a role for Panx3 in mediating the adaptive cellular responses to altered mechanical stress in the IVD, which may buffer aberrant loads transferred to adjacent motion segments.

Crystallization and Thermal Behaviors of Poly(ethylene terephthalate)/Bisphenols Complexes through Melt Post-Polycondensation

Three kinds of modified poly(ethylene terephthalate) (PET) were prepared by solution blending combined with melt post-polycondensation, using 4,4′-thiodiphenol (TDP), 4,4′-oxydiphenol (ODP) and hydroquinone (HQ) as the bisphenols, respectively. The effects of TDP, ODP and HQ on melt post-polycondensation process and crystallization kinetics, melting behaviors, crystallinity and thermal stability of PET/bisphenols complexes were investigated in detail. Excellent chain growth of PET could be achieved by addition of 1 wt% bisphenols, but intrinsic viscosity of modified PET decreased with further bisphenols content. Intermolecular hydrogen bonding between carbonyl groups of PET and hydroxyl groups of bisphenols were verified by Fourier transform infrared spectroscopy. Compare to pure PET, both the crystallization rate and melting temperatures of PET/bisphenols complexes were reduced obviously, suggesting an impeded crystallization and reduced lamellar thickness. Moreover, the structural difference between TDP, ODP and HQ played an important role on crystallization kinetics. It was proposed that the crystallization rate of TDP modified PET was reduced significantly due to the larger amount of rigid benzene ring and larger polarity than that of PET with ODP or HQ. X-ray diffraction results showed that the crystalline structure of PET did not change from the incorporation of bisphenols, but crystallinity of PET decreased with increasing bisphenols content. Thermal stability of modified PET declined slightly, which was hardly affected by the molecular structure of bisphenols.

Nano-Magnesium Silicate Hydroxide/Crumpled Graphene Balls Composites, a Novel Kind of Lubricating Additive with High Performance for Friction and Wear Reduction

In this study, crumpled graphene balls (CGB), a kind of nano-material, was used as an additive to improve the tribological properties of base oil. Nano-magnesium silicate hydroxide (MSH)/CGB composites were prepared by ultrasound-assisted liquid-phase exfoliation. The loading of MSH significantly increased the number of pleats and reduced the lamellar thickness of CGB. Then, in order to improve the compatibility with the base oil, the MSH/CGB composites were decorated with oleic acid and stearic acid to get modified lipophilic composites (ML-MSH/CGB). The ML-MSH/CGB were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). In addition, the tribological properties of the ML-MSH/CGB in base oils were investigated using a ball-on-disc setup tribometer. It indicated that the fantastic tribological behavior of the ML-MSH/CGB in base oil may contribute to a smaller and extremely wrinkled laminated structure. Furthermore, the base oil with 0.005 wt% ML-MSH/CGB composites exhibited the best anti-friction effect, and its average friction coefficient, wearing capacity and wear scar diameter were reduced by 25.4%, 22.1% and 16.7%, respectively. The introduction of ML-MSH/CGB composed materials is an excellent strategy to optimize the friction performance of lubricating oil.