Polymer degradation and stability

This edition of Polymer Degradation and Stability is dedicated to papers which were presented in the session on ‘Chemical Modification’ at the Third International Conference on Modification Degradation and Stabilisation of Polymers (MoDeSt) held in Lyon in August 2004. This was the third meeting of the MoDeSt Society which was set up in the year 2000 under the chairmanship of Professor Franco LaMantia; the earlier meetings were held in Palermo (2000) and Budapest (2002). The overall goal of the MoDeSt Society is to promote the latest research carried out in University laboratories, in public organisations and in industry through publications, and organisation of biannual scientific conferences and workshops that act as forums for scientific developments and for promoting networking between academics and industrialists from across the field of polymer modification, degradation and stabilisation. In September 2004, Professor Norman Billingham was elected as Chairman of the Society. The conference was organised by Dr Alain Michel and Veronique Bounor-Legare of the University Claude Bernard, Lyon 1, attracting over 250 delegates with the ‘Chemical Modification’ Session alone enjoying 54 oral presentations and many more poster presentations. We are all very grateful to the organisers for running such a successful and enjoyable meeting. I wish to thank my co-editors, Professors Philippe Dubois and Domenico Acierno and Dr Alain Michel, for their cooperation in the editorial task of the papers published in this special issue. On behalf of the editors of this issue, I wish to express our appreciation to the Editor-in-Chief of Polymer Degradation and Stability, Professor Norman Billingham, for the support and help received during the preparation of this special issue.

Fibre Bragg grating sensors in polymer optical fibres

This review paper summarises the current state of research into polymer optical fibre grating sensors. The properties of polymers are explored to identify situations where polymers offer potential advantages over more conventional silica fibre sensing technology. Photosensitivity is discussed and the sensitivities of polymer fibre gratings to strain, temperature and water are described. Finally, applications are reported which utilise the unique properties of polymer fibres.

Caracterização e separação física de placas de circuito impresso de computadores obsoletos

The unbridled consumption of electronic equipment associated with fast immersion of new technologies on the market leads to the accelerated growth of electronic waste. Such waste mostly contains printed circuit boards in its structure. Printed circuit boards have many metals, including heavy metals, being highly toxic. Electronic waste is discarded improperly and indiscriminately, usually without any previous treatment and with other municipal waste, contaminating the environment and causing serious problems to human health. Beyond these metals, there are also precious metals and high value-added basis, that can be recovered and recycled, reducing the exploration of natural resources. Thus, due to the high growth potential and reuse of these waste treatment processes, characterization and separation were applied to the printed circuit boards. The printed circuit boards were subjected to physical treatments such as dismantling, crushing, sizing separation, magnetic separation and chemical treatments such as pyrolysis and leaching. Through characterization process (pyrolysis and leaching) the proportions of the components of the granulometric range were determined: 46,08% of metals; 23,32% of polymers and 30,60% of ceramics. It was also observed by particle size separation that metal components tend to concentrate in coarse fractions, while polymeric and ceramic components in fine fractions. From the magnetic separation process was obtained 12,08% of magnetic material and 82,33% of non-magnetic material.

Grafting functional antioxidants on highly crosslinked polyethylene

The problem of interference of antioxidants, such as hindered phenols, with peroxide-initiated crosslinking of polyethylene was addressed through the use of functional (reactive) graftable antioxidants (g-AO). Reactive derivatives of hindered phenol and hindered amine antioxidants were synthesised, characterised and used to investigate their grafting reactions in high density polyethylene; both non-crosslinked (PE) and highly peroxide-crosslinked (PEXa). Assessment of the extent of in-situ grafting of the antioxidants, their retention after exhaustive solvent extraction in PE and PEXa, and the stabilising performance of the grafted antioxidants (g-AO) in the polymer were examined and benchmarked against conventionally stabilised crosslinked & non-crosslinked polyethylene. It was shown that the functional antioxidants graft to a high extent in PEXa, and that the level of interference of the g-AOs with the polymer crosslinking process was minimal compared to that of conventional antioxidants which bear the same antioxidant function. The much higher level of retention of the g-AOs in PEXa after exhaustive solvent extraction, compared to that of the corresponding conventional antioxidants, accounts for their superior long-term thermal stabilising performance under severe extractive conditions.

Desempenho de sementes de soja revestidas com biopolímeros

The use of biopolymers that help to fix pesticides efficiently and degrade easily without harming the environment, and still improve the physiological performance of field soybean seed may bring contributions to the soybean yield. This study aimed to evaluate the effect of cassava starch polymers (AM), sodium alginate (ALG) and polyvinyl alcohol (PVOH), in the concentrations 2, 4 and 6 g / 100 ml of solution, in the physiological attributes of seeds soy, seed speed soaking and performance of soybean seeds after three months of storage. The soybean variety used was the NK 7059 RR. The experimental design used for the three studies was a factorial with 48 experimental units: 3 polymers (AM, ALG and PVOH), 4 different concentrations (0%, 2%, 4% and 6%), with four replications, in a completely randomized design. It was observed the level of significance of the factors and their interactions, applying the test F. The polymers were evaluated by the Tukey test at 5% probability, and the concentrations were evaluated by polynomial regression. The witness obtained better results for most variables studied. Among the polymers, the best coating was observed PVOH because it was the less viscous polymer and visually not served as a substrate for microorganisms. However, also, satisfactory results were obtained for the AM and ALG polymers at a concentration of 2%. There was not interference of the polymers studied with regard to reduction of imbibition rate of soybean seeds. The hydrophilicity of polymers, mainly the AM and ALG accelerated soaking seeds harming germination at concentrations 4% and 6%. In general, the higher the concentration of polymers tended to worse results.

Ad-atoms and their enhancement effects on Pt activity for formic acid oxidation

Formic acid oxidation has been widely studied at Pt as a model reaction to understand fundamental aspects of electrocatalytic reactions in fuel cells. Electrocatalytic oxidation of formic acid takes place through two parallel pathways (direct and indirect). The indirect pathway proceeds via CO as an intermediate, which is known to be responsible for the poisoning of Pt and its consequent decrease in activity. Surface modification of Pt with ad-atoms is known to hinder this poisoning and promote the direct pathway. The incorporation of polymers (polyaniline, polycarbazole, polyindole) as supports also increases activity. Irreversibly adsorbed Sb and Bi on Pt are known to show high electrocatalytic activity for formic acid oxidation. This work presents the dependence of Sb and Bi irreversible adsorption on immersion time, metal solution concentration and pH. The activity of Sb and Bi modified Pt was correlated against immersion time and percent coverage of Pt by ad-atoms. Polyaniline support effects in combination with a Bi modified Pt catalyst showed enhancement in oxidation current compared to Pt-Bi.

Symmetry-breaking in chiral polymerisation

We propose a model for chiral polymerisation and investigate its symmetric and asymmetric solutions. The model has a source species which decays into left- and right-handed types of monomer, each of which can polymerise to form homochiral chains; these chains are susceptible to `poisoning' by the opposite handed monomer. Homochiral polymers are assumed to influence the proportion of each type of monomer formed from the precursor. We show that for certain parameter values a positive feedback mechanism makes the symmetric steady-state solution unstable. The kinetics of polymer formation are then analysed in the case where the system starts from zero concentrations of monomers and chains. We show that following a long induction time, extremely large concentrations of polymers are formed for a short time, during this time an asymmetry introduced into the system by a random external perturbation may be massively amplified. The system then approaches one of the steady-state solutions described above.

Efeito de argilas organofílicas na estrutura e propriedades de nanocompósitos de poli(metacrilato de metila)

Nacomposites of polymers and lamellar clayminerals, has generated high scientific and technological interest, for having mechanical properties and gas barriers differentiated of polymers and conventional composites. In this work, it was developed nanocomposites by single screw extruder and injection, utilizing commercial raw material, with the goal to investigate the quality of new developed materials. It was evaluated the influence of the content and the kind of clay in the structure and in the nanocomposites properties. It was used regular and elastomeric poly (methyl methacrylate) (Acrigel LEP 100 and Acrigel ECP800) and six montmorillonites (Cloisite 10A, 11B, 15A, 20A, 25A e 30B) at the concentration of 1% e 3% in weight. The nanocomposites were characterized by X-ray diffraction (XRD), thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), colorimetric, optical transparency, flexural and tensile tests, Rockwell hardness and esclerometry. It was founded that is possible to obtain intercalated and exfoliated nanocomposites PMMA/MMT, and the top results was obtained in the materials with 1%in clay weight organophilizated with 2M2HT (Cloisite 15A and 20A) presented intercalate and hybrid morphology (exfoliated and flocullated). The ones that was produced with organophilizated clay with 2MHTL8 (Cloisite 30B) had excellent visual quality, but the majority presented hybrid morphology. In the materials processed with organophilizated clay with MT2ETOH (Cloisite 30B), there were color change and loss of transparency. It occurs improvement in a few mechanical properties, mainly in the materials produced with PMMA elastomeric (Acrigel ECP800), being more significant, the increase in the resistance to stripping in those nanocomposites

Comb-like acrylic-based polymer latexes containing nano-sized crystalline or liquid crystalline domains

306 p.

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

CO2 utilization and alternative solvents: effective tools for sustainable applications

The growing concentration of CO2 in the atmosphere and its harmful consequences has led the scientific community to direct its efforts towards sustainable processes. Among the possible approaches, the use of CO2 and alternative solvents are two strategies that are having widespread diffusion. In this work the reuse of CO2 is expressed by using it as a reaction reagent and as trigger to change the physical properties of a catalyst thus facilitating its recovery. As regards the CO2 use as reagent, two catalytic systems have been developed for the conversion of CO2 and epoxides into cyclic carbonates, used in the synthesis of polymers and as aprotic solvents. Homogeneous catalysts made by choline-based eutectic mixtures and heterogeneous catalysts made from biopolymers and waste pyrolysis have been synthesized and tested on this reaction. The carbonate interchange reaction (CIR) of a diol with a linear carbonate (as dimethyl carbonate) is an interesting alternative, for the synthesis of cyclic carbonates; as the second application of CO2 as polarity trigger, it was used for catalyst recovery. In fact DBU, here used as catalyst, is part of the so called “switchable solvents”: they can pass from a less-polar to a more-polar form (and from being soluble to non-soluble in the reaction mixture) when reacting with CO2 in presence of water or alcohols. Also in this case, heterogeneous catalysts made from biopolymers and waste pyrolysis have been synthesized and tested on CIR. As for the use of alternative solvents, this work focuses on the use of Deep Eutectic Solvents (DESs). They are a new generation of solvents composed by a mixture of two or more substances, liquid at room temperature, and non-volatile. New and biobased DESs were here used: i) as reaction media to carry out chemoenzymatic epoxidation; ii) in the extraction of astaxanthin from microalgae culture.

Cure Induced Residual Stresses on Thick Composite Components Manufactured by Additive Process

This study investigates the effect of an additive process in manufacturing of thick composites. Airstone 780 E epoxy resin and 785H Hardener system is used in the analysis since it is widely used wind turbine blade, namely thick components. As a fiber, fabric by SAERTEX (812 g/m2) with a 0-90 degrees layup direction is used. Temperature overshoot is a major issue during the manufacturing of thick composites. A high temperature overshoot leads to an increase in residual stresses. These residual stresses are causing warping, delamination, dimensional instability, and undesired distortion of composite structures. A coupled thermo-mechanical model capable of predicting cure induced residual stresses have been built using the commercial FE software Abaqus®. The possibility of building thick composite components by means of adding a finite number of sub-laminates has been investigated. The results have been compared against components manufactured following a standard route. The influence of pre-curing of the sub-laminates has also been addressed and results compared with standard practice. As a result of the study, it is found that introducing additive process can prevent temperature overshoot to occur and benefits the residual stresses generation during the curing process. However, the process time required increases by 50%, therefore increasing the manufacturing costs. An optimized cure cycle is required to minimize process time and cure induced defects simultaneously.

Dalla Sintesi di Leganti Polimerici alla Realizzazione di Adesivi da Parquet

This final report is part of a research project by Kerakoll S.P.A aimed to the realization and optimization of hybrid adhesive for the parquet using hybrid polyurethane silanizated (STPU). Hybrid polymers belong to polyurethane polymers which undergo an hybridization process where the classic isocyanate groups are converted into a alkoxysilylether terminated chain. The aim of this thesis was to realize hybrid polymers with specific proprieties compared to the indexes wanted by the company; another goal of this project was to use this polymers STPU to realize adhesive for the parquet which should be competitive in the adhesive market. All activities were carried out in a chemistry laboratory with specific tools for the synthesis of polymers and characterization of the finals products. The study led to two prototypes; the second was obtained thanks to the use of the experimental design procedure known as DOE (Design Of Experiment), a recently acquired approach by the company, which allows the rationalization of the formulas and the creation of a database that can be extended and implemented indefinitely.

Biopolyester fibers for sustainable and biocompatible applications

The rising of concerns around the scarcity of non-renewable resources has raised curiosity around new frontiers in the polymer science field. Biopolymers is a general term describing different kind of polymers that are linked with the biological world because of either monomer derivation, end of life degradation or both. The current work is aimed at studying one example of both biopolymers types. Polyhydroxibutyrate (P3HB) is a biodegradable microbial-produced polymer which holds massive potentiality as a substitute of polyolefins such as polypropylene. Though, its highly crystalline nature and stereoregularity of structure make it difficult to work with. The project P3HB-Mono take advantage of polarized Raman spectroscopy to see how annealing of chains with different weights influence the crystallinity and molecular structure of the polymer, eventually reflecting on its mechanical properties. The technique employed is also optimal in order to see how mesophase, a particular conformation of chains different from crystalline and amorphous phase, develops in the polymer structure and changes depending on temperature and mechanical stress applied to the fiber. Polycaprolactone (PCL) on the other hand is a biodegradable fossil-fuel polymer which has biocompatibility and bio-resorbability features. As a consequence this material is very appealing for medical industry and can be used for different applications in this field. One interesting option is to produce narrow and long liquid filled fibers for drug delivery inside human body, using a traditional technique in an innovative way. The project BioLiCoF investigates the feasability of producing liquid filled fibers using melt-spinning techniques and will examine the role that melt-spinning parameters and liquids employed as a core solution have on the final fiber. The physical analysis of the fibers is also interpreted and idea on future developments of the trials are suggested.

Influence of curing protocol on selected properties of light-curing polymers: Degree of conversion, volume contraction, elastic modulus, and glass transition temperature

Objectives. The purpose of this study was to investigate the effect of light-curing protocol on degree of conversion (DC), volume contraction (C), elastic modulus (E), and glass transition temperature (T(g)) as measured on a model polymer. It was a further aim to correlate the measured values with each other. Methods. Different light-curing protocols were used in order to investigate the influence of energy density (ED), power density (PD), and mode of cure on the properties. The modes of cure were continuous, pulse-delay, and stepped irradiation. DC was measured by Raman micro-spectroscopy. C was determined by pycnometry and a density column. E was measured by a dynamic mechanical analyzer (DMA), and T(g) was measured by differential scanning calorimetry (DSC). Data were submitted to two-and three-way ANOVA, and linear regression analyses. Results. ED, PD, and mode of cure influenced DC, C, E, and T(g) of the polymer. A significant positive correlation was found between ED and DC (r = 0.58), ED and E (r = 0.51), and ED and T(g) (r = 0.44). Taken together, ED and PD were significantly related to DC and E. The regression coefficient was positive for ED and negative for PD. Significant positive correlations were detected between DC and C (r = 0.54), DC and E (r = 0.61), and DC and T(g) (r = 0.53). Comparisons between continuous and pulse-delay modes of cure showed significant influence of mode of cure: pulse-delay curing resulted in decreased DC, decreased C, and decreased T(g). Influence of mode of cure, when comparing continuous and step modes of cure, was more ambiguous. A complex relationship exists between curing protocol, microstructure of the resin and the investigated properties. The overall performance of a composite is thus indirectly affected by the curing protocol adopted, and the desired reduction of C may be in fact a consequence of the decrease in DC. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.