金属/聚合物转化陶瓷复合材料的原位反应合成和磁学性能研究

在高温转变陶瓷工艺过程中,通过不同金属元素(Ni、Mn、Co和Fe)的添加,原位反应合成出Si-C- N陶瓷基体的复合材料。由于金属元素的存在,使得所合成的复合材料的质量损失减小,密度增加。富金属相能均匀分布在基体材料中,复合材料无明显缺陷。XRD分析结果表明,Ni、Mn和Fe在高温分解过程中与基体都发生反应,分别生成了Ni_(31)Si_(12)、Mn_5Si_3和Mn_2N_(0．86)、Fe_3Si,而Co没有。由于这些不同富金属相的存在,使得复合材料的磁学性能在低温(77K)和室温(300K)有所不同。

Benthic Diversity of Sessile Organisms in Rocky Reef Habitats of Coastal Brazil: An Insight into the Implementation of Marine Protected Areas

Marine Protected Areas are increasingly becoming a tool of choice for conservation and management of marine resources and ecosystems. Data on biodiversity are necessary to assist in establishing protected areas for conservation objectives to be met. Toward that effect, we investigated reef biodiversity patterns in three large-scale coastal regions of Brazil. The study areas comprised of an upwelling region, an adjacent high impacted region, and a more distant marine park. We surveyed four reef sites in each study region. Species counts of sessile benthic organisms, substrate relief, and average monthly water temperatures were recorded during the surveys. Benthic organisms were identified to the lowest taxa possible using still photos. Biodiversity was estimated using Shannon’s index on richness of organism taxa. Diversity was highest at the upwelling and high-impacted areas. No substrate relief patterns were found. Temperature readings showed lower average values at the upwelling and high impacted regions. Our results favor the upwelling region for establishment of a Marine Protected Area. Moreover, the similar diversity between the upwelling and the high impacted regions showed evidence of spillover effects from the former into the latter region, further demonstrating the importance of the former region for conservation.

Effects of Management Practices and Environmental Factors on Largemouth Bass Abundance in Illinois Inland Lakes

An understanding of the relative importance of natural factors and management practices affecting largemouth bass (Micropterus salmoides) abundance is key for enhanced angling. Standardized fish surveys, management practices, and environmental data were available from 42 man-made, inland lakes between 1960 and 1991. Management practices tested were largemouth bass stocking, lake rehabilitation, water level manipulation, aquatic vegetation controls, small fish removal, and changes in length limits of harvestable fish. Environmental factors not controlled by management were spring water influx, growing and cooling degree days, and snow depth. Lake rehabilitation (complete drainage and reflooding), changes in length limits, and aquatic vegetation controls were the only significant factors affecting largemouth bass abundance. The largest effects were due to lake rehabilitation, which increased next-year young largemouth bass numbers by 566% on average, and more restrictive limits on harvestable size, with an increase of up to 440% in adult numbers.

Trends of Abundance of Salton Sea Fish: A Reversible Collapse or a Permanent Condition?

The Salton Sea is a closed-basin, 980 km2 salt lake in the Sonoran Desert of southern California. Three marine species, bairdiella (Bairdiella icistia), orangemouth corvina (Cynoscion xanthulus), and sargo (Anisotremus davidsoni), established from introductions of over 34 species beginning in 1929. During the late 1960s and early 1970s, a hybrid tilapia (Oreochromis mossambicus × O. urolepis hornorum) invaded the Salton Sea and became dominant by number and weight. Recent surveys show a precipitous decline of all four species above starting sometime between 2001 and 2002. Declines were more evident in nearshore than in estuarine habitats. Corvina has probably declined the soonest, followed by Gulf croaker. Tilapia declines were followed by more recent increases in population numbers. The tilapia rebound observed are probably only sustainable if a curb in Salton Sea salinity levels is realized. The marine species will likely need restocking to reach historic levels, if the salinity of the lake is managed at 40 g•L–1 or below. Restoration alternatives for the Salton Sea must take into consideration estuarine areas as essential fish habitats and fish refuge against high salinities.

Novel C_(sf)/SiBCN composites prepared by densifying C_(sf)/MA-SiBCN with the PIP process:Oxidation behavior and damage mechanism

To improve the oxidation resistance of short carbon fiber(C_(sf))-reinforced mechanically alloyed SiBCN(MA-SiBCN)(C_(sf)/MA-SiBCN)composites,dense amorphous C_(sf)/SiBCN composites containing both MA-SiBCN and polymer-derived ceramics SiBCN(PDCs-SiBCN)were prepared by repeated polymer infiltration and pyrolysis(PIP)of layered C_(sf)/MA-SiBCN composites at 1100℃,and the oxidation behavior and damage mechanism of the as-prepared C_(sf)/SiBCN at 1300–1600℃ were compared and discussed with those of C_(sf)/MA-SiBCN.The C_(sf)/MA-SiBCN composites resist oxidation attack up to 1400℃ but fail at 1500℃ due to the collapse of the porous framework,while the PIP-densified C_(sf)/SiBCN composites are resistant to static air up to 1600℃.During oxidation,oxygen diffuses through preexisting pores and the pores left by oxidation of carbon fibers and pyrolytic carbon(PyC)to the interior of the matrix.Owing to the oxidative coupling effect of the MA-SiBCN and PDCs-SiBCN matrices,a relatively continuous and dense oxide layer is formed on the sample surface,and the interfacial region between the oxide layer and the matrix of the as-prepared composite contains an amorphous glassy structure mainly consisting of Si and O and an incompletely oxidized but partially crystallized matrix,which is primarily responsible for improving the oxidation resistance.

Ta_(4)HfC_(5)-Si_(2)BC_(3)N复相陶瓷的界面结构和晶粒生长行为

超高温陶瓷(UHTC)Ta_(4)HfC_(5)因其优异的热物理和热机械性能而成为适用于高超音速飞行器最有前途的候选材料之一.然而,较差的烧结能力限制了其潜在的使用.为了克服该障碍,采用Si_(2)BC_(3)N陶瓷对钽-铪碳化物固溶体进行了致密化处理.通过热压烧结合成了致密的Ta_(4)HfC_(5)-Si_(2)BC_(3)N陶瓷,所得复相陶瓷由Ta_(4)HfC_(5),SiC和BN(C)相组成.在2100℃下,随着晶粒的快速生长,陶瓷内形成了“蝌蚪”状的SiC和BN(C)连接相,断裂韧性提高到3.47±0.12 MPa m^(1/2).随着烧结温度的升高,Ta_(4)HfC_(5)晶粒的生长活化能从112.4 kJ mol^(−1)增加到250.7±29.3 kJ mol^(−1).

Composition-dependent structural characteristics and mechanical properties of amorphous SiBCN ceramics by ab-initio calculations

The atomic structural features and the mechanical properties of amorphous silicoboron carbonitride ceramics with 13 different compositions in the Si–BN–C phase diagram are investigated employing ab-initio calculations.Both chemical bonds and local structures within the amorphous network relate to the elemental composition.The distribution of nine types of chemical bonds is composition-dependent,where the B–C,Si–N,Si–C,and B–N bonds hold a large proportion for all compositions.Si prefers to be tetrahedrally coordinated,while B and N prefer sp^(2)-like trigonal coordination.In the case of C,the tetrahedral coordination is predominant at relatively low C contents,while the trigonal coordination is found to be the main feature with the increasing C content.Such local structural characteristics greatly influence the mechanical properties of SiBCN ceramics.Among the studied amorphous ceramics,SiB_(2)C_(3)N_(2) and SiB_(3)C_(2)N_(3) with low Si contents and moderate C and/or BN contents have high elastic moduli,high tensile/shear strengths,and good debonding capability.The increment of Si,C,and BN contents on this basis results in the decrease of mechanical properties.The increasing Si content leads to the increment of Si-contained bonds that reduce the bond strength of SiBCN ceramics,while the latter two cases are attributed to the raise of sp^(2)-like trigonal configuration of C and BN.These discoveries are expected to guide the composition-tailored optimization of SiBCN ceramics.

Microstructure and evolution of hafnium carbide whiskers via polymer-derived ceramics:A novel formation mechanism

Polymer-derived ultra-high-temperature ceramic(UHTC)nanocomposites have attracted growing attention due to the increasing demands for advanced thermal structure components in aerospace.Herein,hafnium carbide(HfC)whiskers are successfully fabricated in carbon fiber preforms via the polymer-derived ceramic(PDC)method.A novel carbon nanotube(CNT)template growth mechanism combined with the PDC method is proposed in this work,which is different from the conventional vapor–liquid–solid(VLS)mechanism that is commonly used for polymer-derived nanostructured ceramics.The CNTs are synthesized and proved to be the templates for fabricating the HfC whiskers,which are generated by the released low-molecular-weight gas such as CO,CO_(2),and CH4 during the pyrolysis of a Hf-containing precursor.The formed products are composed of inner single crystal HfC whiskers that are measured to be several tens of micrometers in length and 100–200 nm in diameter and outer HfC/HfO_(2)particles.Our work not only proposes a new strategy to prepare the HfC whiskers,but also puts forward a new thinking of the efficient utilization of a UHTC polymer precursor.

Hard and tough novel high-pressure γ-Si_(3)N_(4)/Hf_(3)N_(4) ceramic nanocomposites

Cubic silicon nitride(-Si_(3)N_(4))is superhard and one of the hardest materials after diamond and cubic boron nitride(cBN),but has higher thermal stability in an oxidizing environment than diamond,making it a competitive candidate for technological applications in harsh conditions(e.g.,drill head and abrasives).Here,we report the high-pressure synthesis and characterization of the structural and mechanical properties of a γ-Si_(3)N_(4)/Hf_(3)N_(4) ceramic nanocomposite derived from single-phase amorphous silicon(Si)-hafnium(Hf)-nitrogen(N)precursor.The synthesis of the-Si_(3)N_(4)/Hf_(3)N_(4) nanocomposite is performed at~20 GPa and ca.1500 ℃ in a large volume multi anvil press.The structural evolution of the amorphous precursor and its crystallization to-Si_(3)N_(4)/Hf_(3)N_(4) nanocomposites under high pressures is assessed by the in situ synchrotron energy-dispersive X-ray diffraction(ED-XRD)measurements at~19.5 GPa in the temperature range of ca.1000-1900℃.The fracture toughness(K_(IC))of the two-phase nanocomposite amounts~6/6.9 MPa·m^(1/2) and is about 2 times that of single-phaseγ-Si_(3)N_(4),while its hardness of ca.30 GPa remains high.This work provides a reliable and feasible route for the synthesis of advanced hard and tough-Si_(3)N_(4)-based nanocomposites with excellent thermal stabililty.

Oxidation behavior of amorphous and nanocrystalline SiBCN ceramics–Kinetic consideration and microstructure

In this study,the structural evolution of SiBCN ceramics during crystallization and its effects on oxidation behavior involving different atomic units or formed phases in amorphous or crystalline SiBCN ceramics were analyzed.The amorphous structure has exceptionally high oxidation activity but presents much better oxidation resistance due to its synchronous oxidation of atomic units and homogeneous composition in the generated oxide layer.However,the oxidation resistance of SiBCN ceramic will degrade during the continual crystallization process,especially for the formation of the nanocapsule-like structure,due to heterogeneous oxidation caused by the phase separation.Besides,the activation energy and rate-controlling mechanism of the atomic units and phases in SiBCN ceramics were obtained.The BNCx(Ea=145 kJ/mol)and SiC(2-x)(Ea=364 kJ/mol)atomic units in amorphous SiBCN structure can be oxidized at relatively lower temperatures with much lower activation energy than the corresponding BN(C)(Ea=209 kJ/mol)and SiC(Ea=533 kJ/mol)phases in crystalline structure,and the synchronous oxidation of the SiC(2-x)and BNCx units above 750C changes the oxidation activation energy of BNCx(Ea=332 kJ/mol)to that similar to SiC(2-x).The heterogeneous oxide layer formed from the nanocapsule-like structure will decrease the activation energy SiC(Ea=445 kJ/mol)and t-BN(Ea=198 kJ/mol).

Micro/nano multiscale reinforcing strategies toward extreme high-temperature applications:Take carbon/carbon composites and their coatings as the examples

Carbon fiber reinforced carbon composites(C/Cs),are the most promising high-temperature materials and could be widely applied in aerospace and nucleation fields,owing to their superior performances.However,C/Cs are very susceptible to destructive oxidation and thus fail at elevated temperatures.Though matrix modification and coating technologies with Si-based and ultra-high temperature ceramics(UHTCs)are valid to enhance the oxidation/ablation resistance of C/Cs,it’s not sufficient to satisfy the increasing practical applications,due to the inherent brittleness of ceramics,mismatch issues between coatings and C/C substrates,and the fact that carbonaceous matrices are easily prone to high-temperature oxidation.To effectively solve the aforementioned problems,micro/nano multiscale reinforcing strategies have been developed for C/Cs and/or the coatings over the past two decades,to fabricate C/Cs with high strength and excellent high-temperature stability.This review is to systematically summarize the most recent major and important advancements in some micro/nano multiscale strategies,including nanoparticles,nanowires,carbon nanotubes/fibers,whiskers,graphene,ceramic fibers and hybrid micro/nano structures,for C/Cs and/or the coatings,to achieve high-temperature oxidation/ablation-resistant C/Cs.Finally,this review is concluded with an outlook of major unsolved problems,challenges to be met and future research advice for C/Cs with excellent comprehensive mechanical-thermal performance.It’s hoped that a better understanding of this review will be of high scientific and industrial interest,since it provides unusual and feasible new ideas to develop potential and practical C/Cs with improved high-temperature mechanical and oxidation/ablation-resistant properties.

ZrC-ZrB_2-SiC ceramic nanocomposites derived from a novel single-source precursor with high ceramic yield

For the first time, ZrC-ZrB_2-SiC ceramic nanocomposites were successfully prepared by a single-source-precursor route, with allylhydridopolycarbosilane(AHPCS),triethylamine borane(TEAB),and bis(cyclopentadienyl) zirconium dichloride(Cp_2 ZrCl_2) as starting materials. The polymer-to-ceramic transformation and thermal behavior of obtained single-source precursor were characterized by means of Fourier transform infrared spectroscopy(FT-IR) and thermal gravimetric analysis(TGA). The results show that the precursor possesses a high ceramic yield about 85% at 1000 ℃.The phase composition and microstructure of formed ZrC-ZrB_2-SiC ceramics were investigated by means of X-ray diffraction(XRD) and high resolution transmission electron microscopy(HRTEM).Meanwhile, the weight loss and chemical composition of the resultant ZrC-ZrB_2-SiC nanocomposites were investigated after annealing at high temperature up to 1800 ℃. High temperature behavior with respect to decomposition as well as crystallization shows a promising high temperature stability of the formed ZrC-ZrB_2-SiC nanocomposites.

Single-source-precursor synthesis and phase evolution of SiC-TaC-C ceramic nanocomposites containing core-shell structured TaC@C nanoparticles

A novel single-source-precursor for SiC-TaC-C nanocomposites was successfully synthesized by the chemical reaction between a polycarbosilane(allylhydridopolycarbosilane,AHPCS)and tantalum(V)chloride(TaCls),which was confirmed by Fourier transform infrared spectra(FTIR)measurement.After pyrolysis of the resultant single-source-precursors at 900"C,amorphous ceramic powders were obtained.The 900 C ceramics were anncaled at different temperatures in the range of 1200-1600℃ to gain SiC-TaC-C nanocomposites.The phase evolution of ceramic nanocomposites was investigated by X-ray diffraction(XRD)and transmission electron microscopy(TEM).The results indicate that the TaC starts to crystallize at lower temperature than theβ-SiC.It is particularly worth pointing out that the unique core-shell structured TaC-C nanoparticles were in-situ formed and homogeneously distributed in the ceramic matrix after annealing at 1400 C.Even at a high temperature of 1600 C,the grain sizes ofβ-SiC and TaC are smaller than 30 nm,flilling the definition of nanocomposites.The present study related to SiC-TaC C nanocomposites paves a new road for enriching ultra-high temperature ceramic family suitable for structural/functional applications in harsh environment.

Si-based polymer-derived ceramics for energy conversion and storage

Since the 1960s,a new class of Si-based advanced ceramics called polymer-derived ceramics(PDCs)has been widely reported because of their unique capabilities to produce various ceramic materials(e.g.,ceramic fibers,ceramic matrix composites,foams,films,and coatings)and their versatile applications.Particularly,due to their promising structural and functional properties for energy conversion and storage,the applications of PDCs in these fields have attracted much attention in recent years.This review highlights the recent progress in the PDC field with the focus on energy conversion and storage applications.Firstly,a brief introduction of the Si-based polymer-derived ceramics in terms of synthesis,processing,and microstructure characterization is provided,followed by a summary of PDCs used in energy conversion systems(mainly in gas turbine engines),including fundamentals and material issues,ceramic matrix composites,ceramic fibers,thermal and environmental barrier coatings,as well as high-temperature sensors.Subsequently,applications of PDCs in the field of energy storage are reviewed with a strong focus on anode materials for lithium and sodium ion batteries.The possible applications of the PDCs in Li–S batteries,supercapacitors,and fuel cells are discussed as well.Finally,a summary of the reported applications and perspectives for future research with PDCs are presented.

Ultra-light, high flexible and efficient CNTs/Ti3C2-sodium alginate foam for electromagnetic absorption application

Ultra-light carboxylic functionalized multi-walled carbon nanotubes(CNTs-COOH) and Ti3C2 MXene hybrids modified sodium alginate(CNTs/Ti3C2-SA) based composite foams were prepared through ice-templated freeze-drying method. The microstructure of the synthesized CNTs/Ti3C2 hybrids and CNTs/Ti3C2-SA foams is characterized by the presence of CNTs inserted between MXene layers which prevents their restacking. The resultant CNTs/Ti3C2 hybrids exhibit a unique sandwich-like hierarchical structure. Scanning electron microscopy(SEM) images show that the CNTs/Ti3C2-SA foam exhibits a heterogeneous anisotropic microstructure and CNTs/Ti3C2 hybrids are homogeneously dispersed in the skeleton of the porous foam. In case that the content of the hybrids amounts 40 mg/cm^3, the CNTs/Ti3C2-SA foam possesses excellent electromagnetic(EM) absorption performance with a minimum reflection coefficient(RCmin) as low as-40.0 dB. In case of a sample thickness of 3.95 mm, the RCminreaches-24.4 dB and the effective absorption bandwidth covers the whole X band from 8.2 to 12.4 GHz. A control test shows that, with the same absorbent content, the CNTs/Ti3C2-SA foam exhibits a far better EM performance than that of CNT-free Ti3C2-SA foam.

Boron-modified perhydropolysilazane towards facile synthesis of amorphous SiBN ceramic with excellent thermal stability

SiBN ceramics are widely considered to be the most promising material for microwavetransparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant.This work focuses on the synthesis and ceramization of single-source precursors for the preparation of SiBN ceramics as well as the investigation of the corresponding microstructural evolution at high temperatures including molecular dynamic simulations.Carbon-and chlorine-free perhydropolysilazanes were reacted with borane dimethyl sulfide complex at different molar ratios to synthesize single-source precursors,which were subsequently pyrolyzed and annealed under N2 atmosphere(without ammonolysis)to prepare SiBN ceramics at 1100,1200,and 1300℃with high ceramic yield in contrast to previously widely-used ammonolysis synthesis process.The obtained amorphous SiBN ceramics were shown to have remarkably improved thermal stability and oxidation resistance compared to amorphous silicon nitride.Particularly,the experimental results have been combined with molecular dynamics simulation to further study the amorphous structure of SiBN and the atomic-scale diffusion behavior of Si,B,and N at 1300℃.Incorporation of boron into the Si–N network is found to suppress the crystallization of the formed amorphous silicon nitride and hence improves its thermal stability in N2 atmosphere.

Heat-treated glassy carbon under pressure exhibiting superior hardness,strength and elasticity

Glassy carbon(GC)is a type of non-graphitizing disordered carbon material at ambient pressure and high temperatures,which has been widely used due to its excellent mechanical properties.Here we report the changes in the microstructure and mechanical properties of GC treated at high pressures(up to 5 GPa)and high temperatures.The formation of intermediate sp2-sp3 phases is identified at moderate treatment temperatures before the complete graphitization of GC,by analyzing synchrotron X-ray diffraction,Raman spectra,and transmission electron microscopy images.The intermediate metastable carbon materials exhibit superior mechanical properties with hardness reaching up to 10 GPa and compressive strength reaching as high as 2.5 GPa,nearly doubling those of raw GC,and improving elasticity and thermal stability.The synthesis pressure used in this study can be achieved in the industry on a commercial scale,enabling the scalable synthesis of this type of strong,hard,and elastic carbon materials.

Two birds with one stone: Simultaneous fabrication of HfC nanowires and CNTs through efficient utilization of polymer-derived ceramics

Carbon nanotubes(CNTs) are fabricated in carbon cloth by ultilizing the waste gasses when fabricating hafnium carbide nanowires(HfC_(NWS)) through thermal pyrolysis of Hf-containing polymer precursor.The formed HfC_(NWS) are distributed uniformly on the surface of the carbon fibers in carbon/carbon(C/C) composites and display perfect single crystal appearance.The pyrolysis of the Hf-containing organic precursor provides hafnium and carbon source for the growth of HfC_(NWS).The released waste gasses containing CO,CH4and CO_(2)are the main carbon source for the growth of CNTs.Specifically,the flexural strength of HfC_(NWS) reinforced carbon/carbon(HfC_(NWS)-C/C) composites is enhanced by ~105% compared with pure C/C,and the CNTs/carbon cloth also displays improved electrochemical performance with respect to capacitor applications.The present study introduces a novel sustainable and eco-friendly process related to polymer-derived ceramics to form advanced ceramic nanocomposites and proposes a deep understanding of the growth mechanism of CNTs.

Erratum to:Si-based polymer-derived ceramics for energy conversion and storage

Besides the original acknowledgements,the authors Ralf Riedel and Magdalena Graczyk-Zajac would like to also acknowledge EU support in the frame of H2020 project SIMBA under grant agreement number 963542.

Editorial of special issue on ultra high temperature ceramic matrix composite: Design and application

Based on systematic studies,Si C ceramic matrix composites(CMC-Si C,mainly including C/Si C,Si C/Si C and their self-healing modified composites)have been successfully used as moderate temperature and moderate loading parts in aero-engines,thermal protective systems and aerospace structures[1–4].To fulfill the application requirements of CMCs in even more extreme environments,preparation and characterization of ultrahigh temperature ceramics(UHTCs),UHTCMCs and multifunctional CMCs have been investigated[5-9].