Mechanical and thermal properties of carbon nanotubes and boron nitride nanotubes for fuel cells and hydrogen storage applications: A comparative review of molecular dynamics studies

The molecular dynamics (MD) simulation method has been widely used to study mechanical and thermal properties of nanomaterials. However, a comprehensive review that compares the thermal and mechanical properties of carbon nanotubes (CNTs), boron nitride nanotubes (BNNTs) and their hybrid structures obtained using the MD simulation method is still lacking. In this paper, we review and document the contradictory results on the mechanical and thermal properties of CNTs and BNNTs published in the literature. We identify, a critical lack of discussion in the literature concerning the thermal and mechanical properties of BNNTs and the influence of encapsulated hydrogen on these properties. We hope that future work will address some of these contradictory data obtained using the MD simulations. We also anticipated that this work would provide important insights into the mechanical and thermal characterisations of these nanotubes for hydrogen storage and fuel cells applications.     

A theoretical first principles computational investigation into the potential of aluminum-doped boron nitride nanotubes for hydrogen storage

Hydrogen storage remains a largely unsolved problem facing the green energy revolution. One approach is physisorption on very high surface area materials incorporating metal atoms. Boron nitride nanotubes (BNNTs) are a promising material for this application as their behaviour is largely independent of the nanoscopic physical features providing a greater degree of tolerance in their synthesis. Aluminum doping has been shown to be a promising approach for carbon nanotubes but has been underexplored for BNNTs. Using first principles density functional theory, the energetics, electronics and structural impacts of aluminum adsorption to both zigzag and armchair polymorphs of BNNTs was investigated along with their potential capacity to adsorb hydrogen. The fine atomic structural and electronic details of these interactions is discussed. We predicted that in an ideal situation, highly aluminum-doped armchair and zigzag BNNTs could adsorb up to 9.4 and 8.6 wt percent hydrogen, well above the United States Department of Energy targets marking these as promising materials worthy of further study.     

Enhanced heat transfer by room temperature deposition of AlN film on aluminum for a light emitting diode package

Heat transfer is crucial to the fabrication of high efficiency light emitting diode (LED) packages. The effectiveness of the heat transfer depends on the package materials and design. This paper presents an application of high thermal conductivity aluminum nitride (AlN) films to replace low thermal conductivity epoxy resin or alumina substrates. The AlN film was directly deposited on an aluminum plate which enabled the removal of thermal interface materials (TIM) such as the adhesive thermal bonding sheets that are used in conventional metal printed circuit board (PCB)-based LED packaging process. A fully dense AlN ceramic film was successfully deposited at room temperature using the aerosol deposition method. The thermal resistance, a parameter of the heat transfer characteristic of an LED package, was measured using a thermal transient tester. The results showed that the thermal resistance of the LED package mounted on the AlN thick film was 28.5 K/W, while an LED package mounted on a conventional epoxy-based metal PCB and a PCB with thermal vias were 47.2 K/W and 36.5 K/W, respectively. This indicates that an aerosol-deposited AlN-based LED package exhibits greatly enhanced heat transfer compared to the conventional metal PCB.     

Boron nitride nanotubes (BNNTs) decorated Pd-ternary alloy (Pd63·2Ni34·3Co2.5) for H2 sensing

The micro-electro-mechanical system (MEMS)-based field effect transistor (FET) sensor for hydrogen detection was fabricated by modifying the gate electrode with boron nitride nanotubes (BNNTs) decorated Pd-ternary alloy (Pd_63·2Ni_34·3Co_2.5) as a hydrogen sensing layer Electro-thermal properties of the micro-heater embedded under sensor membrane were analyzed by a finite element method (FEM) simulation. The structural and morphological properties of the gate electrode were studied by Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM). A variation in gate potential is observed due to the H₂ atmosphere that leads to the variation in the depletion region, therefore, changing the current in the channel (BNNTs decorated Pd-ternary alloy). The BNNTs-decorated Pd ternary alloy displayed high sensing response, fast response and recovery time for H₂ gas, low power consumption, long-term stability, and wide detection range from 1 to 5000 ppm H₂. The drain current of the H₂ FET sensor varied significantly at hydrogen gas exposure and increased with H₂ concentration. As proposed H₂ FET sensor can be utilized to the H₂ leak detection system for safe applications.     

Influence of 2-D nanofillers on the thermal conductivity of composite PCMs

为了探究两种不同二维纳米填料对复合相变材料导热系数的影响,分别制备了以石墨烯纳米片和六方氮化硼纳米片为填料的石蜡基复合相变材料.采用瞬态平面热源法在20 ℃时测量了不同添加量下复合相变材料的导热系数.结果显示,石蜡基复合相变材料的导热系数随纳米填料添加量近似线性增长;六方氮化硼纳米片对复合相变材料导热系数的提升远低于石墨烯纳米片.此外,利用基于有效介质模型的预测公式与试验值进行了比较,计算发现形状,大小和导热系数相近的两种纳米材料,六方氮化硼纳米片的界面热阻却高出石墨烯纳米片两个数量级,是后者具有更显著强化效果的原因之一.     

Sputtered YSZ based protective thin films for SOFCs

Abstract

Protective Zr(Y)O_2–δ based films, deposited using magnetron sputtering, onto apatite type ceramics, were appraised for potential applications in solid oxide fuel cells with silicate based solid electrolytes, where performance may suffer from surface decomposition processes in reducing atmospheres. While as prepared Zr(Y)O_2–δ films without copper additive were already crystallised and single phase, fresh Cu containing Zr(Y)O_2–δ are essentially amorphous, requiring high temperature treatment in air for crystallisation. Deposition rate of 0·50–0·75 μm h^–1 at sputtering power of 300 W was achieved. Surface morphology studies using atomic force microscope revealed typical film structures with small (<50 nm) grains. The hardness of films decreases from 15·8 to 8·4 GPa with increasing copper content. Polarisation studies of electrochemical cell with cermet anodes, applied over protective films, suggested that electrochemical reaction is essentially governed by oxygen anion transfer from zirconia phase and/or hydrogen oxidation in vicinity of zirconia film surface. Copper incorporation into Zr(Y)O_2–δ film leads to higher anode resistivity.     

Synthesis,characterization and application of silver doped graphitic carbon nitride as photocatalyst towards visible light photocatalytic hydrogen evolution

In this study, the series of silver doped graphitic carbon nitride composites (GCN-Agx) were prepared by varying the amount of silver nitrate added in urea for thermal polymerisation reaction among the two precursors. The characterisation study of GCN-Agx composites so obtained was performed using X-ray diffraction, fourier transform infrared spectroscopy, diffused reflectance spectra and Brunauer–Emmett–Teller analysis to explore the effect of silver doping on the various structural, morphological and optical aspects of pure graphitic carbon nitride (GCN-P). In addition, the GCN-Agx composites were analysed for their photoactivity potential and it was found that silver doping can noticeably enhance the photoactivity potential of GCN-P. The phenomenon of enhanced photoactivity was ascribed to the synergistic effect of silver nanoparticles and GCN-P resulting in the increased ability towards visible light absorption, delayed recombination and better separation of photogenerated charge carriers. The synthesized catalyst could be considered as a potential photocatalyst for environmental and energy applications.     

Heat Transfer and Pressure Drop Characteristics of Dilute Alumina–Water Nanofluids in a Pipe at Different Power Inputs

This work addresses the effect of temperature on the thermophysical properties (i.e., density, viscosity, thermal conductivity, and specific heat capacity) of alumina–water nanofluid over a wide temperature range (25°C–75°C). Low concentrations (0–0.5% v/v) of alumina nanoparticles (40 nm size) in distilled water were used in this study. The pressure drop and the effective heat transfer coefficient of nanofluids were also estimated for different power inputs and at different flow rates corresponding to Reynolds numbers in the range of 1500–6000. The trends in variation of thermophysical properties of nanofluids with temperature were similar to that of water, owing to their low concentrations. However, the density, viscosity, and thermal conductivity of nanofluids increased, while the specific heat capacity decreased with increasing the nanoparticle concentration. The convective heat transfer coefficient of the nanofluid and the pressure drop along the test section increased with increasing the particle concentration and flow rate of nanofluid. Results showed that the heat transfer coefficient increases, while the pressure drop decreases slightly with increasing the power input. This is because of the fact that increasing power input to heater increases the bulk mean temperature of nanofluids, resulting in a decreased viscosity. The prepared nanofluids were found to be more effective under turbulent flow than in transition flow.     

Temperature Effect on Young's Modulus of Boron Nitride Sheets

In this article, based on the oscillations of atoms due to the thermal effects (i.e., thermal phonons), Young's modulus of a hexagonal boron nitride sheet at different environment temperatures is investigated. To this end, the density functional theory (DFT) and quasi-harmonic approximation (QHA) are applied to calculate the energies of electrons and phonons, respectively, and then to obtain the total energy of the system. Unlike graphene, Young's modulus of boron nitride sheets tends to considerably increase with the increase of temperature to a specific value about 800 K. For the temperatures greater than 800 K, variation of Young's modulus with temperature is not considerable so that it can be neglected at high temperatures. It is also discerned that when temperature is high, the effect of phonon energy on Young's modulus is negligible.     

A numerical study of heat transfer charcteristics of a car radiator involved nanofluids

To investigate the heat transfer characteristics of a car radiator involved nanofluids, we used GAMBIT & FLUENT softwares and calculated the effective physical parameters using some famous models as a single‐phase mixture. Carbon nanotubes and boron nitride nanotubes have been used in less than 1% volume concentration in flat and twisted tubes. Our results show that nanofluids application in a twisted tube gives a great enhancement in the thermal performance in comparison of the flat tube.     

The effects of various carbon derivative additives on the thermal properties of paraffin as a phase change material

The storage of thermal energy in phase change materials (PCMs) has found wide applications that enable energy conservation and management. Paraffin is a major PCM with its low cost, wide availability, and relatively high latent heat, yet its low thermal conductivity may become a drawback in high‐power applications. In this study, composites of paraffin were prepared with multiwalled carbon nanotubes and activated carbon by a dispersion technique to overcome these drawbacks. Thermal, chemical, and physical influences of incorporating carbon additives with varying structures in paraffin composites on thermal storage capacity were determined. Results indicated that the thermal conductivities of paraffin‐activated carbon composites (PACC) and paraffin multiwalled carbon nanotube composites (PCNC) were improved by a factor of 39.1 and 34.1%, respectively, compared with the conductivity of pure paraffin. As a bonus, the thermal energy storage capacities of PCNCs were enhanced by 9.6%, whereas this remained unchanged for PACCs. Copyright © 2015 John Wiley & Sons, Ltd.     

Steam reforming of liquefied natural gas (LNG) for hydrogen production over nickel–boron–alumina xerogel catalyst

A series of mesoporous nickel–boron–alumina xerogel (x-NBA) catalysts with different boron/nickel molar ratio (x = 0–1) were prepared by an epoxide-driven sol–gel method. The effect of boron/nickel molar ratio on the catalytic activities and physicochemical properties of nickel–boron–alumina xerogel catalysts was investigated in the steam reforming of liquefied natural gas (LNG). All the mesoporous x-NBA catalysts showed similar surface area. Introduction of boron increased interaction between nickel and support. In addition, introduction of boron into x-NBA catalysts reduced methane activation energy and increased nickel surface area. Promotion of boron had a positive effect on the catalytic activity due to the increase of adsorbed methane and nickel surface area. The amount of adsorbed methane and nickel surface area exhibited volcano-shaped trends with respect to boron/nickel molar ratio. LNG conversion and hydrogen yield increased with increasing the amount of adsorbed methane and with increasing nickel surface area. Among the catalysts, 0.3-NBA, which retained the largest amount of adsorbed methane and the highest nickel surface area, showed the best catalytic performance. It was also revealed that x-NBA catalysts showed strong coke resistance during the steam reforming reaction.     

Thermal cycling and degradation mechanisms of compressive mica-based seals for solid oxide fuel cells

Thermal cycling was conducted on compressive mica seals at 800 °C in air. Thin (∼0.1 mm) Muscovite mica was pressed between a metal pipe and an alumina substrate and tested for leak rates at a stress of 100 psi in the plain (mica only) and the hybrid design. The hybrid design involves adding two glass interlayers and was found to greatly reduce the leak rates in an earlier paper. Two metals (Inconel #600 and SS430) with high and low coefficients of thermal expansion (CTE) were used to evaluate the effect of CTE mismatch on thermal cycling. The results showed that the leak rates were lower for the hybrid design than the plain micas. In addition, using the lower CTE (SS430) metal pipe resulted in lower leak rates as compared to Inconel #600 metal (high CTE). In general, the leak rates increased with the number of thermal cycles; however, it tended to level off after several tens of thermal cycles. Microstructure examination using scanning electron microscopy revealed steps, indents, fragmentation and particle formation on the mica after thermal cycling. CTE measurement of the heat-treated Muscovite mica showed a relatively low value of ∼7 ppm/°C. The cause for the degradation of the mica is discussed.     

High‐temperature stability in yttria‐stabilized zirconia

Yttria‐stabilized zirconia has been studied as a candidate standard reference material for the determination of thermal properties. This study evaluated the high‐temperature stability, which is important for yttria‐stabilized zirconia to be used for a standard reference material, using a common material of fine ceramics, Referceram ZR1 (zirconia). The high‐temperature stability was evaluated by measuring the change in the thermal diffusivity before and after heat treatment at temperatures between 200 ^°C and 1500 ^°C. No change in the thermal diffusivity was observed when the samples were treated at temperatures equal to or below 900 ^°C. However, it was revealed that the changes in the thermal diffusivity were caused by the transformation and separation of the crystal phase and the cracks that occur at grain boundaries when the samples were treated at temperatures equal to or above 1000 ^°C. From these results, we confirmed that Referceram ZR1 is sufficiently stable for use as a reference material at temperatures equal to or below 900 ^°C. © 2008 Wiley Periodicals, Inc. Heat Trans Asian Res, 37(2): 57–67, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20193     

Effect of alumina on the curvature, Young's modulus, thermal expansion coefficient and residual stress of planar solid oxide fuel cells

Planar solid oxide fuel cells (SOFCs) are composites consisting of porous and dense functional layers as electrodes and electrolytes, respectively. Because of the thermo-elastic mismatch between the individual layers, residual stresses develop during manufacturing and cause unconstrained cells to warp. The addition of alumina decreases the thermal expansion coefficient (TEC) of the NiO and yttria-stabilized zirconia (YSZ) anode-support material. Correspondingly, the lower TECs have flattened the half cells during fabrication. In addition, the residual stress at room temperature (RT) for samples with more than 4 wt% alumina is only 20% of the residual stress of the samples without alumina, at approximately 100 MPa. The effects of Al₂O₃ on the curvature, Young's modulus, TEC and residual stress of the SOFC with (NiO-YSZ)_1−x(Al₂O₃)_x (x = 1-5 wt%) anode support are discussed in this work.     

Optimizing the hydrogen storage in boron nitride nanotubes by defect engineering

We use ab initio density functional theory calculations to study the interaction of hydrogen with vacancies in boron nitride nanotubes to optimize the hydrogen storage capacity through defect engineering. The vacancies reconstruct by forming B–B and N–N bonds across the defect site, which are not as favorable as heteronuclear B–N bonds. Our total energy and structure optimization results indicate that the hydrogen cleaves these reconstructing bonds to form more stable atomic structures. The hydrogenated defects offer smaller charge densities that allow hydrogen molecule to pass through the nanotube wall for storing hydrogen inside the nanotubes. Our optimum reaction pathway search revealed that hydrogen molecules could indeed go through a hydrogenated defect site with relatively small energy barriers compared to the pristine nanotube wall. The calculated activation energies for different diameters suggest a preferential diameter range for optimum hydrogen storage in defective boron nitride nanotubes.     

Diopside – Mg orthosilicate and diopside – Ba disilicate glass–ceramics for sealing applications in SOFC: Sintering and chemical interactions studies

Diopside (CaMgSi₂O₆) based glasses compositions containing magnesium orthosilicate or barium aluminosilicates phases have been appraised for sealing applications in solid oxide fuel cells (SOFCs) and other solid-electrolyte devices. The sintering behavior and crystalline phase evolution of glass powders has been investigated under isothermal and non-isothermal conditions in the SOFC operating temperature range (800–900 °C). All the glass compositions exhibited two-stage shrinkage behavior resulting in well sintered and mechanically strong glass–ceramics with Augite as the primary crystalline phase. The appropriate coefficient of thermal expansion (CTE), long term thermal stability (300 h at 900 °C), high electrical resistivity, good adhesion and minimal reactivity with SOFC components makes the investigated glass–ceramics potential candidates for further experimentation as SOFC sealants.     

石墨烯/碳纳米管/环氧树脂复合材料的导热性能的实验研究

在微电子领域中,随着元器件的体积微小化,要求导热材料具备体积小、高导热的特点。高分子导热复合材料能很好的解决器件在不同的工作环境中仍能保持正常的散热问题。以环氧树脂(EP)为基体,石墨烯粉末(GP)和多壁碳纳米管(MWCNTs)为导热填料,采用溶剂和超声分散法,制备出石墨烯/碳纳米管/环氧树脂复合材料。实验采用瞬态电热技术测量其导热系数,结果显示,石墨烯与碳纳米管协同作为导热填料时,复合材料导热性优于单独添加导热填料(GP或MWCNTs),且随着GP所占比例的增大复合材料的导热系数越大。当GP和MWCNTs比例分别为0.7%和0.3%时,复合材料导热系数为0.940 W/(m·K),相比于纯EP导热系数提高了286.83%。     

Nickel on a macro-mesoporous Al2O3@ZrO2 core/shell nanocomposite as a novel catalyst for CO methanation

A novel nickel catalyst supported on Al₂O₃@ZrO₂ core/shell nanocomposites was prepared by the impregnation method. The core/shell nanocomposites were synthesized by depositing zirconium species on boehmite nanofibres. This contribution aims to study the effects of the pore structure of supports and the zirconia dispersed on the surface of the alumina nanofibres on the CO methanation. The catalysts and supports were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), H₂ temperature-programmed reduction (H₂-TPR), nitrogen adsorption–desorption, and thermogravimetry and differential thermal analysis (TG-DTA). The catalytic performance of the catalysts for CO methanation was investigated at a temperature range from 300 °C to 500 °C. The results of the characterization indicate that the metastable tetragonal zirconia could be stably and evenly dispersed on the surface of alumina nanofibres. The interlaced nanorods of the Al₂O₃@ZrO₂ core/shell nanocomposites resulted in a macropore structure and the spaces between the zirconia nanoparticles dispersed on the alumina nanofibres formed most of the mesopores. Zirconia on the surface of the support promoted the dispersion and influenced the reduction states of the nickel species on the support, so it prevented the nickel species from sintering as well as from forming a spinel phase with alumina at high temperatures, and thus reduced the carbon deposition during the reaction. With the increase of the zirconia content in the catalyst, the catalytic performance for the CO methanation was enhanced. The Ni/Al₂O₃@ZrO₂-15 exhibited the highest CO conversion and methane selectivity at 400 °C, but they decreased dramatically above or below 400 °C due to the temperature sensitivity of the catalyst. Ni/Al₂O₃@ZrO₂-30 exhibited a high and constant rate of methane formation between 350 °C and 450 °C. The excellent catalytic performance of this catalyst is attributed to its reasonable pore structure and good dispersion of zirconia on the support. This catalyst has great potential to be further studied for the future industrial use.     

Rheological behavior of mechanically stabilized and surfactant-free MWCNT-thermal oil-based nanofluids

The viscosity of nanofluids is one of the important parameter for the design of heat transfer processes. The evolution of usage of nanofluids in heat transfer processes is gaining more industrial consideration due to excellent thermal properties. However, limited attention is focused on the rheological behavior of nanofluids as of today. The multiwall carbon nanotubes (MWCNTs) are stabilized in thermal oil using ultrasonication and high stability is observed. The rheological behavior of thermal-oil based dispersant-free nanofluids are studied at varying high shear rates (100–2000 s^− 1), temperatures (25–90 °C) and nanoparticle concentrations (0.1–1 wt%). The effect on the shear stress and viscosity by the addition of carbon nanotubes in thermal oil is discussed. The measured effective viscosity is compared with different theoretical conventional models. A significant increment in relative viscosity is observed at high concentrations of carbon nanotubes. A correlation is developed based on the temperature, nanomaterial concentration, and shear rate.