Poly(butylene terephthalate-co-5-tert-butyl isophthalate) Copolyesters: Synthesis, Characterization and Properties

A series of poly(butylene terephthalate) copolyesters containing 5-tert-butyl isophthalate units up to 50%-mole, as well as the homopolyester entirely made of these units, were prepared by polycondensation from the melt. The microstructure of the copolymers was determined by NMR to be at random for the whole range of compositions. The effect exerted by the 5-tert-butyl isophthalate units on thermal, tensile and gas transport properties was evaluated. Both Tm and crystallinity as well as the mechanical moduli were found to decrease steadily with copolymerization whereas Tg increased and the polyesters became more brittle. Permeability and solubility sligthly increased also with the content in substituted units whereas the diffusion coefficient remained practically constant. For the homopolyester poly(5-tert-butyl isophthalate), all these properties were found to deviate significantly from the general trend displayed by copolyesters suggesting that a different chain mode of packing in the amorphous phase is likely adopted in this case.

Ecosystem impacts of Alpine water intakes for hydropower: the challenge of sediment management

The natural flow hydrological characteristics (such as the magnitude, frequency, duration, timing, and rate of change of discharge) of Alpine streams, dominated by snowmelt and glacier melt, have been established for many years. More recently, the ecosystems that they sustain have been described and explained. However, natural Alpine flow regimes may be strongly modified by hydroelectric power production, which impacts upon both river discharge and sediment transfer, and hence on downstream flora and fauna. The impacts of barrages or dams have been well studied. However, there is a second type of flow regulation, associated with flow abstraction at intakes where the water is transferred laterally, either to another valley for storage, or at altitude within the same valley for eventual release downstream. Like barrages, such intakes also trap sediment, but because they are much smaller, they fill more frequently and so need to be flushed regularly. Downstream, while the flow regime is substantially modified, the delivery of sediment (notably coarser fractions) remains. The ecosystem impacts of such systems have been rarely considered. Through reviewing the state of our knowledge of Alpine ecosystems, we outline the key research questions that will need to be addressed in order to modify intake management so as to reduce downstream ecological impacts. Simply redesigning river flows to address sediment management will be ineffective because such redesign cannot restore a natural sediment regime and other approaches are likely to be required if stream ecology in such systems is to be improved.

Efeito da adição de Na2O na viscosidade e devitrificação do vidro obtido a partir de cinzas volantes e Li2O

Glass-ceramic materials can be produced by the addition of LiO2 to fly ashes disposible in Southern Brazil. These glass-ceramics are based on the Al2O3-SiO2-Li 2O system. The high viscosity of the obtained glasses, however, makes forming useful articles with these materials difficult. In this study we investigate the effect of adding low cost Na2CO3 on the melt viscosity and on the nature of the developed crystalline phases. It was intended that the ultimate crystalline phase (LiAlSi3O8) should not be altered. With additions up to 3 wt. % Na2CO3, the viscosity was apparently lowered and no new crystalline phase were detected.

Determinação da massa molar por crioscopia: terc-butanol, um solvente extremamente adequado

We intend to divulge an easy experiment that permits the determination of molar masses of various compounds by cryoscopy. The major advantage of this is the use of the tert-butyl alcohol as a solvent, which requires simple apparatus and easy procedures. The melting point of this alcohol is around 25 ºC, which makes it easy to freeze and then melt the solutions. This solvent has a high cryoscopic constant and is miscible with both polar and non-polar compounds. The molar masses of acetone, water, chloroform, dichloro-methane, ethanol, hexane, carbon tetrachloride and toluene were determined. The results were good except for water. Even though there are reliable techniques of molar mass determination nowadays, this method is still frequently taught in undergraduate courses.

Synthesis and NMR characterization of aliphatic-aromatic copolyesters by reaction of poly(ethylene terephthalate) post-consumer and poly(ethylene adipate)

An aliphatic-aromatic copolyester of poly(ethylene terephthalate), PET, and poly(ethylene adipate), PEA, PET-co-PEA, was synthesized by the high temperature melt reaction of post-consumer PET and PEA. As observed by NMR spectroscopy, the reaction yielded random copolyesters in a few minutes through ester-interchange reactions, even without added catalyst. The copolyesters obtained in the presence of a catalyst presented higher intrinsic viscosity than that obtained without the addition of catalyst, due to simultaneous polycondensation and ester-interchange reactions. The structure of the aliphatic-aromatic copolyesters obtained in different PET/PEA ratio is random as observed by NMR analysis.

Avaliação da fotodegradação de poliolefinas através de exposição natural e artificial

Samples of polypropylene (PP) and low-density polyethylene (LDPE) were submitted to ultraviolet radiation, in the natural environment and also in the laboratory. Chemical modifications were quantified by the carbonyl index (CI), mechanical properties and melt flow index. The degradation in the laboratory was comparatively faster than in the environment for both types of polymers. The accelerating factor was determined for the various properties investigated. This parameter, however, showed a large variation with the degradation criteria and the type of polymer. The existence of a "universal accelerating factor", therefore, was not observed in the current study.

Off-Diagonal Magnetoimpedance Dependence of Magnetostriction and Anisotropy in Co-Based and Fe-Based Amorphous Ribbons

The object of this work is the comparison of domain structure and off-diagonal magnetoimpedance effect in amorphous ribbons with different magnetostriction coefficient. The Co66Fe4Ni1Si15B14 and Fe80B20 samples were obtained by melt-spinning. During the quenching procedure a 0.07 T transverse magnetic field was applied to some of the samples. Domain patterns obtained by the Bitter technique confirm that the differences on the samples are related to the different anisotropy and magnetostriction coefficient, and the quenching procedure. Small changes on the anisotropy distribution and the magnetostriction coefficient can be detected by the off-diagonal impedance spectra as a consequence of the different permeability values of the samples

Avaliação das propriedades de compósitos de polipropileno reforçados com casca de aveia

The preparation of oat-reinforced polypropylene nanocomposites with different fiber contents by means of melt-processing was investigated. Composite properties were evaluated by Scanning Electron Microscopy (SEM), Flexural Modulus, Dynamic Mechanical Analysis (DMA), Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). Findings confirmed that the oat composite properties were affected by fiber type and content. Improvements in mechanical properties were obtained using fiber contents < 20% w.t.

Feasibility study for acidic biorefinery concept

The integration a recovery process for spent sulfite liquor from a sulfite cooking process with a kraft pulp mill was studied in this thesis work. The process includes a fermentation process for the production of biofuel. The calculation for three cases was done. The three cases considered were with a spruce sulfite pulp production of 100, 250 and 1000 Adt/day corresponding to 10, 25 and 100% of the total pulp production. A kraft cooking process with prehydrolysis was taken in consideration as reference. Compared to kraft cooking with prehydrolysis a bigger amount of ethanol can be produced by sulfite cooking. In the kraft prehydrolysis case 40 t/day of ethanol and 1000 Adt/day pine pulp is produced and in the sulfite case the production is 113 t/day of ethanol and 1000 Adt/day of spruce pulp. The energy consumption in the sulfite process is assumed to be slightly higher than in the kraft prehydrolysis process. The recovery system for spent liquor mix was studied. The evaporation of the spent cooking liquors should be done separately. The approximately composition of melt was calculated. A comparison of all four cases was done and profitability was estimated.

Genesis and Emplacement of Carbonatites and Lamprophyres in the Svecofennian Domain

A small carbonatite dyke swarm has been identified at Naantali, southwest Finland. Several swarms of shoshonitic lamprophyres are also known along the Archean-Proterozoic boundary in eastern Finland and northwest Russia. These intrusions, along with the carbonatite intrusion at Halpanen, eastern Finland, represent a stage of widespread low-volume mantle-sourced alkaline magmatism in the Svecofennian Domain. Using trace element and isotope geochemistry coupled with precise geochronology from these rocks, a model is presented for the Proterozoic metasomatic evolution of the Fennoscandian subcontinental lithospheric mantle. At ~2.2-2.06 Ga, increased biological production in shallow seas linked to continental rifting, resulted in increased burial rates of organic carbon. Subduction between ~1.93-1.88 Ga returned organic carbon-enriched sediments of mixed Archean and Proterozoic provenance to the mantle. Dehydration reactions supplied water to the mantle wedge, driving arc volcanism, while mica, amphibole and carbonate were brought deeper into the mantle with the subducting slab. The cold subducted slab was heated conductively from the surrounding warm mantle, while pressures continued to gradually increase as a result of crustal thickening. The sediments began to melt in a two stage process, first producing a hydrous alkaline silicate melt, which infiltrated the mantle wedge and crystallised as metasomatic veins. At higher temperatures, carbonatite melt was produced, which preferentially infiltrated the pre-existing metasomatic vein network. At the onset of post-collisional extension, deep fault structures formed, providing conduits for mantle melts to reach the upper crust. Low-volume partial melting of the enriched mantle at depths of at least 110 km led to the formation of first carbonatitic magma and subsequently lamprophyric magma. Carbonatite was emplaced in the upper crust at Naantali at 1795.7 ± 6.8 Ma; lamprophyres along the Archean-Proterozoic boundary were emplaced between 1790.1 ± 3.3 Ma and 1781 ± 20 Ma.

Performance of high power fibre laser cutting of thick-section steel and mediumsection aluminium

Cutting of thick section stainless steel and mild steel, and medium section aluminium using the high power ytterbium fibre laser has been experimentally investigated in this study. Theoretical models of the laser power requirement for cutting of a metal workpiece and the melt removal rate were also developed. The calculated laser power requirement was correlated to the laser power used for the cutting of 10 mm stainless steel workpiece and 15 mm mild steel workpiece using the ytterbium fibre laser and the CO2 laser. Nitrogen assist gas was used for cutting of stainless steel and oxygen was used for mild steel cutting. It was found that the incident laser power required for cutting at a given cutting speed was lower for fibre laser cutting than for CO2 laser cutting indicating a higher absorptivity of the fibre laser beam by the workpiece and higher melting efficiency for the fibre laser beam than for the CO2 laser beam. The difficulty in achieving an efficient melt removal during high speed cutting of the 15 mmmild steel workpiece with oxygen assist gas using the ytterbium fibre laser can be attributed to the high melting efficiency of the ytterbium fibre laser. The calculated melt flow velocity and melt film thickness correlated well with the location of the boundary layer separation point on the 10 mm stainless steel cut edges. An increase in the melt film thickness caused by deceleration of the melt particles in the boundary layer by the viscous shear forces results in the flow separation. The melt flow velocity increases with an increase in assist gas pressure and cut kerf width resulting in a reduction in the melt film thickness and the boundary layer separation point moves closer to the bottom cut edge. The cut edge quality was examined by visual inspection of the cut samples and measurement of the cut kerf width, boundary layer separation point, cut edge squareness (perpendicularity) deviation, and cut edge surface roughness as output quality factors. Different regions of cut edge quality in 10 mm stainless steel and 4 mm aluminium workpieces were defined for different combinations of cutting speed and laserpower.Optimization of processing parameters for a high cut edge quality in 10 mmstainless steel was demonstrated

Thermal behaviour of succinic acid, sodium succinate and its compounds with some bivalent transitions metal ions in dynamic N2 and CO2 atmospheres

Thermal stability and thermal decomposition of succinic acid, sodium succinate and its compounds with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA) in nitrogen and carbon dioxide atmospheres and TG-FTIR in nitrogen atmosphere. On heating, in both atmospheres the succinic acid melt and evaporate, while for the sodium succinate the thermal decomposition occurs with the formation of sodium carbonate. For the transition metal succinates the final residue up to 1180 ºC in N2 atmosphere was a mixture of metal and metal oxide in no simple stoichiometric relation, except for Zn compound, where the residue was a small quantity of carbonaceous residue. For the CO2 atmosphere the final residue up to 980 ºC was: MnO, Fe3O4, CoO, ZnO and mixtures of Ni, NiO and Cu, Cu2O.

Effects of Silica Based Biomaterials on Bone Marrow Derived Cells - Material Aspects of Bone Regeneration

Silica based biomaterials, such as melt-derived bioactive glasses and sol-gel glasses, have been used for a long time in bone healing applications because of their ability to form hydroxyapatite and to stimulate stem cell proliferation and differentiation. In this study, bone marrow derived cells were cultured with bioactive glass and sol-gel silica, and seeded into porous polymer composite scaffolds that were then implanted femorally and subcutaneously in rats to monitor their migration inside host tissue. Bone marrow derived cells were also injected intraperitoneally. Transplanted cells migrated to various tissues inside the host, including the lung, liver spleen, thymus and bone marrow. The method of transplantation affected the time frame of cell migration, with intraperitoneal injection being the fastest and femoral implantation the slowest, but not the target tissues of migration. Transplanted donor cells had a limited lifetime in the host and were later eliminated from all tested tissues. Bioactive glass, however, affected the implanted cells negatively. When it was present in the scaffold no donor cells were found in any of the tested host tissues. Bioactive glass S53P4 was found to support both osteoblastic and osteoclastic phenotype of bone marrow derived cells, but it was resistant to the resorbing effect of osteoclastic bone marrow derived cells, showing that bioactive glass is rather dissolved through physicochemical reactions than resorbed by cells. Fast-dissolving silica sol gel in microparticulate form was found to increase collagen formation by bone marrow derived cells, while slow dissolving silica microparticles enhanced their proliferation, suggesting that the dissolution rate of silica controls the response of bone marrow derived cells.

Spectroscopic monitoring during laser welding of aluminium alloy

The mechanical properties of aluminium alloys are strongly influenced by the alloying elements and their concentration. In the case of aluminium alloy EN AW-6060 the main alloying elements are magnesium and silicon. The first goal of this thesis was to determine stability, repeatability and sensitivity as figures of merit of the in-situ melt identification technique. In this study the emissions from the laser welding process were monitored with a spectrometer. With the information produced by the spectrometer, quantitative analysis was conducted to determine the figures of merit. The quantitative analysis concentrated on magnesium and aluminium emissions and their relation. The results showed that the stability of absolute intensities was low, but the normalized magnesium emissions were quite stable. The repeatability of monitoring magnesium emissions was high (about 90 %). Sensitivity of the in-situ melt identification technique was also high. As small as 0.5 % change in magnesium content was detected by the spectrometer. The second goal of this study was to determine the loss of mass during deep penetration laser welding. The amount of magnesium in the material was measured before and after laser welding to determine the loss of magnesium. This study was conducted for aluminium alloy with nominal magnesium content of 0-10 % and for standard material EN AW-6060 that was welded with filler wire AlMg5. It was found that while the magnesium concentration in the material changed, the loss of magnesium remained fairly even. Also by feeding filler wire, the behaviour was similar. Thirdly, the reason why silicon had not been detected in the emission spectrum needed to be explained. Literature research showed that the amount of energy required for silicon to excite is considerably higher compared to magnesium. The energy input in the used welding process is insufficient to excite the silicon atoms.

Potkurilaitteen ohjausputken laserpinnoitus

Laserpinnoitus on additiivinen prosessi, jossa lasertehon avulla sulatetaan pinnoitusainetta pinnoitettavan kappaleen pintaan. Laserpinnoituksella on mahdollista aikaansaada tiivis sekä kova, kulutusta ja korroosiota kestävä pinnoite kappaleen pintaan. Tässä työssä kohteena oli potkurilaitteen ohjausputken laserpinnoitus. Kyseisessä kohteessa pinnoitteelta vaaditaan hyvää korroosion- ja kulumisen kestoa. Työn tavoitteena oli lisätä tietoisuutta laserpinnoitusprosessista ja siinä vaikuttavista tekijöistä. Myös materiaaliominaisuuksien vaikutuksia sekä pinnoitus- että pinnoitettavien aineiden osalta selvitettiin. Työhön sisältyi myös kokeellinen osuus, jossa tavoitteena oli löytää kustannustehokkain pinnoiteaine tutkittuun kohteeseen. Kokeissa ohjausputki- sekä levyaihioon tehtiin koepinnoituksia. Kokeiden ja edelleen materiaalitutkimuksien avulla tutkittiin neljää eri pinnoitusainetta, jotka olivat Stellitti 21, Inconel 625, AISI 316L ja AISI 431. Kovuus- ja taivutuskokeiden perusteella kyseisistä aineista vain Stelliitti 21 täytti ohjausputken pinnoitteelle asetetut vaatimukset. Näin ollen Stelliitti 21 valikoitui kustannustehokkaimmaksi pinnoitusaineeksi ohjausputkien laserpinnoitukseen.