Mechanical behaviour of biodegradable agricultural films under real field conditions

The mechanical behaviour of various types of biodegradable materials depends on their chemical composition and additives, the processing characteristics and the application conditions. The environmental conditions during storage and usage of these materials strongly influence their mechanical properties and behaviour. Ageing and degradation during the useful lifetime of biodegradable agricultural films causes losses in the mechanical performance of the material, as measured by monitoring the evolution of some of the critical mechanical properties. Such losses may be comparable to the corresponding losses of the conventional polyethylene agricultural films due to ageing, or they may be more drastic. In the present paper, the overall mechanical and ageing/degradation behaviour of experimental specially designed and manufactured low-tunnel and mulching biodegradable films, exposed to full-scale field conditions is analysed. Selected critical mechanical properties of these films manufactured with different grades of Mater-Bi material and additives, different thickness and processing schemes and exposed to real cultivation conditions in four different locations in Europe are investigated in the laboratory and compared against the corresponding behaviour of conventional agricultural films at various stages of their exposure time.     

X-ray, Raman and FTIRS studies of the microstructural evolution of zirconia particles caused by the thermal treatment

Genesis of the structure of zirconia particles prepared by precipitation of amorphous hydrated zirconia by ammonia from the ZrO(NO₃)₂ solution followed by a mild hydrothermal treatment (HTT) of precipitate, washing and calcination under air up to 1000 °C has been studied by X-ray diffraction (XRD), Raman and FTIRS. As revealed by FTIRS of lattice modes, the local structure of amorphous zirconia subjected to HTT is close to that in m-ZrO₂. This helps to obtain nearly single-phase monoclinic nanozirconia (particle size 5-15 nm) already after a mild calcination at 500 °C. Stability of this phase with nanoparticles sizes below the critical value determined by thermodynamic constraints is due to its excessive hydroxylation demonstrated by FTIRS. Dehydroxilation and sintering of these nanoparticles at higher (600-650 °C) temperatures of calcination leads to reappearance of the (111) “cubic” reflection in XRD patterns. Modeling of XRD patterns revealed that this phenomenon could be explained by polysynthetic (001) twinning earlier observed by HRTEM.     

Drying dissipative structures of the aqueous suspensions of monodisperse bentonite particles

Macroscopic and microscopic dissipative structural patterns formed in the course of drying the fractionated and monodisperse bentonite particles (plate-like in their shape) in aqueous deionized suspension and in the presence of NaCl have been studied on a cover glass. The patterns coexisted with the broad ring of the hill accumulated with the particles and with the round hills are formed around the outside edges of the film and in the center, respectively, in the macroscopic scale. By the addition of NaCl the pattern shifts from the broad ring to the round hill in the center. The spoke-like cracks, which have been observed for the suspensions of the spherical particles so often hitherto, are not observed at all for the bentonite suspensions. The characteristic convection flow of the particles and the interactions among the particles and substrate are important for the macroscopic pattern formation. Wrinkled, branch-like and/or star-like fractal patterns are observed in the microscopic scale. These patterns are determined mainly by the electrostatic and polar interactions between the particles and/or between the particle and the substrate in the course of drying.     

SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl toquinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M_w ca. 750) as flexible segments, were synhesized. Thechemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by ~1H-NMR and MALDI-TOF mass spectromeny. The diblock oligomers showed good solubility in common organic solvents and aggregated in wateras characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescenceand formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant thatthis effort might lead to commercial important highly organized functional materials.     

Bi2O3-WO3光催化臭氧氧化降解糖蜜酒精废水的研究

采用固相合成法制备了Bi2O3-WO3光催化剂,研究了Bi2O3-WO3光催化与臭氧氧化协同降解糖蜜酒精废水的多相催化降解过程,并采用X射线衍射光谱(XRD)、紫外漫反射光谱(DRS)、热重-差热扫描(TG-DSC)等手段对Bi2O3-WO3催化剂进行了表征.研究发现:Bi2O3-WO3是一性能良好的光催化剂,臭氧强化了Bi2O3-WO3光催化氧化过程,反应2 h后,糖蜜酒精废水的脱色率可达90.2%.Bi2O3-WO3光催化剂的禁带宽度为2.92 eV,其中γ-Bi2WO6和Bi2W2O9是其活性中心.焙烧温度对Bi2O3-WO3光催化剂的活性有较大的影响,其中1 073 K为适宜的焙烧温度.     

Rheological investigation of the influence of molecular structure on natural and accelerated UV degradation of linear low density polyethylene

Metallocene and Ziegler-Natta (ZN) linear low density polyethylenes (LLDPEs) of different branch types and contents as well as linear high density polyethylene (HDPE) were exposed to natural and accelerated weather conditions. The degree of UV degradation of exposed samples was measured by rheological techniques and results were compared with unexposed polymers. Dynamic shear measurements were performed in an ARES rheometer in the linear viscoelastic range. The degree of enhancement or reduction in viscosity and elasticity was used as a measure of the degree of cross-linking or chain scission, respectively. The degradation results of LLDPE suggest that both cross-linking and chain scission are taking place. Chain scission dominated the degradation at high levels of short chain branching (SCB) and long exposure times. The degradation mechanism of m-LLDPE and ZN-LLDPE is similar; however, m-LLDPE showed a higher degradation rate than ZN-LLDPE of similar M_w and average SCB. ZN-LLDPE was found to be more stable than a similar m-LLDPE. Comonomer type had little influence on degradation. Dynamic shear rheology was very useful in revealing the influence of different molecular parameters and it exposed the degradation mechanism.     

Viscoelastic and thermal characterization of crosslinked PVC

Soft PVC is employed for the manufacturing of a wide range of products with different properties and a relatively low cost. The utilization of soft PVC is restricted by the poor thermal, chemical and mechanical resistance properties. Also, plasticizer migration can modify the properties or can make useless the materials for some applications because of toxicity or a general loss of properties. PVC crosslinking is the most effective way to improve mechanical and transport properties of rigid or flexible PVC at high temperatures, but at the same time the thermal stability of PVC may be significantly reduced. In this work, the crosslinking reaction of plasticized poly(vinyl chloride) (PVC) through difunctional amines was studied. The mechanisms involved in the crosslinking reaction were explained by Fourier transform infrared (FTIR) analysis. The thermal activated crosslinking reaction was studied by cone and plate rheometry, analyzing the evolution of viscoelastic properties of the suspension as a function of time and temperature. The effect of the addition of crosslinking agents on the thermal stability of the polymer was studied by thermogravimetric analysis (TGA), which revealed that crosslinking reactions promote thermal degradation phenomena in the polymer matrix. This is attributed to the formation of HCl and other species promoting polymer degradation during crosslinking, thus leading to higher weight loss during thermal treatment with respect to unmodified PVC plastisols. This was also confirmed by an evident yellowing after crosslinking, especially at higher temperatures.     

Thermal behavior of bismaleimide resin

The cure of a bismaleimide (BMI) neat resin modified with an aromatic diamine and a siloxane elastomer, has been studied by ¹³C solid state nuclear magnetic resonance. Two chemical reactions occur during the cure cycle; at a low temperature, Michael's reaction predominates, while at a high temperature the polymerization of the double bond maleimide creates the network. The degradation of this BMI material was characterized with isothermal and dynamic thermogravimetric analyses in air and in nitrogen. The BMI thermal stability is lower in nitrogen than in air. This behavior is an indication of oxygen participating in reactions at high temperatures. The activation energy (E_a) of thermal degradation was determined from isothermal data using an Arrhenius equation (In V vs. 1/T). The global E_a for the weight loss in air was found to be 91 kJ/mol. The nature and the evolution of the thermal degradation products were the combined analyzed by techniques of pyrolysis, gas chromatography and mass spectrometry. The major thermal decomposition products obtained in the temperature range of 300–700°C are identified as benzene, methyl formamide, aniline, toluene and isocyanate-derived products.     

Fluctuating hydrodynamics and principal oscillation pattern analysis

Principal oscillation pattern (POP) analysis was recently introduced into climatology to analyze multivariate time series x_i(t) produced by systems whose dynamics are described by a linear Markov process x=Bx + . The matrixB gives the deterministic feedback and is a white noise vector with covariances (t) _j (t*Q _ij (t–t. The POP method is applied to data from a direct simulation Monte Carlo program. The system is a dilute gas with 50,000 particles in a Rayleigh-Bénard configuration. The POP analysis correctly reproduces the linearized Navier-Stokes equations (in the matrixB) and the stochastic fluxes (in the matrixQ) as given by Landau-Lifschitz fluctuating hydrodynamics. Using this method, we find the Landau-Lifschitz theory to be valid both in equilibrium and near the critical point of Rayleigh-Bénard convection.     

Thermal stability and degradation of the post-use reclaim milk pouches during multiple extrusion cycles

In the present study, the recyclability of the post-use milk pouches (50/50 LDPE–LLDPE blend) was evaluated with or without adding stabilizer. Thoroughly washed and dried post-use milk pouch films were extruded five times at high temperature (483–513 K) in the open atmosphere. The mode of degradation during extrusion operation was studied by melt flow index (MFI), rheological properties, gel content and FT-IR analysis. The differential scanning calorimetry (DSC) analysis was carried out to evaluate the thermal stability of the stabilized and un-stabilized recycled mass from post-use milk pouch under this investigation. Mechanical properties (tensile strength, % elongation at break, tensile modulus and hardness) of the un-stabilized extruded material were significantly affected as a result of thermooxidative degradation during extrusion in presence of air. After all, stabilization with 0.4% anti-oxidant satisfactorily retains all the initial properties of the recycled material.