Phase transition in swollen gels

Summary The photoelastic behaviour of two networks — polyacrylamide (PAAm) and of a network prepared by the copolymerization of acrylamide with 5 mol.% sodium methacrylate — was investigated in water-acetone mixtures. For the PAAm network the dependence of all photoelastic characteristics on the composition of the mixture is continuous. At 54 vol.% acetone in the mixture, the ionized network undergoes a transition which gives rise to jumpwise changes in the shear modulus, deformational-optical coefficient, C, and in the refractive index of the gel, n_g. While in the collapsed state the optical anisotropy of the statistical segment is negative, –3×10^–24 cm³ (indicating an interaction between the side chains), in the expanded state it is positive, 0.5 × 10^–24 cm³. The dependence of all optical characteristics on the composition of the mixtures suggests that: (a) in both networks we have a transition between two conformational states of the chain; while for the ionized network the transition is a discrete one, for the nonionized network it takes place in the range between 30 and 45 vol.% acetone in the mixture; (b) in both networks the gels are optically homogeneous throughout the whole range of compositions of the mixtures (and thus also in the close vicinity of the collapse of the ionized network).     

The participation of crown ethers in the initiation of group-transfer polymerisation

Summary The use of crown ethers in conjunction with alkali metal salts, as catalysts in group-transfer polymerization, is discussed.     

Anionic polymerization of acrylates. XIV. Synthesis of MMA/acrylate block copolymers initiated with ester-enolate/tert-alkoxide complex

Diblock copolymers of methyl methacrylate (MMA) with 2-ethylhexyl, butyl, ethyl or tert-butyl acrylate (EtHA, BuA, EtA, t-BuA) have been prepared by the ligated anionic polymerization initiated with methyl 2-lithioisobutyrate (MIB-Li) in the presence of an excess of Li tert-butoxide (t-BuOLi) in toluene/THF mixture at −60 or −78 °C. The copolymers, prepared at −60 °C, show MWD with a hint of bimodality, indicating partial deactivation of the living PMMA upon addition of acrylic monomer. At −78 °C, the extent of this deactivation is distinctly lower, the formed block copolymers, in particular, poly(MMA-b-EtHA), have unimodal MWD and exhibit tails only in the lower-molecular-weight region. Poly(MMA-b-EtHA)s were extracted with acetonitrile dissolving PMMA; very small parts of the crude products dissolved, whereas prevailing parts remained as solids documenting thus formation of block copolymer in a high yield. Surprisingly, the highest amount of self terminated PMMA was found in block copolymerization of MMA with t-BuA at both the temperatures, the products of which had clearly bimodal MWDs. This finding is shortly discussed on the basis of relatively slow propagation of t-BuA in comparison with EtHA, BuA and EtA.     

Antagonistic effects on mechanical properties of microfibrillar composites with dual reinforcement: Explanation by FEA model of soft interface

Nanofillers (NF) in microfibrillar composites support melt‐drawing and may lead to improved performance. However, antagonistic effects have also been found. The deterioration of mechanical properties by drawing in the presence of NF, as found by other authors in analogous undrawn systems, has not yet been explained. Experiments indicating the importance of NF migration between the HDPE matrix and the PA6 fibrils in the course of drawing have led to a tentative conclusion of changed crystallinity in the interfacial area resulting in a layer with reduced modulus. This was confirmed by the finite element analysis considering the formation of a “soft” interface as a result of reduced content of HDPE spherulites at the fiber surfaces. The results show a marked impact of this phenomenon on modulus. This original concept presents a basis for explaining some antagonistic effects in multicomponent polymer systems and a tool for the more rational design of composite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44712.     

Impact of particle morphology on structure,crystallization kinetics,and properties of PCL composites with TiO<Subscript>2</Subscript>-based particles

Crystallization kinetics of polycaprolactone (PCL) filled with TiO₂-based particles (TiX) was shown to depend on the TiX particle type and concentration, which were associated with a slight polymer matrix degradation. The partially degraded, shorter, and more mobile polymer chains increased the overall crystallization rate at the initial stage of crystallization, while at the later stages, the non-nucleating TiX particles acted as a sterical hindrance, slowing down the crystallization process. The PCL/TiX composites were prepared by melt-mixing and contained 2.5 and 5 wt% of the filler. The investigated TiX particles included isometric anatase microparticles (mTiO₂) and titanate nanotubes with high-aspect ratio (TiNT). Light and electron microscopy showed very homogeneous dispersion of the mTiO₂ particles in the PCL matrix, while the TiNT formed large agglomerates. In situ polarized light microscopy displayed faster isothermal crystallization of all PCL/TiX composites, but the micrographs indicated that the TiX particles did not act as nucleation centres. Isothermal DSC experiments, evaluated in terms of Avrami theory, confirmed the PLM results and showed that the overall rate of isothermal crystallization increased in the following order: PCL <PCL/TiNT <PCL/mTiO₂. Non-isothermal DSC and rheological measurements revealed the correlation between the crystallization rate and the polymer matrix degradation—the well-dispersed mTiO₂ particles with high specific surface caused the highest PCL degradation and, consequently, the earliest start of non-isothermal crystallization as well as the fastest isothermal crystallization. Microindentation hardness measurements confirmed that the partial degradation of the polymer matrix did not have a significant impact on the mechanical performance of PCL/mTiO₂ composites.     

Long-term studies (1871-2000) on acidification and recovery of lakes in the Bohemian Forest (central Europe)

This paper evaluates long-term changes in the atmospheric depositions of S and N compounds, lake water quality, and biodiversity at eight glacial lakes in the Bohemian Forest over the past 130 years. This time interval covers (i) the 'background' pre-acidification status of the lakes, (ii) a period of changes in the communities that can be partly explained by introduction of fish, (iii) a period of strong lake acidification with its adverse impacts on the communities, (iv) the lake reversal from acidity, which includes the recent status of the lakes. The lake water chemistry has followed-with a characteristic hysteresis-both the sharp increase and decline in the deposition trends of strong anions. Remarkable changes in biota have mirrored the changing water quality. Fish became extinct and most species of zooplankton (Crustacea) and benthos (Ephemeroptera and Plecoptera) retreated due to the lake water acidification. Independent of ongoing chemical reversal, microorganisms remain dominant in the recent plankton biomass as well as in controlling the pelagic food webs. The first signs of the forthcoming biological recovery have already been evidenced in some lakes, such as the population of Ceriodaphnia quadrangula (Cladocera) returning into the pelagial of one lake or the increase in both phytoplankton biomass and rotifer numbers in another lake.     

Microchip sonic spray ionization

The first microchip version of sonic spray ionization (SSI) as an atmospheric pressure ionization source for mass spectrometry (MS) is presented. The microchip used for SSI has recently been developed in our laboratory, and it has been used before as an atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) source. Now the ionization is achieved simply by applying high (sonic) speed nebulizer gas, without heat, corona discharge, or high voltage. The microchip SSI was applied to the analysis of tetra-N-butylammonium, verapamil, testosterone, angiotensin I, and ibuprofen. The limits of detection were in the range of 15 nM to 4 microM. The technique was found to be highly dependent on the position of the chip toward the mass spectrometer inlet, and on the gas and the sample solution flow rates. The microchip SSI provided dynamic linearity following a pattern similar to that used with electrospray, good quantitative repeatability (RSD=16%), and long-term signal stability.     

Biodiesel from rapeseed oil,methanol and KOH. 3. Analysis of composition of actual reaction mixture

Detailed analysis is described of the samples taken after suitable reaction times from the actual reaction mixture during the production of biodiesel fuel using methanolysis of rapeseed oil catalyzed by KOH. Three methods for stoppage of reaction (neutralisation of catalyst, dilution by two suitable solvents) in the sample are used. The contents of mono‐, di‐ and triacylglycerols, methylesters of fatty acids (biodiesel) and potassium salts of fatty acids of rapeseed oil, glycerol (by HPLC method), basicity (by potentiometric titration) and water (by GC and Karl‐Fischer method) in the samples are determined. An example of these determinations is described.     

Gradient Composites of Alkaline Poly(6‐hexanelactam) with Graphite: One‐Step Synthesis,Structure, and Mechanical Properties

In a one‐step synthesis of gradient composites, molten monomer of 6‐hexanelactam was mixed with graphite (5 wt.‐%) and alkaline polymerization was performed under quasi‐isothermal conditions at about 170°C. The following initiator/activator system insensitive to traces of water and other low‐molecular‐weight compounds adsorbed on filler surface was used: the sodium salt was prepared through the reaction of sodium dicaprolactamobis(2‐methoxyethoxo)aluminate with 6‐hexanelactam; N‐acyllactam was formed in situ in molten monomer by solving flexible or rigid polyurethane foam consisting of either toluene diisocyanate or diphenylmethane‐4,4′‐diisocyanate, and a poly(propylene oxide) based polyol. To obtain gradient composites with a compositional variation between plane‐parallel surfaces, the incorporated filler underwent sedimentation due to gravity during initial stages of polymerization. The graphite‐free surface is suitable for treatment with adhesives, while the graphite‐rich surface layer (containing about 11 wt.‐% of graphite) possesses improved friction characteristics. Graphite slightly (i) reduces the polymer yield and the mean spherulite diameter; (ii) increases the crystallinity due to its nucleation activity; (iii) decreases the compliance, but does not affect its time dependence given by the matrix and (iv) reduces the yield strength, tensile strength and elongation at break. The friction coefficient of the graphite‐rich surface is reduced to almost 50% of that found for the graphite‐free surface; composites with cross‐linked matrix also show better wear properties.     

A Complex Evaluation of the In-Vivo Biocompatibility and Degradation of an Extruded ZnMgSr Absorbable Alloy Implanted into Rabbit Bones for 360 Days

The increasing incidence of trauma in medicine brings with it new demands on the materials used for the surgical treatment of bone fractures. Titanium, its alloys, and steel are used worldwide in the treatment of skeletal injuries. These metallic materials, although inert, are often removed after the injured bone has healed. The second-stage procedure—the removal of the plates and screws—can overwhelm patients and overload healthcare systems. The development of suitable absorbable metallic materials would help us to overcome these issues. In this experimental study, we analyzed an extruded Zn-0.8Mg-0.2Sr (wt.%) alloy on a rabbit model. From this alloy we developed screws which were implanted into the rabbit tibia. After 120, 240, and 360 days, we tested the toxicity at the site of implantation and also within the vital organs: the liver, kidneys, and brain. The results were compared with a control group, implanted with a Ti-based screw and sacrificed after 360 days. The samples were analyzed using X-ray, micro-CT, and a scanning electron microscope. Chemical analysis revealed only small concentrations of zinc, strontium, and magnesium in the liver, kidneys, and brain. Histologically, the alloy was verified to possess very good biocompatibility after 360 days, without any signs of toxicity at the site of implantation. We did not observe raised levels of Sr, Zn, or Mg in any of the vital organs when compared with the Ti group at 360 days. The material was found to slowly degrade in vivo, forming solid corrosion products on its surface.