Preparation of closed-pore MgO-MgFe2O4 aggregates with low thermal conductivity and high mechanical properties

MgO-MgFe₂O₄ refractory aggregates with high closed porosity were fabricated using MgO agglomerates and Mg(OH)₂ with introducing Fe₂O₃ additive. The evolutions of pores and microstructure and their relationship with the properties of the specimens were studied. The addition of Fe₂O₃ obviously promoted the MgO grain growth and conversion of large open pores into small closed pores, attributing to the formation of cationic vacancies and intergranular MgFe₂O₄ bonding phase. Owing to the presence of closed pores and networks of intergranular MgFe₂O₄, both thermal insulation and strength were enhanced significantly. Besides, the formed closed pores and MgFe₂O₄ phase could accommodate thermal stress and induce transgranular fracture and crack deflection, therefore effectively improving the thermal shock resistance. The specimen with 15 wt% Fe₂O₃ showed a apparent/closed porosity of 0.7%/10.1%, median pore diameter of 4.37 µm, thermal conductivity of 9.3 W/(m·K) (500 °C), flexural strength of 143.5 MPa, and residual flexural strength of 24.1 MPa after thermal shock.     

Differential scanning calorimetry analysis of an enhanced LiNi0.8Co0.2O2 cathode with single wall carbon nanotube conductive additives

The replacement of traditional conductive carbon additives with single wall carbon nanotubes (SWCNTs) in lithium metal oxide cathode composites has been shown to enhance thermal stability as well as power capability and electrode energy density. The dispersion of 1 wt% high purity laser-produced SWCNTs in a LiNi_0.8Co_0.2O₂ electrode created an improved percolation network over an equivalent composite electrode using 4 wt% Super C65 carbon black; evidenced by additive connectivity in SEM images and an order of magnitude increase in electrode electrical conductivity. The cathode with 1 wt% SWCNT additives showed comparable active material capacity (185–188 mAh g⁻¹), at a low rate, and Coulombic efficiency to the cathode composite with 4 wt% Super C65. At increased cycling rates, the cathode with SWCNT additives had higher capacity retention with more than three times the capacity at 10C (16.4 mA cm⁻²). The thermal stability of the electrodes was evaluated by differential scanning calorimetry after charging to 4.3 V and float charging for 12 h. A 40% reduction of the cathode exothermic energy released was measured when using 1 wt% SWCNTs as the additive. Thus, the results demonstrate that replacing traditional conductive carbon additives with a lower weight loading of SWCNTs is a simple way to improve the thermal transport, safety, power, and energy characteristics of cathode composites for lithium ion batteries.     

Synthesis and properties of sulfonated biphenyl poly(ether sulfone) and its mixed‐matrix membranes containing carbon nanotubes for gas separation

We prepared mixed‐matrix membranes (MMMs) composed of carboxylated single‐walled carbon nanotubes (f‐SWCNTs) and a sulfonated biphenyl poly(ether sulfone) (S‐PPSU) polymer matrix. The thermal stability and properties of the pores of the S‐PPSU and f‐SWCNTs were characterized by thermogravimetric analysis and sorption isotherm curves, respectively; these showed that the surface and pore diameter decreased after the introduction of carboxyl groups to the single‐walled carbon nanotubes (SWCNTs), and the pore properties did not restore original values even when the f‐SWCNTs were preheated to 350 °C to remove carboxyl groups. The gas‐separation measurement showed that the MMMs comprised of the S‐PPSU and f‐SWCNTs possessed better gas‐separation properties than the ones composed of biphenyl poly(ether sulfone) and SWCNTs. The permeability for N₂, O₂, He, and CO₂ and the selectivity for O₂/N₂ and O₂/CO₂ were enhanced simultaneously because of the good dispersion of f‐SWCNTs and the improved interaction between the two phases. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44995.     

Thermally induced variation in redox chemical bonding structures of single-walled carbon nanotubes exposed to hydrazine vapor

The effect of hydrazine (N₂H₄) vapor on the properties of single-walled carbon nanotube (SWCNT) networks was investigated by sheet resistance measurement, scanning electron microscopy, Raman spectroscopy, ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy (XPS). Our results show that, even after an auxiliary thermal desorption treatment at 80 °C, the n-doping effect on our SWCNTs caused by N₂H₄ vapor still persistently remained. Further analysis on the XPS data suggests that a reactive chemical species, nitrene (NH), generated during thermal decomposition of N₂H₄, could react with SWCNTs by cycloaddition to form cyclic nitrogen-containing aziridine structures on SWCNTs. Our results also show that the formed nitrogen-containing bonding structures were thermally metastable and could be significantly eliminated upon further annealing at 350 °C. Moreover, it was found that the N₂H₄ vapor treatment could introduce nitroso groups and carbonyl groups, but not carboxyl groups, to our pristine SWCNTs. The mild oxidation could be attributed to the HNO₂ and H₂O₂ produced from the reactions of NH and N₂H₄ with oxygen, respectively, when a N₂H₄ treatment was performed in air.     

Synthesis of single-walled carbon nanotubes produced using a three layer Al/Fe/Mo metal catalyst and their field emission properties

Single-walled carbon nanotubes (SWCNTs) were synthesized on SiO₂/Si substrates by thermal chemical vapor deposition using an Al/Fe/Mo triple layer catalyst, methane (CH₄) as the carbon source, and a mixture of Ar/H₂ (10% H₂) as the carrier gas. The effects of volume ratio of CH₄ to Ar/H₂ (10% H₂), pretreatment time, growth temperature, and Al underlayer thickness on SWCNT growth were studied. The pretreatment time in Ar/H₂ and Al underlayer thickness were found to be crucial for a high-yield of high-purity SWCNTs, since they both governed the size of the catalyst nanoparticles. The optimum growth conditions were found to be a pretreatment time of 20 min, growth time of 10 min, growth temperature of 900 °C, and CH₄/Ar/H₂ flow rates of 50/900/100 sccm, with a catalyst composed of Al (2 nm)/Fe (1 nm)/Mo (0.5 nm). The SWCNTs grown under these conditions have excellent field emission characteristics with low turn-on and threshold fields of 2.4 and 4.3 V/μm, respectively, and a current density of 38.5 mA/cm² at 5 V/μm.     

Synthesis of radially aligned single-walled carbon nanotubes on a SiO2/Si substrate by introducing sodium chloride

Radially aligned single-walled carbon nanotubes (SWCNTs) were synthesized on a SiO₂/Si substrate with thermal chemical vapor deposition by introducing sodium chloride (NaCl) onto the substrate surface. The growth of such SWCNTs was sensitive to the thickness of the SiO₂ layer on the Si substrate and the speed of the reactive gas flow. Cristobalite crystals were found to be formed on the substrate after the SWCNT growth process and were significant for the growth of radially aligned SWCNTs. The SWCNTs were assumed to be directed by the cristobalite crystals along a certain crystal direction on the (1 0 1) crystal face.     

Highly enhanced gas sensing in single-walled carbon nanotube-based thin-film transistor sensors by ultraviolet light irradiation

Single-walled carbon nanotube (SWCNT) random networks are easily fabricated on a wafer scale, which provides an attractive path to large-scale SWCNT-based thin-film transistor (TFT) manufacturing. However, the mixture of semiconducting SWCNTs and metallic SWCNTs (m-SWCNTs) in the networks significantly limits the TFT performance due to the m-SWCNTs dominating the charge transport. In this paper, we have achieved a uniform and high-density SWCNT network throughout a complete 3-in. Si/SiO₂ wafer using a solution-based assembly method. We further utilized UV radiation to etch m-SWCNTs from the networks, and a remarkable increase in the channel current on/off ratio (I_on/I_off) from 11 to 5.6 × 10³ was observed. Furthermore, we used the SWCNT-TFTs as gas sensors to detect methyl methylphosphonate, a stimulant of benchmark threats. It was found that the SWCNT-TFT sensors treated with UV radiation show a much higher sensitivity and faster response to the analytes than those without treatment with UV radiation.     

Computational study of B- or N-doped single-walled carbon nanotubes as NH3 and NO2 sensors

The adsorption of NH₃ and NO₂ in B- or N-doped (10, 0) single-walled carbon nanotubes (SWCNTs) was investigated by using density functional computations to exploit their potential applications as gas sensors. NH₃ can be chemisorbed only in B-doped SWCNTs with apparent charge transfer, so B-doped SWCNTs can be used as NH₃ sensors. Both B- and N-doping make NO₂ chemisorption feasible in SWCNTs, but the binding of NO₂ with B is too strong, indicating an impractical recovery time as gas sensors. Due to the medium (optimal) adsorption energy and the conductance reduction accompanied with the charge transfer between SWCNTs and gas molecules, N-doped SWCNTs are potentially good NO₂ sensors.     

Role of Mg(OH)2 in pore evolution and properties of lightweight brine magnesia aggregates

Lightweight magnesia aggregates were fabricated using high-purity MgO agglomerates with the addition of Mg(OH)₂ as a pore former. The pore evolution and its relationship to the resulting properties were investigated. Mg(OH)₂ decomposition increased the number of inter-agglomerate pores, which subsequently affected the porosity and pore structure. When Mg(OH)₂ was 0–20 wt%, the inter-agglomerate pores were converted to both open and closed small pores, which effectively reduced the thermal conductivity and improved the thermal shock resistance (TSR) by accommodating thermal stress and inducing crack deflection. Small pores also favored the formation of a dense (Mg, Fe)O corrosion layer, preventing further slag penetration. However, large open pores occurred with further increasing Mg(OH)₂ content, which dramatically deteriorated the TSR and slag resistance. The specimen with 20 wt% Mg(OH)₂ exhibited the best overall performance, with a thermal conductivity of 16.6 W/(m·K) at 500 °C, and a residual flexural strength ratio of 32.3%; its slag resistance was comparable with that of dense magnesia.     

Polymer composites with enhanced thermal conductivity via oriented boron nitride and alumina hybrid fillers assisted by 3-D printing

Herein, oriented boron nitride (BN)/alumina (Al₂O₃)/polydimethylsiloxane (PDMS) composites were obtained by filler orientation due to the shear-inducing effect via 3-D printing. The oriented BN platelets acted as a rapid highway for heat transfer in the matrix and resulted in a significant increase in the thermal conductivity along the orientation direction. Extra addition of spherical Al₂O₃ enhanced the fillers networks and resulted in the dramatic growth of slurry viscosity. This, together with filler orientation induced the synergism and provided large increases in the thermal conductivity. A high orientation degree of 90.65% and in-plane thermal conductivity of 3.64 W/(m∙K) were realized in the composites with oriented 35 wt% BN and 30 wt% Al₂O₃ hybrid fillers. We attributed the influence of filler orientation and hybrid fillers on the thermal conductivity to the decrease of thermal interface resistance of composites and proposed possible theoretical models for the thermal conductivity enhancement mechanisms.     

Surfactant-free assembling of functionalized single-walled carbon nanotube buckypapers

The electrical and textural properties of single-walled carbon nanotube buckypapers were tunned through chemical functionalization processes. Single-walled carbon nanotubes (SWCNTs) were covalently functionalized with three different chemical groups: Carboxylic acids (-COOH), benzylamine (-Ph-CH₂-NH₂), and perfluorooctylaniline (-Ph-(CF₂)₇-CF₃). Functionalized SWCNTs were dispersed in water or dimethylformamide (DMF) by sonication treatments without the addition of surfactants or polymers. Carbon nanotube sheets (buckypapers) were prepared by vacuum filtration of the functionalized SWCNT dispersions. The electrical conductivity, textural properties, and processability of the functionalized buckypapers were studied in terms of SWCNT purity, functionalization, and assembling conditions. Carboxylated buckypapers demonstrated very low specific surface areas (< 1 m²/g) and roughness factor (R_a = 14 nm), while aminated and fluorinated buckypapers exhibited roughness factors of around 70 nm and specific surface areas of 160-180 m²/g. Electrical conductivity for carboxylated buckypapers was higher than for as-grown SWCNTs, but for aminated and fluorinated SWCNTs it was lower than for as-grown SWCNTs. This could be interpreted as a chemical inhibition of metallic SWCNTs due to the specificity of the diazonium salts reaction used to prepare the aminated and fluorinated SWCNTs. The utilization of high purity as-grown SWCNTs positively influenced the mechanical characteristics and the electrical conductivity of functionalized buckypapers.     

Polybenzoxazine/single-walled carbon nanotube nanocomposites stabilized through noncovalent bonding interactions

In this study we prepared a new class of pyrene-functionalized benzoxazines (Py-BZ) through reactions of phenol, paraformaldehyde, and pyren-1-amine (Py-NH₂) in toluene and EtOH. We prepared Py-NH₂ through catalytic reduction of 1-nitropyrene (Py-NO₂), which we had synthesized through electrophilic aromatic substitution of pyrene, using HNO₃ as the nitration agent. ¹H and ¹³C nuclear magnetic resonance spectroscopy and Fourier transform infrared (FTIR) spectroscopy confirmed the chemical structure of this new monomer; differential scanning calorimetry (DSC) and FTIR spectroscopy revealed the curing behavior of the Py-BZ polymers. The presence of the pyrene-functionalized benzoxazine enhanced the solubility of single-walled carbon nanotubes (SWCNTs) in THF, leading to the formation of highly dispersible Py-BZ/SWCNT organic/inorganic hybrid complex materials. Fluorescence emission spectroscopy revealed significant π–π stacking interactions between the Py-BZ and the SWCNTs in these complexes. In addition, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis revealed that incorporating the SWCNTs into the Py-BZ matrix significantly enhanced the thermal stability of the polymer after thermal curing.     

Sensitivity of single wall carbon nanotubes to oxidative processing: structural modification, intercalation and functionalisation

The effect of oxidation on modification of single wall carbon nanotubes (SWCNTs) through successive purification steps has been studied. The efficient elimination of metal impurities has been followed by induced coupled plasma spectroscopy. Upon acid treatment, Raman spectroscopy clearly proofed that HNO₃ molecules were intercalated into the bundles of SWCNTs. At the same time, SWCNTs also have suffered a high degree of degradation and defects were introduced. The subsequent thermal processes led to the removal of further defect carbon materials and to the almost complete de-intercalation of the HNO₃ molecules. Changes in the structure of the SWCNT bundles have been observed by transmission electron microscopy. While bundles tend to separate upon acid treatment, after the complete purification process, the remaining SWCNTs tend to form thick bundles again. The existence of functional groups in the raw single wall carbon nanotubes material and their modification and almost complete removal after the final annealing step has been studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and temperature programmed desorption. Nitrogen adsorption isotherms analysed according to Brunauer-Emmet-Teller showed important changes in the pore volume and surface area through the purification steps.     

Fluidized-bed synthesis of sub-millimeter-long single walled carbon nanotube arrays

The rapid growth method for vertically aligned, single walled carbon nanotube (SWCNT) arrays on flat substrates was applied to a fluidized-bed, using ceramic beads as catalyst supports as a means to mass produce sub-millimeter-long SWCNT arrays. Fe/Al₂O_x catalysts were deposited on the surface of Al₂O₃ beads by sputtering and SWCNTs were grown on the beads by chemical vapor deposition (CVD) using C₂H₂ as a feedstock. Scanning electron microscopy and transmission electron microscopy showed that SWCNTs of 2–4 nm in diameter grew and formed vertically aligned arrays of 0.5 mm in height. Thermogravimetric analysis showed that the SWCNTs had a catalyst impurity level below 1 wt.%. Furthermore, they were synthesized at a carbon yield as high as 65 at.% with a gas residence time as short as <0.2 s. Our fluidized-bed CVD, which efficiently utilizes the three-dimensional space of the reactor volume while retaining the characteristics of SWCNTs on substrates, is a promising option for mass-production of high-purity, sub-millimeter-long SWCNT arrays.     

Direct methanol fuel cells with reticulated vitreous carbon,uncompressed graphite felt and Ti mesh anodes

Reticulated vitreous carbon (RVC, 39 pores per cm), uncompressed graphite felt (UGF) and Ti mesh were investigated as 3-D anode catalyst supports for direct liquid methanol fuel cells with the aim of improving the catalyst mass specific activity. Mesoporous Pt–Ru layers composed of nano-particle agglomerates were electrodeposited on the 3-D substrates using a micellar deposition media composed of Triton X-100, isopropanol, and an aqueous phase containing H₂PtCl₆ and (NH₄)₂RuCl₆. The effect of deposition current density, support type, and counter electrode design on the catalyst layer morphology, mass loading and elemental composition is discussed. In direct methanol fuel cell experiments using 1 M CH₃OH—0.5 M H₂SO₄ the 3-D anodes with PtRu load between 2.8 g m⁻² (on Ti mesh) and 12.0 g m⁻² (on RVC) and Pt:Ru atomic ratio of about 4:1 provided peak power outputs based on catalyst mass of 50.4 W g⁻¹ and 40.5 W g⁻¹, respectively, at 333 K. The mass specific activity of the catalyst supported on the 3-D matrix is determined by the synergy between catalyst deposition procedure and support physico-chemical properties.     

Efficiency of C60 incorporation in and release from single-wall carbon nanotubes depending on their diameters

We show that the efficiency of incorporating C₆₀ in single-wall carbon nanotubes (SWCNTs) and that of the incorporated C₆₀’s release from the SWCNTs depend on the SWCNT diameter. Through transmission electron microscopy, we found that the C₆₀ incorporation efficiency reached its maximum at diameters of 1-2 nm, while the efficiency of C₆₀ release from SWCNTs in toluene was maximized at 3-5 nm. The difficulty of C₆₀ release from SWCNTs with diameters of 5-6 nm might reflect either the effective packing of C₆₀ inside SWCNTs or a flattened SWCNT structure. We occasionally observed C₆₀ molecules arranged in a line along the sidewall inside SWCNTs with large diameters/width (>7 nm), indicating that large diameter SWCNTs were sometimes flattened.     

Elucidating the effect of heating induced structural change on electrical and thermal property improvement of single wall carbon nanotube

We have clarified that the electrical and thermal properties of single-walled carbon nanotubes (SWCNTs) are improved by multiple structural changes (wall number, diameter, and crystallinity) induced by high temperature treatment. Focusing on the relationship between structural change and electrical and thermal properties, high-purity SWCNTs were fabricated using the water-assisted CVD method and treated at high temperatures (1500–2000 °C) in an argon atmosphere. We showed that the electrical and thermal properties of the SWCNTs were improved by ∼2.9 and 3.0, respectively, which required lower treatment temperatures than for multi-walled CNTs (MWCNTs). In addition to the crystallinity improvement, the wall number and diameter increased with treatment temperature. When compared to as-grown SWCNTs of similar wall number and diameter, the heat treated SWCNTs exhibited higher electrical and thermal properties, which suggested that the property improvements could be attributed to not only to the wall number and diameter but also to the improvement in crystallinity.     

Characterisation and properties of low-conductivity microporous magnesia based aggregates with in-situ intergranular spinel phases

Development of microporous magnesia based aggregates serving as working-line refractories have great significance in reducing energy loss and saving resource. Microporous magnesia-based aggregates were fabricated at 1780 °C by in-situ decomposition of magnesite with addition of nano-sized Al₂O₃. Intergranular MgAl₂O₄ phases formed in situ decreased the closed-pore size, thermal conductivity and improved the ceramic bonding and thermal shock resistance. Furthermore, the results suggested that pore size distribution was the dominate factor affecting thermal conductivity. Thermal contact resistance owing to networks of intergranular spinel in magnesia could improve thermal insulation performance effectively. The mismatch of thermal expansion coefficient between spinel and magnesia and the micro-scale closed pores enhanced thermal shock resistance by accommodating thermal stress and suppressing crack propagation. Microporous magnesia-based aggregates with 3 wt% nano-sized Al₂O₃ presented a mean pore size of 3.42 μm, thermal conductivity of 5.76 W m^?1 k^?1 (800 °C), a cold compressive strength of ~285 MPa, and a residual strength retention rate of 65.0% after thermal shock cycles. The low-conductivity microporous magnesia-based aggregates with excellent thermal shock resistance show promise for future application in working-lining lightweight refractories.     

Electric field enhancements in In2O3-coated single-walled carbon nanotubes

In₂O₃ nanoparticles are coated on the surfaces of single-walled carbon nanotubes (SWCNTs) by a successive ionic layer adsorption and reaction process. The thickness of the In₂O₃ nanoparticle film is tuned by controlling the number of coating cycles. The electric field around the In₂O₃-coated SWCNTs is compared with that of pristine SWCNTs. Field enhancement of the In₂O₃-coated SWCNTs is confirmed by conductive atomic force microscopy at low electric field (contact mode: 1 V to −1 V) and also field emission (FE) analysis at high electric field (0–4.2 V/μm). The uniformity and emission stability are also measured via FE analysis. Near infrared and X-ray photoemission spectroscopy data are suggested to explain the charge transfer, bandgap change between the In₂O₃ nanoparticles and SWCNTs, and the electric field enhancements in the In₂O₃-coated SWCNTs at both low and high electric field.     

Anodic titanium oxide: A new template for the synthesis of larger diameter multi-walled carbon nanotubes

Carbon nanotubes (CNTs) with larger diameter were synthesized over anodic titanium oxide (ATO) template by CVD method using acetylene as carbon source. The porous titanium oxide was obtained by anodization of titanium metal in a mixture of 1 M H₂SO₄ + 0.5% HF electrolyte at a constant applied potential of 40 V. The XRD analysis of anodized titanium revealed that rutile and anatase forms of TiO₂ are formed due to anodization. Further, SEM analysis was used to follow the development of pores on titanium surface. The TEM analysis revealed that the formed CNTs are straight and hollow with uniform wall thickness as well as larger diameter (70–80 nm). HRTEM study showed that the formed CNTs are multi-walled and their wall thickness is around 2–3 nm. Further, the structural features of the formed CNTs were studied by XRD. Raman spectroscopy was used to study the degree of graphitization of CNTs. The Lewis acid sites of TiO₂ present in the internal surface of the pores play an important role in the catalytic decomposition of acetylene and hence the formation of CNTs. When increasing the carbon deposition time, the wall thickness of CNTs is not increased significantly, indicating that the decomposition of acetylene is due to Lewis acid sites of TiO₂ and not due to thermal decomposition. Further, the morphology of CNTs formed over ATO template was compared with that of CNTs formed on Co electrodeposited ATO. There is no significant difference in morphology as well as wall thickness was observed between the CNTs grown over ATO with and without Co catalyst. But, still further investigations are necessary to study the structural differences between the CNTs grown over ATO with and without Co catalyst.