Effect of polymerization catalyst technology on the melt processing stability of polyethylenes,Part 3: Additives blends performance

This article considers the interaction between additives that occur during the stabilization process. The simultaneous effects of the additives and associated interactions on melt processing stability and processing discoloration were of particular interest. Melt stability is an important factor to consider because physical changes in the processed polymer can occur during the compounding and fabrication steps. Furthermore, discoloration is one of the most important problems affecting commercial polymers. Most discoloration manifests itself as yellowing, especially in the case of polyolefins. Although yellowing can often be associated with degradation processes caused by various agents, such as light or heat, this is not always the case; yellowing can also be due to the interaction of additives in the stabilizer packages. Blends of primary antioxidants (AOs), secondary AOs, and hindered amine light stabilizers have been studied with the intention of further improving stabilization performance together with cost reduction of the stabilized polymer. Although synergism between AOs and a stabilizer is fairly common, antagonism was also observed in terms of melt flow protection and in color stability in some of the AOs tested. The effects of a range of thermal and light stabilizers on the melt stability (investigated via multiple pass extrusion) and color stability of three different polyethylenes (PEs) were examined. The PEs varied in terms of the catalyst system used to synthesize the polymers and included a high‐density polyethylene (HDPE) produced by using a chromium‐based Phillips catalyst and two linear low‐density polyethylenes (LLDPEs) produced via chromium‐based metallocene and titanium‐based Ziegler‐Natta catalysts. The apparent lack of influence of polymerization catalyst system on the mode of stabilizer interaction should lead to the reassessment of stabilizer formulation strategies in relation to PE type/catalyst system and associated commercial/economic considerations. J. VINYL ADDIT. TECHNOL., 22:117–127, 2016. © 2014 Society of Plastics Engineers     

Chemical Interactions Promoting the ZrO2 Tetragonal Stabilization in ZrO2–SiO2 Binary Oxides

Metastable tetragonal ZrO₂ phase has been observed in ZrO₂–SiO₂ binary oxides prepared by the sol–gel method. There are many studies concerning the causes of ZrO₂ tetragonal stabilization in binary oxides such as Y₃O₂–ZrO₂, MgO–ZrO₂, or CaO–ZrO₂. In these binary oxides, oxygen vacancies cause changes or defects in the ZrO₂ lattice parameters, which are responsible for tetragonal stabilization. Since oxygen vacancies are not expected in ZrO₂–SiO₂ binary oxides, tetragonal stabilization should just be due to the difficulty of zirconia particles growing in the silica matrix. Furthermore, changes in the tetragonal ZrO₂ crystalline lattice parameters of these binary oxides have recently been reported in a previous paper. The changes of the zirconia crystalline lattice parameters must result from the chemical interactions at the silica–zirconia interface (e.g., formation of Si–O–Zr bonds or Si–O⁻ groups). In this paper, FT-IR and ²⁹Si NMR spectroscopy have been used to elucidate whether the presence of Si–O–Zr or Si–O⁻ is responsible for tetragonal phase stabilization. Moreover, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy have also been used to study the crystalline characteristics of the samples.     

Effects of Dry Grinding on the Structural Changes of Kaolinite Powders

The present study examined the effects of dry grinding, using ball-milling, on the structure of reference well-crystallized (KGa-1) and poorly crystallized (KGa-2) kaolinite powders from Georgia. Grinding produced a strong structural alteration, mainly along the c axis, resulting in disorder and total degradation of the crystal structure of the kaolinite and the formation of an amorphous product. The surface area increased with grinding time, mainly in KGa-2 (maximum value 50.27 m²/g), a result associated with particle-size reduction. These particles became more agglomerated with grinding, and the surface area decreased after 30 min, as confirmed by scanning electron microscopy and particle-size-distribution analysis. There was a limit to particle-size reduction with grinding time. When grinding time was increased, the original endothermic differential thermal analysis (DTA) effects of dehydroxylation in both samples shifted to lower temperatures, decreased in intensity, then disappeared completely after 120 min of grinding. The temperature of the characteristic first exothermic effect shifted slightly to lower temperatures with grinding, although the DTA effects did not increase with grinding time in either kaolinite sample, at least up to 325 min. The amorphous, mechanically activated kaolinite converted into low-crystalline mullite nuclei at a lower temperature than did the unground samples, as deduced by thermal and X-ray observations. This effect was especially important for the KGa-2 sample. Grinding did not seem to influence the formation of silicon-aluminum spinel from kaolinite. The present results may explain why ground kaolinite samples prepared via different routes—e.g., with differences in grinding—behave differently during high-temperature transformations, as reported in the related literature.     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Characterization of artisanally and semiautomatically extracted argan oils from Morocco

The present study was conducted to know the possible influence of the seed treatment, method of extraction and geographical origin on the quality and chemical composition of argan oil. Artisanally and semiautomatically extracted argan oils, from roasted and unroasted seeds, from interior and coast areas, were studied. The quality parameters analyzed were acid value, peroxide value, K₂₃₂ and K₂₇₀, triacylglycerols and fatty acid composition, polar compounds, total phenols, tocopherol content and oil stability index (OSI). Seed treatment and extraction method showed a higher influence on quality parameters than geographical area; the quality parameters of the different oils were discussed. The total phenolic content in all analyzed samples was lower than 10 ppm. γ‐Tocopherol was the major tocopherol (84.4–86.4%) with a high contribution to the total tocopherol content (383–485 ppm). The OSI of the argan oil samples were well correlated (R = 0.97) with the tocopherol contents. The argan oil samples obtained from roasted seeds presented higher stability (26–38 h) than the oils from unroasted seeds (16–32 h).     

Constrained Sintering of a Glass Ceramic Composite: I. Asymmetric Laminate

The camber of asymmetric laminates has been experimentally measured and predicted. Two cases are distinguished: (i) sintering of a viscous layer on a viscous substrate and (ii) sintering of a viscous layer on an elastic substrate. In the first case, particular attention is paid to the microstructure of the shrinking layer: a gradient in porosity as well as in pore size has been found along the thickness. Microstructural observations have been rationalized through an asymmetric stress state in the shrinking layer. In the second case, substrate cracking is predicted as function of Young's modulus and thickness ratio of the elastic substrate.     

Fracture Statistics Based on Pore/Grain-Size Interaction

The statistics of fracture in ceramics are discussed based on a model that describes crack instability that occurs at a configuration of a microcrack positioned in the stress-concentrating effect of a large pore. The interaction of pore size and grain-size distribution is considered, and the effect of a locally varying stress field is included. Results are presented as predictions of the critical pore size and microcrack size that cause fracture for the two assumed average grain sizes of 1 and 5 µm.     

An easy entry to novel early–late oligonuclear transition metal complexes containing π-conjugated systems

Heterotrinuclear Ti–Cu–Ru (5) and heterotetranuclear Ti–Cu–Pt–Fe (7) containing complexes are accessible by using {[Ti](CC^tBu)₂}CuMe (1) ([Ti]=(η⁵-C₅H₄SiMe₃)₂Ti) as key molecule; in 5 and 7, the corresponding early and late transition metal atoms are linked by π-conjugated organic moieties.     

Tailored-Made Polydopamine Nanoparticles to Induce Ferroptosis in Breast Cancer Cells in Combination with Chemotherapy

Ferroptosis is gaining followers as mechanism of selective killing cancer cells in a non-apoptotic manner, and novel nanosystems capable of inducing this iron-dependent death are being increasingly developed. Among them, polydopamine nanoparticles (PDA NPs) are arousing interest, since they have great capability of chelating iron. In this work, PDA NPs were loaded with Fe³⁺ at different pH values to assess the importance that the pH may have in determining their therapeutic activity and selectivity. In addition, doxorubicin was also loaded to the nanoparticles to achieve a synergist effect. The in vitro assays that were performed with the BT474 and HS5 cell lines showed that, when Fe³⁺ was adsorbed in PDA NPs at pH values close to which Fe(OH)₃ begins to be formed, these nanoparticles had greater antitumor activity and selectivity despite having chelated a smaller amount of Fe³⁺. Otherwise, it was demonstrated that Fe³⁺ could be released in the late endo/lysosomes thanks to their acidic pH and their Ca²⁺ content, and that when Fe³⁺ was co-transported with doxorubicin, the therapeutic activity of PDA NPs was enhanced. Thus, reported PDA NPs loaded with both Fe³⁺ and doxorubicin may constitute a good approach to target breast tumors.