Linear free energy relationships between reaction rate constants and equilibrium constants of complex compounds——III. Kinetics and mechanisms of ternary complex formation between (5-X-1, 10-phenanthroline)copper(II) and threonine

The kinetics of ternary complex formation involving Cu(5-X-1, 10-phen) and threonine (CuAL, A=5-X-1, 10-phen; L=threonine or represented by O-N; X=NO_2, Cl, H, CH_3) has been studied by temperature-jump and stopped-flow methods. The formation rate constants, k_f(M^(-1).s^(-1)), for the complexation reaction, CuA + LCuAL, are as follows; X=NO_2, 8.68×10~8; X=Cl, 7.13×10~8; X=H, 6.12×10~8; X=CH_3, 5.42×10~8. The rate constants for zwitterion attack are nil within experimental error. It has been found that a linear free energy relationship exists between the stability(logK_(CuAL)^(CuA) of the complexes CuAL and log kf as follows: IogK_(CuAL)^(CuA)=0.13 + 0.83 logk_f, r=0.99. It suggested that the formation rate governed the stability of the ternary complexes. The rates of formation of the ternary complexes increased with decreasing electron-donating property of the substituents. A linear relationship was found to exist as expressed by the following equation: log(k_f^R/k_F^O) = 0.097σ, r=0.96. A mechanism involves a rapid equilibrium between CuA and L followed by a slow ring closure of L.

Bio-inspired clay nanosheets/polymer matrix/mineral nanofibers ternary composite films with optimal balance of strength and toughness

Although remarkable progress has been witnessed in mimicking the nacre-like architecture in laboratory,it remains a great challenge for understanding the unique balancing mechanism of toughness and strength in biological materials. Here,taking advantage of the synergistic effect of different dimensional nanoscale building blocks,we fabricate nacre-like films that reconcile high strength and toughness.The obtained ternary lamellar composite films are constructed by one-dimensional xonotlite nanowires and two-dimensional montmorillonite nanosheets with the assistance of poly（vinyl alcohol）. The ternary composite films show high strength（（241.8±10.2）MPa） and toughness（（5.85±0.46） MJ m^-3）,both of which are higher than that of the single nanofibrillar xonotlite network films or the binary montmorillonite/poly（vinyl alcohol） composite films. The excellent mechanical properties of the nacre-like ternary composite films are aroused by the synergistic toughening mechanism of the different dimensional building blocks. This strategy provides a facile approach to integrate the nacre-like composite films with potential applications in tissue engineering scaffold,strong air barrier coatings,and fire-retardant packing materials.

Microstructure, Microsegregation, and Mechanical Properties of Directional Solidified Mg–3.0Nd–1.5Gd Alloy

The microstructure, microsegregation, and mechanical properties of directional solidified Mg–3.0Nd–1.5Gd ternary alloys were experimentally studied. Experimental results showed that the solidification microstructure was composed of dendrite primary a（Mg） phase and interdendritic a（Mg） · Mg12（Nd, Gd） eutectic and Mg5 Gd phase. The primary dendrite arm spacing k1 and secondary dendrite arm spacing k2 were found to be depended on the cooling rate R in the form k1= 8.0415 9 10-6R-0.279 and k2= 6.8883 9 10-6R-0.205, respectively, under the constant temperature gradient of40 K/mm and in the region of cooling rates from 0.4 to 4 K/s. The concentration profiles of Nd and Gd elements calculated by Scheil model were found to be deviated from the ones measured by EPMA to varying degrees, due to ignorance of the back diffusion of the solutes Nd and Gd within a（Mg） matrix. And microsegregation of Gd depended more on the growth rate, compared with Nd microsegregation. The directionally solidified experimental alloy exhibited higher strength than the non-directionally solidified alloy, and the tensile strength of the directionally solidified experimental alloy was improved,while the corresponding elongation decreased with the increase of growth rate.