PE Chains Research Articles

Coarse-Grained Simulations on Polyethylene Crystal Network Formation and Microstructure Analysis.

Understanding and characterizing semi-crystalline models with crystalline and amorphous segments is crucial for industrial applications. A coarse-grained molecular dynamics (CGMD) simulations study probed the crystal network formation in high-density polyethylene (HDPE) from melt, and shed light on tensile properties for microstructure analysis. Modified Paul-Yoon-Smith (PYS/R) forcefield parameters are used to compute the interatomic forces among the PE chains. The isothermal crystallization at 300 K and 1 atm predicts the multi-nucleus crystal growth; moreover, the lamellar crystal stems and amorphous region are alternatively oriented. A one-dimensional density distribution along the alternative lamellar stems further confirms the ordering of the lamellar-stack orientation. Using this plastic model preparation approach, the semi-crystalline model density (ρcr) of ca. 0.913 g·cm-3 and amorphous model density (ρam) of ca. 0.856 g·cm-3 are obtained. Furthermore, the ratio of ρcr/ρam ≈ 1.06 is in good agreement with computational (≈1.096) and experimental (≈1.14) data, ensuring the reliability of the simulations. The degree of crystallinity (χc) of the model is ca. 52% at 300 K. Nevertheless, there is a gradual increase in crystallinity over the specified time, indicating the alignment of the lamellar stems during crystallization. The characteristic stress-strain curve mimicking tensile tests along the z-axis orientation exhibits a reversible sharp elastic regime, tensile strength at yield ca. 100 MPa, and a non-reversible tensile strength at break of 350%. The cavitation mechanism embraces the alignment of lamellar stems along the deformation axis. The study highlights an explanatory model of crystal network formation for the PE model using a PYS/R forcefield, and it produces a microstructure with ordered lamellar and amorphous segments with robust mechanical properties, which aids in predicting the microstructure-mechanical property relationships in plastics under applied forces.

Effect of reaction media on hydrogenolysis of polyethylene plastic waste: Polymer-surface interactions in small alkane/polymer blends

The polymer reaction media and its properties can be altered by recycling a fraction of liquid products or adding alkane solvents. Less clear is whether this strategy affects hydrogenolysis. Herein, we investigated the effect of short-chain alkanes Cn consisting of n carbons (n=8, 16, and 32) on the upcycling of high-density polyethylene (HDPE) plastic waste to lubricant-range products over Ru/TiO2 catalysts by multiscale simulations and experiments. First, we trained a force field for polymer/surface interactions on a Ru22 nanoparticle (NP) supported on TiO2. Using replica exchange molecular dynamics simulations, we studied the effect of small hydrocarbons on the adsorption of a surrogate polymer, C142, on the catalyst. We found segregation of long chains (C142) at the catalyst surface due to the enthalpy gained by adsorbing more C-C bonds of the long chains, compensating for entropic losses upon adsorption. Short-chain molecules decrease the adsorbed carbons of long chains on the Ru NP due to blocking Ru active sites. Compared to the bulk chains, competitive adsorption results in a broader, heavy-tailed distribution of end-to-end distance of adsorbed chains. Our experiments demonstrated that catalyst activity declines significantly beyond simple dilution due to changes in polymer adsorption, and tuning the reaction media by creating suitable blends impacts hydrogenolysis. Density distributions for a 50:50%wt mixture of PP and PE show that PE chains are segregated at the surface, so they are prone to C-C bond breaking much faster than PP chains. H/D exchange experiments show preferential deuteration of PE, while CH3 groups of PP remain undeuterated. This may be explained by the preferential sorption of PE over PP, leading to specific distribution in the polymer blend.

Microscopic mechanism for CO2-assisted co-gasification of polyethylene and softwood lignin: A reactive force field molecular dynamics study

Co-gasification of biomass and waste plastic to produce syngas and value-added products is an attractive technology for renewable energy utilization and waste disposal. CO2 as a gasifying agent has received much attention as it can act as carbon source and oxidant in the reaction. In this paper, the feasibility and characteristics of CO2-assisted co-gasification of polyethylene and softwood lignin were explored. Simulation results showed that the lignin macromolecule began to decompose through C–O–C bond breaking and the PE chain gradually decomposed through C–C bond breaking. CO2-assisted co-gasification showed a negative synergistic effect on gas yield at the early stage, which delayed the reaction, but showed a positive synergistic effect at the late stage. The reaction between CO2 and carbon-containing fragments greatly promoted CO production. The hydrogen and hydrocarbon radicals from PE were actively involved in H2 and hydrocarbon gas production. Compared with O2-assisted co-gasification, the CO2-assisted and CO2/O2-assisted co-gasification yielded more CO, hydrocarbon gases and combustible gases and increased the lower heating value of gas product. This work sheds light on the underlying mechanisms of CO2-assisted co-gasification of polyethylene and softwood, and would be helpful for the development of this technology.

Effects of Overload on Thermal Decomposition Kinetics of Cross-Linked Polyethylene Copper Wires.

During an overload fault in an energized wire, the hot metal core modifies the structure of the insulation material. Therefore, understanding the thermal decomposition kinetics of the insulation materials of the overloaded wire is essential for fire prevention and control. This study investigates the thermal decomposition process of new and overloaded cross-linked polyethylene (XLPE) copper wires using thermogravimetry-Fourier-transform infrared spectroscopy and cone calorimetry. The thermal decomposition onset temperature and activation energy of the overloaded XLPE insulation materials were reduced by approximately 15 K and 20 kJ mol-1, respectively, and its reaction mechanism function changed from D-ZLT3 to A2 (0 < α < 0.5). The FTIR shows that the major spectral components produced during the pyrolysis of the XLPE insulation material are C-H stretching, H2O, CO2, C-H scissor vibrations, and C=O and C=C stretching. Additionally, the four functional groups in the PE chains produced the spectral components in the following decreasing order of wavenumber: C-H stretching > CO2 > C-H scissor vibration > C=O and C=C stretching.

Copolymerization of ω‐Alkenyltrimethylsilane with Ethylene by MgCl2/TiCl4 Catalyst: Effect of Alkenyl Length on Comonomer Incorporation

Abstractω‐Alkenyltrimethylsilanes of different alkenyl moieties, i.e., 3‐butenyltrimethylsilane, 5‐hexenyltrimethylsilane, and 7‐octenyltrimethylsilane, are used as model compounds to study the alkenyl length effect in copolymerization of ethylene with steric‐hindered tri‐substituted silane‐functionalized α‐olefins over MgCl2/TiCl4 catalysts. The experimental results reveal that 3‐butenyltrimethylsilane tops the three α‐olefins in incorporation rate into PE while 7‐octenyltrimethylsilane is slightly better than 5‐hexenyltrimethylsilane. The coordination‐insertion events for different ω‐alkenyltrimethylsilanes are investigated by DFT simulation. The results suggest that the three ω‐alkenyltrimethylsilanes encounter similar energy barriers during insertion, with similar repulsive interactions between the bulky trimethylsilane substituent and growing PE chain found in the energy decomposition of transition state configuration. However, complexation abilities at the Ti active site for the three ω‐alkenyltrimethylsilanes follow the order of 3‐butenyltrimethylsilane &gt; 5‐hexenyltrimethylsilane &gt; 7‐octenyltrimethylsilane, in line with their molecular compactness, which are deemed to be where the alkenyl length effect originates in the ω‐alkenyltrimethylsilane/ethylene copolymerization.

Boron nitride nanosheet reinforced polyethylene nanocomposite film for high-performance hot-melt adhesive type thermal interfacial material

In this study, we report an effective synthesis approach for fabricating low-density polyethylene (LDPE)-based multi-functional composite through hybridization with short PE chain branched boron nitride nanosheet (BNNS) to be applied as a high-performance hot-melt adhesive (HMA) type thermal interface material (TIM). To enhance the thermal and mechanical properties of BNNS/LDPE, the BNNS surface was modified with short PE chain (PE–g–BNNS) via nitrene coupling reaction to improve the interfacial bonding force between the BNNS with LDPE. As a result, PE–g–BNNS/LDPE exhibited 22% increase in through-plane and 66% increase in in-plane thermal conductivity compared to the BNNS/LDPE. Its heat radiation performance was also increased by about 11% compared to the bare LDPE. In addition, the PE–g–BNNNS/LDPE shows 66% increase in tensile strength and 350% enhancement in modulus compared to the bare LDPE, suggesting that the PE–g–BNNNS/LDPE could be used as a TIM to meet the requirements for application in high-tech electronic devices.

Manufacturing of wood plastic composite from polyethylene/poly(ethylene terephthalate) waste/ultra high molecular weight polyethylene blends and rice husk fiber: Effect of blends ratio and peroxide/silane crosslink system

Lowering processing temperature of poly(ethylene terephthalate) waste (rPET) and ultra-high molecular weight polyethylene (UHMWPE) by blending to avoid decomposition of rice husk fiber (RHF) during the manufacturing of wood plastic composite (WPC) was one of the main goals of the research study. (rPET/LDPE)-g-MA and (HDPE/LDPE/UHMWPE)-g-MA blends were prepared with good flowability at 240°C. The MA grafted chain in the blends were verified by FTIR. Good miscibility and compatibility of the blends were revealed by SEM. The effect of blends ratios employed as blended matrices on performance properties of the manufactured WPC were explored. MFI and HDT were increased with decreasing (rPET/LDPE)-g-MA ratio. The reversed domain phase between rPET and blended PE mixture was pronounced at 50:50 ratio. Mechanical performances were generally reduced upon decreasing the (rPET/LDPE)-g-MA ratios. The reduction of high strength rPET fraction in the blended matrices was taken as the main cause. Exceeding the reversed phase ratio, the declining of the toughness was retarded due to rising on the interfacial strength and UHMWPE toughener fraction. The effect of DCP/VTMS crosslinker on the properties of the macro crosslinked WPC (XWPC) was investigated. The elastomeric bridges on the sauna cured WPC samples were revealed by SEM. High crosslink density upon increasing the crosslinker fraction had an obvious effect on MFI, HDT, toughness and ductility of the macro crosslinked XWPC. However, the flexible characteristic of the elastomeric amorphous PE chains in the blended matrices at high DCP/VTMS usage was manifested as brittleness retardant for the macro crosslinked XWPC.

Amphiphilic olefin block copolymers synthesized by successive coordinative chain transfer and ring-opening polymerizations

Introducing polarity is a necessity for widening the application scope of polyolefins specifically for developing biocompatible products. To this end, we exploit a two-step polymerization process to synthesize poly(ethylene‑b‑caprolactone) PE‑PCL block copolymers, which contain both polar and non-polar segments. First ethylene is polymerized by a generic metallocene catalyst in the presence of ZnEt2 as the chain transfer agent according to the coordinative chain transfer polymerization (CCTP) technique. Terminal zinc atoms are subsequently replaced by hydroxyl groups (PE‑OH) by exposing dormant polymer chains to oxygen. Afterward, ring-opening polymerization (ROP) of ε‑caprolactone is initiated by PE‑OH to form PE‑PCL block copolymers. Successful formation of both blocks is verified by FTIR and NMR spectroscopy. The presence of PCL blocks greatly lowers the crystallinity of ethylene sequences according to XRD and DSC results. Moreover, a second type of PE crystals with more chain folds and lower lamella thickness is found in block copolymers, which is absent in the equivalent physical blend. The diverse crystal structure of block copolymers suggest that phase separation exists between PE and PCL segments. The SEM image of the equivalent physical blend confirms the tendency of PCL and PE chains to phase separate, and infers a compatibilization in the presence of PE‑PCL block copolymers. This phase separation is detected by rheological measurements, as well, where block copolymers show deviations from Maxwell behavior in the terminal relaxation zone at low frequencies. Rheology results also show that the order-disorder transition temperature (TODT) of these block copolymers is higher than 180 °C. These results provide a clear picture from the morphology and utility of such block copolymers specifically for compatibilizing blends of polar polymers and non-polar polyolefins, which significantly broaden the utility of polyolefins.

Proposing a novel deep network for detecting COVID-19 based on chest images

The rapid outbreak of coronavirus threatens humans’ life all around the world. Due to the insufficient diagnostic infrastructures, developing an accurate, efficient, inexpensive, and quick diagnostic tool is of great importance. To date, researchers have proposed several detection models based on chest imaging analysis, primarily based on deep neural networks; however, none of which could achieve a reliable and highly sensitive performance yet. Therefore, the nature of this study is primary epidemiological research that aims to overcome the limitations mentioned above by proposing a large-scale publicly available dataset of chest computed tomography scan (CT-scan) images consisting of more than 13k samples. Secondly, we propose a more sensitive deep neural networks model for CT-scan images of the lungs, providing a pixel-wise attention layer on top of the high-level features extracted from the network. Moreover, the proposed model is extended through a transfer learning approach for being applicable in the case of chest X-Ray (CXR) images. The proposed model and its extension have been trained and evaluated through several experiments. The inclusion criteria were patients with suspected PE and positive real-time reverse-transcription polymerase chain reaction (RT-PCR) for SARS-CoV-2. The exclusion criteria were negative or inconclusive RT-PCR and other chest CT indications. Our model achieves an AUC score of 0.886, significantly better than its closest competitor, whose AUC is 0.843. Moreover, the obtained results on another commonly-used benchmark show an AUC of 0.899, outperforming related models. Additionally, the sensitivity of our model is 0.858, while that of its closest competitor is 0.81, explaining the efficiency of pixel-wise attention strategy in detecting coronavirus. Our promising results and the efficiency of the models imply that the proposed models can be considered reliable tools for assisting doctors in detecting coronavirus.

Comparative retrieval analysis of antioxidant polyethylene: bonding of vitamin-E does not reduce in-vivo surface damage

BackgroundWith the Persona® knee system a new polyethylene formulation incorporating vitamin-E which aims to reduce oxidation and maintain wear resistance was introduced. Although in-vitro studies have demonstrated positive effects of the vitamin-E antioxidants on UHMWPE, no retrieval study has looked at polyethylene damage of this system yet. It was the aim to investigate the in-vivo performance of this new design, by comparing it with its predecessor in retrieval analysis.Methods15 NexGen® and 8 Persona® fixed-bearing implants from the same manufacturer (Zimmer Biomet) were retrieved from two knee revision centres. For retrieval analysis, a macroscopic analysis of polyethylene using a peer-reviewed damage grading method was used (Hood-score). The roughness of all articulating metal components was measured using a contact profilometer. The reason(s) for TKA revision were recorded. Statistical analyses (t-test) were performed to investigate differences between the two designs.ResultsThe mean Hood score for Persona® inserts was 109.3 and for NexGen® 115.1 without significant differences between the two designs. Results from the profilometer revealed that Persona® and NexGen® femoral implants showed an identical mean surface roughness of 0.14 μm. The Persona® tibial tray showed a significantly smoother surface (0.06 μm) compared to the NexGen® (0.2 μm; p < 0.001). Both Hood score and surface roughness were influenced by the reasons for revision (p < 0.01).ConclusionsThe bonding of the antioxidant vitamin-E to the PE chain used in the novel Persona® knee system does not reduce in-vivo surface damage compared to highly crosslinked PE without supplemented vitamin-E used in its predecessor knee system NexGen®. However, the Persona® titanium alloy tibial tray showed a significantly smoother surface in comparison to the NexGen® titanium alloy tibial tray. This study provides first retrieval findings of a novel TKA design and may help to understand how the new Persona® anatomic knee system performs in vivo.

A feasible strategy for preparing an all-in-one theranostic nanoplatform

The facile construction of an appropriate all-in-one multifunctional agent is still a major challenge for precise cancer therapy. Poly-2-phenyl-benzobisthiazole (PPB) is a new polymer with high photothermal efficiency but poor hydrophilicity. Herein, we precisely used Fe(III) to crosslink the pectin (Pe) chain, as well as to initiate the copolymerization of dicyanobenzene and 2,5-dimercapto-1,4-phenylenediamine to obtain PPB. The obtained theranostic agent Pe-PPB compounded the pectin chain with PPB chain, which well resolved its water solubility. The complexed Fe(III) of Pe-PPB had good magnetic resonance imaging (MRI) signal. Additionally, Pe-PPB has good photoacoustic imaging (PAI) signal and excellent photothermal performance.

The effect of phase separation on crystallization of polyethylene/poly(ethylene-alt-propylene) blend

The influence of liquid–liquid phase separation (LLPS) on crystallization kinetics in off-critical and near-critical blends of polyethylene/poly(ethylene-alt-propylene) (PE/PEP) is studied to explore the origin of the two crystallization peaks in differential scanning calorimetry with the same long period. The PE/PEP blend systems show upper critical solution temperature (UCST) type of phase diagram and the crystallization temperature of PE component is much lower than the UCST, LLPS occurs first. The crystal nuclei first form at the interface region of two phases and then it is necessary for the PE chains to diffuse there to continue the crystallization process from both PE-rich and PEP-rich regions. As a result, the crystallization kinetics pathway is dynamically influenced by LLPS period of time, quench depth and initial composition because they control inter-diffusion coefficient in both phases. In the off-critical blend, the LLPS is extremely slow. The area ratio of the two DSC crystallization peaks doesn't fit with the ratio of coexistence compositions of PE in PE-rich and PEP-rich phases until LLPS has reached its equilibrium before crystallization. The crystallization of PE dominates the final morphology. Small and randomly dispersed crystals could be observed because the inter-diffusion of PE chains in PEP-rich phase is greatly hindered and they could not contribute to the formation of more perfect crystals. In the near-critical blend, LLPS kinetics is comparatively much faster, so the area of the two DCS crystallization peaks agrees with the coexistence compositions of PE. LLPS is the key factor to determine the final morphology.

An FPGA‐Based Convolutional Neural Network Coprocessor

In this paper, an FPGA‐based convolutional neural network coprocessor is proposed. The coprocessor has a 1D convolutional computation unit PE in row stationary (RS) streaming mode and a 3D convolutional computation unit PE chain in pulsating array structure. The coprocessor can flexibly control the number of PE array openings according to the number of output channels of the convolutional layer. In this paper, we design a storage system with multilevel cache, and the global cache uses multiple broadcasts to distribute data to local caches and propose an image segmentation method that is compatible with the hardware architecture. The proposed coprocessor implements the convolutional and pooling layers of the VGG16 neural network model, in which the activation value, weight value, and bias value are quantized using 16‐bit fixed‐point quantization, with a peak computational performance of 316.0 GOP/s and an average computational performance of 62.54 GOP/s at a clock frequency of 200 MHz and a power consumption of about 9.25 W.

Conformational properties of complexes of poly(propylene imine) dendrimers with linear polyelectrolytes in dilute solutions.

This study investigates the conformational properties of complexes of poly(propylene imine) dendrimers with a linear polyelectrolyte (LPE) at neutral pH in an aqueous solution via molecular dynamics simulations. Various conformational properties, such as the atomic density profile, counterion density distribution, charge distribution, cavity volume, and the static structure factor are studied as a function of the charge and chain length of the LPE. The lower generation dendrimer complexes encapsulate the shorter linear PE chains, while the longer PE chains are adsorbed on the dendrimer surface that screen the surface charge and prevent the penetration of the counterions and water molecules. However, the overall charge of the higher generation dendrimers is not neutralized by the charge of the PE chains, which results in chloride counterion penetration within the dendrimers. The adsorption of the PE chains on the dendrimers is also verified from the charge distribution of the dendrimer-PE complexes. The charge on the lower generation dendrimer complexes is overcompensated by the longer PE chains resulting in an overall negative charge on the complexes, while the PE chains do not completely neutralize the charge of the higher generation dendrimers and produce positively charged complexes. The results of the structure factor indicate a conformational transition of the dendrimer-PE complexes from a dense compact structure to an open one with an increase in the PE chain length. This transition is characterized by an increase in the cavity volume in dendrimers with an increase in the PE chain length.

CT imaging of pulmonary embolism in patients with COVID-19 pneumonia: a retrospective analysis.

ObjectivesTo describe imaging and laboratory findings of confirmed PE diagnosed in COVID-19 patients and to evaluate the characteristics of COVID-19 patients with clinical PE suspicion. Characteristics of patients with COVID-19 and PE suspicion who required admission to the intensive care unit (ICU) were also analysed.MethodsA retrospective study from March 18, 2020, until April 11, 2020. Inclusion criteria were patients with suspected PE and positive real-time reverse-transcription polymerase chain reaction (RT-PCR) for SARS-CoV-2. Exclusion criteria were negative or inconclusive RT-PCR and other chest CT indications. CTPA features were evaluated and severity scores, presence, and localisation of PE were reported. d-dimer and IL-6 determinations, ICU admission, and previous antithrombotic treatment were registered.ResultsForty-seven PE suspicions with confirmed COVID-19 underwent CTPA. Sixteen patients were diagnosed with PE with a predominant segmental distribution. Statistically significant differences were found in the highest d-dimer determination in patients with PE and ICU admission regarding elevated IL-6 values.ConclusionPE in COVID-19 patients in our series might predominantly affect segmental arteries and the right lung. Results suggest that the higher the d-dimer concentration, the greater the likelihood of PE. Both assumptions should be assessed in future studies with a larger sample size.Key Points • On CT pulmonary angiography, pulmonary embolism in COVID-19 patients seems to be predominantly distributed in segmental arteries of the right lung, an assumption that needs to be approached in future research. • Only the highest intraindividual determination of d-dimer from admission to CT scan seems to differentiate patients with pulmonary embolism from patients with a negative CTPA. However, interindividual variability calls for future studies to establish cut-off values in COVID-19 patients.• Further studies with larger sample sizes are needed to determine whether the presence of PE could increase the risk of intensive care unit (ICU) admission in COVID-19 patients.

Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants

Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key step in refining pyrolysis oil of BFRs. Chemical reactions underpinning this process are poorly understood. Herein, we utilize accurate density functional theory (DFT) calculations to report thermo-kinetic parameters for the reaction of solid polyethylene, PE, (as a surrogate model for aliphatic polymers) with prime products sourced from thermal decomposition of BFRs, namely, HBr, bromophenols; benzene, and phenyl radical. Facile abstraction of an ethylenic H by Br atoms is expected to contribute to the formation of abundant HBr concentrations in practical systems. Likewise, a relatively low energy barrier for aromatic Br atom abstraction from a 2-bromophenol molecule by an alkyl radical site, concurs with the reported noticeable hydro-debromination capacity of PE. Pathways entailing a PE-induced bromination of a phenoxy radical should be hindered in view of high energy barrier for a Br transfer into the para position of the phenoxy radical. Adsorption of a phenoxy radical onto a Cu(Br) site substituted at the PE chain affords the commonly discussed PBDD/Fs precursor of a surface-bounded bromophenolate adduct. Such scenario arises due to the heterogeneous integration of metals into the bromine-rich carbon matrix in primitive recycling of e-waste and their open burning.

Comparative Study on Factors Governing Binding Mechanisms in Polylactic Acid-Hydroxyapatite and Polyethylene-Hydroxyapatite Systems via Molecular Dynamics Simulations.

Binding mechanisms in polylactic acid-hydroxyapatite (PLA-HAp) and polyethylene-hydroxyapatite (PE-HAp) systems are comparatively elucidated on HAp (110) surfaces in unprecedented detail using molecular dynamics simulations conducted with the systematically varying number of monomers (N) between 10 and 400 at 310 K (NVT). Although PE seems to gradually cover the HAp surface more effectively compared to PLA, evident from the corresponding radius of gyration and occupied area values, the interface density and total binding energy in PLA-HAp systems is higher compared to those of PE-HAp systems. It is shown that a linear relationship between the binding energy and the surface area occupied by the monomer exists, consistent with our finding that binding energy converges to a limiting value with respect to monomer size on a constant surface area. The major constituent of the total binding energy is, rather surprisingly, shown to be the energy change in the bulk structure in HAp upon interaction; the next most important contributor is found to be the energy corresponding to surface-polymer interactions. The interplay between mainly these two contributors, acting in different fashions in two systems investigated here, seems to control the total binding energies. Increasing monomer size N initially results in enhanced densification of the interface in the HAp-PLA system up until N ≈ 200 with the positioning of mainly ═O units of PLA onto the HAp surface, consistent with the increasing Ca-O coordination numbers. Further increases in PLA size (N > 200) result in decreasing intensities of the peaks in the concentration profile consistent with the decreasing surface-polymer interaction energies while increased stabilization of the energy of the bulk is pronounced in this region. On the other hand, increasing N leads to a constantly increasing concentration at the interface in PE-HAp systems; -H atoms of the PE chain are positioned closer to the HAp surface than are -C atoms. These changes are coupled with increasing surface-polymer interaction energies in PE-HAp complexes, while slight destabilization in the energy of the bulk is observed for N > 100. A detailed examination of binding mechanisms in these technologically important systems as presented here is essential in material discovery; this valuable information, that will not be available from experiments can be attained through molecular simulations. The current study, to the best of our knowledge, comprises one of the first steps in achieving this goal for PLA/PE-HAp systems.

Self-assembly of polyelectrolyte diblock copolymers within mixtures of monovalent and multivalent counterions.

In this study, the self-assembly behavior of polyelectrolyte (PE) diblock copolymers in solutions containing mixtures of monovalent and multivalent counterions was investigated using molecular dynamics simulation. The properties of the assembled micelles and counterion condensations at different charge fractions of multivalent ions have been discussed. The bridging effect of multivalent ions induces the electrostatic correlations of the PE chains, leading to the fusion of large micelles and the formation of bulky aggregates. Notably, lamellar and well-organized face-centered cubic (FCC) arrangements of the assembled micelles were observed in the mixture of monovalent and trivalent ions. At large fractions of multivalent ions, cylindrical and lamellar precipitates composed of the assembled micelles were formed owing to the inter-connecting coronas. The mixtures of monovalent and multivalent counterions allow the regulation of the electrostatic interactions and tuning of the properties in assembled micelles.

Simple and feasible strategy to fabricate microcellular poly(butylene succinate) foams by chain extension and isothermal crystallization induction

ABSTRACTIn this article, a facile and efficient isothermal crystallization induction method was proposed to fabricate microcellular poly(butylene succinate) (PBS) foams with supercritical CO2. The good regularity of PE chain segments and high reactive epoxy groups in ethylene‐glycidyl methacrylate copolymer (PE‐g‐GMA) serving as a chain extender were employed to improve the crystallization behaviors, viscoelasticity, and foaming behaviors of PBS through chain extension reaction. The effect of PE‐g‐GMA content on the thermal properties, rheological performances, and cellular morphology of various PBS samples was investigated systematically. When the PE‐g‐GMA content switched from 7.5 to 10 wt %, an interesting transition from fine cells to microcells was observed in PBS/PE‐g‐GMA foams. Microcellular PBS foam modified by 10 wt % PE‐g‐GMA was successfully prepared at the foaming temperature of 87 °C and the induction time of 7 min, in which its cell size and cell density could reach 6.63 ± 1.93 μm and 3.75 × 109 cells cm−3, respectively. The formation of abundant but tiny spherocrystals in chain extended PBS samples made a considerable contribution for preparing microcellular PBS foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48850.

Identification of the Starting Group on the First PE Chain Produced by the Phillips Catalyst

Upon contact with ethylene, the Phillips Cr/silica catalyst must self-alkylate before polymerization can begin. How this happens has been a mystery for over 60 years, being not only of scientific interest but also of commercial importance. Consequently, many controversial schemes have been proposed, including some that hold the initial PE chain to be different from all subsequent chains, starting with a vinyl group, instead of the usual methyl group. In this study, polymer chains produced by the Cr(II)/silica–titania catalyst at low yield were analyzed in an effort to identify the starting group on the first chain produced. The PE/Cr yield was deliberately kept low to avoid diluting that initial chain with other chains produced afterward. The polymer was then characterized by gel permeation chromatography and 13C NMR (natural abundance). Strong signals from methyl end groups were present, but terminal vinyl groups were not detected. Likewise, analysis by proton (1H) NMR also indicated a general lack of vinyl chain ends. An attempt was also made to identify the first species on the initial chain through isotopic labeling. Deutero-ethylene (C2D4), deutero-propylene (C3D6), or 13C-ethylene was first “preadsorbed” onto the divalent catalyst at −78 °C, where polymerization does not occur. After evacuating the excess isotopically labeled monomer, polymerization was conducted with unlabeled ethylene (C2H4) at higher temperatures. Deuterium (2H) NMR analysis of the polymers again indicated a strong methyl signal but no resonance from deuterium-containing vinyl chain ends. Comparison of the different NMR methods indicated a high degree of deuterium enrichment in the methyl chain ends. These results indicate that the initial chain in these experiments began with a methyl group, not a vinyl group as has sometimes been contemplated. Although helpful, this information still leaves the mechanism of site alkylation unclear because there is not enough hydrogen in ethylene to produce a methyl-initiated chain, without some other (still undefined) reaction also being involved to furnish the additional hydrogen, such as the creation of a permanent ligand.