Preparation of low density carbon foams by foaming molten sucrose using an aluminium nitrate blowing agent

Low density carbon foams have been prepared by thermo-foaming of molten sucrose using aluminium nitrate as a blowing agent to produce solid organic foams followed by dehydration and carbonization. Gas bubbles are generated in the molten sucrose due to water vapour produced by the acid catalysed condensation between sucrose hydroxyl groups and NO_x gases produced by the thermal decomposition of the aluminium nitrate. Higher melt viscosity achieved by cross-linking of the condensation products of sucrose through co-ordination of the aluminium ions with the hydroxyl groups stabilizes the bubbles against coalescence and rupture. The foam volume, foaming time and setting time depend on the aluminium nitrate concentrations. The carbon obtained by the pyrolysis of the solid organic foams has turbostratic graphite structure. The foams produced have an interconnected near-spherical cellular structure. The carbon foams prepared at aluminium nitrate concentrations in the range of 0.5–4 wt.% have a density and average cell size in the ranges of 0.085–0.053 g/cc and 1.55–0.83 mm, respectively. The alumina (～0.17–1.34 wt.%) produced from the aluminium nitrate is concentrated more on the surface of cell walls, ligaments, and struts.     

Preparation of alumina foams by the thermo-foaming of powder dispersions in molten sucrose

The alumina powder disperses in molten sucrose due to the hydrophilic interaction between the particle surface and sucrose hydroxyls. The thermo-foaming of the dispersions is due to the bubbles created by the water vapour produced by the OH condensation at 150 °C which are stabilized by the alumina particles adsorbed on the gas–liquid interface as well as the increase in viscosity. The foaming time, the foam setting time and the foam volume depend on the alumina powder to sucrose weight ratio. The alumina foams have interconnected cellular microstructure and the cells are having a near spherical morphology. The porosity (97.84–93.29 vol.%.) decreased and the average cell size (0.54–1.2 mm) increased with the increase in alumina powder to sucrose weight ratio (0.4–1.4). The alumina foams with density in the range of 0.239–0.267 g/cc showed compressive strength in the range of 1.02–1.47 MPa.     

Processing factors influencing the free carbon contents in boron carbide powder by rapid carbothermal reduction

High quality boron carbide powder without free carbon is desired for many applications. In this study, the factors that influence free carbon content in boron carbide powders synthesized by rapid carbothermal reduction reaction were evaluated. The dominant factors affecting free carbon contents in boron carbide powder were reaction temperature, precursor homogeneity, the particle size of reactants, and excess boron reactant amount. The reaction temperature at 1850 °C was sufficient to synthesize boron carbide with low free carbon content. Depending on process conditions, precursor homogeneity was also affected by the calcination temperature and time. Smaller particle size of reactants contributed to less carbon content and more uniformity in synthesized boron carbide. Excess boric acid effectively compensated for B₂O₃ volatilization. In the optimal sample, using 80 mol% excess nano boric acid and calcined at 500 °C, the free carbon in the synthesized boron carbide was negligible (0.048 wt.%).     

Boron-doped mullite derived from single-phase gels

Mullite with low dielectric constant and high transparency in infrared and microwave range has potential applications in communication industry. To improve the above properties of mullite, boron-doped mullite single-phase gels with a constant molar ratio of Al/Si = 3/1 and various B/Al ratios (B/Al = 0–0.4/3) were prepared in this study by slow hydrolysis of aluminum nitrate, boric acid and tetraethoxysilane. It was found that boron reduces the mullite formation temperature and suppresses spinel formation. The cell unit lattice parameters and cell volume in boron-doped mullite generally decrease with the increase of boron amount. The SEM observation shows that a small amount of boron reduces the grain sizes of mullite sintered bodies while a large amount of boron facilitates the formation of elongated grains and the amorphous glass phase. Boron decreases the transmittance of mullite ceramic and produces additional intensive absorption bond at 3.9 μm and also reduces the dielectric constants in the frequent range of 1 M–1 GHz.     

Selective boron extraction by polymer supported 2-hydroxylethylamino propylene glycol functions

Boron sorption ability of polymer supported 2-hydroxyethylamino propylene glycol functions was investigated. 2-hydroxyethylamino propylene glycol was prepared by reaction of glycidol with excess ethanolamine in N-methyl, 2-pyrrolidone (NMP). This was reacted with terpolymer of glycidyl metacrylate (0.4 mol) with methyl metacrylate (0.5 mol) and divinylbenzene (0.1 mol) which was prepared in spherical beads form (210–422 μm) by suspension polymerization.The resulting terpolymer having hydroxyethylamino propylene glycol functions (1.82 mmol g⁻¹) was found to be as efficient as previously reported iminodipropylene glycol functional resins in removal of trace boron from water. The resin showed a boron loading capacity of 1.6 mmol g⁻¹. Nearly second-order kinetics, with respect to the boric acid (k = 1.65 mol l⁻¹ s⁻¹, with a correlation factor of 0.99129) was determined in non-buffered conditions.It was observed that, more than 95% of boron is extracted by this resin from very dilute H₃BO₃ solution (100 ppm initial concentration) in less than 30 min of contact time. Splitting of sorbed boron can be achieved by simple acid leaching (4 M HCl) and regenerated by NaOH (0.1 M) solution.     

Indirect electrochemical reduction of carbon dioxide to carbon nanopowders in molten alkali carbonates: Process variables and product properties

Carbon was deposited on a mild steel cathode during electrolysis in the molten mixture of Li₂CO₃ and K₂CO₃ (mole ratio: 62:38) under CO₂ or mixed N₂ and CO₂ atmospheres at 3.0–5.0 V and 540–700 °C. In a three-electrode cell, cyclic voltammetry was applied on a platinum working electrode to study the reduction and deposition processes. A two-electrode cell helped correlate electrolysis variables, e.g. temperature and voltage, with the deposition rate, current efficiency, and properties of the deposited carbon powders. High current efficiency (>90%) and deposition rate (>0.11 g cm⁻² h⁻¹) were achieved in the study. Elemental analysis of the electro-deposits, following washing with HCl solutions (2.3–7.8 mol L⁻¹), showed carbon as the dominant element (75–95 wt.%) plus oxygen (5–10 wt.%) and small amounts of other elements related to materials of the electrolytic cell. Thermogravimetry detected fairly low onset combustion temperatures (310–430 °C), depending on the electrolysis and acid washing conditions. Amorphous and various nanostructures (sheet, rings and quasi-spheres) were revealed by electron microscopy in carbon samples deposited under different process conditions. The specific surface area of the carbon deposited at 5.0 V and 540 °C was as high as 585 m² g⁻¹. An analysis of the energy consumption suggests several ways for efficiency improvement so that the electrolytic carbon from CO₂ will become commercially attractive.     

Preparation of carbon foams by thermo-foaming of activated carbon powder dispersions in an aqueous sucrose resin

Thermo-foaming of activated carbon (AC) powder dispersions in an aqueous sucrose resin followed by carbonization has been studied to prepare carbon foams. The dispersions were characterized by viscosity measurements and sedimentation studies. The OH to OH condensation reactions, leading to the cross-linking of the sucrose polymer, were retarded by the AC powder. The AC particles adsorbed on the gas–liquid interface stabilized the gas bubbles that resulted in foaming of the poorly cross-linked sucrose polymer resin having low viscosity. The carbon produced by the carbonization of the sucrose polymer binds the AC particles as in reaction bonding. The carbon foams have an interconnected cellular structure. Density (0.138–0.22 g/cc), cell size (0.62–3 mm) and compressive strength (0.42–3.4 MPa) of the carbon foams depends on the AC powder to sucrose weight ratio. Incorporation of the AC powder in the sucrose resin decreases the carbonization shrinkage that enables the preparation of large carbon foam bodies without warping. The carbon foam prepared at an AC powder to sucrose weight ratio of 0.1 shows the highest density and compressive strength and the lowest cell size.     

Superconductivity in diamond

We survey methods of synthesis of boron doped diamond with high pressure-high temperature techniques. New route is proposed for synthesis of relatively large heavily boron doped diamond single crystals, which exhibit superconductivity. Superconducting boron-doped diamond samples were synthesized with isotopes of ¹⁰B, ¹¹B, ¹³C and ¹²C. We claim the presence of a carbon isotope effect on the superconducting transition temperature, which supports the “diamond–carbon”-related nature of superconductivity and the importance of the electron–phonon interaction as the mechanism of superconductivity in diamond. Isotope substitution permits us to relate almost all bands in the Raman spectra of heavily boron-doped diamond to the vibrations of carbon atoms. The 500 cm^? 1 Raman band shifts with either carbon or boron isotope substitution and may be associated with vibrations of paired or clustered boron.     

Ultralow cost reticulated carbon foams from household cleaning pad wastes

A very simple method is described for preparing ultra lightweight and ultralow cost carbon foams (density 0.04–0.075 g cm⁻³ and porosity 98–96%) by impregnation with sucrose of household cleaning pad wastes used as sacrificial templates, followed by pyrolysis in inert atmosphere. Scanning electron microscopy showed that the resultant reticulated vitreous carbon (RVC) foams had a fully open and interconnected porous structure. These materials are more thermally insulating (thermal conductivity 0.042–0.065 W m⁻¹ K⁻¹) than commercial RVC foams having similar compressive strengths (0.11–0.23 MPa) and similar densities.     

Nitrogen-, phosphorous- and boron-doped carbon nanotubes as catalysts for the aerobic oxidation of cyclohexane

Nitrogen-, phosphorous- and boron-doped carbon nanotubes (N-CNTs, P-CNTs and B-CNTs) were prepared by a chemical vapor deposition method using xylene as carbon source and aniline-NH₃, triphenyl phosphine and triethyl borate as nitrogen, phosphorous and boron precursors, respectively. By tailoring the composition of reactants and reaction atmosphere, N-CNTs with nitrogen contents from 0% to 4.36% and P-CNTs with phosphorous contents from 0.55% to 5.14% were synthesized. N- and P-CNTs are active for the oxidation of cyclohexane in the liquid phase with molecular oxygen as oxidant. The highest mass-normalized activity, 761 mmol g⁻¹ h⁻¹, was achieved over N-CNTs synthesized from aniline in an NH₃ atmosphere, while the highest surface-area-normalized activity, 28 mmol m⁻² h⁻¹, was observed over P-CNTs. B-doping does not improve the activity of CNTs. The effect of the number of nitrogen functionalities and defects was investigated to reveal the structure–activity relationship of the doped CNTs. By using the work function as an indicator of the electron donation of carbon, an exponential dependence of specific activity on work function was discovered for N- and P-CNTs, suggesting that the electron transfer on the surfaces of CNTs plays a central role in the CNT-catalyzed oxidation of cyclohexane.     

Raman scattering by defect-induced excitations in boron-doped diamond single crystals

Polarized Raman spectra of the oriented boron-doped diamond with a different content of boron (≤ 200 ppm) were obtained with 514.5 and 1064 nm excitations. The additional bands were found in the region below 1200 cm^− 1. Their intensity increased with doping. It was shown that in polarized spectra these bands were in agreement with the singularities of density of phonon states (DOS) of diamond for the A_1g, E_g and F_2g symmetries. It was assumed that the ~ 900 cm^− 1 band which does not coincide with any DOS peak and has the highest resonance character may be attributed to the localized mode of boron in a diamond lattice. The spectra were accompanied by continuum that had the same symmetry F_2g as optical phonon at 1333 cm^− 1.     

Chemical analysis and vibrational properties of boronated tetrahedral amorphous carbon films

Boronated tetrahedral amorphous carbon (ta-C:B) films were prepared by filtered cathodic vacuum arc technique using boron mixed graphite targets. The effect of boron content on the chemical bonding and vibrational properties of these films has been investigated by X-ray photoelectron spectroscopy, Raman spectroscopy and Fourier transform infrared spectroscopy. It has been found that boron atoms are predominantly configured in a graphitic network, while the carbon atoms in the ta-C:B films are mainly in sp³ hybridization which tend to decrease as boron content increases. The Raman and infrared spectra of ta-C:B films both show prominent features in the regions of 1100–1900 cm^− 1 and 900–1600 cm^− 1 respectively. It was identified that the Raman parameters are strongly correlated with the boron content which is due to the clustering of sp² domains induced by B introduction. The activation of infrared spectrum of ta-C:B film is a consequence of heteroatomic (C–B) vibration combined with changes in the sp² carbon configuration. And the enhanced infrared absorption of ta-C:B with increased boron incorporation results from the increased effective charges in the delocalized sp² carbon phase.     

Hydrothermally treated aminated tannin as precursor of N-doped carbon gels for supercapacitors

Aminated tannin submitted to hydrothermal treatment led to nitrogen-doped gels in the absence of any cross-linker. Such gels were subcritically dried, freeze-dried or supercritically dried to obtain organic xerogels, cryogels and aerogels, respectively, having nitrogen contents between 3.0 and 3.7 wt.%. After pyrolysis at 900 °C, the materials presented nitrogen contents ranging from 1.9 to 3.0 wt.%, and surface areas as high as 860, 754 and 585 m² g⁻¹ for carbon aerogels, cryogels and xerogels, respectively. All of them displayed micropores associated with different mesopore volumes, depending on both the drying method and initial dilution of the precursor. When tested as supercapacitor electrodes, these carbon gels presented outstanding specific and normalised capacitances, up to 387.6 F g⁻¹ and 69.5 μF cm⁻², respectively, at a scan rate of 2 mV s⁻¹ in 4 mol L⁻¹ H₂SO₄ aqueous solution. These performances are higher than those obtained with high apparent surface area-activated carbons, as the measured capacitances are indeed among the highest ever reported. The influence of nitrogen- and oxygen-based moieties was investigated, and optimal N and O contents of 2–3 and 17–18 wt.%, respectively, were observed.     

Graphene-supported Pd–Ru nanoparticles with superior methanol electrooxidation activity

Pd–Ru bimetallic nanoparticles dispersed on graphene nanosheets (GNS) have been obtained by a microwave-assisted polyol reduction method and investigated for methanol electrooxidation in 1 M KOH + 1 M CH₃OH at 25 °C. Structural and electrochemical characterizations of electrocatalysts are carried out by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, CO stripping voltammetry and chronoamperometry. The study shows that introduction of Ru (1–10 wt.%) into 40 wt.%Pd/GNS produces an alloy of Pd and Ru with the face centered cubic crystal structure. The electrocatalytic activity increased with increasing percentage of Ru in the Pd–Ru alloy showing maximum with 5 wt.%Ru. The electrocatalytic activity of the 40 wt.%Pd–5 wt.%Ru/GNS electrode at E = −0.10 V vs. Hg/HgO was ∼2.6 times greater than that of the base (40 wt.%Pd/GNS) electrode. Based on the methanol oxidation current, measured at 1 h during the chronoamperometry tests at E = −0.10 V vs. Hg/HgO, the active 40 wt.%Pd–5 wt.%Ru/GNS electrode exhibited ∼72% and ∼675% higher poisoning tolerance as compared to 40%Pd/GNS and 40%Pd/multiwalled carbon nanotube electrodes, respectively.     

Anelastic spectroscopy for studying O vacancies in perovskites

We present the results of anelastic relaxation experiments (2–30 kHz) on ceramic SrTiO₃ subjected to reduction in H₂ atmosphere, which yield a balance between V_O and (OH)⁻ defects. The resulting anelastic spectrum contains, besides the well-known structural transformation near 110 K, several thermally activated relaxation processes between 200 and 700 K. The two main elastic energy loss peaks are proposed to provide the first measurement of the hopping rate of V_O –(OH)⁻ defects in pure SrTiO₃.     

Improved cyclability of lithium–sulfur battery cathode using encapsulated sulfur in hollow carbon nanofiber@nitrogen-doped porous carbon core–shell composite

Hollow carbon nanofiber@nitrogen-doped porous carbon (HCNF@NPC) core–shell composite, which was carbonized from HCNF@polyaniline, was prepared as an improved high conductive carbon matrix for encapsulating sulfur as a cathode composite material for lithium–sulfur batteries. The prepared HCNF@NPC-S composite with high sulfur content of 77.5 wt.% showed an obvious core–shell structure with an NPC layer coating on the surface of the HCNFs and sulfur homogeneously distributed in the coating layer. This material exhibited much better electrochemical performance than the HCNF-S composite, delivered initial discharge capacity of 1170 mAh g⁻¹, and maintains 590 mAh g⁻¹ after 200 cycles at the current density of 837.5 mA g⁻¹ (0.5 C). The significantly improved electrochemical performance of the HCNF@NPC-S composite was attributed to the synergetic effect between HCNF cores, which provided electronic conduction pathways and worked as mechanical support, and the NPC shells with relatively high surface area and pore volume, which could trap sulfur/polysulfides and provide Li⁺ conductive pathways.     

Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors

A series of nitrogen-doped porous carbons are prepared through KOH activation of a nonporous nitrogen-enriched carbon which is synthesized by pyrolysis of the polymerized ethylenediamine and carbon tetrachloride. The porosity and nitrogen content of the nitrogen-doped porous carbons depend strongly on the weight ratio of KOH/carbon. As the weight ratio of KOH/carbon increases from 0.5 to 2, the specific surface area increases from 521 to 1913 m² g⁻¹, while the nitrogen content decreases from 10.8 to 1.1 wt.%. The nitrogen-doped porous carbon prepared with a moderate KOH/carbon weight ratio of 1, which possesses a balanced specific surface area (1463 m² g⁻¹) and nitrogen content (3.3 wt.%), exhibits the largest specific capacitance of 363 F g⁻¹ at a current density of 0.1 A g⁻¹ in 1 M H₂SO₄ aqueous electrolyte, attributed to the co-contribution of double-layer capacitance and pseudocapacitance. Moreover, it shows excellent rate capability (182 F g⁻¹ remained at 20 A g⁻¹) and good cycling stability (97% capacitance retention over 5000 cycles), making it a promising electrode material for supercapacitors.     

Graphite foam from pitch and expandable graphite

Graphite foams were prepared from a coal tar pitch that was partially converted into mesophase. Expandable graphite was used instead of an inert gas to “foam” the pitch. The resulting foam was subjected to a series of heat treatments with the objective of first crosslinking the pitch, and thereafter carbonizing and graphitizing the resulting foam. XRD confirmed that the graphitization at 2600 °C resulted in a highly graphitic material. The porosity of this foam derives from the loose packing of the vermicular exfoliated graphite particles together with their internal porosity. During the foaming process the pitch tends to coat the outside surface of the expanding graphite flakes. It also bonds them together. The graphite foam prepared with 5 wt.% expandable graphite had a bulk density of 0.249 g cm⁻³, a compressive strength of 0.46 MPa and a thermal conductivity of 21 W m⁻¹ K⁻¹. The specific thermal conductivity (thermal conductivity divided by the bulk density) of this low-density carbon foam was 0.084 W m² kg⁻¹ K⁻¹ which is considerably higher than that of copper metal (0.045 W m² kg⁻¹ K⁻¹) traditionally used in thermal management applications.     

Thermoelectric transport properties of boron-doped nanocrystalline diamond foils

Natural diamond is known for its outstanding thermal conductivity and electrical insulation. However, synthetic production allows for doping and tailoring microstructural and transport properties. Despite some motivation in the literature and the ongoing search for abundant and non-toxic thermoelectric materials, the first experimental study on a set of eight substrate-free boron-doped nanocrystalline diamond foils is presented herein. All transport coefficients were determined in the same direction within the same foils over a broad temperature range up to 900 °C. It is found that nanostructuring reduces the thermal conductivity by two orders of magnitude, but the mobility decreases significantly to around 1 cm² V⁻¹ s⁻¹, too. Although degenerate transport can be concluded from the temperature dependence of the Seebeck coefficient, charge carriers notably scatter at grain boundaries where sp²-carbon modifications and amorphous boron-rich phases form during synthesis. A detailed analysis of doping efficiency yields an acceptor fraction of only 8–18 at%, meaning that during synthesis excess boron thermodynamically prefers electrically inactive sites. Decent power factors above 10⁻⁴ W m⁻¹ K⁻² at 900 °C are found despite the low mobility, and a Jonker-type analysis grants a deeper insight into this issue. Together with the high thermal conductivity, the thermoelectric figure of merit zT does not exceed 0.01 at 900 °C.     

Synthesis of superconducting boron-doped diamond compacts with high elastic moduli and thermal stability

Polycrystalline bulk compacts (3.5–4.0 mm in diameter and 2.5 mm in height) of superconducting boron-doped diamond with high elastic moduli have been synthesized from mixtures of graphite and boron carbide at pressures 8–9 GPa and temperature of 2500 K. We show that graphite-to-diamond transformation in the presence of liquid boron–carbon growth medium leads to formation of polycrystalline diamond matrix at B₄C concentration in the initial mixture ranging from 3.5 to 5%. Resistive transition of the samples to the superconducting state starts at 4 K and ends at 2.2 K. The thermal conductivity of the samples slightly increases in the temperature range of 230 to 400 K, and at room temperature it is as low as ~ 0.4 W/cm K. The boron-doped diamond demonstrates very high oxidation resistance up to 1200 K, and can be used as electrical structural material that can be exploited at elevated temperatures in air.