Jelena Macan

Study of thermal stability of (3-aminopropyl) trimethoxy silane-grafted titanate nanotubes for application as nanofillers in polymers

Protonated titanate nanotubes (TiNT-H) were surface-modified with (3-aminopropyl)trimethoxy silane (APTMS) by a novel method suitable for the syntheses of large amounts of materials at a low cost. The usage of prepared nanotubes for polymer reinforcement was studied. Since the thermal stability of the nanofiller was important to preserve its functional properties, its stability was studied by in situ high-temperature measurements. The most thermally stable nanotubes were silanized for 20 min and used for the preparation of epoxy-based nanocomposites. The nanofiller formed smaller (a few hundred nm) and larger (a few μm) aggregates in the polymer matrix, and the amount of aggregates increased as the nanofiller content increased. The APTMS-modified titanate nanotubes bonded well with the epoxy matrix since amine groups on the TiNTs surface can react with an epoxy group to form covalent bonds between the matrix and the nanofiller. A very small addition (0.19-1.52 wt%) of the nanotubes significantly increased the glass transition temperature and the modulus in the rubbery state of the epoxy-based polymer. Smaller nanofiller content leads to a larger increase in these parameters and therefore better dynamic mechanical properties due to the smaller amount of large aggregates. APTMS-modified titanate nanotubes have proven to be a promising nanofiller in epoxy-based nanocomposites.

Determination of anionic surfactants in real samples using a low-cost and high sensitive solid contact surfactant sensor with MWCNTs as the ion-to-electron transducer

Multi-walled carbon nanotubes (MWCNTs) were used as a conducting substrate for construction of an all solid contact anionic surfactant sensor, which used the 1,3-didecyl-2-methylimidazolium–tetraphenylborate (DMI–TPB) ion pair as the sensing element implemented in PVC membranes. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) were used for morphological and electrochemical characterisation of the sensor. The investigated sensor showed a Nernstian response for lauryl sulfate (LS), 57.1 mV per decade of activity between 2.0 × 10−7 and 1.1 × 10−3 M; and a sub-Nernstian response for dodecylbenzenesulfonate (DBS), 51.1 mV per decade of activity between 3.6 × 10−7 and 6.6 × 10−4 M. For each ten-fold concentration change, the response time was 7 s (in the range from 1 × 10−6 M to 5 × 10−4 M). The detection limits for LS and DBS in water were 1.2 × 10−7 and 2.6 × 10−7 M, respectively. The sensor revealed a stable potentiometric response at pH 3–13 with a signal drift of 1.9 mV h−1 and exhibited outstanding selectivity performances for LS toward the majority of organic and inorganic anions that are most frequently employed in commercial formulations based on surfactants. The new sensor was applied for end-point location at potentiometric anionic surfactant titrations. Cetyltrimethylammonium bromide (CTAB) was used as a standard cationic titrant in all titrations. Ethoxylated non-ionic surfactants (EONSs) with a higher content of ethoxylated groups in the molecule and higher concentrations of EONSs reduce the magnitude of inflexion of titration curves and may cause a remarkable distortion during anionic surfactant (AS) determination. The sensor was tested by determination of ASs in commercial detergent products. The standard two-phase titration method and a conventional PVC liquid membrane surfactant sensor (PVCSS) showed satisfactory mutual agreement. The low-cost surfactant sensor developed had an operational lifetime of ca. six months.

Environmentally acceptable sorbents of chemical warfare agent simulants

Development of environmentally acceptable decontaminants of chemical weapons and other highly toxic chemicals is important because of security, economical, health, political, and environmental reasons. The efficiency of natural zeolite (clinoptilolite) and synthetic zeolite, metal oxides, and their mixtures as chemical and physical sorbents of chemical warfare agents (CWA) was investigated. Commonly studied chemical warfare agent simulants dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (2-CEES) were included in this study. Organic solutions of DMMP and 2-CEES were passed through a column filled with natural and synthetic zeolites and their mixtures with metal oxides. After passing through the column filled with different sorbents, all eluents were filtered and centrifuged before the gas chromatography–mass spectroscopy (GC–MS) analysis. The efficiency of investigated adsorbents was estimated based on the obtained data. All investigated sorbents exhibited absorption efficiency for both simulants of chemical warfare agents. Infrared spectroscopy was used for the detection of DMMP and 2-CEES adsorbed to the investigated adsorbents. Since GC–MS analysis results indicate very good sorption properties of both simulants, the detection of adsorbed CWA simulants was a matter of routine.

Nomenklaturni prikaz: Nazivlje za agregiranje i samoudruživanje u znanosti o polimerima (IUPAC-ove preporuke 2013.)

Nekoc su se agregiranje i samoudruživanje molekula povezivali prvenstveno s micelnim i koloidnim molekulskim sustavima. Međutim, razvoj supramolekulske kemije omogucio je mnogo dublje razumijevanje molekulskog samoudruživanja, a time i stvaranje raznolikih oblika i velicina, uz konstrukciju novih i ocaravajucih molekulskih topologija. Cilj ovog dokumenta jest definirati vise od 150 naziva vezanih uz agregiranje i samoudruživanje makromolekula. Popis je ogranicen na najcesce nazive.

Nomenclature Note: Terminology for Aggregation and Self-Assembly in Polymer Science (IUPAC Recommendations 2013)

Nekoc su se agregiranje i samoudruživanje molekula povezivali prvenstveno s micelnim i koloidnim molekulskim sustavima. Međutim, razvoj supramolekulske kemije omogucio je mnogo dublje razumijevanje molekulskog samoudruživanja, a time i stvaranje raznolikih oblika i velicina, uz konstrukciju novih i ocaravajucih molekulskih topologija. Cilj ovog dokumenta jest definirati vise od 150 naziva vezanih uz agregiranje i samoudruživanje makromolekula. Popis je ogranicen na najcesce nazive.

Formation mechanisms of sol-gel derived cordierite

Gels with cordierite stoichiometry, Mg2Al4Si5O18, were prepared by sol-gel technique using three different starting aluminum sources: nano-sized γ-Al2O3, aluminium nitrate nonahydrate and Al-sec-butoxide, as aluminum sources, using tetraetoxysilane (TEOS) and magnesium nitrate hexahydrate in all three gels as sources for silicon and magnesium. The influence of Al-precursors on formation mechanism and sintering behavior of gels was studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and dilatometry. Gels calcined at 700°C were characterized by different specific surface area, pore sizes and different crystallization sequences. For gel with nano-sized γ-Al2O3 α-cordierite was formed at 1220°C through intermediate MgAl2O4 phase. If aluminum was introduced as Al-sec-butoxide μ-cordierite crystallized in two steps (760 and 1070°C) and the transformation μ-cordierite→α-cordierite occurred at 1250°C. When Al(NO3)3·9H2O was introduced as intermediate phase crystallized MgAl2O4 at ~870°C and μ- cordierite at ~950°C. Both phases reacted with amorphous silica forming α-cordierite at ~1210°C. Compacts prepared from gels with aluminum-nitrates and Al-sec-butoxide, respectively, sintered between 700 and 1000°C, whereas the gel derived from γ-Al2O3 sintered in two steps; between 700- 1000°C and 1010 and 1250°C.