Microstructures and bond strengths of the calcium phosphate coatings formed on titanium from different simulated body fluids

Calcium phosphate (Ca-P) coatings were deposited on Ti substrates by a biomimetic method from m-SBF and 10× SBF, respectively. Comparative study of microstructures and bond strengths of the Ca-P coatings deposited from those different SBFs was carried out. Effect of the surface roughness of the substrates on the bond strength of the Ca-P coatings was also studied. Scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transformed infrared spectroscopy (FTIR), inductive coupled plasma spectrometry (ICP) and thermogravimetry (TG) were used to characterize the Ca-P coatings. The bond strengths between the coatings and Ti substrates were measured using an adhesive strength test. Results indicated that the ionic concentrations of the SBFs and the surface roughness of the substrate had a significant influence on the formation, morphology and bond strength of the Ca-P precipitates. The induction period of time to deposit a complete Ca-P layer from the m-SBF is much longer, but the Ca-P coating is denser and has higher bond strength than that formed from the 10× SBF. The Ti with a surface roughness of R_a 0.64 µm and R_z 2.81 µm favoures the formation of a compact Ca-P coating from the m-SBF with the highest bond strength of approximately 15.5 MPa.

Simultaneous removal of ammonia and phosphate from wastewater by precipitation of struvite using magnesia

A thorough investigation of conditions required for the precipitation of magnesium ammonium phosphate hexahydrate using magnesia as the source of magnesium was carried out and two computer models were used to make predictions as to optimum conditions for production of suitable crystal size and structure for a successful process. A process was developed and a bench scale model operated for a number of high ammonia wastes. Removal of ammonia was affected to levels of up to 97% with 94% ammonia removal being achievable consistently.

Influence of praseodymium - synergistic corrosion inhibition in mixed rare-earth diphenyl phosphate systems

Mixed rare-earth organophosphates have been investigated as potential corrosion inhibitors for AA2024-T3, and previously have shown synergistic inhibition behavior; however, the mechanism was not identified. In this paper, a key factor contributing to corrosion inhibition of AA2024-T3 with mischmetal diphenyl phosphate [Mm(dpp)3] is the unique stability of Pr(dpp)3 compared to other key rare earths in mischmetal. Although increasing pH causes precipitation of other components, the Pr compound is stable at higher pH. Electrochemically, a synergy is evident when Ce(dpp)3 and Pr(dpp)3 are combined. Raman mapping indicates the Pr(dpp)3 inhibitor leads to a more uniform coverage of the alloy.

Ceramic-polymer interface in composite electrolytes of lithium aluminium titanium phosphate and polyetherurethane polymer electrolyte

Composite electrolytes of the lithium-ion-conducting ceramic Li_1.3Al_0.3Ti_1.7(PO₄)₃ and polyetherurethane/lithium triflate polymer electrolyte have been prepared. Microscopy has shown that adhesion between the ceramic and polymer phases is poor, with gaps up to 1 μm at the interface. When dry, the composites are no more conductive than the pure polymer electrolyte. Exposing the samples to the vapour of solvents such as DMF, acetonitrile or water produces a significant increase in conductivity, over and beyond simple plasticization of the polymer. Pretreating the ceramic with a compatibilizing agent improves adhesion at the interface with the polymer, but decreases overall conductivity in the case investigated.

A new class of proton-conducting ionic plastic crystals based on organic cations and dihydrogen phosphate

Choline dihydrogen phosphate ([N_1.1.1.2OH]DHP) and 1-butyl-3-methylimidazolium dihydrogen phosphate ([C₄mim]DHP) were synthesized as a new class of proton-conducting ionic plastic crystals. Both [N_1.1.1.2OH]DHP and [C₄mim]DHP showed solid–solid phase transition(s) and showed a final entropy of fusion lower than 20 J K⁻¹ mol⁻¹ which is consistent with Timmerman’s criterion for molecular plastic crystals. The ionic conductivity of [N_1.1.1.2OH]DHP was in the range of 10⁻⁶ S cm⁻¹–10⁻³ S cm⁻¹ in the plastic crystalline phase. On the other hand, the ionic conductivity of [C₄mim]DHP showed about 10⁻⁵ S cm⁻¹ in the plastic crystalline phase. [N_1.1.1.2OH]DHP showed one order of magnitude higher ionic conductivity than [C₄mim]DHP in the temperature range where the plastic phase is stable.

Investigation of proton dynamics and the proton transport pathway in choline dihydrogen phosphate using solid-state NMR

Choline dihydrogen phosphate has previously been shown to be a good ionic conductor as well as an excellent host for acid doping, leading to high proton conductivities required for e.g., electrochemical devices including proton membrane fuel cells and sensors. A combination of variable-temperature ¹H solid-state NMR and 2D NMR pulse sequences, including ³¹P and ¹³C CODEX and ¹H BaBa, show that the proton conduction mechanism primarily involves assisted transport via a restricted three-site motion of the phosphate unit around the P–O bond that is hydrogen bonded to the choline and exchange of protons between these anions. In other words, proton transport at ambient temperatures appears to occur most favorably along the crystallographic b axis, from phosphate dimer to dimer. At elevated temperatures exchange between the protons of the hydroxyl group on the choline cation and the hydrogen-bonded dihydrogen phosphate groups also contributes to the structural diffusion of the protons in this solid state conductor.

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H₃PO₄, were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10⁻² S cm⁻¹. The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H⁺ cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid sample indicate that all three ions are mobile, however the H⁺ diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high; i.e. no significant mass loss below 200 °C.

Fluorescent and electrochemical sensing of (poly)phosphate nucleotides by ferrocene functionalised with two (ZnII-TACN-pyrene) complexes

The [Fc[BOND]bis{ZnII(TACN)(Py)}] complex, comprising two ZnII(TACN) ligands (Fc=ferrocene; Py=pyrene; TACN=1,4,7-triazacyclononane) bearing fluorescent pyrene chromophores linked by an electrochemically active ferrocene molecule has been synthesised in high yield through a multistep procedure. In the absence of the polyphosphate guest molecules, very weak excimer emission was observed, indicating that the two pyrene-bearing ZnII(TACN) units are arranged in a trans-like configuration with respect to the ferrocene bridging unit. Binding of a variety of polyphosphate anionic guests (PPi and nucleotides di- and triphosphate) promotes the interaction between pyrene units and results in an enhancement in excimer emission. Investigations of phosphate binding by 31P NMR spectroscopy, fluorescence and electrochemical techniques confirmed a 1:1 stoichiometry for the binding of PPi and nucleotide polyphosphate anions to the bis(ZnII(TACN)) moiety of [Fc[BOND]bis{ZnII(TACN)(Py)}] and indicated that binding induces a trans to cis configuration rearrangement of the bis(ZnII(TACN)) complexes that is responsible for the enhancement of the pyrene excimer emission. Pyrophosphate was concluded to have the strongest affinity to [Fc[BOND]bis{ZnII(TACN)(Py)}] among the anions tested based on a six-fold fluorescence enhancement and 0.1 V negative shift in the potential of the ferrocene/ferrocenium couple. The binding constant for a variety of polyphosphate anions was determined from the change in the intensity of pyrene excimer emission with polyphosphate concentration, measured at 475 nm in CH3CN/Tris-HCl (1:9) buffer solution (10.0 mM, pH 7.4). These measurements confirmed that pyrophosphate binds more strongly (Kb=(4.45±0.41)×106 M−1) than the other nucleotide di- and triphosphates (Kb=1–50×105 M−1) tested.

Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate

Cerium diphenyl phosphate (Ce(dpp)3) has previously been shown to be a strong corrosion inhibitor for aluminium-copper magnesium alloy AA2024-T3 and AA7075 in chloride solutions. Surface characterisation including SEM and ToF-SIMS coupled with electrochemical impedance spectroscopy (EIS) measurements are used to propose a mechanism of corrosion inhibition which appears to involve the formation of a complex oxide film of aluminium and cerium also incorporating the organophosphate component. The formation of a thin complex film consisting of hydrolysis products of the Ce(dpp)3 compound and aluminium oxide is proposed to lead to the observed inhibition. SEM analysis shows that some intermetallics favour the creation of thicker deposits predominantly containing cerium oxide compounds.