Crystallization and Melting of β-Nucleated Isotactic Polypropylene

Ca salts of suberic (Ca-Sub) and pimelic acid (Ca-Pim) were synthesized and used as β-nucleating agents in different grades of isotactic polypropylene (IPP). Propylene homo-, random- and block-copolymers containing these additives crystallize principally in pure β-modification as demonstrated in isothermal and non-isothermal crystallization experiments. Ca-Sub proved the most effective β-nucleating agent known, so far. It broadens the upper crystallization temperature range of pure β-IPP formation up to 140°C. The effect of the additives on the crystallization and melting characteristics of the polymers was studied. The degree of crystallinity of the β-modification was found to be markedly higher than that of α-IPP. High temperature melting peak broadening was first observed and discussed in literary results regarding the same phenomenon for α-IPP. This revised version was published online in August 2006 with corrections to the Cover Date.     

Morphology,Crystallization Behavior and Tensile Properties of β-Nucleated Isotactic Polypropylene Fibrous Membranes Prepared by Melt Electrospinning

β-nucleated isotactic polypropylene(iPP) fibers with diameters less than 5 μm were prepared through melt electrospinning. The effects of electrospinning process and rare earth β-nucleating agent(WBG) on the crystal structure of iPP fibers were investigated. The results indicate that the addition of WBG can improve the fluidity of iPP melt remarkably and help the formation of fine fibers with thinner diameter, while the electrostatic force applied on the iPP melt is not favorable for the formation of β-crystal in iPP fibers. In addition, the morphology and crystalline structure of WBG/iPP electrospun fibers depended on the content of WBG. Both the crystallinity and the percentage of β-crystal form of WBG/iPP electrospun fibers increase with the rise of the content of nucleating agent, which endows the prepared electrospun fibers excellent mechanical properties. The β-nucleated iPP electrospun fibrous membranes prepared in this study can be used for protective clothing material, filtration media, reinforcement for composites and tissue engineering scaffolds.     

Mechanistic Insights into the Shear Effects on Isotactic Polypropylene Crystallization Containing β-Nucleating Agent

The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5(iPP/TMB-5) were investigated by synchrotron radiation wide angel X-ray diffraction(SR-WAXD), differential scanning calorimeter(DSC) and polarized light microscope(PLM). It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within mesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.     

Synthesis and Characterization of Multi‐Walled Carbon Nanotube/Polythiophene Composites

Multi‐walled carbon nanotube (MWCNT)/polythiophene (PTh) composites have been prepared by in situ chemical oxidative polymerization. PTh is synthesized onto the sidewalls of the MWCNTs, which play a role as hard templates for PTh to produce one‐dimensional nanostructures. The morphology and structures of the MWCNT/PTh composites are characterized by High‐resolution transmission electron microscopy, x‐ray diffraction, and Fourier transform infrared spectrometry. Their electrical property and thermal stability are determined using vector network analyzer and thermal gravimetric analyzer. Moreover, the mechanism of MWCNT/PTh nanowire formation is described. The studies show that the composites are nanowires with core‐shell structure, in which the outer shells and inner cores are formed by PTh and MWCNTs, respectively. The addition of MWCNTs does not change the backbone structure of PTh and affect the amorphous condition of PTh very slightly, however, it improves the electrical conductivity and thermal stability of PTh.     

Effect of a Nematic Liquid Crystalline Polymer as Highly Active β-Nucleator on Crystallization Structure and Morphology of Isotactic Polypropylene

The effects of nematic liquid crystalline polymer as a new β-nucleator (LCP-N) on crystallization structure and morphology of isotactic polypropylene (iPP) were investigated using wide-angle X-ray diffraction and polarized optical microscopy. The experimental results showed that LCP-N could lead to substantial changes in the crystallization structure and morphology of iPP. The nucleating activity of LCP-N mainly depended on its content, mesogenic molecules, and thermal history of processing. A high content of β-form (K _β) was obtained by the combined effect of the optimum LCP-N content and crystallization temperature. The maximum K _β reached 84% when the LCP-N content and crystallization temperature and time were 0.4 wt.%, 125°C, and 1 h, respectively. In addition, the birefringence of β spherulite was stronger than that of α spherulite; this difference is related to their particular way of growing and lamellar morphology. Due to its particular sheaf-like growth, the β spherulite was brighter and more colorful.     

Electrophysical Properties of Composites Based on Polyethylene Modified with Multi-Walled Carbon Nanotubes with High Content of Fe–Co-Catalyst

Russian Journal of Applied Chemistry - The effect of the residual catalyst for the synthesis of multi-walled carbon nanotubes (MWCNTs) on the electrophysical properties of MWCNT–polyethylene...     

Effect of Annealing Temperature on Low-temperature Toughness of β-Nucleated Polypropylene Random Copolymer/Ethylene-Propylene-Diene Terpolymer Blends

In this study, the effect of annealing temperature on the impact toughness of β-nucleated polypropylene random copolymer(PPR) and ethylene-propylene-diene terpolymer(EPDM) blends was investigated by differential scanning calorimetry(DSC), wide-angle X-ray diffraction(WAXD), dynamic mechanical analysis(DMA) and scanning electron microscopy(SEM). Interestingly, the impact strength of β-PPR/20 EPDM blend annealed at 120 ℃ is 1.8 times as high as that of unannealed samples. In addition, the crystalline structure, the relaxation of chain segments and fracture morphology of β-PPR/EPDM blends were also investigated to explore the toughening mechanism related to annealing. The results show that annealing at moderate temperatures results in the improvement of integrity of the crystal structure and the relative content of β-phase. The work provides a possible method to toughen the semicrystalline polymer at low temperatures by annealing.     

Synthesis of a New Liquid Crystalline Polymer as a Highly Active β-Nucleator and Its Effect on Melting and Crystallization Behaviors of Isotactic Polypropylene

A new nematic liquid crystalline polymer as a highly active β-nucleator (LCP-N) of isotactic polypropylene (iPP) was synthesized and characterized. The effect of LCP-N on thermal behavior of the iPP was investigated with differential scanning calorimetry. LCP-N showed a melting transition at 85.0°C and a nematic to isotropic phase transition at 278.0°C. The incorporation of LCP-N could lead to substantial changes in the thermal behavior of the iPP. The nucleating activity of LCP-N mainly depended on its content, mesogenic molecular structure, and thermal history of processing. A high content of β-form could be obtained by the combined effect of the optimum LCP-N concentration and crystallization temperature and time. The Φ_β reached 77% when the LCP-N content, crystallization temperature, and crystallization time were 0.4 wt.%, 125°C, and 1 h, respectively.     

Crystallization Behavior and Dynamic Mechanical Properties of Poly(ε-caprolactone)/Octaisobutyl-Polyhedral Oligomeric Silsesquioxanes Composites Prepared via Different Methods

Two octaisobutyl-polyhedral oligomeric silsesquioxanes(oib-POSS)reinforced biodegradable poly(ε-caprolactone)(PCL)composites were prepared via two different methods,i.e.,melt compounding and solution casting,which were named as m PCL/oib-POSS and s PCL/oibPOSS,respectively,in this work.Oib-POSS dispersed finely in both composites;moreover,oib-POSS aggregates were larger in m PCL/oib-POSS than in s PCL/oib-POSS.Despite the different preparation methods,oib-POSS obviously promoted the crystallization of PCL,especially in s PCL/oib-POSS,but did not modify the crystal structure of PCL.The storage moduli of PCL were improved significantly in both composites.PCL/oib-POSS composites with enhanced crystallization behavior and improved dynamic mechanical properties were successfully prepared through both methods;moreover,the solution casting method was more effective than the melt compounding method.     

Synthesis of PtCu/С Electrocatalysts with Different Structures and Study of Their Functional Characteristics

PtCu/C electrocatalysts with similar compositions but different distributions of components in bimetallic nanoparticles were obtained by simultaneous and sequential reduction of copper(II) and platinum( IV) in a carbon suspension. The catalyst obtained by multistage synthesis while sequentially increasing the Pt(IV) concentration in the precursor solution added at each stage showed the highest stability and activity in oxygen electroreduction in acidic media. This catalyst was least liable to selective dissolution of copper during its operation. The influence of the architecture of bimetallic PtCu nanoparticles on the electrochemical behavior of the catalysts is due to the peculiarities of the structure rearrangement of nanoparticles during the enrichment of the protective surface layer with platinum.

     

Preparation and Properties of Poly（ether ether ketone）/Carbon Nanotube Modified Polypropylene Janus Composite Separator北大核心CSCD

Lithium-ion batteries （LIBs）have attracted wide attention because of their broad prospects in electric vehicles. However,the safety problems and low multiplier performance of the commercial polyolefin separator limit their further development,due to the poor dimensional thermal stability and low electrolyte absorption rate. Poly（ether ether ketone）（PEEK）and carbon nanotube（CNT）are compounded to coat on polypropylene （PP） to prepare Janus composite separator （PP@C） through the phase inversion method. PP@C composite separator does not deform at 180 ℃ for 0. 5 h（only slight deformation）,illustrating excellent thermal stability. The electrolyte absorption rate of PP@C2 is 193. 8%. The electrolyte uptake rate of the PP@C2 composite membrane was 193. 8%,which was 64. 5% higher than the PP membrane,showing a superduper electrolyte permeability. As a result,the specific discharge capacity of LIBs assembled with PP@C2 composite separator is 157. 6 mA·h/g at 0. 2 C and 129. 8 mA·h/g at 2 C,showing good rate performance with the capacity recovery rate of more than 99%. This might be attributed to the ultra-high thermal stability of PEEK,the good affinity of the electrolyte,the high conductivity of CNT,as well as the uniform dispersion of Li+ ,so that the separator can have excellent electrochemical performance while improving safety. © 2022, Science Press (China). All rights reserved.     

Simultaneously Improving the Tensile and Impact Properties of Isotactic Polypropylene with the Cooperation of co-PP and β-nucleating Agent through Pressure Vibration Injection Molding

In this article, crystalline morphology and molecular orientation of isotactic polypropylene(i PP), random copolymerized polypropylene(co-PP) and ?-nucleating agent(?-NA) composites prepared by pressure vibration injection molding(PVIM) have been investigated via polarized light microscopy, scanning electron microscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Results demonstrated that the interaction between co-PP and i PP molecular chains was beneficial for the mechanical improvement and the introduction of ?-NA further improved the toughness of i PP. In addition, after applying the pressure vibration injection molding(PVIM) technology, the shear layer thickness increased remarkably and the tensile strength improved consequently. Thus, the strength and toughness of i PP/co-PP/?-NA composites prepared by PVIM were simultaneously improved compared to those of the pure i PP prepared by conventional injection molding(CIM): the impact toughness was increased by five times and tensile strength was increased by 9 MPa. This work provided a new method to further enhance the properties of i PP/co-PP composites through dynamic processing strategy.     

Inclusion Behavior of Dimer β-CyclodextrinBridged with Aspartic Acid Derivative

The capped cyclodextrins (CDs) are very useful macromolecular hosts in supramolecular chemistry. Previously, we demonstrated that the dimer cyclodextrin bridged with 1,2-diaminoethane causes significant enhancement of affinity to a small organic guest molecule1. A variety of interesting peptides have been developed as artificial enzymes. Here our designed peptide, Adm-Trp-Arg-Arg-NH2, named ATA was synthesized by the usual solid-phase Fmoc strategy2 with trityl resin in Shimadzu-PSSM8 p…     

Voltammetric Determination of Hydroquinone using β‐Cyclodextrin/Poly(N‐Acetylaniline)/Carbon Nanotube Composite Modified Glassy Carbon Electrode

Abstract

An electrochemical sensor for hydroquinone (HQ) using β‐cyclodextrin/poly(N‐acetylaniline)/carbon nanotube composite (β‐CD/PAA/MWNTs) modified glassy carbon electrode has been successfully developed. Based on the synergistic effect of MWNTs and conducting PAA polymer and the accumulation effect of β‐CD, the analytical response of the β‐CD/PAA/MWNTs film to the electrochemical behavior of HQ was better than that of a β‐CD/PAA film, a PAA/MWNTs film, a PAA film, or a bare glassy carbon (GC) electrode. Under the conditions chosen, the anodic currents increased linearly with HQ concentration from 1×10^?6 to 5×10^?3 mol l^?1 and the detection limit was 8×10^?7 mol l^?1. This electrochemical sensor showed excellent reproducibility, stability and recovery for the determination of HQ.     

Studies on Pervaporation Separation of Ethanol/Water Mixtures with Membranes of Polypropylene Sulfonate Salts

Sulfonated polypropylene membranes loaded with different kinds of counter-ions were prepared by heterogeneous chiorosulfonation reaction of polypropylene membrane followed by hydrolysis and ion-exchange reaction. The membranes obtained were used for selective separation of ethanol/water mixtures by pervaporation. The effects of counter-ion species, ion-exchange capacity, solution composition, thickness of membrane and temperature on the separation behavior of the membranes were investigated. Microstructure and morphology of the membranes were examined by X-ray and SEM as well.     

Preparation of LLDPE/MgAl-LDH Exfoliation Nanocomposites with Enhanced Thermal Properties by Melt Intercalation

The interlayer surface of MgAl layered double hydroxide(MgAl-LDH)was modified by exchanging about halfof the interlayer nitrate anions by dodecyl sulfate anions(DS)to get MgAl(H-DS)LDH,and then the MgAl(H-DS)was melt intercalated by LLDPE to get the LLDPE/MgAl-LDH exfoliation nanocomposites.The samples werecharacterized by Fourier transform infrared(FTIR)spectroscopy,X-ray diffraction(XRD),ion chromatography,transmission electron microscopy(TEM),and thermogravimetry analysis(TGA).The nanoscale dispersion ofMgAl-LDH layers in the LLDPE matrix was verified by the disappearance of(001)XRD reflection of the modifiedMgAl-LDH and by the TEM observation.The TGA profiles of LLDPE/MgAl-LDH nanocomposites show a fastercharring process between 210 and 370℃ and a higher thermal stability above 370℃ than LLDPE.The decomposi-tion temperature of the nanocomposites with 10 wt% MgAl(H-DS)can be 42℃ higher than that of LLDPE at 40%weight loss.     

Electrochemical Detection of β-Lactoglobulin Allergen Using Titanium Dioxide/Carbon Nanochips/Gold Nanocomposite-based Biosensor

A label-free electrochemical immunosensor was developed for the ultra-sensitive detection of β-lactoglobulin (β-LG). The novel nanocomplex of carbon nanochips, colloidal gold nanoparticles and titanium dioxide nanoparticles TiO₂/CNC/AuC were constructed on conducting polymer, chitosan, and were characterised using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). This nanocomplex interface was studied using cyclic voltammetry (CV) and showed great improvement at the gold electrode surface with enhanced electrochemical performance, sensitivity and selectivity for β-lactoglobulin. Under optimal parameters, the square wave voltammetry (SWV) response curve was determined from 0.01 pg/mL to 500 pg/mL using [Fe(CN)₆]^3−/4−] redox probe. The calibration plot illustrates a linear relationship between log β-LG concentration and SWV current, with the limit of detection determined to be 0.01 pg/mL. This immunosensor displayed high sensitivity, selectivity, reproducibility and stability, and can be utilised for the detection of β-LG in real food samples.     

Distribution and Transfer of Gatifloxacin Between Two Microemulsion Phases with Different Structures in SDS/n-C5H11 OH/H2O System

At a weight ratio of n‐C₅H₁₁OH/H₂O=50/50, when the total content of sodium dodecyl sulfate (SDS) was less than 6.0%, the ternary mixture of SDS/n‐C₅H₁₁OH/H₂O coexisted in two immiscible microemulsions. The distribution and transfer of gatifloxacin (GTFX) between the two phases were studied using UV‐Vis and electrochemistry AC impedance spectra. The results show that GTFX transferred from the upper phase (W/O) to the lower phase (O/W or bicontinuous microemulsion), but a small amount of SDS transferred from the lower phase to the upper phase correspondingly with the increase of the total SDS content at a total GTFX concentration of 1.0×10^?5 mol/L. The addition of GTFX did not change the structures of the two different phases fundamentally, but resulted in the transfer and redistribution of GTFX and SDS, so the electric properties of the system were changed correspondingly.     

Computational investigation of enol/keto chloramphenicol with β-cyclodextrin

PM3 and ONIOM2 were carried out to investigate the structures and properties for the inclusion complexes of chloramphenicol tautomers into β-cyclodextrin (at 1:1 stoichiometry). Two possible orientations into host cavity were considered for both enol and keto chloramphenicol. The PM3 results gives that B orientation is more preferred for enol and keto form, the preference is of 0.63 and 1.67 kcal/mol respectively. This preference is greater in the case of ONIOM2 calculations. Finally, the chemical shifts (ppm) of free and complexed chloramphenicol were calculated at B3LYP/6-31G(d) by (GIAO method) and compared with experimental data taken from the literature.