Preparation and structure analysis of nano-iron/mesocarbon microbead composites made from a coal tar pitch with addition of ferrocene

Nano-iron/mesocarbon microbead composites have been synthesized from a coal tar pitch by heating at 415 °C with ferrocene under pressure. The resulting composites were characterized using the combined techniques including SEM, TEM, XRD and EDS. The effect of ferrocene addition on the growth and structure of mesocarbon microbeads was discussed. It was found that nano-iron particles were of sizes 10-40 nm and mainly existed in the form Fe-O and Fe_1−xS. The iron particles, which had dispersed homogeneously in pristine and carbonized spheres, accelerated the nucleation and growth of spheres and consequently enhanced the structural ordering of spheres. The addition of ferrocene introduced a tendency to order in the microtexture of spheres.     

Ab initio simulation of the electronic structure of poly(vinylidene fluoride) during carbonization

The modification observed in the electronic structure of poly(vinylidene fluoride) during carbonization is investigated. The total and partial densities of states and the band gap at different degrees of carbonization of the polymer molecule are calculated from first principles. The results of the calculations are in agreement with experimental data.     

Fabrication of optical devices in poly(dimethylsiloxane) by proton microbeam

Optical diffraction grating and micro Fresnel zone plate type structures were fabricated in relatively thin poly(dimethylsiloxane) (PDMS) layers using proton beam writing technique and the performance of these optical devices was tested. PDMS is a commonly used silicon-based organic polymer, optically clear, generally considered to be inert, non-toxic and biocompatible. PDMS has been used as a resist material for direct-write techniques only in very few cases. In this work, PDMS was used as a resist material; the structures were irradiated directly into the polymer. We were looking for a biocompatible, micropatternable polymer in which the chemical structure changes significantly due to proton beam exposure making the polymer capable of proton beam writing. We demonstrated that the change in the structure of the polymer is so significant that there is no need to perform any development processes. The proton irradiation causes refractive index change in the polymer, so diffraction gratings and other optical devices like Fresnel zone plates can be fabricated in this way. The observed high order diffraction patterns prove the high quality of the created optical devices.     

Electrical properties of expanded graphite/poly(styrene-co-acrylonitrile) composites

A four probe method was used to measure the electrical conductivities of poly(styrene-co-acrylonitrile)/expanded graphite composites. The composites showed excellent electrical conductivities in both a- and c-axes. The different effects of temperature and the applied current on the conductivities in a-axis and in c-axis were observed. It was found that the conductive behaviors of the composite were different from those of semiconductor and carbon black loaded polymer composites. All these differences and excellent conductivity were considered to be related to the structure of the composites.     

Study of the combined carbonization of poly(vinylidene fluoride) by X-Ray photoelectron spectroscopy

The surface composition of two samples synthesized by the combined carbonization of poly(vinylidene fluoride) (PVDF) films is studied by X-ray photoelectron spectroscopy. One of them is successively exposed only to chemical and radiation impacts, and the treatment of the other includes chemical, heat, and radiation exposure. The chemical preparation of both samples is the same. It is shown that the magnitude and direction of the gradient of the residual fluorine concentration in the surface layer of PVDF carbonization products can be controlled. Since dehydrofluorination decreases the surface electrical resistance of the material, a combination of chemical, heat, and radiation treatments can be used to create a predetermined sequence of heterolayers with different fluorine concentration on a flexible and transparent polymer base and, therefore, with different conductivities.     

Inclusion of poly[bis(methoxyethoxyethoxy)phosphazene] into layered graphite oxide

The highly ionically conducting polymer poly[bis(methoxyethoxyethoxy)phosphazene] (MEEP) has been complexed with lithium triflate and intercalated between the layers of graphite oxide (GO). The resulting composite was characterized by powder X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and ionic conductivity measurements.     

Synthesis of fluorescent carbon dots from one-step pyrolysis of frontal-polymerized poly(acrylamide-co-4-vinylpyridine)

We report herein the synthesis of carbon dots (CDs) by a one-step pyrolysis from poly(acrylamide-co-4-vinylpyridine) [poly(AAM-co-4-VP)]. The poly(AAM-co-4-VP) was fabricated using frontal polymerization within 5 min in an easy and rapid way and then was pyrolyzed to afford CDs. The as-prepared CDs show crystalline structure and excellent dispersibility with particle sizes in the range of 2–4 nm. The optical properties were throughly investigated, and we found the CDs exhibit strong blue fluorescence with quantum yield of ~18 % and excellent photoluminescent stability, which is rarely influenced by the external conditions. This process can be exploited as an effective path for synthesis CDs with polymers by a facile and rapid way.     

Reactive sputtering TiO2 films for surface coating of poly(dimethylsiloxane)

Titanium dioxide (TiO₂) films were prepared on poly(dimethylsiloxane) (PDMS) substrate by direct current (DC) reactive sputtering to change surface physical properties of PDMS. The effects of the changes were investigated by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, water contact angle measurements and protein adsorption tests. Improved wettability and reduced adsorption properties were observed on PDMS surface coated TiO₂ films.     

Growth mechanism of carbon nanotubes produced by pyrolysis of a composite film of poly (vinyl alcohol) and fly ash

We produced carbon nanotubes (CNTs) by pyrolysis of a composite film of poly (vinyl alcohol) (PVA) with fly ash (FA) at 500°C for 10 min under nitrogen. The composite films were prepared by a suspension of PVA and FA in deionized water and cast onto glass petri dishes. The morphologies of the CNTs were observed in the images of scanning and transmission electron microscopy, showing different types of structures, e.g. whiskers, branches, ropes and graphene sheets. The widths of the CNTs measured varied in the range 18–80 nm. X-ray photoelectron spectroscopy analysis showed five types of carbon binding peaks, C–C/C–H (∼77%), C–O–H (∼9%), –C–O–C (∼5%), C=O (∼5%) and –O–C=O (∼3%). From an image of a broken CNT, a mechanism was proposed for the formation of CNTs. The CNTs grown on FA surfaces have potential for the fabrication of high-strength composite materials with polymer and metal.     

Influence of carbon coating on the electrochemical performance of SiO@C/graphite composite anode materials

Silicon monoxide(SiO) has been considered as one of the most promising anode materials for next generation highenergy-density Li-ion batteries(LiBs) thanks to its high theoretical capacity. However, the poor intrinsic electronic conductivity and large volume change during lithium intercalation/de-intercalation restrict its practical applications. Fabrication of SiO/C composites is an effective way to overcome these problems. Herein, a series of micro-sized SiO@C/graphite(Si0@C/G) composite anode materials, with designed capacity of 600 mAh·g~(-1), are successfully prepared through a pitch pyrolysis reaction method. The electrochemical performance of SiO@C/G composite anodes with different carbon coating contents of 5 wt%, 10 wt%, 15 wt%, and 35 wt% is investigated. The results show that the SiO@C/G composite with15-wt% carbon coating content exhibits the best cycle performance, with a high capacity retention of 90.7% at 25℃ and90.1% at 45 0 C after 100 cycles in full cells with LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2 as cathodes. The scanning electron microscope(SEM) and electrochemistry impedance spectroscopy(EIS) results suggest that a moderate carbon coating layer can promote the formation of stable SEI film, which is favorable for maintaining good interfacial conductivity and thus enhancing the cycling stability of SiO electrode.     

Surface modification of poly(propylene carbonate) by oxygen ion implantation

Poly(propylene carbonate) (PPC) was implanted by oxygen ion with energy of 40 keV. The influence of experimental parameters was investigated by varying ion fluence from 1 × 10¹² to 1 × 10¹⁵ ions/cm². XPS, SEM, surface roughness, wettability, hardness, and modulus were employed to investigate structure and properties of the as-implanted PPC samples. Eight chemical groups, i.e., carbon, CH, COC, CO, OCO, CO, , and groups were observed on surfaces of the as-implanted samples. The species and relative intensities of the chemical groups changed with increasing ion fluence. SEM images displayed that irradiation damage was related strongly with ion fluence. Both surface-recovering and shrunken behavior were observed on surface of the PPC sample implanted with fluence of 1 × 10¹⁵ ions/cm². As increasing ion fluence, the surface roughness of the as-implanted PPC samples increased firstly, reached the maximum value of 159 nm, and finally decreased down the minimum value. The water droplet contact angle of the as-implanted PPC samples changed gradually with fluence, and reached the minimum value of 70° with fluence of 1 × 10¹⁵ ions/cm². The hardness and modulus of the as-implanted PPC samples increased with increasing ion fluence, and reached their corresponding maximum values with fluence of 1 × 10¹⁵ ions/cm². The experimental results revealed that oxygen ion fluence closely affected surface chemical group, morphology, surface roughness, wettability, and mechanical properties of the as-implanted PPC samples.     

Crystallization of a poly(ethylene-co-octene): I A precursor structure and two competing mechanisms

Observations of a sample of poly(ethylene-co-octene)in a polarizing optical microscope reveal peculiarities in its crystallization behavior. When cooled from the melt to a fixed crystallization temperature, at first a structure of diffuse appearance with variations on the length scale of micrometers forms rapidly. The transformation into the final semi-crystalline state then proceeds in two ways, by a continuous change of the inner structure of m-sized objects and by the growth of spherulites. Time dependent small angle and wide angle X-ray scattering experiments corroborate the occurrence of the two crystallization mechanisms. Atomic force microscopy indicates that the change of the inner structure of the preformed objects is due to an in-filling of crystallites.     

Electron emission features of the derivatives of radiation carbonization of poly(vinylidene fluoride)

It has been studied how photoelectron and CKVV spectra of partially crystalline poly(vinylidene fluoride) (PVDF) are modified during a long-term degradation of its surface under soft X-rays (AlK _α), which is accompanied by a flow of secondary electrons having different energies, and upon exposure to a unfocused beam of 600 eV Ar⁺ ions. In both cases, the surface layer of the sample is enriched with carbon owing to defluorination. The shape of the electron emission spectra of the carbonized layer depends on an external effect; that is, whether soft X-ray photons or ions are used for defluorination. In the case of bombardment with Ar⁺, there is clear evidence for the dominance of the sp2 bonds between carbon atoms, as can be seen from the specific shape of the C KVV band and the C1s spectrum. The most surprising result of this study is that both photons and ions produce the same depth gradient of residual fluorine at an equal fluorine concentration in the carbonized surface layer. The reason for this is not clear and needs further investigation.     

Hydrophobic recovery of UV/ozone treated poly(dimethylsiloxane): adhesion studies by contact mechanics and mechanism of surface modification

Silicone elastomers (Sylgard 184 and 170), based on poly(dimethylsiloxane) (PDMS), were surface treated by a combined exposure to UV and ozone. The effects of the treatments were analyzed as a function of time elapsed after stopping the treatments using different standard surface characterization techniques, such as water contact angle measurements, XPS and atomic force microscopy (AFM). However, the primary focus of this study was to apply the Johnson–Kendall–Roberts (JKR) contact mechanics approach to investigate PDMS samples prior to and following UV/ozone surface treatment. A gradual formation of a hydrophilic, silica-like surface layer with increasing modulus was observed with increasing UV/ozone exposure. A subsequent hydrophobic recovery after UV/ozone exposure was observed, as indicated by increasing contact angles. This supports the hypothesis that the hydrophobic recovery is mainly caused by the gradual coverage of a permanent silica-like structure with free siloxanes and/or reorientation of polar groups. PDMS containing a homogenously dispersed filler (Sylgard 184), exhibited a decreasing surface roughness (by AFM) when the oxidized surface region “collapsed” into a smooth SiO_x layer (final surface roughness <2 nm). PDMS containing heterogeneously distributed, aggregated filler particles (Sylgard 170), exhibited an increasing surface roughness with treatment dose, which was attributed to the “collapse” of the oxidized surface region thus exposing the contours of the underlying filler aggregates (final surface roughness ∼140 nm). A dedicated device was designed and built to study the contact mechanics behavior of PDMS prior to, and following surface treatment. The value of the combined elastic modulus obtained for PDMS lens and semi-infinite flat surface system showed an increase in full agreement with the formation of a silica-like layer exhibiting a high elastic modulus (compared with untreated PDMS). The work of adhesion observed in JKR experiments exhibited an increasing trend as a function of treatment done in agreement with contact angle data. JKR experiments showed hydrophobic recovery behavior as anticipated from contact angle measurements. Single pull-off force measurements by JKR and numerical analysis of full-approach JKR curves were in quantitative agreement regarding practical work of adhesion values.     

The synthesis of multi-walled carbon nanotubes (MWNTs) by catalytic pyrolysis of the phenol-formaldehyde resins

A series of carbon nanomaterials, particularly multi-walled carbon nanotubes (MWNT), are obtained as products from catalytic pyrolysis of the cross-linked phenol-formaldehyde resins with different ferrocene under inert atmosphere. The morphology and structure of the samples were evaluated by TEM and XRD techniques. CNTs morphology is dependent on the iron nanoparticles and their forms (Fe, Fe₃C) resulted from ferrocene decomposition. The amount of nanotubes increases with iron content released from ferrocene catalyst during the pyrolysis process. Fe₃C nanoparticles drive the nucleation and the growth of carbon nanotubes during the pyrolysis process. Long (up to microns) well-defined MWNTs with small defects, ropes and disordered carbon are representatives in the pyrolyzed resins composition.     

Hydrothermal conversion of graphite to carbon nanotubes (CNTs) induced by bubble collapse

Cu–Fe–CNTs and Ni–Fe–CNTs coatings were deposited on gray cast iron by a hydrothermal approach. It was demonstrated that, the flaky graphite of gray cast iron was exfoliated to graphene nanosheets under hydrothermal reactions, and graphene nanosheets were scrolled to CNTs. After high temperature treatments, the volume losses of Cu–Fe–CNTs and Ni–Fe–CNTs coatings were 52.6 % and 40.0 % of gray cast iron substrate at 60 min wear tests, respectively, obviously increasing the wear properties of gray cast iron. During hydrothermal reactions, water jets and shock waves were produced by bubble collapse. Induced by the water jets and shock waves, exfoliation of flaky graphite was performed, producing exfoliated graphene nanosheets. Attacked by the radially distributed water jets and shock waves, graphene nanosheets were curved, shaped to semicircle morphology and eventually scrolled to tubular CNTs.     

Catholic discharge of graphite fluoride, (CF)n, prepared from several carbon materials, in lithium organic electrolyte batteries

Discharge characteristic of (CF)_n prepared from four kinds of carbon material, that is, natural graphite, petroleum coke, carbon black, and active carbon, were studied on the cell combined with a lithium anode and an organic electrolyte. (CF)_n from natural graphite and petroleum coke showed more stable discharge potential and higher energy density than those from carbon black and active carbon. This is explained in terms of the structures of their starting carbon materials. The orientation of the crystalline in (CF)_n, which inherited from the starting carbon, determines the potential stability. The overpotential (η) at the earlier discharge state was influenced by the interlayer spacing [d(001)] rather than the kind of carbon materials. A plot of η against d(001) of each (CF)_n indicates a negative linear correlation, viz., η decrease with increasing d(001). To study the effect of the degree of the regular layer-stacking, three (CF)_n having the nearly same d(001) but different β(001), the half-value of the (001) peak in the X-ray diffraction pattern, were prepared from natural graphite, and their discharge behavior compared with each other. The discharge potential increased with increasing β(001).     

Hematite reaction with tar to produce carbon/iron composites for the reduction of Cr(VI) contaminant

In this work, highly reactive carbon–iron composites were prepared using a waste, i.e. tar, as carbon precursor and a simple iron oxide, i.e. hematite. Tar was impregnated on Fe₂O₃ with different tar/hematite weight ratios of 1:1; 2:1 and 4:1, and thermally treated under N₂ atmosphere (400°C, 600°C and 800°C). Mössbauer, XRD and magnetization measurements suggested that treatment at 400°C and 600°C produces Fe₃O₄ but treatment at 800°C produced mainly Fe°. Raman and TG analyses of the different composites suggested the formation of carbon contents of 18, 24 and 32 wt.% as amorphous and graphitic highly dispersed on the Fe surface. The composites obtained at 800°C showed high efficiency to reduce Cr(VI) as CrO $_{4}^{2-}$ in aqueous medium with much better results compared to finely ground commercial Fe°.