Synthesis and Microstructural Characterization of Substoichiometric Ti2Al(CxNy) Solid Solutions and Related Ti2AlCx and Ti2AlN End‐Members

Ti, TiC, Al and AlN powders were mixed to synthesize Ti₂Al(C_xN_y) (x + y < 1) solid solutions, Ti₂AlC_x (x < 1) and Ti₂AlN‐related end‐members by hot isostatic pressing at 1400°C/80 MPa for 4 h. For the pure carbides, it is demonstrated that single‐phased samples can only be obtained when about 15% of substoichiometry on the carbon site is applied. Such a result likely implies that Ti₂AlC_x can only exist in a narrow range of carbon composition. Ti₂AlN nitride can be synthesized with y = 1. Assuming that vacancy content varies linearly from 0 to 0.15 going from Ti₂AlN to Ti₂AlC_0.85 in the solid solutions, element concentrations have been calculated to synthesize different solid solutions. Thus, it is demonstrated that single‐phased and fully dense Ti₂Al(C_0.23N_0.71), Ti₂Al(C_0.45N_0.45), and Ti₂Al(C_0.66N_0.22) carbonitrides can be synthesized.     

Polymerization of β-butyrolactone initiated with Al(OiPr)3

Polymerization of β-butyrolactone has been studied in toluene with Al(OⁱPr)₃ as an initiator. The ring-opening polyaddition proceeds through a coordination–insertion mechanism at a very low rate. Well defined α-isopropylester, ω-hydroxy poly(β-butyrolactone)s (PBL) are formed with a narrow molecular weight distribution at low monomer-to-initiator molar ratios, When this ratio is higher (ca. 170), a competition occurs between propagation and side reactions, i.e. elimination, inter- and intra-molecular transesterifications and thermal degradation, which is responsible for a loss of control of the PBL molecular charcteristics. The addition of a Lewis base (1 equivalent of nicotine/Al) to the Al-alkoxide initiator has no significant effect on the polymerization rate, although the chain microstructure is deeply affected since predominantly syndiotactic PBL chains are formed (63% syndio-diads) in contrast to a completely atactic polymer in the absence of nicotine.     

Synthesis and Anticancer Properties of Oxazepines Related to Azaisoerianin and IsoCoQuines

In this article, we report the synthesis and biological properties of a series of novel oxazepines related to isoCA-4 having significant antitumor properties. Among them, three oxazepin-9-ol derivatives display a nanomolar or a sub-nanomolar cytotoxicity level against five human cancer cell lines (HCT116, U87, A549, MCF7, and K562). It was demonstrated that the lead compound in this series inhibits tubulin assembly with an IC₅₀ value of 1 μM and totally arrests the cellular cycle in the G2/M phase at the low concentration of 5 nM in HCT116 and K562 cells. Molecular modeling studies perfectly corroborates these promising results.     

Design of New Cardanol Derivative: Synthesis and Application as Potential Biobased Plasticizer for Poly(lactide)

A novel biobased plasticizer made of cardanol is designed for poly(lactide) (PLA). This cardanol‐derived plasticizer, i.e., methoxylated hydroxyethyl cardanol (MeCard), is synthesized through methoxylation of the double bonds on the side chain of cardanol, and characterized by ¹H NMR and mass spectrometry. The plasticization effect of MeCard on the molecular structure, morphology, thermal and mechanical properties of PLA is evaluated and compared to that of a commercial cardanol, i.e., hydroxyethyl cardanol (pCard). The plasticization efficiency of MeCard is demonstrated by a substantial decrease of the glass transition temperature and storage modulus together with a significant increase of the elongation at break as compared to neat PLA. Moreover, MeCard exhibits higher plasticization performance than pCard toward PLA. Such behavior is related to a higher miscibility and compatibility between PLA and MeCard thanks to the methoxylation of the double bonds on the side chain of cardanol as shown by SEM micrographs.

     

Self-Propagating High-Temperature Synthesis of Ti3SiC2: Study of the Reaction Mechanisms by Time-Resolved X-Ray Diffraction and Infrared Thermography

Ti₃SiC₂ is synthesized by self-propagating high-temperature synthesis (SHS) of elemental titanium, silicon, and graphite powders. The reaction paths and structure evolution are studied in situ during the SHS of the 3Ti+Si+2C mixture by time-resolved X-ray diffraction coupled with infrared thermography. The proposed reaction mechanism suggests that Ti₃SiC₂ might be formed from Ti–Si liquid phase and solid TiC _x . Finally, the effect of the powders starting composition on the Ti₃SiC₂ synthesis is studied. For the investigated initial mixtures, TiC _x is always formed as a major impurity together with the Ti₃SiC₂ phase.     

Quantitative Fourier transform infrared analysis for anisidine value and aldehydes in thermally stressed oils

A Fourier transform infrared (FTIR) transmission-based spectroscopic method was investigated for the simultaneous monitoring of aldehyde formation and the determination of anisidine value (AV) in thermally stressed oils. Synthetic calibration standards were prepared by adding known amounts of hexanal,t-2-hexenal andt,t-2,4-decadienal to canola oil (these compounds considered representative of aldehydic compounds formed during oxidation) plus random amounts of other compounds representative of oxidation by-products. The standards were analyzed for their chemical AV. With the partial least squares (PLS) technique, an FTIR spectrometer was calibrated to predict both the concentrations of individual aldehyde types and AV, with the individual aldehyde contributions being related to the chemical AV by multiple linear regression to derive “apparent” AV values. The predictive capability of the PLS calibrations was assessed by analyzing canola oils that were thermally stressed at 120, 155, and 200°C. The apparent AV, predicted for these samples, matched the chemical AV values within ±1.65 AV units. A PLS calibration also was derived by using thermally stressed samples as calibration standards. This approach provided similar predictive accuracy as the use of synthetic calibration standards. As such, quantitative determination of AV by FTIR spectroscopy was shown to be feasible, and the synthetic calibration approach provided additional information on the aldehyde types present in a sample and allowed the use of a simple gravimetric approach for calibrating an FTIR spectrometer. This study provides the basis for the development of a rapid, automated FTIR method for the direct analysis for AV of thermally stressed fats and oils in their neat form without the use of chemical reagents. The implementation of such a method as a quality control tool would eliminate the use and disposal of hazardous solvents and reagents, required by the conventional chemical method, and drastically reduce analysis time (∼2 min/sample). Possible applications include monitoring of the oxidative state of frying oils or evaluation of oxidative stability of biodegradable lubricants.     

Vapor barrier properties of polycaprolactone montmorillonite nanocomposites: effect of clay dispersion

Different compositions of poly(ε-caprolactone) (PCL) and (organo-modified) montmorillonite were prepared by melt blending or catalyzed ring opening polymerization of ε-caprolactone. Microphase composites were obtained by direct melt blending of PCL and sodium montmorillonite (MMT-Na⁺). Exfoliated nanocomposites were obtained by in situ ring opening polymerization of ε-caprolactone with an organo-modified montmorillonite (MMT-(OH)₂) by using dibutyltin dimethoxide as an initiator/catalyst. Intercalated nanocomposites were formed either by melt blending with organo-modified montmorillonite or in situ polymerization within sodium montmorillonite. The barrier properties were studied for water vapor and dichloromethane as an organic solvent. The sorption (S) and the zero concentration diffusion coefficient (D₀) were evaluated for both vapors. The water sorption increases with increasing the MMT content, particularly for the microcomposites containing the unmodified MMT-Na⁺. The thermodynamic diffusion parameters, D₀, were compared to the value of the parent PCL: both microcomposites and intercalated nanocomposites show diffusion parameters very near to PCL. At variance exfoliated nanocomposites show much lower values, even for small montmorillonite content. In the case of the organic vapor, the value of sorption at low relative pressure is mainly dominated by the amorphous fraction present in the samples, not showing any preferential adsorption on the inorganic component. At high relative pressure the isotherms showed an exponential increase of sorption, due to plasticization of the polyester matrix. The D₀ parameters were also compared to those of the unfilled PCL; in this case, both the exfoliated and the intercalated samples showed lower values, due to a more tortuous path for the penetrant molecules.     

Recent Advances in Reactive Extrusion Processing of Biodegradable Polymer‐Based Compositions

This review reports on recent advances in the design of biodegradable polymers built from petroleum and renewable resources using reactive extrusion processing. Reactive extrusion represents a unique tool to manufacture biodegradable polymers upon different types of reactive modification in a cost‐effective way. Partially based on our ongoing research, ring‐opening polymerization of biodegradable polyesters will be approached as well as the chemical modification of biodegradable polymers, particularly natural polymers. The development of environmentally friendly polymer blends as well as (nano)composites from natural polymers, including natural fibers and nanoclays, through reactive extrusion, as an efficient way to improve the interfacial adhesion between these components, will be also discussed.

     

Melt‐stable poly(1,4‐dioxan‐2‐one) (co)polymers by ring‐opening polymerization via continuous reactive extrusion

Bulk polymerization of ?‐caprolactone (CL), 1,4‐dioxan‐2‐one (PDX), and mixtures of PDX and CL was carried out by initiation with Al(O^secBu)₃ in a co‐rotating twin‐screw extruder through a fast single‐step process. Both homopolymerizations and copolymerization of PDX and CL proceed very rapidly and reach almost complete (co)‐ monomer(s) conversion as soon as 8 mol% of CL are added in the feed. Even though poly(1,4‐dioxan‐2‐one) (PPDX) is known to thermally degrade mainly through unzipping depolymerization promoted from the hydroxyl end‐groups and yielding PDX monomer, it turns out that the thermal stability of PPDX chains is substantially improved by the copolymerization of PDX with limited amounts of CL. Interestingly, DSC analysis of the so‐obtained P(PDX‐co‐CL) copolymers has demonstrated that a CL molar fraction as high as 11 mol% does not prevent the crystallization of the resulting copolymer, which retains a melting temperature close to 95°C. This last observation has been explained by the formation of a blocky‐like copolymer structure, in which short PPDX and PCL sequences are randomly distributed. POLYM. ENG. SCI., 45:622–629, 2005. © 2005 Society of Plastics Engineers.