Hydrolytic degradation of nanocomposites based on poly(l‐lactic acid) and layered double hydroxides modified with a model drug

Hydrolytic degradation of a nanocomposite of poly(L‐lactic acid), PLA, and a layered double hydroxide (LDH) modified with the drug 4‐biphenyl acetic acid (Bph) has been studied. PLA/LDH‐Bph nanocomposite was prepared by solvent casting with 5 wt % of drug modified LDH and the hydrolytic degradation was carried out in a PBS solution at pH 7.2 and 37 °C. Neat PLA with 5 wt % 4‐biphenyl acetic acid was studied as reference material (PLA/Bph). The materials were studied by WAXS, TEM, TGA, DSC, SEM, FTIR, SEC and contact angle measurements. For PLA/Bph, an acid catalytic effect, caused by the drug, accelerates PLA mass loss. However, for PLA/LDH‐Bph, the presence of LDH produces a barrier effect that initially reduces the diffusion of the oligomers produced during hydrolytic degradation. DSC results demonstrate that Bph induces faster PLA crystallization and this effect is reduced in PLA/LDH‐Bph nanocomposites because of their lower drug content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43648.     

Flexible aliphatic poly(isocyanurate–oxazolidone) resins based on poly(ethylene glycol) diglycidyl ether and 4,4′‐methylene dicyclohexyl diisocyanate

New flexible aliphatic oxazolidone‐isocyanurate networks (AISOX) are obtained by reacting a low molecular weight diisocyanate (4,4′‐methylene dicyclohexyl diisocyanate, H₁₂MDI) and a macro‐diepoxyde (poly(ethylene glycol) diglycidyl ether, M_n = 526, PEGDGE) in different molar ratio. The curing reaction, carried out from 25 °C to 200 °C, is studied by using DSC and FTIR. The effect of the molar ratio of the two monomers on thermal and mechanical properties of AISOX resins is investigated by DSC, thermogravimetric analysis, stress?strain measurements and optical microscopy. Independently from the feed composition, it is observed that the reaction steps are: (i) partial hydrolysis of isocyanate caused by water traces, (ii) incomplete trimerization of isocyanate to give isocyanurate, and (iii) formation of oxazolidone and complete conversion of isocyanate. At the highest concentration of the soft macrodiepoxyde (PEGDGE), the AISOX resin is in the rubbery state at room temperature and shows an elastomeric behavior. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43404.     

Aromatic triblock polymers from natural sources as protective coatings for stone surfaces

Aromatic triblock polymers were synthesized, characterized, and tested as protective coatings for stone surfaces. Syntheses were carried out by a ring opening polymerization process from specifically synthesized monomers ((3S)‐6‐methyl‐3‐phenyl‐1,4‐dioxan‐2,5‐dione or 1,4‐benzodioxepin‐3‐methyl‐2,5‐dione) and a perfluoropolyether diol (Fluorolink D10‐H), as chain initiator. Polymers were characterized through spectroscopic and analytical techniques while their stability under photo‐oxidative conditions was tested using a Solar Box. An excellent stability to environmental conditions was noticed with very low degradation during accelerated aging tests up to 1000 h, as detected by FTIR, molecular weight, DSC and weight loss. Furthermore, these polymers formed an excellent protective coating on the stone surface as shown by capillary water absorption test. Finally, as expected, very stable coatings were obtained as shown by aging tests. The stone surface showed negligible changes of color and a good hydrorepellency confirming a good durability of treatments. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43377.     

Application of the dry‐spinning method to produce poly(ε‐caprolactone) fibers containing bovine serum albumin laden gelatin nanoparticles

We designed and manufactured a polymeric system with combined hydrophilic–hydrophobic properties by loading gelatin nanoparticles (GNPs) containing bovine serum albumin (BSA) into poly(ε‐caprolactone) (PCL) fibers. Our ultimate goal was to create a device capable of carrying and releasing protein drugs. Such a system could find several biomedical applications, such as those in controlled release systems, surgical sutures, and bioactive scaffolds for tissue engineering. A two‐step desolvation method was used to produce GNPs, whereas PCL fibers were produced by a dry‐spinning method. The morphological, mechanical, and thermal properties of the produced system were investigated, and the distribution of nanoparticles both inside and on the surface of the fibers was examined. The effect of the particles on the biodegradability of the fibers was also evaluated. In vitro preliminary tests were performed to study the release of BSA from nanoparticle‐laden fibers and to compare this with its release from free nanoparticles. Our results indicate that the distribution of particles inside the fibers was quite homogeneous and only a few of them were present on the surface. The presence of the particles in the fibers did not affect the thermal properties of the PCL polymer matrix, although it created voids that affected the degradation characteristics so the PCL fibers favored faster erosion compared to the plain fibers. Preliminary results indicate that the release from GNP‐laden fibers occurred much more slowly compared to that in the free GNPs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44233.     

Mechanochemical Processing of Mn and Co Oxides: An Alternative Way to Synthesize Mixed Spinels for Protective Coating

High‐Energy Ball Milling (HEBM) is proposed as a cost effective and environmental friendly technique to produce Co‐ and Mn‐ based oxides suitable for application as protective coating. Mixtures of manganese and cobalt oxides in different molar ratio (Co:Mn = 1:1 and Co:Mn = 2:1) were subjected to mechanochemical treatment up to 100 h and morpho‐structural evolution was evaluated. XRD analysis results show that the HEBM treatment promotes the solid‐state reaction of the starting compounds, with the formation of different crystalline phases when compared to high‐temperature solid‐state synthesis. SEM observations and N₂ adsorption measurements suggest that all processed powders are composed by aggregates of nanometric particles. While long milling time is required to complete the reaction, 10 hours are enough to activate the powders to obtain the desired phases after a mild thermal treatment, as evidenced by in situ thermal XRD analysis. Electrical conductivity measures performed with the Van der Pauw method on sintered pellets evidence a significant difference between the two compositions, related to the dual‐phase nature of Co:Mn = 1:1 material at intermediate temperatures (i.e., T < 700°C), Co:Mn = 2:1 sample showing higher conductivity values in the whole tested range (500°C–800°C).     

Direct Ink Writing of a Preceramic Polymer and Fillers to Produce Hardystonite (Ca2ZnSi2O7) Bioceramic Scaffolds

The direct ink writing of an ink composed of a preceramic polymer and fillers was used to produce hardystonite (Ca₂ZnSi₂O₇) bioceramic scaffolds. Suitable formulations were developed for the extrusion of fine filaments (350 μm diameter) through a nozzle. The preceramic polymer was employed with the double purpose of contributing to the rheology of the ink by increasing its viscosity and of forming the hardystonite phase upon heat treatment by reacting with the fillers. A control of the rheology is essential when spanning features have to be produced, and therefore the main rheological characteristics of the inks were measured (flow curves, dynamic oscillation tests, viscosity recovery tests) and compared to models reported in the literature. Highly porous scaffolds (up to 80% total porosity) were produced and heat treated in air or in nitrogen atmosphere. The influence of the heat‐treatment atmosphere on the morphology, crystalline phase assemblage, and compressive strength of the scaffolds was investigated.     

Effect of Silicon and Graphite Degeneration on High-Temperature Oxidation of Ductile Cast Irons in Open Air

Oxidation of Metals - The use of high silicon ductile irons is increasing as they offer some advantages with respect to conventional pearlitic–ferritic grades such as high elongation at...     

Multicriteria optimization as enabler for Sustainable Ceramic Matrix Composites

Over the past 40 years, development of Ceramic Matrix Composites (CMCs) has focused mainly on the improvement of material performance and optimization of cost-efficient production routes. Recently, more fields of application have opened up for CMCs, in which environmental impacts are relevant. These impacts have barely been investigated so far but receive growing interest due to increasing awareness of the environmental consequences. Our innovative approach frames material properties in relation to environmental impacts (e.g., global warming potential in CO₂ emission) by varying process parameters to balance optimum performance against environmental considerations. First, the process of wet filament winding has been investigated up to the Carbon Fiber Reinforced Plastic (CFRP) state by changing both the curing and tempering temperatures. During the production of CFRP plates, mass and energy flows were tracked in each step. Three point-bending and interlaminar shear tests have been performed on the resulting samples to identify basic mechanical properties. The environmental impacts are determined by a cradle-to-gate Life Cycle Assessment (LCA), using the software SimaPro. The resulting tradeoffs between mechanical properties and environmental impacts show nonlinear behavior, thus revealing optimum points above which improved mechanical properties are associated with significantly higher CO₂ emissions.