Preparation and electrochemical lithium storage performance of porous silicon microsphere composite with metal modification and carbon coating

This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.

Recent progress in self-repairing coatings for corrosion protection on magnesium alloys and perspective of porous solids as novel carrier and barrier

Featuring low density and high specific strength, magnesium(Mg) alloys have attracted wide interests in the fields of portable devices and automotive industry. However, the active chemical and electrochemical properties make them susceptible to corrosion in humid, seawater, soil,and chemical medium. Various strategies have revealed certain merits of protecting Mg alloys. Therein, engineering self-repairing coatings is considered as an effective strategy, because they can enable the timely repair for damaged areas, which brings about long-term protection for Mg alloys. In this review, self-repairing coatings on Mg alloys are summarized from two aspects, namely shape restoring coatings and function restoring coatings. Shape restoring coatings benefit for swelling, shrinking, or reassociating reversible chemical bonds to return to the original state and morphology when coatings broken;function self-repairing coatings depend on the release of inhibitors to generate new passive layers on the damaged areas. With the advancement of coating research and to fulfill the demanding requirements of applications, it is an inevitable trend to develop coatings that can integrate multiple functions(such as stimulus response, self-repairing, corrosion warning,and so on). As a novel carrier and barrier, porous solids, especially covalent organic frameworks(COFs), have been respected as the future development of self-repairing coatings on Mg alloys, due to their unique, diverse structures and adjustable functions.

Surface Modification With Zinc and Zn-Ni Alloy Compositionally Modulated Multilayer Coatings

Zinc and Zn-Ni alloy compositionally modulated multilayer （CMM） coatings were electrodeposited on to a steel substrate by the successive deposition of zinc and Zn-Ni alloy sublayers from dual baths. The coated samples were evaluated in terms of the surface appearance, surface and cross-sectional morphologies, as well as corrosion resistance. The microstructural characteristics that were examined using the field emission gun scanning electron microscopy （FEGSEM） confirmed the layered structure, grain refinement of the zinc and Zn-Ni alloy CMM coatings, and revealed the existence of microcracks caused by the internal stress in the thick Zn-Ni alloy sublayers. The corrosion resistance that was evaluated by means of the salt spray test shows that the zinc and Zn-Ni alloy CMM coatings were more corrosion-resistant than the monolithic coatings of zinc or Zn-Ni alloy of the same thickness. The possible reasons for the better protective performance of Zn-Ni/Zn CMM coatings were given on the basis of the analysis on the micrographic features of zinc and Zn-Ni alloy CMM eoatings after the corrosion test. A probable corrosion mechanism of zinc and Zn-Ni alloy CMM coatings was also proposed.

Porous a-Al_2O_3 thermal barrier coatings with dispersed Pt particles prepared by cathode plasma electrolytic deposition

Porous α-Al2O3 thermal barrier coatings （TBCs） containing dispersed Pt particles were prepared by cathode plasma electrolytic deposition （CPED）. The influence of the Pt particles on the microstructure of the coatings and the CPED process were studied. The prepared coatings were mainly composed of α-Al2O3. The average thickness of the coatings was approximately 100 μm. Such single-layer TBCs ex- hibited not only excellent high-temperature cyclic oxidation and spallation resistance, but also good thermal insulation properties. Porous α-Al2O3 TBCs inhibit further oxidation of alloy substrates because of their extremely low oxygen diffusion rate, provide good thermal insu- lation because of their porous structure, and exhibit excellent mechanical properties because of the toughening effect of the Pt particles and because of stress relaxation induced by deformation of the porous structure.

Corrosion behaviors of zinc and Zn-Ni alloy compositionally modulated multilayer coatings

Zinc and Zn-Ni alloy compositionally modulated multilayer （CMM） coatings were electrodeposited from dual baths. The coated samples were evaluated in terms of surface appearance, surface and cross-sectional morphologies, as well as corrosion resistance. The results obtained from the salt spray test show that the zinc and Zn-Ni alloy CMM coatings are more corrosion-resistant than the monolithic coatings of zinc or Zn-Ni alloy alone with a similar thickness. The corrosion potential measurement and anodic polarisation tests were undertaken to examine the probable corrosion mechanisms of zinc and Zn-Ni alloy CMM coatings. Analysis on the micrographic features of zinc and Zn-Ni alloy CMM coatings after the corrosion test explains the probable reasons why the Zn-Ni/Zn CMM coatings have a better protective performance. Surface morphologies and compositional analysis of the remaining coating material of Zn-Ni alloy deposit after the corrosion test confirms the dezincification mechanism of the Zn-Ni alloy deposit during the corrosion process.

Diamond Like Carbon Film Deposited on Porous Silicon as Passivation Coating

By depositing diamond like carbon (DLC) film with radio frequency plasma chemical vapor deposition (RFPCVD) method, a new surface passivation technique for photoluminescence porous silicon (PS) has been studied. The surface microstructure and photoelectric properties of both porous silicon and DLC coated PS have been analyzed by using AFM, FTIR and PL spectrotrieters. The results show the DLC film with dense and homogenous nanometer grains can be deposited on the PS used as passivation coating as it can terminate oxide reaction on the surface of the PS. Furthermore, certain ratio of hydrogen existed in the DLC film can be improved to form hydride species on the DLC/PS interface as the centers of the luminescence so that the DLC coating is of benefit not only to the passivation of the PS but also to the improvement of its luminescent intensity.

Porous Microspheres Comprising CoSe2 Nanorods Coated with N-Doped Graphitic C and Polydopamine-Derived C as Anodes for Long-Lived Na-Ion Batteries

Metal–organic framework-templated nitrogen-doped graphitic carbon(NGC)and polydopaminederived carbon(PDA-derived C)-double coated one-dimensional CoSe_(2) nanorods supported highly porous threedimensional microspheres are introduced as anodes for excellent Na-ion batteries,particularly with long-lived cycle under carbonate-based electrolyte system.The microspheres uniformly composed of ZIF-67 polyhedrons and polystyrene nanobeads(φ=40 nm)are synthesized using the facile spray pyrolysis technique,followed by the selenization process(P-CoSe_(2)@NGC NR).Further,the PDA-derived C-coated microspheres are obtained using a solution-based coating approach and the subsequent carbonization process(P-CoSe_(2)@PDA-C NR).The rational synthesis approach benefited from the synergistic effects of dual carbon coating,resulting in a highly conductive and porous nanostructure that could facilitate rapid diffusion of charge species along with efficient electrolyte infiltration and effectively channelize the volume stress.Consequently,the prepared nanostructure exhibits extraordinary electrochemical performance,particularly the ultra-long cycle life stability.For instance,the advanced anode has a discharge capacity of 291(1000th cycle,average capacity decay of 0.017%)and 142 mAh g^(-1)(5000th cycle,average capacity decay of 0.011%)at a current density of 0.5 and 2.0 A g^(-1),respectively.

In vitro biodegradability and biocompatibility of porous Mg-Zn scaffolds coated with nano hydroxyapatite via pulse electrodeposition

The biodegradability and biocompatibility of porous Mg-2Zn（mass fraction, %） scaffolds coated with nano hydroxyapatite（HAP） were investigated. The nano HAP coating on Mg-2Zn scaffolds was prepared by the pulse electrodeposition method. The as-deposited scaffolds were then post-treated with alkaline solution to improve the biodegradation behavior and biocompatibility for implant applications. The microstructure and composition of scaffold and nano HAP coating, as well as their degradation and cytotoxicity behavior in simulated body fluid（SBF） were investigated. The post-treated coating is composed of needle-like HAP with the diameter less than 100 nm developed almost perpendicularly to the substrate, which exhibits a similar composition to natural bone. It is found that the products of immersion in SBF are identified to be HAP,（Ca,Mg）3（PO4）2 and Mg（OH）2. The bioactivity, biocompatibility and cell viabilities for the as-coated and post-treated scaffold extracts are higher than those for the uncoated scaffold. MG63 cells are found to adhere and proliferate on the surface of the as-coated and post-treated scaffolds, making it a promising choice for medical application. The results show that the pulse electrodeposition of nano HAP coating and alkaline treatment is a useful approach to improve the biodegradability and bioactivity of porous Mg-Zn scaffolds.

Adsorption and Desorption Mechanisms of Methylene Blue Removal with Iron-Oxide Coated Porous Ceramic Filter

Adsorption and desorption mechanisms of methylene blue (MB) removal with iron-oxide coated porous ce-ramics filter (IOCPCF) were investigated in batch and column mode. The results revealed that MB removal mechanisms included physical adsorption and chemical adsorption, of which chemical adsorption by surface ligand complex reaction played a dominant role after infrared spectrum analysis. Recycling agents were se-lected from dilute nitric acid (pH=3), sodium hydroxide solution (pH=12) and distilled water. Among three agents, dilute metric acid (pH=3) was the best recycling agent. Regeneration rate of IOCPCF arrived at 82.56% at batch adsorption and regeneration was finished in 75min at column adsorption. Adsorp-tion-desorption cycles of IOCPCF after batch and column adsorption were four and three times, respectively. Further, compared with fresh IOCPCF, MB removal rate with these desorbed IOCPCF adsorption only slightly decreased, which suggested that IOCPCF should be used repeatedly.

Photoluminescence Properties of LaF₃-Coated Porous Silicon

This work reports the coating of porous silicon (PS) with LaF3 and its influence on the photoluminescence (PL) property of PS. PS samples, prepared by electrochemical etching in a solution of HF and ethanol, were coated with e-beam evaporated-LaF3 of different thicknesses. It was observed that the thin LaF3 layer on PS led to a good enhancement of PL yield of PS. But with the increasing thickness of LaF3 layer PL intensity of PS was decreasing along with a small blue-shift. It was also observed that all the coated samples showed degradation in PL intensity with time, but annealing could recover and stabilize the degraded PL.

Mixed plastics waste valorization to high-added value products via thermally induced phase separation and spin-casting

Plastic waste is an underutilized resource that has the potential to be transformed into value-added materials.However,its chemical diversity leads to cost-intensive sorting techniques,limiting recycling and upcycling opportunities.Herein,we report an open-loop recycling method to produce graded feedstock from mixed polyolefins waste,which makes up 60%of total plastic waste.The method uses heat flow scanning to quantify the composition of plastic waste and resolves its compatibility through controlled dissolution.The resulting feedstock is then used to synthesize blended pellets,porous sorbents,and superhydrophobic coatings via thermally induced phase separation and spin-casting.The hybrid approach broadens the opportunities for reusing plastic waste,which is a step towards creating a more circular economy and better waste management practices.

Influence of Biomimetic Apatite Coating on the Biobehavior of TiO_(2)Scaffolds

Immersion of scaffolds in Simulated Body Fluid(10SBF)is a standardized method for evaluating their bioactivity,simulating in vivo conditions where apatite deposits can be formed on the surface of scaffold,facilitating bone integration and ensuring their suitability for bone implant purposes,ultimately contributing to long-term implant success.The effect of apatite deposition on bioactivity and cell behavior of TiO_(2)scaffolds was studied.Scaffolds were soaked in 10SBF for different durations to form HAP layer on their surface.The results proved the development of a hydroxyapatite film resembling the mineral composition of bone Extracellular Matrix(ECM)on the TiO_(2)scaffolds.The XRD test findings showed the presence of hydroxyapatite layer similar to bone at the depth of 10 nm.A decrease in the specific surface area(18.913 m^(2)g^(−1)),the total pore volume(0.045172 cm^(3)g^(−1)(at p/p0=0.990)),and the mean pore diameter(9.5537 nm),were observed by BET analysis which confirmed the formation of the apatite layer.It was found that titania scaffolds with HAP coating promoted human osteosarcoma bone cell(MG63)cell attachment and growth.It seems that immersing the scaffolds in 10SBF to form HAP coating before utilizing them for bone tissue engineering applications might be a good strategy to promote bioactivity,cell attachment,and implant fixation.

A drug-loaded composite coating to improve osteogenic and antibacterial properties of Zn-1Mg porous scaffolds as biodegradable bone implants

Zinc(Zn)alloy porous scaffolds produced by additive manufacturing own customizable structures and biodegradable functions,having a great application potential for repairing bone defect.In this work,a hydroxyapatite(HA)/polydopamine(PDA)composite coating was constructed on the surface of Zn-1Mg porous scaffolds fabricated by laser powder bed fusion,and was loaded with a bioactive factor BMP2 and an antibacterial drug vancomycin.The microstructure,degradation behavior,biocompatibility,antibacterial performance and osteogenic activities were systematically investigated.Compared with as-built Zn-1Mg scaffolds,the rapid increase of Zn2+,which resulted to the deteriorated cell viability and osteogenic differentiation,was inhibited due to the physical barrier of the composite coating.In vitro cellular and bacterial assay indicated that the loaded BMP2 and vancomycin considerably enhanced the cytocompatibility and antibacterial performance.Significantly improved osteogenic and antibacterial functions were also observed according to in vivo implantation in the lateral femoral condyle of rats.The design,influence and mechanism of the composite coating were discussed accordingly.It was concluded that the additively manufactured Zn-1Mg porous scaffolds together with the composite coating could modulate biodegradable performance and contribute to effective promotion of bone recovery and antibacterial function.

Biomimetic hydroxyapatite coating on the 3D-printed bioactive porous composite ceramic scaffolds promoted osteogenic differentiation via PI3K/AKT/mTOR signaling pathways and facilitated bone regeneration in vivo

The architecture and surface modifications have been regarded as effective methods to enhance the bi-ological response of biomaterials in bone tissue engineering.The porous architecture of the implanta-tion was essential conditions for bone regeneration.Meanwhile,the design of biomimetic hydroxyap-atite(HAp)coating on porous scaffolds was demonstrated to strengthen the bioactivity and stimulate osteogenesis.However,bioactive bio-ceramics such asβ-tricalcium phosphate(β-TCP)and calcium sili-cate(CS)with superior apatite-forming ability were reported to present better osteogenic activity than that of HAp.Hence in this study,3D-printed interconnected porous bioactive ceramicsβ-TCP/CS scaf-fold was fabricated and the biomimetic HAp apatite coating were constructed in situ via hydrothermal reaction,and the effects of HAp apatite layer on the fate of mouse bone mesenchymal stem cells(mBM-SCs)and the potential mechanisms were explored.The results indicated that HAp apatite coating en-hanced cell proliferation,alkaline phosphatase(ALP)activity,and osteogenic gene expression.Further-more,PI3K/AKT/mTOR signaling pathway is proved to have an important impact on cellular functions.The present results demonstrated that the key molecules of phosphatidylinositol 3-kinase(PI3K),protein kinase B(AKT)and mammalian target of rapamycin(mTOR)were activated after the biomimetic hydrox-yapatite coating were constructed on the 3D-printed ceramic scaffolds.Besides,the activated influence on the protein expression of Runx2 and BMP2 could be suppressed after the treatment of inhibitor HY-10358.In vivo studies showed that the constructed HAp coating promoted bone formation and strengthen the bone quality.These results suggest that biomimetic HAp coating constructed on the 3D-printed bioac-tive composite scaffolds could strengthen the bioactivity and the obtained biomimetic multi-structured scaffolds might be a potential alternative bone graft for bone regeneration.

Performance of carbon-coated nano-ZnO prepared by carbonizing gel precursor as anodic material for secondary alkaline Zn batteries

Although carbon coating can improve the cycle life of anode for alkaline Zn batteries, the specific capacity reported is still lower compared with nanosized ZnO. Herein, carbon-coated nanosized ZnO(nano-ZnO@C) was synthesized by one-step heat treatment from a gel precursor in N2. Commercial ZnO and homemade ZnO prepared similarly in air atmosphere were studied for comparison. Structure analysis displayed that both nano-ZnO@C and homemade ZnO had a porous hierarchical agglomerated architecture produced from primary nanoparticles with a diameter of approximately 100 nm as building blocks. Electrochemical performance measurements showed that nano-ZnO@C displayed the highest electrochemical activity, the lowest electrode resistance, the highest discharge capacity(622 m A·h/g), and the best cyclic stability. These properties were due to the combination of nanosized ZnO and the physical capping of carbon, which maintained the high utilization efficiency of nano-ZnO, and simultaneously prevented dendrite growth and densification of the anode.

Novel technique of insulin loading into porous carriers for oral delivery

The increasing demand for oral macromolecule delivery encouraged the development of mi-croencapsulation technologies to protect such drugs against gastric and enzymatic degra-dation. However, microencapsulation often requires harsh conditions that may jeopardizetheir biological activity. Accordingly, many trials attempted to load macromolecules intoporous drug carriers to bypass any formulation induced instability. In this study, we pre-pared chitosan coated porous poly(d, l-lactide-co-glycolide)(PLGA) microparticles(MPs)loaded with insulin using a novel loading technique; double freeze-drying. The resultsshowed a significant increase in drug loading using only 5 mg/ml initial insulin concen-tration and conveyed a sustained drug release over uncoated MPs. Furthermore, SEM andconfocal microscopy confirmed pore blocking and insulin accumulation within the MPs re-spectively. The oral pharmacodynamic data on rats also proved the preservation of insulinbioactivity after formulation. Finally, the new coating technique proved to be efficient inproducing robust layer of chitosan with higher insulin loading while maintaining insulinactivity.

An Innovative Approach for Improving the Reliability of Reticulated Porous Ceramics

An innovative approach has been developed to fabricate reticulated porous ceramics (RPCs) with uniform macrostruc-ture by using the polymeric sponge as the templates. In this approach, the coating process comprises of two stages. In the first stage, the thicker slurry was used to coat: uniformly the sponge substrate. The green body was preheated to produce a reticulated preform with enough handling strength after the sponge was burned out. In the second stage, the thinner slurry was used to coat uniformly the preform. The population of the microscopic and macroscopic flaws in the structure is reduced significantly by recoating process. A few filled cells and cell faces occur in the fabrication and the struts were thickened. A statistical evaluation by means of Weibull statistics was carried out on the bend strength data of RPCs, which were prepared by the traditional approach and innovative approach, respectively. The result shows that the mechanical reliability of RPCs is improved by the innovative approach. This innovative approach is very simple and controlled easily, and will open up new technological applications for RPCs.

An Effective Green Porous Structural Adhesive for Thermal Insulating,Flame-Retardant,and Smoke-Suppressant Expandable Polystyrene Foam

To develop an efficient way to overcome the contradiction among flame retardancy,smoke suppression,and thermal insulation in expanded polystyrene(EPS)foams,which are widely used insulation materials in buildings,a novel"green"porous bio-based flame-retard ant starch(FRS)coating was designed from starch modified with phytic acid(PA)that simultaneously acts as both a flame retardant and an adhesive.This porous FRS coating has open pores,which,in combination with the closed cells formed by EPS beads,create a hierarchically porous structure in FRS-EPS that results in superior thermal insulation with a lower thermal conductivity of 27.0 mW·(m·K)^(-1).The resultant FRS-EPS foam showed extremely low heat-release rates and smoke-production release,indicating excellent fire retardancy and smoke suppression.The specific optical density was as low as 121,which was 80.6%lower than that of neat EPS,at 624.The FRS-EPS also exhibited self-extinguishing behavior in vertical burning tests and had a high limiting oxygen index(LOI)value of 35.5%.More interestingly,after being burnt with an alcohol lamp for 30 min,the top side temperature of the FRS-EPS remained at only 140℃with ignition,thereby exhibiting excellent fire resistance.Mechanism analysis confirmed the intumescent action of FRS,which forms a compact phosphorus-rich hybrid barrier,and the phosphorus-containing compounds that formed in the gas phase contributed to the excellent flame retardancy and smoke suppression of FRS-EPS.This novel porous biomass-based FRS system provides a promising strategy for fabricating polymer foams with excellent flame retardancy,smoke suppression,and thermal insulation.

UV-triggered Polymerization of Polyelectrolyte Composite Coating with Pore Formation and Lubricant Infusion

Porous coatings with the features of muti-interfaces and high specific surface area have emerged as an excellent material platform for the manipulation of porous structures.Layer-by-layer(Lb L)assembly technique has been widely used in preparing porous polyelectrolyte coatings.However,the efficient construction of stable film from the Lb L technique is still a question.Herein,we reported a new solution to construct a stabilized polyelectrolyte coating with porous structures.Inspired by the mechanical reinforcement of double-network hydrogel,we constructed the poly(ethylenimine)(PEI)/poly(acrylic acid)(PAA)coating by in situ photopolymerization of acrylic acid in the PEI network instead of assembling PEI and PAA.Compared with the Lb L films,the in situ polymerized coating kept higher stability after 30 iterations of friction.Porous structures could also be constructed after acid treatment,which was utilized to load lubricant to enhance the lubricating property of the coating.This work provides a new method for the construction of dynamic and stable polyelectrolyte coatings,expediting more development of practical applications.