High-performance imidazole-containing polymers for applications in high temperature polymer electrolyte membrane fuel cells

This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.

Defect chemistry engineering of Ga-doped garnet electrolyte with high stability for solid-state lithium metal batteries

Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivity.However,the typical synthesis of Ga-LLZO is usually accompanied by the formation of undesired LiGaO_(2) impurity phase that causes severe instability of the electrolyte in contact with molten Li metal during half/full cell assembly.In this study,we show that by simply engineering the defect chemistry of Ga-LLZO,namely,the lithium deficiency level,LiGaO_(2) impurity phase is effectively inhibited in the final synthetic product.Consequently,defect chemistry engineered Ga-LLZO exhibits excellent electrochemical stability against lithium metal,while its high room temperature ionic conductivity(~1.9×10^(-3)S·cm^(-1))is well reserved.The assembled Li/Ga-LLZO/Li symmetric cell has a superior critical current density of 0.9 mA·cm^(-2),and cycles stably for 500 hours at a current density of 0.3 mA·cm^(-2).This research facilitates the potential commercial applications of high performance Ga-LLZO solid electrolytes in ASSLBs.

Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_(0.5)Mn_(1.5)O_(4) spinel cathode materials

The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.

Stability of Titanium-aluminium Nitride (Ti_2AlN) at High Pressure and High Temperatures

The stability of Ti2AlN at high pressure of 5 GPa and different temperatures of 700-1 600 ℃ was investigated using X-ray diffraction （XRD）,scanning electron microscopy （SEM） equipped with an energy dispersive spectrometer （EDS）.Ti2AlN was found to be stable at temperatures as high as 1 400 ℃under 5 GPa for 20 min,and was proved that it held better structure stability than Ti2AlC under 5 GPa through comparative experiments of Ti2AlN and Ti2AlC （representative compounds of M2AX phases （211 phase））.The reaction process at high pressure had some difference from that at ambient pressure/vacuum,and Ti2AlN directly decomposed to TiN and TiAl at 5 GPa and 1 500 ℃ for 20 min.Moreover,the mechanism of phase segregation was discussed.In addition,the behavior of Ti2AlN contacting with Zr at high pressure and high temperature （HPHT） was also studied.

Study of High-Temperature Stability of Pyrochlore Zirconates

Based on defect chemistry theory and molecular dynamics,the defect formation energy and its relationship with the mechanism of pyrochlore-fluorite phase change were investigated,so as to reveal the underlying mechanism of high-temperature stability of pyrochlore zirconates.Results showed that with the rise of the atom mass of A,the defect formation energies decreased that meant the crystal structure tended to become more disordered.Noticeably,the first nearest cation antisite dominated the pyrochlore disorder transformation process.In addition,it was found that the diffusion of oxygen atoms was far higher than that of cations,and was increased with the temperature,thus also promoting the pyrochlore-fluorite transformation process.

Transient multi-physics behavior of an insert high temperature superconducting no-insulation coil in hybrid superconducting magnets with inductive coupling

A transient multi-physics model incorporated with an electromagneto-thermomechanical coupling is developed to capture the multi-field behavior of a single-pancake(SP)insert no-insulation(NI)coil in a hybrid magnet during the charging and discharging processes.The coupled problem is resolved by means of the finite element method(FEM)for the magneto-thermo-elastic behaviors and the Runge-Kutta method for the transient responses of the electrical circuits of the hybrid superconducting magnet system.The results reveal that the transient multi-physics responses of the insert NI coil primarily depend on the charging/discharging procedure of the hybrid magnet.Moreover,a reverse azimuthal current and a compressive hoop stress are induced in the insert NI coil during the charging process,while a forward azimuthal current and a tensile hoop stress are observed during the discharging process.The induced voltages in the insert NI coil can drive the currents flowing across the radial turns where the contact resistance exists.Therefore,it brings forth significant Joule heat,causing a temperature rise and a uniform distribution of this heat in the coil turns.Accordingly,a thermally/mechanically unstable or quenching event may be encountered when a high operating current is flowing in the insert NI coil.It is numerically predicted that a quick charging will induce a compressive hoop stress which may bring a risk of buckling instability in the coil,while a discharging will not.The simulations provide an insight of hybrid superconducting magnets under transient start-up or shutdown phases which are inevitably encountered in practical applications.

Two-way shape memory effect and its stability in Ti-Ni-Hf high temperature shape memory alloy

The two-way shape memory effect（TWSME） in a Ti36Ni49Hf15 high temperature shape memory alloy（SMA） was systematically studied by bending tests. In the TiNiHf alloy, the martensite deformation is an effective method to get two-way shape memory effect even with a small deformation strain. The results indicate that the internal stress field formed by the bending deformation is in the direction of the preferentially oriented martensite variants formed during the bending deformation. Upon cooling the preferentially oriented martensite variants form under such an oriented stress field, which should be responsible for the generation of the two-way shape memory effect. Proper training process benefits the formation of the oriented stress field, resulting in the improvement of the two-way shape memory effect. A maximum TWSME of 0.88% is obtained in the present alloy.

Study of the Stability of Beef Tallow at High Temperatures and Comparison with Other Fatty Materials

Beef tallow is a byproduct of the slaughter industry. As a consequence, meat producer countries obtain a high amount of this low value-added fatty material. In Uruguay, it is generally used for food purposes or for biodiesel production. Globally, around half of the beef tallow produced worldwide is used for the manufacturing of food. To the best of our knowledge there are no published studies concerning the stability of beef tallow when exposed to high temperatures. The aim of this work was to study some Uruguayan beef tallow brands and compare its stability with that of the most frequently used frying oils in Uruguay （sunflower high oleic, rice bran and sunflower oil） to assess its suitability for frying. Stability was assessed by the oxidative stability index and thermoxidation in absence of food. Even though beef tallow＇s inherent stability indicated that it should be highly stable to oxidation, the majority of the analyzed samples exhibited a similar or lower stability than sunflower high oleic. This might be explained by a different composition in pro-oxidants and/or antioxidants between the beef tallows and the oils. According to the thermoxidation assays, which are carried out in similar conditions to those of a frying process, three of the beef tallow samples, sunflower high oleic and rice bran oil would be similarly suitable for frying, while sunflower oil and the other two samples of beef tallow evidenced a lower thermoxidative stability, thus not being recommended for this use.

Effect of yttrium and manganese addition on catalytic soot combustion activity and anti-high-temperature stability of CeO_(2) catalyst

In order to analyze the influence of the addition of yttrium and manganese on the soot combustion performance and high temperature stability of CeO_(2) catalyst,a series of Y/Mn-modified CeO_(2) catalysts were prepared.The effects of structural properties,textural properties,oxygen vacancies,Ce^(3+),surface adsorbed oxygen species,reduction properties and desorption properties of oxygen species on the activity were analyzed by various characterization methods.The results of the activity test show that the addition of manganese is beneficial to enhancement of the activity,while the addition of yttrium increases the amount of reactive oxygen species,but decreases the activity.After aging at 700℃,the activity of the CeMn catalyst decreases most sharply,while the catalytic activity of the CeY catalyst can be maintained to a certain extent.Interestingly,the addition of yttrium and manganese at the same time can stabilize the activity.The fundamental reason is that yttrium and manganese move to the surface of the solid solution after aging,which increases the reduction performance of the catalyst,thus contributing to the increase of activity.Although the activity of CeYMn catalyst decreases after aging at 800℃,it is still higher than that of other catalysts aged at 700℃.

Future Changes in Extreme High Temperature over China at 1.5℃-5℃ Global Warming Based on CMIP6 Simulations

Extreme high temperature(EHT)events are among the most impact-related consequences related to climate change,especially for China,a nation with a large population that is vulnerable to the climate warming.Based on the latest Coupled Model Intercomparison Project Phase 6(CMIP6),this study assesses future EHT changes across China at five specific global warming thresholds(1.5℃-5℃).The results indicate that global mean temperature will increase by 1.5℃/2℃ before 2030/2050 relative to pre-industrial levels(1861-1900)under three future scenarios(SSP1-2.6,SSP2-4.5,and SSP5-8.5),and warming will occur faster under SSP5-8.5 compared to SSP1-2.6 and SSP2-4.5.Under SSP5-8.5,global warming will eventually exceed 5℃ by 2100,while under SSP1-2.6,it will stabilize around 2℃ after 2050.In China,most of the areas where warming exceeds global average levels will be located in Tibet and northern China(Northwest China,North China and Northeast China),covering 50%-70%of the country.Furthermore,about 0.19-0.44 billion people(accounting for 16%-41%of the national population)will experience warming above the global average.Compared to present-day(1995-2014),the warmest day(TXx)will increase most notably in northern China,while the number of warm days(TX90p)and warm spell duration indicator(WSDI)will increase most profoundly in southern China.For example,relative to the present-day,TXx will increase by 1℃-5℃ in northern China,and TX90p(WSDI)will increase by 25-150(10-80)days in southern China at 1.5℃-5℃ global warming.Compared to 2℃-5℃,limiting global warming to 1.5℃ will help avoid about 36%-87%of the EHT increases in China.

Plastic Flow Modeling of Ti-5 Al-2 Sn-2 Zr-4 Mo-4 Cr Alloy at Elevated Temperatures and High Strain Rates

The true stress-sWain relationships of Ti-5A1-2Sn-2Zr-4Mo-4Cr（TC17） alloy with a wide range of strain rates were investigated by tmiaxial quasi-static and dynamic compression tests, respectively. Quasi- static compression tests were carried out with Instron 8874 test machine, while dynamic compression tests were performed with the split Hopkinson pressure bar （SHPB） which was installed with heating device and synchro- assembly system. The dynamic mechanical behaviors tests of TC17 were carded out from room temperature to 800 ℃ at intervals of 200 ℃ and at high sWain rates （5 500-1 9200 s-l）. The stress-strain curves considering temperature-sWain rate coupling actions were obtained. The Johnson-Cook constitutive model was developed through data fitting of the stress-sWain curves. The material constants in the developed constitutive model can be determined using isothermal and adiabatic stress-strain curves at different strain rates. The Johnson-Cook constitutive model provided satisfied prediction of the plastic flow stress for TC17 alloy.

High temperature polyimide nanocomposites containing twodimensional nanofillers for improved thermal stability and capacitive energy storage performance

Future electronic devices toward high integration and miniaturization demand reliable operation of dielectric materials at high electric fields and elevated temperatures.However,the electrical deterioration caused by Joule heat generation remains a persistent challenge to overcome.Here,the solution-processed polyimide(PI)nanocomposites with unique two-dimensional(2D)alumina nanoplates are reported.Substantial improvements in the breakdown strength,charge–discharge efficiency and discharged energy density at elevated temperatures have been demonstrated in the composites,owing to simultaneously suppressed conduction loss and increased thermal conductivity upon the incorporation of 2D Al_(2)O_(3) nanofillers possessing excellent dielectric insulation and thermophysical properties.The predominance of Al_(2)O_(3) nanoplates in enhancing thermal stability and high-temperature capacitive performance over nanoparticles and nanowires is validated experimentally and is further rationalized via finite element simulations.Notably,the Al_(2)O_(3) nanoplates filled PI nanocomposite exhibits a hightemperature capability up to 200℃ and remarkable efficiency(e.g.≥95% at 200 MV/m)over a wide temperature range,which outperforms commercial dielectric polymers and rivals the state-of-the-art polyimide nanocomposites.

High thermal stability of diamond-cBN-B_4C-Si composites

Improving the thermal stability of diamond and other superhard materials has great significance in various applications. Here, we report the synthesis and characterization of bulk diamond–cBN–B4C–Si composites sintered at high pressure and high temperature（HPHT, 5.2 GPa, 1620–1680 K for 3–5 min）. The results show that the diamond, cBN, B4C,BxSiC, SiO2 and amorphous carbon or a little surplus Si are present in the sintered samples. The onset oxidation temperature of 1673 K in the as-synthesized sample is much higher than that of diamond, cBN, and B4C. The high thermal stability is ascribed to the covalent bonds of B–C, C–N, and the solid-solution of BxSiC formed during the sintering process. The results obtained in this work may be useful in preparing superhard materials with high thermal stability.

A novel polymer gel with high-temperature and high-salinity resistance for conformance control in carbonate reservoirs

Plugging agents have been widely used to enhance oil recovery in fractured-vuggy carbonate reservoirs.However,the harsh conditions of fractured-vuggy carbonate reservoirs yield a significant challenge in maintaining a long-term stabilization of plugging agents.In this work,we developed an anti-hightemperature and high-salinity polymer gel(APG)with excellent resistance to high temperature(140℃)and ultra-high salinity(240000 mg/L).The rheology and microstructure of APG were characterized before and after gelation.Core plugging tests on fractured cubic cores were conducted to quantify the plugging performance of the gel system.Experimental results showed that the Sclerglucan and Cobalt(Ⅱ)Chloride Hexahydrate filled the three-dimensional(3-D)network with various morphologies,providing extra protection to the cross-linking points of the 3D network structure of APG and thus,leading to a prolongation of the dehydration time.The dehydration rate of APG was only 5%within 30days,and the strength of APG could be maintained at a rigid or near-rigid level over 150 days.Moreover,APG exhibited satisfactory shear and scour resistance.Core plugging tests showed that APG could achieve a plugging rate of 90%and demonstrate ignorable minor damage to the substrate.Our results indicate that APG can serve as a great candidate in channel plugging in fractured-vuggy carbonate reservoirs where fractures are fully developed.

镀铝对CoCrNiAlY-YSZ-LaMgAl_(11)O_(19)双陶瓷热障涂层高温抗氧化行为的影响

采用电弧离子镀(AIP)技术在CoCrNiAlY-YSZ-LaMA双陶瓷涂层表面沉积一层Al镀层,利用XRD、SEM和EDS等微尺度分析表征方法,全面解析涂层在大气暴露过程中的高温氧化行为。研究结果表明,未镀铝LaMA层在氧化过程中发生严重体积收缩,导致纵向微裂纹萌生和扩展。这些微裂纹成为氧气向内部扩散的通道,导致涂层呈现持续氧化增重趋势、TGO快速生长和严重的元素扩散,并最终加剧涂层断裂失效。但镀铝涂层样品表现出更好的高温抗氧化性能与结构稳定性,高温氧化过程中,表面Al镀层与氧气发生原位反应生成致密Al2O3屏障层,有效阻止或延迟氧气内部渗透,使TGO缓慢生长,其氧化增重从20h时的8.59mg/cm^(2)略微上升到80h时的9.46mg/cm^(2)。本研究结果为双陶瓷热障涂层的延寿设计与界面热生长应力调控开辟出全新技术途径和理论视野。

Prospect of HDR geothermal energy exploitation in Yangbajing,Tibet,China,and experimental investigation of granite under high temperature and high pressure

Hot dry rock （HDR） geothermal energy, almost inexhaustible green energy, was first put forward in the 1970s. The development and testing of HDR geothermal energy are well reported in USA, Japan, UK, France and other countries or regions. In this paper, the geological characters of Yangbajing basin were first analyzed, including the continental dynamic environments to form HDR geothermal fields in Tibet, the tectonic characteristics of south slope of Nyainqentanglha and Dangxiong-Yangbajing basin, and the in-situ stresses based on the investigations conducted, and then the site-specific mining scheme of HDR geothermal resources was proposed. For the potential development of HDR geothermal energy, a series of experiments were conducted on large-scale granite samples, 200 mm in diameter and 400 mm in length, at high temperature and high triaxial pressure for cutting fragmentation and borehole stability. For the borehole stability test, a hole of 40 mm in diameter and 400 mm in length was aforehand drilled in the prepared intact granite sample. The results indicate that the cutting velocity obviously increases with temperature when bit pressure is over a certain value, while the unit rock-breaking energy consumption decreases and the rock-breaking efficiency increases with temperature at the triaxial pressure of 100 MPa. The critical temperature and pressure that can result in intensive damage to granite are 400-500℃ and 100-125 MPa, respectively.

Cr_(2)O_(3)掺杂BS-PMS-PZT大功率压电陶瓷的电学性能及温度稳定性

采用固相烧结法制备掺杂不同原子分数(0~0.8%)Cr_(2)O_(3)的0.05BiScO_(3)-0.05Pb(Mn_(1/3)Sb_(2/3))O_(3)-0.9Pb(Zr_(0.45)Ti_(0.55))O_(3)陶瓷,研究了Cr_(2)O_(3)掺杂量对陶瓷微观结构、电学性能及温度稳定性的影响。结果表明:不同Cr_(2)O_(3)掺杂量陶瓷均为钙钛矿结构,未检测到杂相峰;随着Cr_(2)O_(3)掺杂量的增加,陶瓷的三方相逐渐出现且含量增加,四方相含量略有下降,平均晶粒尺寸不断增大,相对密度先增大后减小。随着Cr_(2)O_(3)掺杂量的增加,陶瓷的压电常数与机械品质因数均先升后降,介电损耗增大,机电耦合系数基本先增后减,居里温度降低;当Cr_(2)O_(3)原子分数为0.4%时,陶瓷的综合电学性能最佳,并且温度稳定性良好,从室温到260℃,压电常数下降率仅为32%,低于DM-8型商用PZT-8改性压电陶瓷(53%)。

CHZ-Ⅱ海洋重力仪研制与实践

海洋重力仪是获取高精度高分辨率海洋重力场的重要仪器,主要应用于资源勘探、大地水准面精化、海洋科学研究和重力辅助惯性导航等领域。我国现有的海洋重力仪主要依靠国外进口,不仅价格高,而且在仪器的引进、维护等方面存在诸多的不便。在科技部首批重大科学仪器专项的支持下,基于CHZ海洋重力仪成功研制出具有完全自主知识产权的CHZ-Ⅱ弹簧式海洋重力仪。该新型重力仪采用金属零长弹簧作为测量元件,其独特的轴对称垂直悬挂结构可克服交叉耦合效应;高精度伺服控制技术及强阻尼的应用可克服载体扰动的影响,确保仪器在不同海况下保持测量精度;高精度恒温技术及温度补偿技术可消除环境温度波动对仪器测量精度的影响。本文介绍了该仪器的工作原理、系统构成、技术特点及测试结果。静态试验表明其月漂移优于3 mGal;码头系泊试验表明其动态精度达到0.2 mGal,能清晰反映海潮的重力变化特征;总航程超过5万海里船载试验表明其综合测量精度优于1 mGal。仪器在精度和稳定性上达到与国内外同类仪器并跑水平,可替代当前国外进口的海洋重力仪。

粉末冶金制备22Cr-ODS合金的高温氧化行为研究

采用粉末冶金热等静压工艺制备了氧化物弥散强化FeCrAl合金,探究在1000℃空气环境中合金的高温氧化行为。通过X射线衍射、扫描电子显微镜等对合金在1000℃氧化不同时间后的氧化层表面成分、物相及截面成分、厚度等进行研究,结果表明:该工艺制备的22Cr-ODS合金在1000℃空气环境中能够形成完整致密的α-Al_(2)O_(3)表面氧化层,氧化10 h、25 h、50 h、100 h、200 h后氧化层厚度分别为0.52μm、0.91μm、1.42μm、1.47μm和1.76μm,合金内部晶粒未发生明显粗化,表明该合金具有良好的高温抗氧化性能和组织稳定性。

Characteristics of urea under high pressure and high temperature

The properties of urea under high pressure and high temperature(HPHT) are studied using a China-type large volume cubic high-presentation apparatus(CHPA)(SPD-6 × 600).The samples are characterized by scanning electron microscopy(SEM), x-ray diffraction(XRD), and Raman spectroscopy.By directly observing the macroscopic morphology of urea with SEM, it is confirmed that the melting point of urea rises with the increase of pressure.The XRD patterns of urea residues derived under different pressures show that the thermal stability of urea also increases with the increase of pressure.The XRD pattern of the urea residue confirms the presence of C3H5N5O(ammeline) in the residue.A new peak emerges at 21.80°, which is different from any peak of all urea pyrolysis products under normal pressure.A more pronounced peak appears at 708 cm^-1 in the Raman spectrum, which is produced by C-H off-plane bending.It is determined that the urea will produce a new substance with a C-H bond under HPHT, and the assessment of this substance requires further experiments.