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.     

Evaluation of the PSMA-Binding Ligand 212Pb-NG001 in Multicellular Tumour Spheroid and Mouse Models of Prostate Cancer

Radioligand therapy targeting the prostate-specific membrane antigen (PSMA) is rapidly evolving as a promising treatment for metastatic castration-resistant prostate cancer. The PSMA-targeting ligand p-SCN-Bn-TCMC-PSMA (NG001) labelled with ²¹²Pb efficiently targets PSMA-positive cells in vitro and in vivo. The aim of this preclinical study was to evaluate the therapeutic potential of ²¹²Pb-NG001 in multicellular tumour spheroid and mouse models of prostate cancer. The cytotoxic effect of ²¹²Pb-NG001 was tested in human prostate C4-2 spheroids. Biodistribution at various time points and therapeutic effects of different activities of the radioligand were investigated in male athymic nude mice bearing C4-2 tumours, while long-term toxicity was studied in immunocompetent BALB/c mice. The radioligand induced a selective cytotoxic effect in spheroids at activity concentrations of 3–10 kBq/mL. In mice, the radioligand accumulated rapidly in tumours and was retained over 24 h, while it rapidly cleared from nontargeted tissues. Treatment with 0.25, 0.30 or 0.40 MBq of ²¹²Pb-NG001 significantly inhibited tumour growth and improved median survival with therapeutic indexes of 1.5, 2.3 and 2.7, respectively. In BALB/c mice, no signs of long-term radiation toxicity were observed at activities of 0.05 and 0.33 MBq. The obtained results warrant clinical studies to evaluate the biodistribution, therapeutic efficacy and toxicity of ²¹²Pb-NG001.     

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.     

退火温度对新型锆合金薄板带材析出相和织构的影响

采用扫描电镜和超高分辨透射电镜,对具有良好冲制性能的新型锆合金薄板成品带材进行含晶粒、第二相粒子等在内的显微组织研究,并探索真空退火处理条件下温度对带材显微组织的影响。结果显示:新型锆合金薄板成品带材晶粒平均尺寸2.17 μm,存在{0001}<1010>和{0001}<1120>两种织构,大部分晶粒<1120>平行带材RD方向,较少晶粒<1010>平行带材RD方向;第二相粒子分布在晶粒内部及晶界,平均尺寸114 nm,尺寸较大的为不规则椭圆形的Zr-Nb-Fe相,尺寸较小的为圆形的β-Nb相;热处理退火温度降低,带材晶粒尺寸减小,第二相粒子细小弥散分布;新型锆合金薄板成品带材良好冲制性能主要源于轧制积累应变诱发再结晶过程进行充分,导致晶粒细小及孪晶发生破碎;相对轧制变形,退火对带材冲制性能影响不显著。