Impact of TiO2 nanoparticles and nanowires on corrosion protection performance of chemically bonded phosphate ceramic coatings

The impact of the addition of TiO₂ nanoparticles and nanowires on the morphology, phase characteristics, contact angle, and electrochemical performance of chemically bonded phosphate ceramic coatings (CBPCs) was investigated. The chemical composition and surface morphology of the TiO₂ nanoparticle and nanowire modified with and without (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane were characterized. Results indicated that the hydrophobic –CF₂– and –CF₃ groups were successfully introduced into the TiO₂ nanoparticles and nanowires after modification. Corrosion resistance of CBPCs with TiO₂ was evidently improved compared with that without TiO₂. Such improvement was mainly due to the combined effects of low surface energy materials and micro/nano structures. In addition, CBPCs with TiO₂ nanowires exhibited higher hydrophobicity and corrosion resistance than those with TiO₂ nanoparticles because of the special columnar structure of the nanowires.     

Multi-objective planning and optimization of microgrid lithium iron phosphate battery energy storage system consider power supply status and CCER transactions

Lithium iron phosphate battery (LIPB) is the key equipment of battery energy storage system (BESS), which plays a major role in promoting the economic and stable operation of microgrid. Based on the advancement of LIPB technology and efficient consumption of renewable energy, two power supply planning strategies and the china certified emission reduction (CCER) model are proposed respectively. Based on it, the multi-objective planning optimization model with economic benefits, environmental benefits and power supply stability as the objective function is established for the first time, and the Newton Weighted Sum Frisch method (NWSFA) solution model is adopted. In the planning process, rain flow counting method is used to research the life of BESS, which improves the accuracy of energy storage annual cost calculation. A park in northern China is taken as a case study to demonstrate the application of this model. The simulation results show that the annual economic operating cost of BESS is decreased by 18.81%, the energy supply reliability is increased by 0.15%, and the optimal electricity price adjustment ratio of the system is 15%.     

Enhancement in the osteogenesis and angiogenesis of calcium phosphate cement by incorporating magnesium-containing silicates

Based on the good osteogenic and angiogenic effects of silicon and magnesium elements, three types of micro-nano magnesium-containing silicates (MS), including akermanite (Ake, Ca₂MgSi₂O₇), diopside (Dio, CaMgSi₂O₆) and forsterite (For, Mg₂SiO₄), were incorporated into calcium phosphate cement (CPC) to improve its osteogenic and angiogenic performances for clinical application. In this present work, the physicochemical properties, osteogenesis and angiogenesis of MS/CPCs (Ake/CPCs, Dio/CPCs and For/CPCs) were investigated systematically and comparatively. The results showed that all MS/CPCs had good biomineralization and significantly stimulated the osteogenic differentiation of mBMSCs and angiogenic differentiation of HUVECs, respectively. Besides, the stimulating effects were related to not only the category of MS, but also the content of MS. The For/CPCs had a good angiogenic property but their initial setting times were beyond 60 min. The Dio/CPCs showed the lowest biological performance among the three groups of MS/CPCs due to the lower ion release (Si and Mg). The Ake was the ideal modifier that could provide CPC with appropriate physicochemical properties, better osteogenesis and angiogenesis. Simultaneously, a higher addition (10 wt%) of akermanite resulted in the best potential to bone regeneration. Taken together, this research provides an effective approach to improve the overall performance of CPC, and 10Ake/CPC is of great promising prospect in bone repair.     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

Preparation and characterization of calcium phosphate cement with enhanced tissue adhesion for bone defect repair

Anti-washout and tissue adhesion properties are essential for the clinical application of injectable bone materials. In this study, we prepared calcium phosphate cement (CPC) with anti-washout and tissue adhesion properties and attempted to build covalent bonds between CPC and the amino groups in bone tissue under a self-regulating pH system in the CPC (acidic to basic). The results of push-out tests demonstrated that a significant enhancement (from 6.42 ± 0.76 N to 61.5 ± 4.09 N) in tissue adhesion was obtained with the addition of 6% (w/w) oxidized sodium alginate (OSA) in CPC. The FTIR, XRD, anti-washout test, XPS, pH test, and SEM results suggested that the synergistic effect of OSA-citric acid (CA) led to the formation of a three-dimensional gel network structure in the CPC, and the Schiff base reaction between aldehyde and amino groups induced adhesion between CPC and the bone tissue. Further, the addition of less OSA had no significant negative effect on the hydration properties of CPC. Our work aims to promote the development of injectable bone material in clinical applications.     

Multi-scale characteristics of magnesium potassium phosphate cement modified by metakaolin

Workability and early-ages mechanical properties are important indicators of magnesium potassium phosphate cement (MKPC) as a repair material. The effect of metakaolin (MK) on the setting time, fluidity and early-ages strength of MKPC paste was studied, and its influence mechanism was analyzed through pore structure, microstructure and nanomechanical properties. The results show that 10% and 20% of MK prolong the setting time of MKPC paste, but excessive MK shortens the setting time of MKPC paste. Meanwhile, incorporating MK reduces the fluidity of MKPC paste, and the early-ages strength of MKPC specimens increases when the substitution ratio of MK is 10%. When 10% of MK is incorporated to the MKPC paste, the 30-d shrinkage of the sample is only 69% of the control group. Meanwhile, a proper amount of MK can improve the pore structure of the MKPC specimen and make its microstructure denser by generating amorphous aluminosilicate phosphate gel. It is observed from the nano-scale characteristics that incorporating 10% MK can reduce the content of pore phase and unreacted MgO phase, and increase the volume fraction of hydration products.     

Improvement of a commercial calcium phosphate bone cement by means of drug delivery and increased injectability

Calcium phosphate cements (CPCs) have been increasingly used as synthetic bone substitutes for repair and regeneration of bone defects given their biocompatibility, resemblance to bone and malleability. Moreover, their use as local antibiotic delivery systems is of main interest against bone infections, avoiding the adverse effects of high dosages of conventional therapy. The main goals of this work were to improve the properties of a commercial CPC (Neocement®), turning it injectable, and to provide it with a new functionality as a drug delivery system able to ensure a sustained release of an antibiotic commonly used in orthopaedics (gentamicin sulphate, GS). For this, the influence of the liquid phase amount (%LP) and type of polymer contained in the formulation (chitosan, Chi, or hydroxypropyl methylcellulose, HPMC) on the basic properties of the material was evaluated. It was found that the formulation containing 42%LP + HPMC+1.87% wt GS was the best one. It showed suitable setting and mechanical properties, and injectability around 87% (much superior to the original Neocement®, with 31%). It ensured a sustained release of GS for at least 14 days, at antibacterial levels. The antibiotic released is highly effective against S. epidermidis, but also presents some antibacterial activity against S. aureus. The CPC revealed to be non-cytotoxic. Moreover, it demonstrated good flowability and connectivity with human cadaveric trabecular bone.     

Electrical polarization and ionic conduction properties of β-tricalcium phosphate bioceramics with controlled vacancies by sodium ion substitution

With the aim to understand electric polarization mechanisms of β-tricalcium phosphate as an advanced biomaterial, Na ion-substituted β-Ca₃(PO₄)₂ (Na-β-TCPs) ceramics with controlled lattice vacancies were synthesized and structural refinement was performed by the Rietveld method. The Rietveld analysis revealed that Ca and vacancies at Ca(4) sites in the β-TCP structure decreased with an increase in Na substitution. Electrical measurements by the complex impedance method revealed that the conductivity and the activation energy calculated from Cole-Cole plots rapidly decreased to a constant value with an increase in Na substitution and decrease in vacancies. The thermally stimulated depolarization current (TSDC) curve of the electrically polarized Na-β-TCP showed one large peak at 530–610 °C. However, the accumulated charge decreased with an increase in Na ions and decrease in vacancies up to 2.37 mol%, after which it became constant. These results are consistent with the presumed formation of a dipole moment between aligned Ca²⁺ ions and their vacancies along the direction of the external polarization field applied at high temperature. We conclude that the large amount of stored charge in β-TCP caused by electrical polarization is due to the low site occupancy of calcium ions and vacancies at Ca(4) sites in the β-TCP structure, which is not the case for hydroxyapatite (HAp), as previously reported.     

Migration analysis,antioxidant, and mechanical characterization of polypropylene-based active food packaging films loaded with BHA,BHT, and TBHQ

Polypropylene (PP) based active composite films were prepared by adding butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), and tertiary butylated hydroquinone (TBHQ) antioxidants using the extrusion molding process. All concentrations of BHT, 2% to 3% BHA, and 3% TBHQ significantly increased the tensile strength (TS) of the composite films compared with control films. Increasing antioxidant concentration decreased TS values for BHT films, whereas an opposite trend was observed for BHA and TBHQ films. BHA at < 2%, BHT at > 2%, and TBHQ at all added concentrations significantly reduced elongation at break (E_b) of the composite films compared to control films. Water vapor permeability (WVP) of 1% BHT film was not significantly different from control. However, other antioxidants especially at increased concentrations significantly increased WVP values. TBHQ films with 300% to 662% increase had the highest WVP and BHT films with 5% to 81% increase had the lowest WVP among composite films. All three antioxidants had a negative effect on the transparency of the films; however the effect of BHA at higher concentrations was greater. The antioxidants did not change the color attributes of the films. Films containing all antioxidants showed 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity, which increased with increase in their concentration, especially for those containing 3 wt.% BHT and TBHQ. Overall, incorporating BHA and BHT into a PP matrix improved mechanical, barrier, antioxidant properties, and film appearance and consequently were proposed for the development of antioxidant active PP films. TBHQ film is not recommended for food packaging because of its weak mechanical properties (lower E_b and TS values, higher WVP, and greater migration).     

响应面曲线法优化贵州某磷块岩浮选工艺研究

对贵州某沉积钙质磷块岩进行了浮选工艺研究。采用H₂SO₄为氟磷灰石抑制剂、BW-1为白云石捕收剂,进行了浮选单因素试验; 在此基础上进行了正交试验,并采用响应面曲线法进行了浮选条件优化。确定了最佳浮选条件为: 磨矿细度-0.074 mm粒级占60%、H₂SO₄用量13.20 kg/t和BW-1用量400 g/t。采用一段反浮选试验流程,可得到精矿品位30.94%、回收率92.45%的磷精矿。研究结果表明,磨矿细度与H₂SO₄用量的交互作用对精矿品位影响显著,H₂SO₄用量和BW-1用量的交互作用对精矿回收率影响显著。