Solid‐State NMR Study of Mn2+ for Ca2+ Substitution in Thermally Processed Hydroxyapatites

In the present study calcium hydroxyapatites enriched at 0.08 wt% in Mn²⁺ ions (Mn–HA) and their unsubstituted forms (HA) were synthesized using the same standard wet chemical route. Mn‐HA and HA were both calcined at 800°C to give Mn‐HAc and HAc, respectively or sintered at 1250°C, to give Mn‐HAs and HAs, respectively. The influence of the heat treatment on physicochemical properties of Mn‐HA was investigated using powder X‐ray diffraction (PXRD), scanning, and transmission electron microscopy (SEM and TEM), and solid‐state nuclear magnetic resonance (ssNMR). Mn‐HAc and Mn‐HAs were compared to each other and to HAc and HAs, respectively. Assignment of the proton ssNMR peaks from high‐temperature‐treated apatites has been revised. It was found that Mn–HAc and HAc were nanocrystalline, while Mn‐HAs and HAs comprised micrometer sized, partially fused particles (SEM and TEM). PXRD and ssNMR demonstrated that the incorporation of Mn²⁺ into the crystal lattice of hydroxyapatite significantly facilitates its dehydroxylation and decomposition to oxyhydroxyapatite during calcination at 800°C, and induces its transformation to tetracalcium phosphate (TTCP) and alpha‐tricalcium phosphate (α‐TCP) at 1250°C. Contamination by CaO has also been detected. The ¹H→³¹P NMR cross‐polarization experiments have indicated that the Mn²⁺ ions preferentially occupied the Ca(I) position in the crystallographic unit cell of Mn‐HAc. In Mn‐HAs, the Mn²⁺ ions were evenly distributed between the Ca(I) and Ca(II) positions.     

Spatial practice,conceived space and lived space: Hong Kong’s ‘Piers saga’ through the Lefebvrian lens

By applying the Lefebvrian lens, this paper tries to understand why unlike previous similar cases, the latest removal of the Star Ferry and Queen’s Pier was so controversial. To Lefebvre, embedded in ‘spatial practices’ that ‘secrete’ a place are two contradicting spaces: ‘conceived spaces’ produced by planners to create exchange values and ‘lived spaces’ appropriated by citizens for use values. Applying Lefebvre’s framework to examine the ‘Piers saga’, it is found that the pre‐Second World War (WWII) piers were ‘conceived’ by spatial practices of a colonial and racially segregated trading enclave. The public space in the commercial heart that housed the previous generations of piers was not accessible to the Chinese community, thus denying them opportunities to appropriate them and turn them into ‘lived’ spaces. It was only after WWII when the Government carried out further reclamation to meet the needs of an industrializing economy that inclusive public spaces were conceived in the commercial heart, enabling the general public to ‘appropriate’ them as ‘lived’ space. When the Government planned to remove this very first ‘lived’ space in the political and economic heart of the city to conceive further reclamation for the restructuring economy, the more enlightened citizens were determined to defend it.     

Influence of the characteristics of a water-in-CO2 microemulsion on the separation of metal species

In this study, AOT [sodium bis(2-ethylhexyl) sulfosuccinate] combined with fluorinated cosurfactant or alcohol was used to form a water-in-CO₂ (W/C) microemulsion. The amount of water uptake in the microemulsion was closely related to the PFPE-PO₄/AOT (P/A) ratio. The stability of the microemulsion decreased with the amount of water. Lower temperature and higher pressure stabilize W/C microemulsions. The extraction efficiencies of metals (Cd, Co, Cu, Pb, Zn), when this W/C microemulsion method was used, exceeded 90% (AOT + octanol). The efficiencies for the extraction of Eu, La, and Sr could exceed 94% (AOT + PFPE-PO₄) in sc-CO_2.     

Toughening of syndiotactic polypropylene with chalk

We hypothesized that polymer crystal anisotropy is advantageous for toughening of polymer composites involving easy slip network of oriented crystalline layers around filler particles. To this end, composites of syndiotactic polypropylene (sPP) with high concentration of submicrometer calcium carbonate particles were prepared and examined because usual sPP crystals exhibit high packing anisotropy. The specific orientation of sPP lamellae around chalk grains was found, which is supposed to facilitate the plastic deformation of polymer matrices. The compression molded bars of the composite exhibited markedly higher Izod impact strength than those of neat sPP. Toughening was even enhanced in the injection molded composite, for which 4.5‐fold increase in the impact strength was achieved. Injection‐induced orientation of the disordered form I sPP crystals was enhanced in the composite. The injection molded tensile specimens exhibited also a good drawability. Debonding at chalk–sPP interface occurred both during the impact and tensile tests facilitating the plastic deformation of sPP matrix. Chalk did not have any significant influence on the thermal properties of the composites but it affected the rheological behavior, increasing the loss and storage moduli, and the viscosity. Highly filled sPP composite exhibited solid‐like behavior in a molten state with the storage modulus exceeding the loss modulus in the entire frequency range. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43651.     

The influence of electron beam irradiation,plastic deformation,and re‐irradiation on crystallinity degree,mechanical and sclerometric properties of GUR 1050 used for arthroplasty

The article describes the influence of an electron beam irradiation (I), plastic deformation (D), and re‐irradiation (R) on the properties of ultrahigh molecular weight polyethylene (GUR 1050). It was found that the modification through irradiation entailed a gradual increase in the degree of crystallinity (after irradiation–I). After plastic deformation and re‐irradiation (IDR) the degree of crystallinity decreases which had a direct influence on the mechanical properties. The polymer irradiation only (technique I) resulted in an increase in the maximum stress as compared with the material in the initial state. The application of deformation and re‐irradiation (technique IDR) allowed increasing the deformation resistance by more than 40%. Moreover, the irradiation with an electron beam resulted in the increase in hardness (H) and Young's modulus (E) proportionally to the applied irradiation dose and in the reduction of total indentation work (W_tot) and its components. After deformation and re‐irradiation the polyethylene hardness went down. The application of technique (I) caused an improvement to the material abrasion resistance (reduction of parameter PD–working scratch depth) with the increasing irradiation dose. The introduction of deformation and re‐irradiation did not have a material impact on parameter (PD) increasing at the same time elastic properties of UHMWPE (increase in parameter NPS–elastic recovery). Modification IDR has changed the wear mechanism (β) toward ploughing and has increased the abrasion‐resistance index (W_β) and also significantly reduced the coefficient of friction (μ) of GUR 1050. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43683.     

Optimization of subtractive-transformative hybrid processes supported by the technological heredity concept

This paper presents the optimization procedure of a hybrid removal-forming type process based on the minimum energy consumption and demanded surface roughness which is supported by the analysis of transformation of the surface and sublayer properties termed as the technological heredity. The experimental investigation covers an alloy steel hardened to 35 HRC and 55 HRC which was initially turned using coated carbide and CBN tools and subsequently burnished to produce surfaces with Ra roughness parameter of about 0.15 μm. The modifications of the initial surface profiles, microstructure and microhardness of the sublayer were determined and relevant technological limits are selected.     

Use of FIB to Study ZDDP Tribofilms

Focussed ion beam milling (FIB) followed by TEM has been used to study ZDDP tribofilms on rubbed steel surfaces. It has been found that the impact of high energy platinum and gallium ions during FIB causes significant morphological and structural changes to the uppermost 30–50 nm of a ZDDP tribofilm. This can be prevented by the low energy deposition of a quite thick gold layer prior to installation of the sample in the FIB facility. This problem, and its solution, have been quite widely reported in the non-tribology literature but have not previously been highlighted in the application of FIB to study tribological surfaces. It has also been found, using this gold pre-deposition method, that the bulk of the ZDDP tribofilm studied has a polycrystalline structure.