Tuning the crystallinity of titanium nitride on copper-embedded carbon nanofiber interlayers for accelerated electrochemical kinetics in lithium-sulfur batteries

The development of lithium-sulfur(Li-S)batteries is hindered by the disadvantages of shuttling of polysulfides and the sluggish redox kinetics of the conversion of sulfur species during discharge and charge.Herein,the crystallinities of a titanium nitride(TiN)film on copper-embedded carbon nanofibers(Cu-CNFs)are regulated and the nanofibers are used as interlayers to resolve the aforementioned crucial issues.A low-crystalline TiN-coated Cu-CNF(L-TiN-Cu-CNF)interlayer is compared with its highly crystalline counterpart(H-TiN-Cu-CNFs).It is demonstrated that the L-TiN coating not only strengthens the chemical adsorption toward polysulfides but also greatly accelerates the electrochemical conversion of polysulfides.Due to robust carbon frameworks and enhanced kinetics,impressive highrate performance at 2 C(913 mAh g^(-1)based on sulfur)as well as remarkable cyclic stability up to 300 cycles(626 mAh g^(-1))with capacity retention of 46.5%is realized for L-TiN-Cu-CNF interlayer-configured Li-S batteries.Even under high loading(3.8 mg cm^(-2))of sulfur and relatively lean electrolyte(10μL electrolyte per milligram sulfur)conditions,the Li-S battery equipped with L-TiN-Cu-CNF interlayers delivers a high capacity of 1144 mAh g^(-1)with cathodic capacity of 4.25 mAh cm^(-2)at 0.1 C,providing a potential pathway toward the design of multifunctional interlayers for highly efficient Li-S batteries.

Crystallinity-defect matching relationship of g-C_(3)N_(4): Experimental and theoretical perspectives

Good crystallinity can reduce the charge recombination centers caused by defects,whilst structures with strong polycondensation have high charge mobility,leading to more charge transfer to the material surface for reaction.Much effort has been put into the preparation of a highly efficient g-C_(3)N_(4) with defects to improve its application potential under the premise in high crystallinity.Hence,this review paper emphasizes the importance to balance the defect and crystallinity of g-C_(3)N_(4).In addition,detailed discussion on the relationship between defects and activity of g-C_(3)N_(4) was carried out based on its applications in environmental purification(e.g.,VOCs oxidation,NO_(x) oxidation,H_(2)O_(2) evolution,sterilization,pesticide oxidation)and energy conversion(H_(2) evolution,N_(2) fixation and CO_(2) reduction).Lastly,the challenge in developing more efficient defective g-C_(3)N_(4) photocatalytic materials is summarized.

Constructing long-cycling crystalline C_(3)N_(4)-based carbonaceous anodes for sodium-ion battery via N configuration control

Carbon nitrides with two-dimensional layered structures and high theoretical capacities are attractive as anode materials for sodium-ion batteries while their low crystallinity and insufficient structural stability strongly restrict their practical applications.Coupling carbon nitrides with conductive carbon may relieve these issues.However,little is known about the influence of nitrogen(N)configurations on the interactions between carbon and C_(3)N_(4),which is fundamentally critical for guiding the precise design of advanced C_(3)N_(4)-related electrodes.Herein,highly crystalline C_(3)N_(4)(poly(triazine imide),PTI)based all-carbon composites were developed by molten salt strategy.More importantly,the vital role of pyrrolic-N for enhancing charge transfer and boosting Na+storage of C_(3)N_(4)-based composites,which was confirmed by both theoretical and experimental evidence,was spot-highlighted for the first time.By elaborately controlling the salt composition,the composite with high pyrrolic-N and minimized graphitic-N content was obtained.Profiting from the formation of highly crystalline PTI and electrochemically favorable pyrrolic-N configurations,the composite delivered an unusual reverse growth and record-level cycling stability even after 5000 cycles along with high reversible capacity and outstanding full-cell capacity retention.This work broadens the energy storage applications of C_(3)N_(4) and provides new prospects for the design of advanced all-carbon electrodes.

Biodegradation of Crystalline Chitin:A Review of Recent Advancement,Challenges,and Future Study Directions

Chitin is the second most abundant renewable polysaccharide on Earth.The degradation of chitin into soluble and bioactive N-acetyl chitooligosaccharides(NCOSs)and N-acetyl-D-glucosamine(GlcNAc)has emerged as a pivotal step in the efficient and sustainable utilization of chitin resources.However,because of its dense structure,high crystallinity,and poor solubility,chitin typically needs pretreatment via chemical,physical,and other methods before enzymatic conversion to enhance the accessibility between substrates and enzyme molecules.Consequently,there has been considerable interest in exploring the direct biological degradation of crystalline chitin as a cost-effective and environment-friendly technology.This review endeavors to present several biological methods for the direct degradation of chitin.We primarily focused on the importance of chitinase containing chitin-binding domain(CBD).Additionally,various modification strategies for increasing the degradation efficiency of crystalline chitin were introduced.Subsequently,the review systematically elucidated critical components of multi-enzyme catalytic systems,highlighting their potential for chitin degradation.Furthermore,the application of microorganisms in the degradation of crystalline chitin was also discussed.The insights in this review contribute to the explorations and investigations of enzymatic and microbial approaches for the direct degradation of crystalline chitin,thereby fostering advancements in biomass conversion.

Synthesis of crystalline g-C_(3)N_(4) with rock/molten salts for efficient photocatalysis and piezocatalysis

Graphitic carbon nitride(g-C_(3)N_(4))is emerging as a promising visible-light photocatalyst while the low crystallinity with sluggish charge separation/migration dynamics significantly restricts its practical applications.Currently,synthesizing highly crystalline g-C_(3)N_(4) with sufficient surface activities still remains challenging.Herein,different from using alkali molten salts which is commonly reported,we propose an approach for synthesis of highly crystalline g-C_(3)N_(4) with FeCl3/KCl rock/molten mixed salts.The rock salt can serve as the structure-directing template while molten salt provides the required liquid medium for re-condensation.Intriguingly,the synthesized photocatalyst showed further enhanced crystallinity and improved surface area along with high p/p*excitation compared with crystalline C_(3)N_(4) prepared from conventional molten-salt methods.These catalytically advantageous features lead to its superior photocatalytic and piezocatalytic activities with a high reactivity for overall water splitting that is not commonly reported for C_(3)N_(4).This work provides an effective strategy for structural optimization of organic semiconductor based materials and may inspire new ideas for the design of advanced photocatalysts.

Three-dimensional topological crystalline insulator without spin-orbit coupling in nonsymmorphic photonic metacrystal

By including certain point group symmetry in the classification of band topology,Fu proposed a class of threedimensionaltopological crystalline insulators(TCIs)without spin-orbit coupling in 2011.In Fu’s model,surface states(ifpresent)doubly degenerate atГandM when time-reversal and C4 symmetries are preserved.The analogs of Fu’s modelwith surface states quadratically degenerate atM are widely studied,while surface states with quadratic degeneracy atГare rarely reported.In this study,we propose a three-dimensional TCI without spin-orbit coupling in a judiciously designednonsymmorphic photonic metacrystal.The surface states of photonic TCIs exhibit quadratic band degeneracy in the(001)surface Brillouin zone(BZ)center(Гpoint).The gapless surface states and their quadratic dispersion are protected by C4and time-reversal symmetries,which correspond to the nontrivial band topology characterized by Z_(2)topological invariant.Moreover,the surface states along lines fromГto the(001)surface BZ boundary exhibit zigzag feature,which is interpretedfrom symmetry perspective by building composite operators constructed by the product of glide symmetries with timereversalsymmetry.The metacrystal array surrounded with air possesses high order hinge states with electric fields highlylocalized at the hinge that may apply to optical sensors.The gapless surface states and hinge states reside in a cleanfrequency bandgap.The topological surface states emerge at the boundary of the metacrystal and perfect electric conductor(PEC),which provide a pathway for topologically manipulating light propagation in photonic devices.

Effect of high-energy Ne ions irradiation on mechanical properties difference between Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5)metallic glass and crystalline W

In this paper,high-energy Ne ions were used to irradiate Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) metallic glass(MG)and crystalline W to investigate their difference in mechanical response after irradiation.The results showed that with the irradiation dose increased,the tensile micro-strain increased,nano-hardness increased from 7.11 GPa to 7.90 GPa and 8.62 GPa,Young’s modulus increased,and H3/E2 increased which indicating that the plastic deformability decreased in crystalline W.Under the same irradiation conditions,the Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG still maintained the amorphous structure and became more disordered despite the longer range and stronger displacement damage of Ne ions in Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG than in crystalline W.Unlike the irradiation hardening and embrittlement behavior of crystalline W,Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG showed the gradual decrease in hardness from 6.02 GPa to 5.89 GPa and 5.50 GPa,the decrease in modulus and the increase in plastic deformability with the increasing dose.Possibly,the irradiation softening and toughening phenomenon of Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG could provide new ideas for the design of nuclear materials.

Shock-induced energy localization and reaction growth considering chemical-inclusions effects for crystalline explosives

Chemical inclusions significantly alter shock responses of crystalline explosives in macroscale gap experiments but their microscale dynamics origin remains unclear.Herein shock-induced energy localization,overall physical responses,and reactions in a-1,3,5-trinitro-1,3,5-triazinane(a-RDX)crystal entrained various chemical inclusions were investigated by the multi-scale shock technique implemented in the reactive molecular dynamics method.Results indicated that energy localization and shock reaction were affected by the intrinsic factors within chemical inclusions,i.e.,phase states,chemical compositions,and concentrations.The atomic origin of chemical-inclusions effects on energy localization is dependent on the dynamics mechanism of interfacial molecules with free space volume,which includes homogeneous intermolecular compression,interfacial impact and shear,and void collapse and jet.As introducing various chemical inclusions,the initiation of those dynamics mechanisms triggers diverse decay rates of bulk RDX molecules and hereby impacts on growth speeds of final reactions.Adding chemical inclusions can reduce the effectiveness of the void during the shock impacting.Under the shockwave velocity of 9 km/s,the parent RDX decay rate in RDX entrained amorphous carbon decreases the most and is about one fourth of that in RDX with a vacuum void,and solid HMX and TATB inclusions are more reactive than amorphous carbon but less reactive than dry air or acetone inclusions.The lessdense shocking system denotes the greater increases in local temperature and stress,the faster energy liberation,and the earlier final reaction into equilibrium,revealing more pronounced responses to the present intense shockwave.The quantitative models associated with the relative system density(RD_(sys))were proposed for indicating energy-localization mechanisms and evaluating initiation safety in the shocked crystalline explosive.RD_(sys)is defined by the density ratio of defective RDX to perfect crystal after dynamics relaxation and reveals the global density characteristic in shocked systems filled with chemical inclusions.When RD_(sys)is below 0.9,local hydrodynamic jet initiated by void collapse dominates upon energy localization instead of interfacial impact.This study sheds light on novel insights for understanding the shock chemistry and physical-based atomic origin in crystalline explosives considering chemical-inclusions effects.

Organic Compounds Possessing the Plastic Crystalline Phase: Calculation of Their Fusion Enthalpies

For the first time, for different organic and inorganic compounds possessing the plastic crystalline phase, a new semiempirical equation describing dependence of their fusion enthalpies on such physico-chemical quantities as normal melting temperature, surface tension, molar volume and critical molar volume is received on the base of the principle of corresponding states and the energy equipartition theorem. Moreover, the proposed equation allows one to take into account the particularities of one-particle molecular rotation in the plastic crystalline phase.

Isolation of Microcrystalline Cellulose from Wood and Fabrication of Polylactic Acid(PLA)Based Green Biocomposites

An innovative microcrystalline cellulose(MCC)natural fibre powder-reinforced PLA biocomposite was investigated using the hand lay-up technique.The polymer matrix composite(PMC)samples were prepared by varying the weight percentages(wt.%)of both PLA matrix and MCC reinforcement:pure PLA/100:0,90:10,80:20,70:30,60:40 and 50:50 wt.%,respectively.From the results obtained,MCC powder,with its impressive aspect ratio,proved to be an ideal reinforcement for the PLA,exhibiting exceptional mechanical properties.It was evident that the 80:20 wt.%biocomposite sample exhibited the maximum improvement in the tensile,flexural,notched impact,compressive strength and hardness by 28.85%,20.00%,91.66%,21.53%and 35.82%,respectively compared to the pure PLA sample.Similarly,during the thermogravimetric analysis(TGA),the same 80:20 wt.%biocomposite sample showed a minimum weight loss of 20%at 400℃,among others.The morphological study using Field Emission Scanning Electron Microscopy(FE-SEM)revealed that the uniform distribution of cellulose reinforcement in the PLA matrix actively improved the mechanical properties of the biocomposites,especially the optimal 80:20 wt.%sample.Importantly,it was evident that the optimal PLA/cellulose biocomposite sample could be a suitable and alternative sustainable,environmentally friendly and biodegradable material for semi/structural applications,replacing synthetic and traditional components.

Strength criterion for crystalline rocks considering grain size effect and tensile-compressive strength ratio

The macroscopic mechanical properties of rocks are significantly influenced by their microstructure.As a material bonded by mineral grains,the grain morphology of crystalline rock is the primary factor influencing the strength.However,most strength criteria neglect the strength variations caused by different grain characteristics in rocks.Furthermore,the traditional linear criteria tend to overestimate tensile strength and exhibit apex singularity.To address these shortcomings,a piecewise strength criterion that considers the grain size effect has been proposed.A part of an ellipse was employed to construct the envelope of the tensive-shear region on the meridian plane,to accurately reproduce the low tensile-compressive strength ratio.Based on the analysis of experimental data,both linear and exponential modification functions that account for grain size effects were integrated into the proposed criterion.The corresponding finite element algorithm has been implemented.The accuracy and applicability of the proposed criterion were validated by comparing with the experimental data.

Laser-Constructing 3D Copper Current Collector with Crystalline Orientation Selectivity for Stable Lithium Metal Batteries

The practical application of lithium(Li)metal anodes in high-capacity batteries is impeded by the formation of hazardous Li dendrites.To address this challenge,this research presents a novel methodology that combines laser ablation and heat treatment to precisely induce controlled grain growth within laser-structured grooves on copper(Cu)current collectors.Specifically,this approach enhances the prevalence of Cu(100)facets within the grooves,effectively lowering the overpotential for Li nucleation and promoting preferential Li deposition.Unlike approaches that modify the entire surface of collectors,our work focuses on selectively enhancing lithiophilicity within the grooves to mitigate the formation of Li dendrites and exhibit exceptional performance metrics.The half-cell with these collectors maintains a remarkable Coulombic efficiency of 97.42%over 350 cycles at 1 mA cm^(−2).The symmetric cell can cycle stably for 1600 h at 0.5 mA cm^(−2).Furthermore,when integrated with LiFePO4 cathodes,the full-cell configuration demonstrates outstanding capacity retention of 92.39%after 400 cycles at a 1C discharge rate.This study introduces a novel technique for fabricating selective lithiophilic three-dimensional(3D)Cu current collectors,thereby enhancing the performance of Li metal batteries.The insights gained from this approach hold promise for enhancing the performance of all laser-processed 3D Cu current collectors by enabling precise lithiophilic modifications within complex structures.

Preparation and Performance Study of Cementitious Capillary Crystalline Waterproof Materials

Cementitious capillary crystalline waterproof materials(CCCW for short)offer durability and excellent waterproofing properties,making them a popular option for building waterproofing.Some scholars have studied the proportioning of such materials.However,these studies lack the relationship between the impermeability pressure of mortar and the components,and the mechanism of action is somewhat debatable.Therefore,we adopted a two-step method in our experiments.Firstly,we screened out the components that significantly impact impermeability from a variety of active components by orthogonal test.We then optimized the design of the active group ratio using the simplex lattice method.Lastly,we conducted a performance test of the optimal ratio and explored the waterproofing mechanism of homemade CCCW.

Influence of synthesis parameters on the crystallinity and Si/Al ratio of NaY zeolite synthesized from kaolin

Well-crystallized high-silica NaY zeolites （Si/Al〉2.5） were prepared from a reaction mixture consisting of metakaolin, sodium silicate solution and seed solution via optimization of the mixture composition and reaction conditions. The transformation from kaolin to high-silica NaY zeolite was confirmed by XRD, SEM and IR techniques. Subsequently, the influence of synthesis parameters, i.e. initial SIO2/Al2O3, initial Na2O/SiO2, initial H2O/SiO2, aging time of the seed solution, crystallization temperature and crystallization time, on the NaY growth was investigated in terms of crystallinity and Si/Al ratio. The results showed that the effects of initial SiO2/Al2O3, initial Na2O/SiO2 and initial H2O/ SiO2 on the crystaIlinity and Si/Al ratio of NaY zeolite are similar to those observed in the conventional syntheses of NaY zeolites only using sodium silicate solution as silicon source. However, due to the use of metakaolin as the main silicon and aluminum sources in the present study, a long crystallization induction period of 20 h was achieved, which can be attributed to the dissolution of metakaolin. In addition, different from the conventional syntheses of zeolite NaY, pure NaY zeolites （i.e. without NaP zeolite impurity） were still obtained even at 120℃ because of the use of a large quantity of seed solution （23 wt%） in the reaction mixture. As the aging time of the seed solution increased from 3.5 h to 22 h, the relative crystallinity of the NaY zeolite first increased sharply and then reached a plateau, while the Si/Al ratio first increased rapidly up to a maximum value of 2.75 corresponding to an aging time of 6.5 h, and then decreased sharply with the aging time.

Correlation between aggregation structure and tailing mineral crystallinity

Direct reduction is an emerging technology for the utilization of refractory iron ore. With this technology, iron oxides in the ore can be reduced to recoverable elemental iron. The structure of granular aggregates in direct reduction products was investigated by X-ray diffraction （XRD）. The results show that iron is mainly generated as a shell in the outer edge of the aggregates. The thermal conductivity of the iron shell is higher than that of other minerals. Thus, minerals close to the iron shell cool faster than those in the inner shells and do not crystallize well. These minerals mainly become stage 2 tailings. Hence the XRD intensity of stage 2 tailings is lower than that of stage 1 tailhags. When iron is mainly generated in the interior of the aggregates, the crystallinity of stage 2 tailings will be higher than that of stage 1 tailings. This indicates that the crystallinity of tailings can be used as a marker for the aggregate structure.

EFFECT OF CRYSTALLINITY ON POLARIZATION FATIGUE OF FERROELECTRIC P(VDF-TrFE)COPOLYMER FILMS

The dependence of polarization fatigue on crystallinity of vinylidene fluoride and trifluoroethylene copolymer films was studied.Experimental data indicated that the higher the crystallinity of the film was,the slower the fatigue rate of the film became.A possible explanation was put forward,and it was regarded that the space charges,trapped at the boundaries of crystallites and/or captured by the defects lying both in amorphous and crystalline phases,should make the major contribution to polarization fatig...

TEXTURE AND CRYSTALLINITY EVOLUTION IN ISOTACTIC POLYPROPYLENE INDUCED BY ROLLING AND THEIR INFLUENCE ON MECHANICAL PROPERTIES

The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.

Different crystallinity of poly(d,l-lactide-co-p-dioxanone) copolymers acquired by control of chain microstructure

Poly（d,l-lactide-co-p-dioxanone） （P（LA-co-PDO）） copolymers with different chain microstructures were synthesized by onestep or two-step bulk ring-opening polymerizations of d,l-lactide （LA） and p-dioxanone （PDO） monomers using stannous octoate [Sn（Oct）2]/n-dodecanol as the initiating system. The average sequence lengths of the lactidyl （LLA） and dioxanyl （LpDo） units were calculated from the ^1H NMR spectra. It was found that both LLA and Lpoo values from the two-step syntheses were significantly longer than those from the corresponding one-step syntheses, indicating more blocky structure achieved for the twostep copolymers. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline, while the one-step copolymers were completely amorphous. In conclusion, the crystallinity of P（LA-co-PDO） copolymers could be adjusted conveniently to meet specific applications by changing the microstructure of the copolymers via different polymerization routes.

Effects of rapid thermal annealing on crystallinity and Sn surface segregation of Ge1-xSnx films on Si (100) and Si (111)

Germanium-tin films with rather high Sn content （28.04% and 29.61%） are deposited directly on Si （100） and Si （111） substrates by magnetron sputtering. The mechanism of the effect of rapid thermal annealing on the Sn surface segregation of Ge1-xSnx films is investigated by x-ray photoelectron spectroscopy （XPS） and atomic force microscopy （AFM）. The x-ray diffraction （XRD） is also performed to determine the crystallinities of the Ge1-xSnx films. The experimental results indicate that root mean square （RMS） values of the annealed samples are comparatively small and have no noticeable changes for the as-grown sample when annealing temperature is below 400℃. The diameter of the Sn three-dimensional （3D） island becomes larger than that of an as-grown sample when the annealing temperature is 700℃. In addition, the Sn surface composition decreases when annealing temperature ranges from 400℃ to 700℃. However, Sn bulk compositions in samples A and B are kept almost unchanged when the annealing temperature is below 600℃. The present investigation demonstrates that the crystallinity of Ge1-xSnx/Si （111） has no obvious advantage over that of Ge1-xSnx/Si （100） and the selection of Si （111） substrate is an effective method to improve the surface morphologies of Ge1-xSnx films. We also find that more severe Sn surface segregation occurs in the Ge1-xSnx/Si （111） sample during annealing than in the Ge1-xSnx/Si （100） sample.

Illite Crystallinity Mapping of Very Low Grade Metamorphism of Triassic Metapelites in the Zoigê Area,Western China

X-ray diffraction methods for estimating the metamorphic grade of diagenetic, anchizone and epizone in metapelites are reviewed and applied to samples from a 7000 m＋ borehole in western China and surface samples from the surrounding Zoige area. Kiibler＇s illite crystallinity （IC） measurements provide more consistent results than calculated values of percentage of illite in the I/S mixed layers and percentage of I/S mixed layers. Down-borehole IC values display a typical burial metamorphic relationship between stratigraphic level and IC. A method for preparing very low grade metamorphic maps is described, and isograds plotted on a regional geological map at selected values of IC, delineating a high temperature diagenetic zone, an anchizone, and an epizone. The map shows that IC values are controlled by stratigraphic level in the north of the study area （i.e. burial metamorphism）, and proximity to an igneous intrusive body in the south （i.e. contact metamorphism）.