Thermogravimetric analysis of water release from wheat flour and wheat bran suspensions

Bran is hygroscopic and competes actively for water with other key components in baked cereal products like starch and gluten. Thermogravimetric analysis (TGA) of flour–water mixtures enriched with bran at different incorporation levels was performed to characterise the release of compartmentalised water. TGA investigations showed that the presence of bran increased compartmentalised water, with the measurement of an increase of total water loss from 58.30 ± 1.93% for flour only systems to 71.80 ± 0.37% in formulations comprising 25% w/w bran. Deconvolution of TGA profiles showed an alteration of the distribution of free and bound water, and its interaction with starch and gluten, within the formulations. TGA profiles showed that water release from bran-enriched flour is a prolonged event with respect to the release from non-enriched flour, which suggests the possibility that bran may interrupt the normal characteristic processes of texture formation that occur in non-enriched products.

Influence of experimental factors on results of thermogravimetric analysis

Thermogravimetric results are influenced by a series of experimental factors, such as furnace heating rate and atmosphere, velocity of carrier gas, sample mass, etc. In this work a practical evaluation of these parameters are showed for calcium oxalate, with teaching objectives, considering that undergraduate text books discuss but do not show experimental details for these cases.

Use of high-resolution thermogravimetric analysis (HRTG) technique in spent FCC catalyst/Portland cement pastes

Thermogravimetric analysis is one of the most common instrumental techniques used for the characterization of pastes, mortars and concretes based on both calcium hydroxide and Portland cement. Important information about pozzolanic materials can be assessed concerning calcium hydroxide consumption and the formation of new hydrated products. Nevertheless, in some cases, problems associated with the overlapped decomposition processes for hydrates make the analysis of obtained data difficult. In this paper, the use of high-resolution thermogravimetric analysis, a powerful technique that allows separating decomposition processes in analysis of hydrated binders, was performed for spent FCC catalyst-Portland cement pastes. These pastes were monitored for 1, 4, 8 h and 1, 2, 3, 7 and 28 curing days. In order to study the influence of the pozzolanic material (spent FCC catalyst), Portland cement replacements of 5, 15 and 30 % by mass were carried out. The presence of spent FCC catalyst in blended pastes modified the amount and the nature of the formed hydrates, mainly ettringite and stratlingite.

Thermogravimetric analysis of the pyrolysis of several materials used in the preparation of commercial cigarettes

Comunicación presentada en forma de póster en el "12th Mediterranean Congress of Chemical Engineering", Barcelona (Spain), November 15-18, 2011

Kinetic study of the pyrolysis of miscanthus and its acid hydrolysis residue by thermogravimetric analysis

The kinetic parameters of the pyrolysis of miscanthus and its acid hydrolysis residue (AHR) were determined using thermogravimetric analysis (TGA). The AHR was produced at the University of Limerick by treating miscanthus with 5 wt.% sulphuric acid at 175 °C as representative of a lignocellulosic acid hydrolysis product. For the TGA experiments, 3 to 6 g of sample, milled and sieved to a particle size below 250 μm, were placed in the TGA ceramic crucible. The experiments were carried out under non-isothermal conditions heating the samples from 50 to 900 °C at heating rates of 2.5, 5, 10, 17 and 25 °C/min. The activation energy (EA) of the decomposition process was determined from the TGA data by differential analysis (Friedman) and three isoconversional methods of integral analysis (Kissinger–Akahira–Sunose, Ozawa–Flynn–Wall, Vyazovkin). The activation energy ranged from 129 to 156 kJ/mol for miscanthus and from 200 to 376 kJ/mol for AHR increasing with increasing conversion. The reaction model was selected using the non-linear least squares method and the pre-exponential factor was calculated from the Arrhenius approximation. The results showed that the best fitting reaction model was the third order reaction for both feedstocks. The pre-exponential factor was in the range of 5.6 × 1010 to 3.9 × 10+ 13 min− 1 for miscanthus and 2.1 × 1016 to 7.7 × 1025 min− 1 for AHR.

Tortoiseshell or Polymer? Spectroscopic Analysis to Redefine a Purported Tortoiseshell Box with Gold Decorations as a Plastic Box with Brass

The study and preservation of museum collections requires complete knowledge and understanding of constituent materials that can be natural, synthetic, or semi-synthetic polymers. In former times, objects were incorporated in museum collections and classified solely by their appearance. New studies, prompted by severe degradation processes or conservation-restoration actions, help shed light on the materiality of objects that can contradict the original information or assumptions. The selected case study presented here is of a box dating from the beginning of the 20th century that belongs to the Portuguese National Ancient Art Museum. Museum curators classified it as a tortoiseshell box decorated with gold applications solely on the basis of visual inspection and the information provided by the donor. This box has visible signs of degradation with white veils, initially assumed to be the result of biological degradation of a proteinaceous matrix. This paper presents the methodological rationale behind this study and proposes a totally non-invasive methodology for the identification of polymeric materials in museum artifacts. The analysis of surface leachates using 1H and 13C nuclear magnetic resonance (NMR) complemented by in situ attenuated total reflection infrared spectroscopy (ATR FT-IR) allowed for full characterization of the object s substratum. The NMR technique unequivocally identified a great number of additives and ATR FT-IR provided information about the polymer structure and while also confirming the presence of additives. The pressure applied during ATR FT-IR spectroscopy did not cause any physical change in the structure of the material at the level of the surface (e.g., color, texture, brightness, etc.). In this study, variable pressure scanning electron microscopy (VP-SEM-EDS) was also used to obtain the elemental composition of the metallic decorations. Additionally, microbiologic and enzymatic assays were performed in order to identify the possible biofilm composition and understand the role of microorganisms in the biodeterioration process. Using these methodologies, the box was correctly identified as being made of cellulose acetate plastic with brass decorations and the white film was identified as being composed mainly of polymer exudates, namely sulphonamides and triphenyl phosphate.

Kinetic study of the thermal degradation of high density polyethylene

The thermal degradation of high density polyethylene has been modelled by the random breakage of polymer bonds, using a set of population balance equations. A model was proposed in which the population balances were lumped into representative sizes so that the experimentally determined molecular weight distribution of the original polymer could be used as the initial condition. This model was then compared to two different cases of the unlumped population balance which assumed unimolecular initial distributions of 100 and 500 monomer units, respectively. The model that utilised the experimentally determined molecular weight distribution was found to best describe the experimental data. The model fits suggested a second mechanism in addition to random breakage at slow reaction rates. (c) 2005 Elsevier Ltd. All rights reserved.

Synthesis and characterisation of hybrid gold/polymer nanoparticles for bioassay application

A bioassay technique, based on surface-enhanced Raman scattering (SERS) tagged gold nanoparticles encapsulated with a biotin functionalised polymer, has been demonstrated through the spectroscopic detection of a streptavidin binding event. A methodical series of steps preceded these results: synthesis of nanoparticles which were found to give a reproducible SERS signal; design and synthesis of polymers with RAFT-functional end groups able to encapsulate the gold nanoparticle. The polymer also enabled the attachment of a biotin molecule functionalised so that it could be attached to the hybrid nanoparticle through a modular process. Finally, the demonstrations of a positive bioassay for this model construct using streptavidin/biotin binding. The synthesis of silver and gold nanoparticles was performed by using tri-sodium citrate as the reducing agent. The shape of the silver nanoparticles was quite difficult to control. Gold nanoparticles were able to be prepared in more regular shapes (spherical) and therefore gave a more consistent and reproducible SERS signal. The synthesis of gold nanoparticles with a diameter of 30 nm was the most reproducible and these were also stable over the longest periods of time. From the SERS results the optimal size of gold nanoparticles was found to be approximately 30 nm. Obtaining a consistent SERS signal with nanoparticles smaller than this was particularly difficult. Nanoparticles more than 50 nm in diameter were too large to remain suspended for longer than a day or two and formed a precipitate, rendering the solutions useless for our desired application. Gold nanoparticles dispersed in water were able to be stabilised by the addition of as-synthesised polymers dissolved in a water miscible solvent. Polymer stabilised AuNPs could not be formed from polymers synthesised by conventional free radical polymerization, i.e. polymers that did not possess a sulphur containing end-group. This indicated that the sulphur-containing functionality present within the polymers was essential for the self assembly process to occur. Polymer stabilization of the gold colloid was evidenced by a range of techniques including, visible spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and Raman spectroscopy. After treatment of the hybrid nanoparticles with a series of SERS tags, focussing on 2-quinolinethiol the SERS signals were found to have comparable signal intensity to the citrate stabilised gold nanoparticles. This finding illustrates that the stabilization process does not interfere with the ability of gold nanoparticles to act as substrates for the SERS effect. Incorporation of a biotin moiety into the hybrid nanoparticles was achieved through a =click‘ reaction between an alkyne-functionalised polymer and an azido-functionalised biotin analogue. This functionalized biotin was prepared through a 4-step synthesis from biotin. Upon exposure of the surface-bound streptavidin to biotin-functionalised polymer hybrid gold nanoparticles, then washing, a SERS signal was obtained from the 2-quinolinethiol which was attached to the gold nanoparticles (positive assay). After exposure to functionalised polymer hybrid gold nanoparticles without biotin present then washing a SERS signal was not obtained as the nanoparticles did not bind to the streptavidin (negative assay). These results illustrate the applicability of the use of SERS active functional-polymer encapsulated gold nanoparticles for bioassay application.

Thermogravimetric and mass-spectrometric study of the thermal decomposition of PBCT resins

The thermal decomposition of three commercial samples of carboxy-terminated polybutadiene (PBCT) resins was studied by thermogravimetric analysis (TGA) at heating rates varying from 2° to 100°C/min. Kinetic parameters of the decomposition process at different heating rates were evaluated by means of the Fuoss method.1 The decomposition process and the activation energy values are found to be dependent on heating rate. Mass-spectrometric analysis of the decomposition products shows that the pyrolysis products of PBCT resins are mainly low molecular weight hydrocarbons: ethylene, acetylene, butadiene, propadiene, vinylcyclohexene, etc. The rates of evolution of these hydrocarbon products vary with the carboxy content of the PBCT resin. Based on this, a carbonium ion mechanism has been suggested for the thermal decomposition. The data generated from this work are of importance for a consideration of the mechanism of combustion of composite solid propellants based on PBCT binders.

Thermal analysis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) irradiated under vacuum

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was irradiated by Co-60 gamma-rays (doses of 50, 100 and 200kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one-step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight-loss step change. The onset degradation temperature (T-o) and the temperature of maximum weight-loss rate (T-p) of control and irradiated PHBV were in line with the heating rate (degreesC min(-1)). T-o and T-p of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that Co-60 gamma-radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T-m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

High-performance composite from epoxy and glass fibers : morphology, mechanical, dynamic mechanical, and thermal analysis

Diglycidyl ether of bisphenol-A type epoxy resin cured with diamino diphenyl sulfone was used as the matrix for fiber-reinforced composites to get improved mechanical and thermal properties for the resulting composites. E-glass fiber was used for fiber reinforcement. The morphology, tensile, flexural, impact, dynamic mechanical, and thermal properties of the composites were analyzed. The tensile, flexural, and impact properties showed dramatic improvement with the addition of glass fibers. Dynamic mechanical analysis was performed to obtain the Tg of the cured matrix as well as the composites. The improved thermal stability of the composites was clear from the thermogravimetric analysis. Scanning electron micrographs were taken to understand the interfacial adhesion between the fiber and the matrix. The values of mechanical properties were compared with modified epoxy resin composite system. Predictive models were applied using various equations to compare the mechanical data obtained theoretically and experimentally.