Microbalance Techniques in Design and Control of Synthetic Carbons

Peculiarities of carbonization of two styrene/divinylbenzene precursors (one sulfonated, another aminated and phosphorylated) have been investigated by thermogravimetry and differential thermal analysis. It was shown that phosphorus compounds incorporate into carbon structure and cause delayed carbonization. Porous structure and surface properties of synthetic carbons have been investigated by standard (BET, α_s method, DA) and advanced (AED, PSD, regularization) methods from benzene and water adsorption isotherms. It was shown that phosphorus-containing carbon is less microporous and shows highly hydrophilic surface. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and characterization of bimodal porous carbons derived from a styrene-divinylbenzene copolymer

A styrene/divinylbenzene copolymer has been used as precursor for making porous carbons with bimodal pore size distributions (i.e., with both microporosity and mesoporosity). Pretreatment of the as-received copolymer by mild oxidation in air, significantly increased the carbon yield after carbonization. Reactivity studies of the polymer-based chars to CO₂ clearly show the influences of some important factors such as carbonization temperature, heating rate, soak time on char reactivities. Bimodal porous carbons were prepared by carbonization of the preoxidized styrene/divinylbenzene copolymer in N₂, followed by activation in CO₂ at different temperatures to different levels of burnoff. The pore structures of the porous carbons produced have been characterized by various techniques such as gas adsorption and mercury porosimetry. The surfaces of the porous carbons produced, and a commercial carbon adsorbent, have been modified with HNO₃ and H₂O₂ treatment at various conditions. Characterization of the surface oxygen functionality, both quantitatively and qualitatively, has been achieved using techniques such as Linear Temperature Programed Desorption (LTPD) and selective neutralization of bases.     

Novel synthesis of polymer and carbonaceous nanomaterials via a micelle/silicate nanostructured precursor

Mesoporous carbonaceous materials with relatively high surface area have been synthesized by a new method composed of in situ polymerization of divinylbenzene in the hydrophobic phase of a hexagonally arrayed micelle/silicate nanocomposite and subsequent carbonization and hydrofluoric acid treatments, while rod-like carbons were obtained from a direct incorporation of divinylbenzene into the mesopores of MCM-41.     

Synthesis, characterization, and electrochemical properties of ordered mesoporous carbons containing nickel oxide nanoparticles using sucrose and nickel acetate in a silica template

New ordered mesoporous carbons containing nickel oxide nanoparticles have been successfully synthesized by carbonization of sucrose in the presence of nickel acetate inside SBA-15 mesoporous silica template. The obtained samples were characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, and transmission electron microscopy (TEM). The NiO nanoparticles were embedded inside the mesoporous carbon framework due to the simultaneous pyrolysis of nickel acetate during carbonization. The electrochemical testing of the as-made nanocomposites showed a large specific capacitance of 230 F g⁻¹ using 2 M KOH as the electrolyte at room temperature. This is attributed to the nanometer-sized NiO formed inside mesoporous carbons and the high surface area of the mesopores in which the NiO nanoparticles are formed. Furthermore, the synthetic process is proposed as a simple and general method for the preparation of new functionalized mesoporous carbon materials, for various applications in catalysis, sensor or advanced electrode material.     

Influence of Mobile Phase Gradients on the Retention and Separation of Peptides from a Cytochrome-c Digest by Reversed-Phase Liquid Chromatography

Eight new carbon adsorbents derived from polyimide copolymer of 4,4'-bis (maleimododiphenyl)methane and divinylbenzene (BM-DVB) were prepared using a variety of methods. The influence of carbonization, steam or phosphoric acid activation on chemical structure and texture of the carbons has been studied. Adsorption-desorption properties of the carbons were estimated based on recovery determinations for, phenol, its chlorinated derivatives and naphthalene from aqueous solution. The results showed that the best adsorption-desorption properties have polymer-based carbons obtained by high temperature steam activation.Revised: 13 February 2006 and 3 April 2006     

Vitrimers: directing chemical reactivity to control material properties

The development of more sustainable materials with a prolonged useful lifetime is a key requirement for a transition towards a more circular economy. However, polymer materials that are long-lasting and highly durable also tend to have a limited application potential for re-use. This is because such materials derive their durable properties from a high degree of chemical connectivity, resulting in rigid meshes or networks of polymer chains with a high intrinsic resistance to deformation. Once such polymers are fully synthesised, thermal (re)processing becomes hard (or impossible) to achieve without damaging the degree of chemical connectivity, and most recycling options quickly lead to a drop or even loss of material properties. In this context, both academic and industrial researchers have taken a keen interest in materials design that combines high degrees of chemical connectivity with an improved thermal (re)processability, mediated through a dynamic exchange reaction of covalent bonds. In particular vitrimer materials offer a promising concept because they completely maintain their degree of chemical connectivity at all times, yet can show a clear thermally driven plasticity and liquid behavior, enabled through rapid bond rearrangement reactions within the network. In the past decade, many suitable dynamic covalent chemistries were developed to create vitrimer materials, and are now applicable to a wide range of polymer matrices. The material properties of vitrimers, however, do not solely rely on the chemical structure of the polymer matrix, but also on the chemical reactivity of the dynamic bonds. Thus, chemical reactivity considerations become an integral part of material design, which has to take into account for example catalytic and cross-reactivity effects. This mini-review will aim to provide an overview of recent efforts aimed at understanding and controlling dynamic cross-linking reactions within vitrimers, and how directing this chemical reactivity can be used as a handle to steer material properties. Hence, it is shown how a focus on a fundamental chemical understanding can pave the way towards new sustainable materials and applications.

In this minireview, we survey recent advances in the development of vitrimer materials. Focus on how to chemically control their material properties is used to highlight challenges for boosting the potential of this emerging class of polymer materials.     

Efficient thermal conversion of polyyne-type conjugated polymers to nano-structured porous carbon materials

Summary Some aromatic based conjugated polymers having carbon-carbon triple bonds moiety were synthesized and carbonized. The polymers were efficiently carbonized by heating up to 900°C under an argon atmosphere, affording porous carbons in high yields. The polymer characteristics were appropriate to form nano-structured carbons in the pyrolytic carbonization process. The carbon materials were consisted of 2-4 nm sized graphitic crystallites and had slit-shaped micropores with ca. 0.7 nm pore width. Structural defects in the pre-carbon materials caused generation of mesopores with ca. 4 nm pore width after carbonization.     

Application of Thermal Analysis to the Study of Some Waste Agricultural Products for the Preparation of Active Carbons

TG, DTG and DTA methods were used for the investigation of some waste agricultural products, such as grape seeds, walnut shells, plum and peach stones, which can serve as raw materials for the production of active carbons. It was demonstrated that thermo analytical methods are appropriate to study the thermal characteristics of the above wastes and the data obtained can be applied to the technological processes of active carbon preparation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres

~~Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres~~     

Thermal study and evaluation of new menthol-based ionic liquids as polymeric additives

Thermal properties of new ionic liquids (ILs) were investigated by thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC). Chlorides, tetrafluoroborates and hexafluorophosphates of (−)mentholpyrrolidinium and (−)-mentholimidazolium cations revealed good thermal stability at air atmosphere. Morphological characteristics of poly(methyl methacrylate) (PMMA) matrices doped with 10% of these ILs were also investigated by DRX and water absorption test. Into the matrix, they exhibited a very satisfactory pattern concerning the polymer thermal stabilization. DSC results show that some of these ILs also present plasticizer features since they can lower the polymer glass transition temperature (T _g) up to 317.15 K.     

Thermal studies of chitin–chitosan derivatives

New poly(azo) amino-chitosan compounds were obtained from the azo coupling reaction of N-benzyl chitosan and diazonium salts. The thermal behavior of these compounds was studied by thermogravimetric analysis (TG), differential thermogravimetric analysis (DTG), TG coupled with a Fourier-transform infrared, and differential scanning calorimetry (DSC). TG/DTG curves of chitin–chitosan polymer showed two thermal events attributed to water loss and decomposition of the polysaccharide after cross-linking reactions. Thermal analysis of the poly(azo) amino-chitosan compounds showed that the decomposition temperatures decreased when compared to the starting chitin–chitosan and N-benzyl chitosan. DSC results showed an agreement with the TG/DTG analyses. Thermal behavior of poly(azo) amino-chitosans suggest that these compounds could be considered as potential thermal sensors.     

Thermal stability of ionene polymers

Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer–clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na⁺ and little Ca²⁺. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol^?1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol^?1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene.     

New Regional Editor

Thermal decomposition of an agrowaste, namely banana trunk fibers (BTF) were investigated by thermogravimetry (TG) and derivative thermogravimetry (DTG) up to 900 °C at different heating rates (from 5 to 100 °C/min). The BTF was subjected to modification by means of various known chemical methods (mercerization, acetylation, peroxide treatment, esterification, and sulfuric acid treatment). Various degradation models, such as the Kissinger, Friedman, and Flynn–Wall–Ozawa were used to determine the apparent activation energy. The obtained apparent activation energy values (149–210 kJ/mol) allow in developing a simplified approach to understand the thermal decomposition behavior of natural fibers as a function of polymer composite processing.     

Sago/PVA blend membranes for the recovery of ethyl acetate from water

Sago starch is a relatively new polymeric material for development of a hydrophilic membrane for dehydration of alcohol/water. In this study sago based membranes were developed through casting technique for the dehydration of ethyl acetate at azeotropic conditions via pervaporation. Sago was blended with polyvinyl alcohol (PVA) to produce blended sago–PVA membranes with improved physical and chemical properties. The membranes were cross-linked using three different approaches; firstly, using glutaraldehyde, secondly using thermal treatment (80 °C) and thirdly by using both glutaraldehyde and thermal treatment. The effects of various cross-linking methods on the intrinsic properties of hydrophilic polymer membrane were investigated. The membranes were characterized using Fourier transform infrared (FTIR), differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The effect of operating conditions such as feed temperature and concentration on the separation factor and flux was discussed. Sago starch polymer shows very high performance and very good stability after polymer blending and cross-linking, which is promising for use in industrial applications.     

Cross-linking copolymers of acrylates’ gel electrolytes with high conductivity for lithium-ion batteries

The cross-linking gel copolymer electrolytes containing alkyl acrylates, triethylene glycol dimethacrylate, and liquid electrolyte were prepared by in situ thermal polymerization. The gel polymer electrolytes containing 15 wt% polymer content and 85 wt% liquid electrolyte content with sufficient mechanical strength showed the high ionic conductivity around 5?×?10^?3 Scm^?1 at room temperature. The gel electrolytes containing different polymer matrices were prepared, and their physical observation and conductivity were discussed carefully. The cross-linking copolymer gel electrolytes of alkyl acrylates with other monomers were designed and synthesized. The results showed that copolymerization can improve the mechanical properties and ionic conductivities of the gel electrolytes. The polymer matrices of gels had excellent thermal stability and electrochemical stability. The scanning electron microscope analysis showed the gel electrolyte was the homogeneous structure, and the cross-linking polymer host was the porous three-dimensional network structure, which demonstrated the high conductivity of the gel electrolytes. The gel polymer Li-ion battery was prepared by this in situ thermal polymerization. The cell exhibited high charge-discharge efficiency at 0.1 C. The results of LiFePO4-PEA-Li cell and graphite-PEA-Li cell showed that gel polymer electrolytes have good compatibility with the battery electrodes materials.     

Investigating parameters on the preparation of mesoporous activated carbons by the combination of chemical and physical activations using the Taguchi method

Mesoporous activated carbons were prepared from coconut shell by the combination of chemical and physical activation methods. Zinc chloride and CO₂ were used as chemical and physical agents, respectively. Optimum parameters were obtained from investigating the effect of various factors at different levels on the methane storage of wet activated carbons using the Taguchi experimental design method. Soaking time, carbonization temperature, and carbonization time were found as effective parameters in the methane storage. Finally, after achieving optimum levels for each factors based on the enhancement of methane storage, a confirmation experiment was conducted. Methane uptakes of the activated carbons were measured at temperature of 2?^°C up to the pressure of 80 bar and it turned out that the maximum amount of methane storage (241?V/V) had a good agreement with the predicted result from the Taguchi method.     

Synthesis of polymer nanocomposite ion-exchange membranes from sulfonated polystyrene and study of their properties

Methods for the preparation of composite ion-exchange membranes from polymer (polyvinylidene fluoride (PVDF), ultrahigh molecular weight polyethylene (UHMWPE), and polypropylene (PP)) matrices were considered. Polystyrene (PS) was introduced in the matrices by thermal polymerization of the monomer followed by sulfonation of the implant. The fundamentals of membrane synthesis from industrial polytetrafluoroethylene (PTFE, Teflon F-4) films by thermal polymerization of styrene in a film stretched in a monomer solution followed by sulfonation of incorporated PS were described. The literature on radiation- chemical synthesis of composite ion-exchange membranes based on polymer matrices with embedded polystyrene and its subsequent sulfonation was analyzed. Some problems of the kinetics and mechanism of thermal implantation of PS into various polymer matrices under different conditions were discussed. The physicochemical characteristics, structure, and transport properties of the membranes synthesized by thermal implantation of PS were reported. The obtained membranes were tested in low-temperature fuel cells.     

Thermal degradation of natural and treated hemp hurds under air and nitrogen atmosphere

Sustainability goals are essential driving principles for the development of innovative materials in the construction industry. Natural fibers represent an attractive alternative as reinforcing material due to good mechanical properties and sustainability prerequisites. The study has been focused on the comparative investigation of chemical and physical treatments of hemp hurds and their influence on the thermal behavior of main hemp constituents in air and nitrogen atmosphere. Thermal decomposition of hemp hurds involves several parallel reactions related to heat and mass transfer processes. A comparison of DSC and TG/DTG results of hemp hurds samples before and after treatments demonstrates a better thermal stability for treated samples. It is caused by changes in chemical composition due to a partial removal of non-cellulosic components from hemp hurds structure, an increase in cellulose content and decrease in its degree of polymerization. The results show different thermal behavior of the hurds samples heated under nitrogen and air atmosphere. Based on DTG records, several-stage process of mass loss has been found for the samples under air, whereas only two-stage process under nitrogen.

     

Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic paths, applications, and perspectives

Utilization of metallic nanoparticles in various biotechnological and medical applications represents one of the most extensively investigated areas of the current materials science. These advanced applications require the appropriate chemical functionalization of the nanoparticles with organic molecules or their incorporation in suitable polymer matrices. The intensified interest in polymer nanocomposites with silver nanoparticles is due to the high antimicrobial effect of nanosilver as well as the unique characteristics of polymers which include their excellent structural uniformity, multivalency, high degree of branching, miscellaneous morphologies and architectures, and highly variable chemical composition. In this review, we explore several aspects of antimicrobial polymer silver nanocomposites, giving special focus to the critical analysis of the reported synthetic routes including their advantages, drawbacks, possible improvements, and real applicability in antibacterial and antifungal therapy. A special attention is given to "green" synthetic routes exploiting the biopolymeric matrix and to the methods allowing preparing magnetically controllable antimicrobial polymers for targeting to an active place. The controversial mechanism of the action of silver against bacteria, fungi and yeasts as well as perspectives and new applications of silver polymeric nanocomposites is also briefly discussed.     

Mesoporous Activated Carbon from Agricultural Byproducts

 Several different activated carbons have been prepared, from olive stones, solvent-extracted olive pulp and peach stones. Both a two-step procedure, carbonization followed by steam activation, and a single-step procedure, carbonization and activation in a single stage, have been applied at temperatures from 770 to 850 °C. The effect of such variables as heating rate during carbonization and activation, final temperature, soaking time and starting material, on the development of pore structure, have been investigated. Porosity and surface area have been evaluated by adsorption of nitrogen at 77 K. Mesoporosity and macroporosity were determined by mercury porosimetry. Scanning electron microscopy and X-ray diffraction analysis revealed useful information on the surface texture and structure respectively. Two-step physical activation of olive stones, with steam, yielded mesoporous structures. Extended time of activation favoured mesopore development. The parent olive stones showed the most homogeneous surfaces. All the activated carbons prepared were amorphous. Their well-developed porosity and large surface area combined with their chemical composition render the activated carbons from agricultural by-products an attractive product.