Preparation of high-yield multi-walled carbon nanotubes by catalytic decomposition of mixture of natural gas and propylene and their electrothermal properties

Abstract

Multi-walled carbon nanotubes (MWNTs) with high-yield were prepared by pyrolysis of mixture of natural gas (NG) and propylene (C₃H₆) over Fe-Ni/Al₂O₃-MgO catalyst. For C₃H₆/NG flow rate ratio ranging from 0 to 0.33, the carbon yield was increased from 903% to 4400%. The synthesized MWNTs after purification were dispersed by ball milling method and mixed with waterborne polyurethane to fabricate the electrothermal film. The mass fraction of CNT filler in the cured electrothermal film was controlled at 50%. The coating after drying was ca. 6?μm and the coating’s volume resistivity was 0.053 Ω·cm. The time-dependent temperature curves indicated that the heating rate of the electrothermal film was very fast under different low voltage and the steady-state temperatures were achieved within 100?s. The steady-state temperature reached 47.9?°C, 76.8?°C, and 102.8?°C, respectively at 10?V, 15?V, and 18?V.     

Temperature dependence of oriented growth of Pb[Yb(1/2)Nb(1/2)]O(3)-PbTiO(3) thin films deposited on LNO/Si substrates

(1-x)Pb[Yb(1/2)Nb(1/2)]O(3)-xPbTiO(3) (PYbN-PT, x=0.5)(001) oriented thin films were deposited onto LaNiO3 (LNO)/Si(001) substrates by sol-gel processing. The crystallographic texture of the films was controlled by the annealing temperature and heating rate. Highly (001) oriented LNO thin films were prepared by a simple metal organic decomposition technique, and the samples were annealed at 700 °C and 750 °C using a rapid thermal annealing process and furnace, respectively. X-ray diffraction analysis revealed that the films of PYbN-PT were highly (001) oriented along LNO/Si substrates. The degree of PYbN-PT orientation is dependent on the heating rate and annealing temperature. Annealing heating rate of 10 °C/s and high annealing temperature near 750 °C produce the greatest degree of (001) orientation, which gives rise to improved dielectric properties.     

Effect of heat treatment on characteristics of nanocrystalline ZnO films by electron beam evaporation

Zinc oxide thin films have been grown on glass substrate at room temperature by electron beam evaporation and then were annealed in annealing pressure 600 mbar at different temperatures ranging from 250 to 550 °C for 30 min. Electrical, optical and structural properties of thin films such as electrical resistivity, optical transmittance, band gap and grain size have been obtained as a function of annealing temperature. X-ray diffraction has shown that the maximum intensity peak corresponds to the (002) predominant orientation for ZnO films annealed at various temperatures. The full width at half maximum, decreases after annealing treatment which proves the crystal quality improvement. Scanning electron microscopy images show that the grain size becomes larger by increasing annealing temperature and this result agrees with the X-ray diffraction analysis.     

Preliminary studies on molybdenum-doped indium oxide thin films deposited by radio-frequency magnetron sputtering at room temperature

Thin films of molybdenum-doped indium oxide (IMO) were prepared by a 3-source, cylindrical radio-frequency magnetron sputtering at room temperature. The films were post-annealed and were characterized by their structural (X-ray diffraction) and optical (UV-VIS-NIR spectrophotometer) properties. The films were studied as a function of oxygen volume percentage (O₂ vol.%) ranging from 3.5 to 17.5. The structural studies revealed that the as-deposited amorphous films become crystalline on annealing. In most cases, the (222) reflection emerged as high intensive peak. The poor visible transmittance of the films as-deposited without oxygen was increased from ∼ 12% to over 80% on introducing oxygen (3.5 O₂ vol.%). For the films annealed in open air, the average visible transmittance in the wavelength ranging 400-800 nm was varied between 77 and 84%. The films annealed at high temperatures (> 300 °C) decreased the transmittance to as low as < 1%. The optical band gap of the as-deposited films increased from the range 3.83-3.90 to 3.85-3.98 eV on annealing at different conditions.     

Electrospun carbon nanofiber-based flexible films for electric heating elements with adjustable resistance,ultrafast heating rate,and high infrared emissivity

Carbon nanomaterials have shown great potential as electric heating elements in electrothermal applications. However, carbon-based heating elements with high flexibility, ultrafast electrothermal response, low driving voltage, high heating temperature, and stretchability are still lacking. Here, continuous electrospun carbon nanofiber films (CNFFs) and corresponding composite films additionally containing silicone (CSCFs) as electric heating elements are proposed. CNFFs were prepared by electrospinning and subsequent heat treatment, and CSCFs were prepared by composing CNFFs with silicone via hot-pressing procedure. Both of them have shown excellent performance as electrothermal films, such as ultrafast electrothermal response, high resistance adjustability, high flexibility, high operation stability, and high infrared emissivity. In particular, a temperature as high as 200 °C can be reached within 2 s at 8 V. Suitable robustness and flexibility allow CSCFs to bear various deformations, such as bending, twisting, folding, and even stretching by a factor of 1.3, without worsening electrothermal performance. Also, excellent water resistance has been confirmed. The superior electrothermal performance is mainly attributed to the high electrical conductivity, continuous fiber structure, high specific surface area, and adjustability of nanofiber stacking density and thickness of CNFFs.

Graphical abstract

     

Stress Evolution With Temperature in Titanium‐Rich NiTi Shape Memory Alloy Films

Abstract: The effect of deposition temperature on residual stress evolution with temperature in Ti‐rich NiTi films deposited on silicon substrates was studied. Ti‐rich NiTi films were deposited on 3″ Si (100) substrates by DC magnetron sputtering at three deposition temperatures (300, 350 and 400 °C) with subsequent annealing in vacuum at their respective deposition temperatures for 4 h. The initial value of residual stress was found to be the highest for the film deposited and annealed at 400 °C and the lowest for the film deposited and annealed at 300 °C. All the three films were found to be amorphous in the as‐deposited and annealed conditions. The nature of the stress response with temperature on heating in the first cycle (room temperature to 450 °C) was similar for all three films although the spike in tensile stress, which occurs at ～330 °C, was significantly higher in the film deposited and annealed at 300 °C. All the films were also found to undergo partial crystallisation on heating up to 450 °C and this resulted in decrease in the stress values around 55–60 °C in the cooling cycle. The stress response with temperature in the second thermal cycle (room temperature to 450 °C and back), which is reflective of the intrinsic film behaviour, was found to be similar in all cases and the elastic modulus determined from the stress response was also more or less identical. The three deposition temperatures were also not found to have a significant effect on the transformation characteristics of these films such as transformation start and finish temperatures, recovery stress and hysteresis.     

Highly elastic and transparent multiwalled carbon nanotube/polydimethylsiloxane bilayer films as electric heating materials

Highly elastic and transparent bilayer films composed of MWCNT and polydimethylsiloxane (PDMS) layers were fabricated by spin-coating of MWCNT aqueous solution on glass plates and following curing of PDMS applied on the MWCNT layer. Morphological feature, optical transparency, tensile property, electrical property, and electric heating behavior of the bilayer films with different MWCNT layer thicknesses of 65–185 nm were investigated. SEM images confirmed that pristine MWCNTs were uniformly deposited on glass substrates and the PDMS layer was combined well with the MWCNT layer, resulting in high structural stability of the bilayer films to high elongational or twisting deformations. With the increase of the thickness of the MWCNT layer, the sheet resistance of the bilayer films decreased substantially from ~ 10⁵ Ω/sq to ~ 10³ Ω/sq, in addition to the change of the optical transmittance from ~ 75% to ~ 40% at a 550 nm wavelength. The electric heating behavior of MWCNT/PDMS bilayer films was strongly dependent on the thickness of the MWCNT layer as well as the applied voltage. Even under high twisting by 540° or continuous stepwise voltage changes for long periods of time, the MWCNT/PDMS bilayer films retained stable electrical heating performance in aspects of temperature responsiveness, steady-state maximum temperature, and electric power efficiency.     

Bi3.45Eu0.55Ti3O12铁电薄膜的光学性能

采用化学溶液沉积法在石英衬底上制备了Bi3.45Eu0.55Ti3O12(BEuT)铁电薄膜,研究了BEuT薄膜的结构和光学性能。XRD测试结果表明,BEuT薄膜皆形成铋层状钙钛矿型结构,其晶粒尺寸随着退火温度的提高而增加。薄膜的光学透过率曲线显示,在大于500nm的波段BEuT的透过率比较高,而其禁带宽度大约为3.61eV。BEuT薄膜的发光强度随着退火温度的提高,先是增强后减弱,在700℃时达到最大。这与薄膜的结晶状况有关。     

Effect of annealing on molybdenum doped indium oxide thin films RF sputtered at room temperature

Thin films of molybdenum doped indium oxide (IMO) were deposited on glass at room temperature using an in-built three-source RF magnetron sputtering. The films were studied as a function of oxygen volume percentage (O₂ vol. %; ranging from 0.0 to 17.5%) in the sputtering chamber. The as-deposited amorphous films were crystallized on post-annealing. The as-deposited films are low conducting and Hall coefficients were undetectable; whereas post-annealed films possess fairly high conductivity. The lowest transmittance (11.96% at 600 nm) observed from the films deposited without oxygen increased to a maximum of 88.01% (3.5 O₂ vol. %); whereas this transmittance was decreased with the increasing O₂ vol. % to as low as 81.04% (15.6 O₂ vol. %); a maximum of 89.80% was obtained from the films annealed at 500 °C in open air (3.5 O₂ vol. %). The optical band gap of 3.80 eV obtained from the films deposited without oxygen increased with increasing O₂ vol. % to as high as 3.91 eV (17.5 O₂ vol. %). A maximum of 3.92 eV was obtained from the films annealed at 300 °C in N₂:H₂ gas atmosphere (17.5 O₂ vol. %).     

On the Maintenance of Saturated Standard Cells at 3°C through the Use of Thermoelectric Cooling

Saturated standard cells at temperatures between 20°C and 40°C exhibit a high negative-voltage coefficient with respect to temperature and have required temperature stabilization within ±0.01°C over an extended period to achieve a voltage stability of ±1 ?V. Examination of standard cell data in the vicinity of 0°C, on the other hand, indicated higher voltages and a much lower temperature coefficient. In fact, the cell voltage reaches a maximum and consequently the voltage coefficient is zero at approximately 3°C, and is near zero over a range of several degrees. A cell maintenance temperature of 3°C, therefore, appears the most appropriate operating environment for a saturated cell in order to obtain maximum voltage stability. Heretofore, a convenient, high-stability, maintenance-free temperature bath operating near 3°C has not been available for laboratory use. The utilization of thermoelectricity to cool (Peltier effect) is currently available, and this method has been employed to provide a stable low-temperature ambient for saturated cells. This paper describes a practical air chamber-controller combination with thermoelectric heat pumping designed to test the behavior of saturated cells near 3°C. Details of the thermal and electrical characteristics of the unit will be discussed. Results show a ±0.2°C control is adequate to provide a primary voltage reference with ±1 ?V stability at 3.1°C. Advantages and precautions in maintaining cells at low temperatures will also be presented.     

The electrical and interface properties of metal-ferroelectric (lanthanum substituted bismuth titanate: BLT)-insulator-semiconductor (MFIS) structures with various insulators

We have investigated metal-ferroelectric-insulator semiconductor (MFIS) structures with lanthanum substituted bismuth titanate (BLT) as a ferroelectric layer and lanthanum oxide (LO) or zirconium silicate (ZSO) as an insulating buffer layer between BLT and Si substrate. The morphology of BLT films deposited on LO or ZSO oxide was not changed due to the good thermal stability of LO and ZSO films. But an interface reaction between BLT and buffer layer started at high annealing temperature (750 °C), which was confirmed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The maximum memory window was 3.59 V at a sweep voltage of 7 V with the LO film annealed at 650 °C and a thickness of 5 nm. With BLT/LO annealed at 750 °C, the window was decreased due to the reaction between the BLT film and LO. The memory window was about 1 V lower with a ZSO film because ZSO film has a lower dielectric constant than LO film. The MFIS structure annealed at 750 °C had a lower leakage current density because the electrical properties of the buffer layer (La oxide or Zr silicate) were improved by the thermal process.     

石墨烯修饰的柔性多彩电热致变色薄膜的制备及性能研究

通过化学氧化还原法并辅以抽滤法制备RGO导电薄膜, 通过丝网印刷法制备变色层, 构筑了多层结构的多彩(红-蓝-白以及橙红-黄-白等)柔性电热致变色薄膜。采用SEM、XRD以及Raman等分析薄膜的结构性质。采用红外热成像以及吸收光谱研究了薄膜(红-蓝-白)的热学以及变色性能。结果表明：当加热时间为3.4 s时, 薄膜温度能达到38℃, 变为蓝色; 当加热时间为6.3 s时, 薄膜温度达到45℃, 变为白色。在较低电压下(6 V), 该薄膜能实现多色彩可逆变色, 其变色时间约为6.3 s, 褪色时间约为9.2 s。该柔性电热致变色薄膜以混合纤维素滤膜为基体, 保证了薄膜良好的柔性, 在可穿戴显示领域有着一定的应用价值。     

Effects of heat treatment on properties of ITO films prepared by rf magnetron sputtering

Indium tin oxide (ITO) films were deposited on glass substrates by rf magnetron sputtering using a ceramic target (In₂O₃-SnO₂, 90-10 wt%) without extra heating. The post annealing was done in air and in vacuum, respectively. The effects of annealing on the structure, surface morphology, optical and electrical properties of the ITO films were studied. The results show that the increase of the annealing temperature improves the crystallinity of the films, increases the surface roughness, and improves the optical and electrical properties. The transmittance of the films in visible region is increased over 90% after the annealing process in air or in vacuum. The resistivity of the films deposited is about 8.125×10⁻⁴ Ω cm and falls down to 2.34×10⁻⁴ Ω cm as the annealing temperature is increased to 500°C in vacuum. Compared with the results of the ITO films annealed in air, the properties of the films annealed in vacuum is better.     

Influence of post-annealing temperature on the properties exhibited by ITO, IZO and GZO thin films

In this work we present a study on the effect of annealing temperatures on the structural, morphological, electrical and optical characteristics of gallium doped zinc oxide (GZO), indium zinc oxide (IZO) and indium-tin-oxide (ITO) films. GZO and IZO films were deposited at room temperature by r.f. magnetron sputtering, whereas the ITO films were commercial ones purchased from Balzers. All films were annealed at temperatures of 250 and 500 °C in open air for 1 h. The GZO and ITO films were polycrystalline. The amorphous structure of as-deposited IZO films becomes crystalline on high temperature annealing (500 °C). The sheet resistivity increased with increase in annealing temperature. GZO films showed an increase of 6 orders of magnitude. The optical transmittance and band gap of as-deposited films varied with annealing. The highest transmittance (over 95 %) and maximum band gap (3.93 eV) have been obtained for ITO films.     

Characterization of poly(vinylidene fluoride-trifluoroethylene) 50/50 copolymer films as a gate dielectric

Thin films of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) 50/50 copolymer were prepared by spin coating on p-Si substrate. Thermal behavior of the film was observed by measuring the film thickness with ellipsometry as a function of the temperature and abrupt volume expansion was observed at 130–150 °C. Capacitance-voltage (C-V) and current-voltage (I-V) behavior of the aluminum/P(VDF-TrFE)/p-Si MIS (metal-insulator-semiconductor) structures were studied and dielectric constant of the P(VDF-TrFE) film was measured to be about 15.3 at optimum condition. No hysteresis was observed in the C-V curve for films as deposited and annealed (70–200 °C). Films annealed at temperatures higher than the volume expansion temperature showed substantial surface roughness due to the crystallization. Flat band voltage (V_FB) of the MIS structure with as deposited films was about −0.3 V and increased up to −2.0 V with annealing. This suggested that positive charges were generated in the film. Electronic properties of the annealed P(VDF-TrFE) film at above melting temperature were degraded substantially with larger shift in flat band voltage, low dielectric constant and low breakdown voltage. Organic thin film transistor with pentacene active layer and P(VDF-TrFE) as a gate dielectric layer showed a mobility of 0.31 cm²/V·s and threshold voltage of −0.45 V.     

Effect of tungsten on the electrochromic behaviour of sol-gel dip coated molybdenum oxide thin films

The paper describes the results obtained on the performance of Mo oxide and mixed W/Mo oxide thin films for possible electrochromic applications. Mo and W/Mo oxide films were deposited on conductive (FTO) glass substrates using sol-gel dip coating method. The films were annealed at 250 °C for 30 min. The structure and morphology of Mo and W/Mo oxide films were examined using XRD, SEM and EDS. XRD results indicate the amorphous nature of the Mo and W/Mo oxide films annealed for 30 min. The CV measurements revealed that the films prepared with 10 wt.% of tungsten exhibit maximum anodic/cathodic diffusion coefficient of 24.99/12.71 × 10⁻¹¹ cm²/s. The same film exhibits a maximum transmittance variation (ΔT%) of 83.4% at 630 nm and 81.06% at 550 nm with the optical density of 1.00 and 1.13 respectively.     

Microstructural, photocatalysis and electrochemical investigations on CeTi2O6 thin films

The properties of sol–gel derived CeTi₂O₆ thin films deposited using a solution of cerium chloride heptahydrate and titanium propoxide in ethanol are discussed. The effect of annealing temperature on structural, optical, photoluminescence, photocatalysis and electrochemical characteristics has been examined. Lowest annealing temperature for the formation of crystalline CeTi₂O₆ phase in these samples is identified as 580 °C. The optical transmittance of the films is observed to be independent of the annealing temperature. The optical energy bandgap of the 600 °C annealed film for indirect transition is influenced by the presence of anatase phase of TiO₂ in its structure. Fourier transform infrared spectroscopy investigations have evidenced increased bond strength of the Ti–O–Ti network in the films as a function of annealing temperature. The photoluminescence intensity of the films has shown dependence on the annealing temperature with the films fired at 450 °C exhibiting the maximum photoluminescence activity. The decomposition of methyl orange and eosin (yellow) under UV–visible light irradiation in the presence of crystalline CeTi₂O₆ films shows the presence of photoactivity in these films. The photocatalytic response of CeTi₂O₆ films is found to be superior to the TiO₂ films. In comparison to crystalline films, the amorphous films have shown superior electrochemical characteristics. The 500 °C annealed amorphous films have exhibited the most appropriate properties for incorporation in electrochromic devices comprising tungsten oxide as the primary electrochromic electrode.     

焦耳热处理降低石墨烯/环氧树脂发热涂层的体积电阻率

石墨烯基发热涂层一项重要的用途是降低其体积电阻率。文中结合发热涂层本身可以产热的特点,对涂层施加电压让其产热来对涂层进行焦耳热处理以降低涂层的体积电阻率。首先研究了通电焦耳热处理后的涂层体积电阻率随处理温度、时间和周期的变化,然后用X射线衍射和扫描电镜说明了涂层体积电阻率降低的原因以及该过程与外热处理的区别,讨论了石墨烯含量、片径大小对处理后的涂层体积电阻率降低的影响,最后对处理前后涂层的发热温度进行了比较:对涂层进行130℃,30 min的处理后,涂层在60 V电压下,表面发热温度由67.6℃升高到120.4℃     

A three-step process for epitaxial growth of (111)-oriented C60 films on alkali–halide substrates

Epitaxial (111)-oriented C₆₀ films have been grown on alkali–halide substrates, KCl (100), KBr (100) and NaCl (100) by a three-step process: (1), substrate surface cleaning by high temperature heating; (2), initial deposition with a low deposition rate to grow two or three monolayers (ML); and (3), deposition with a high deposition rate to grow a film with expected thickness. It was found that (111)-oriented epitaxial C₆₀ films could be grown at low temperatures in a wide temperature range, from 40 to 120°C. By this three-step process, we can also grow epitaxial C₆₀ films at deposition rates as high as 35 Å/min.     

Magnetic and field emission studies of atom beam sputtered Ni:SiO2 granular films

Ni:SiO₂ granular films have been prepared by atom beam sputtering technique under ambient conditions. These films have been subsequently annealed at 200-600 °C temperature. GAXRD and TEM analyses show the growth of Ni particles and improvement in crystallinity with increase in annealing temperature. Selected area electron diffraction and XPS analyses show the presence of a small quantity of NiO phase in addition to metallic Ni. Room temperature magnetic measurements indicate that the films annealed at lower temperatures (≤400 °C) are superparamagnetic and the film annealed at 600 °C is ferromagnetic. Magnetic results at 5 K are explained on the basis of exchange bias between Ni particles and surrounding nickel oxide. Systematic field emission studies on as-deposited and annealed films show a turn-on field ∼6.2-13.5 V/μm corresponding to an emission current density of ∼1 A/m². Field emission results are explained on the basis of electrical inhomogeneity effects.