Influence of zirconia on biomimetic apatite formation in pure titanium coated via plasma electrolytic oxidation

This work demonstrated the effect of zirconia incorporation on the formation of biomimetic apatite in pure titanium coated by plasma electrolytic oxidation (PEO) method. To incorporate zirconia particles into the oxide layer, electrochemical coating was carried out under AC condition in an electrolyte containing zirconia powder. After PEO coatings, zirconia particles were distributed uniformly throughout the titanium oxide layer while the size and distribution of micro-pores remained unchanged when compared to titanium coated by PEO in an electrolyte without zirconia. It was found that a number of fine zirconia particles played an important role in triggering the occurrence of biomimetic apatite on top of the PEO-coated titanium in a simulated body fluid solution. This was mainly attributed to increased surface roughness of the oxide layer as well as inherent activation of zirconia particles to form biomimetic apatite.     

电泳沉积碳纳米管的微波等离子体改性

采用电泳法在Si基底上沉积了碳纳米管(CNTs)薄膜, 并利用Ar微波等离子体对CNTs薄膜进行了改性处理, 研究了改性前后CNTs的微观结构和场发射性能. 高分辨透射电子显微镜(HRTEM)和拉曼光谱的表征结果表明, 等离子体改性明显改变了CNTs的微观结构, 形成了大量的管壁结构缺陷、纳米级突起和“针形”尖端; 场发射测试结果表明, CNTs经Ar等离子体改性处理后开启电场较改性前?略有增大, 等离子体改性10min的CNTs薄膜表现出最佳的场发射J-E特性, 阈值电场由改性前的3.12V/μm降低到2.54V/μm, 当电场强度为3.3V/μm时, 场发射电流密度由改性前的18.4mA/cm²增大到60.7mA/cm². 对Ar微波等离子体改性增强CNTs薄膜场发射性能的机理进行了分析.     

Formation and bioactivity of porous and nanostructured TiO2/beta-TCP coating on titanium

Titanium and its alloys have been widely used as hard tissue implants due to their excellent mechanical properties and biocompatibility. However, their near bio-inertness and metallic ion release are still the problems with clinical uses. In this paper, porous and nanostructured TiO2/beta-tricalcium phosphate (beta-TCP) composite coatings were prepared on titanium substrates by plasma electrolytic oxidation (PEO) in a Ca and P-containing electrolyte. The influence of PEO electric current density on phase composition and bioactivity of the coatings were studied. X-ray diffraction, scanning electron microscopy and Fourier transfer infrared spectroscopy were utilized to characterize the phase composition and microstructure of the coatings. Simulated body fluid immersion tests were employed on the coatings to evaluate their bioactivity. The results reveal that TiO2/beta-TCP composite coating with pores size less than 10 microm and grains of 50-100 nm in size was prepared. The electric current density of PEO is an important factor in the formation of the composite coating. The TiO2/beta-TCP composite coating shows good bioactivity, which are attributed to the incorporation of beta-TCP.     

Corrosion behavior of friction stir welded AZ31B magnesium alloy with plasma electrolytic oxidation coating formed in silicate electrolyte

A protective ceramic coating of about 50 μm thick on a friction stir welded (FSW) joint of AZ31B magnesium alloy was prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte. Electrochemical corrosion behavior of uncoated and coated FSW joints was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The equivalent circuits of EIS plots for uncoated and coated FSW magnesium alloy were suggested. The corrosion resistance of FSW magnesium alloy depended on microstructure of the FSW joint. The heat-affected zone with severe grain growth was more susceptible to corrosion than the stir zone and base metal. The PEO coating consisted of a porous outer layer and a dense inner layer. The inner layer of PEO coating played a key role on corrosion protection of the FSW joint of magnesium alloy. Meanwhile, corrosion potential, corrosion current density and impedance at different zones of coated FSW joint were almost the same. The PEO surface treatment significantly improved the corrosion resistance of FSW joints of AZ31B magnesium alloy.     

Corrosion resistance of in-situ growth of nano-sized Mg(OH)2 on micro-arc oxidized magnesium alloy AZ31—Influence of EDTA

One of the major obstacles for the clinical use of biodegradable magnesium (Mg)-based materials is their high corrosion rate. Micro-arc oxidation (MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)₂ film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium (EDTA-2Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)₂ hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)₂ coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating. The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)₂ film. The current density of Mg(OH)₂-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)₂-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.     

Characterization of silicon oxide gas barrier films with controlling to the ion current density (ion flux) by plasma enhanced chemical vapor deposition

Silicon oxide gas barrier films were deposited on polyethylene terephthalate (PET) substrates by plasma enhanced chemical vapor deposition (PE-CVD) for applications to transparent barrier packaging. The barrier properties of the silicon oxide coated film were optimized by varying the bias conditions and input power in the radio frequency plasma. The plasma diagnostics, ion current density and substrate temperature were characterized by optical emission spectrometry (OES), an oscilloscope and thermometer, respectively. The coating properties were examined by Fourier transform infrared (FT-IR) spectroscopy and the water vapor transmission rate (WVTR). A high intensity of O and H ions and a high ion current density (ion flux) with a low temperature plasma process were found to be suitable for improving the barrier properties of the silicon oxide film coatings. The Si-O cage-like structure adversely affected the gas barrier properties of the deposited coating. The energy provided by ion bombardment (ion flux) can induce changes in the film density and composition similar to those that may occur by the increase in deposition temperature through rf bias. In addition, the film properties depend not only on a high ion current density (ion flux) and input power, but are also related to a silicon oxide film with a widely distributed planar ring size.     

A spectroscopic and microstructural study of oxide coatings produced on a Ti–6Al–4V alloy by plasma electrolytic oxidation

In this study, we have used PEO (plasma electrolytic oxidation) for the production of oxide coatings on a Ti–6Al–4V alloy at two different current modes, namely pulsed unipolar and bipolar. Optical emission spectroscopy (OES) in the visible and near UV band (280–800 nm) was used to characterize the PEO plasma. The emission spectra were recorded and the plasma temperature profile versus processing time was constructed using a line intensity ratios method. The aim of this work was to study the effect of the process parameters, including current mode and pulse duration time, on the plasma characteristics, surface morphology and microstructure and corrosion resistance of oxides grown on Ti–6Al–4V by PEO process. Scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDS) and X-ray diffraction (XRD) were used to study the coating microstructure, morphology and phase composition. The corrosion resistance of the coated and uncoated samples was examined by potentiodynamic polarization in a 3.5% NaCl solution. It was found that the plasma temperature profiles are significantly influenced by changing the current mode from unipolar to bipolar. The strongest discharges that are initiated at the interface between the substrate and the coating can be reduced or eliminated by using a bipolar current mode. This produces a thinner, denser and more corrosion-resistant coating.     

Effective electron emitters by molybdenum oxide-coated carbon nanotubes core–shell nanostructures

In this article, we showed that simple metal oxide coatings such as MoO₃ can be an effective enhancer for carbon nanotubes (CNTs) in field emission (FE) performance. For comparison, the FE properties of the pristine vertically aligned multi-walled CNTs with the metal oxide-coated CNTs were investigated. The metal oxide coating of the pristine CNTs was carried out by metal–organic chemical vapor deposition (MOCVD) method at 400 °C using Mo(CO)₆ as the precursor. The core–shell structure of the nanocomposite was studied by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) results showed that the surface of the coating material was mainly MoO₃. FE test indicated that the MoO₃-coated CNTs film exhibited an enhanced performance than the pristine CNTs with a turn-on field of 1.33 V μm⁻¹ and a field enhancement factor β estimated to be ~7000. Ultraviolet photoelectron spectroscopy (UPS) results confirmed a lower electron emission barrier height for MoO₃-coated CNTs than for the pristine CNTs. The mechanism of the enhanced FE performance is discussed based on Schottky barrier effect.     

浮动催化CVD法CNTs膜及CNTs膜/环氧复合材料拉伸特性

针对浮动催化化学气相沉积(CVD)法制备的碳纳米管(CNTs)膜,首先采用红外光谱表征分析了包覆在CNTs表面的无定形物质的组成,然后分别采用热处理和酸洗处理方法,考察了CNTs膜中无定形物和残留Fe催化剂对CNTs膜拉伸取向行为的影响。结果表明:采用CVD法制备的CNTs膜中CNTs表面无定形物为含氧或烷烃、烯烃类低聚物,可通过350℃有氧热处理基本去除。该CNTs膜的牵伸取向重排行为受组成影响显著,CNTs表面的低聚物可增强CNTs的管间黏结作用,Fe催化剂颗粒成为CNTs网络结构的交联结点,两者均有利于提高CNTs的取向程度和聚并成束的尺寸,进而提高CNTs膜的拉伸稳定性和断裂韧性。牵伸取向后CNTs膜与环氧树脂溶液的浸润性提高,其CNTs膜/环氧复合材料的拉伸强度和模量达到1228MPa和94.5GPa,相比初始无规CNTs膜/环氧复合材料的分别提高了337%和729%。      

Effect of catalyst thickness and plasma pretreatment on the growth of carbon nanotubes and their field emission properties

We demonstrated that the diameter and the density of carbon nanotubes (CNTs) which had a close relation to electric-field-screening effect could be easily changed by the control of catalytic Ni thickness combined with NH3 plasma pretreatment. Since the diameter and the density of CNTs had a tremendous impact on the field-emission characteristics, optimized thickness of catalyst and application of plasma pretreatment greatly improved the emission efficiency of CNTs. In the field emission test using diode-type configuration, well-dispersed thinner CNTs exhibited lower turn-on voltage and higher field enhancement factor than the densely-packed CNTs. A CNT film grown using a plasma-pretreated 25 angstroms-thick Ni catalyst showed excellent field emission characteristics with a very low turn-on field of 1.1 V/microm @ 10 microA/cm2 and a high emission current density of 1.9 mA/cm2 @ 4.0 V/microm, respectively.     

ZnO-C三维网络结构涂层的制备及其储锂性能研究

通过简单的刮涂工艺成功地在铜箔表面制备出具有三维网络结构的ZnO-C复合涂层。采用X射线衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)和透射电镜(TEM)对复合涂层的晶体结构及微观形貌进行研究。结果表明: 该涂层由宽度为0.1~1 μm的碳基枝条相互连接形成连续的三维网络结构, 碳基枝条内包含ZnO纳米粒子和尺寸约为2 nm的微孔。该涂覆在铜箔表面的复合涂层可直接用作锂离子电池的负极。电化学测试结果表明: ZnO-C复合涂层负极材料在0.1 A/g电流密度下经过100次循环后的比容量为855 mAh/g, 并且在循环过程中未出现容量衰减现象; 在5A/g大电流密度下的比容量为418 mAh/g, 是0.1 A/g电流密度下比容量的51.3%。     

Young's modulus of electroplated Ni thin film for MEMS applications

The Young's modulus of an electroplated nickel (Ni) thin film suitable for microelectromechanical applications has been investigated as a function of process variables: the plating temperature and current density. It was found that the Young's modulus is approximately 205 GPa at plating temperatures less than 60 °C, close to that of bulk Ni, but drastically drops to approximately 100 GPa at 80 °C. The inclusion of ammonium and sulphate ions by hydrolysis is believed to be responsible for the sharp drop. The Young's modulus of 205 GPa is for a Ni film plated at J=2 mA/cm² and it decreases to 85 GPa as the plating current density is increased to 30 mA/cm². The results imply that at low current density, the plating speed is slow and there is sufficient time for the as-plated Ni atoms to rearrange to form a dense coating. At high currents, the plating speed is high, and the limited mass transport of Ni ions leads to a less dense coating.     

Structural modification and enhanced electron emission from multiwalled carbon nanotubes grown on Ag/Fe catalysts coated Si-substrates

Multiwalled carbon nanotubes and carbon nano-filaments were grown using Fe as the main catalyst and Ag as a co-catalyst by microwave plasma enhanced chemical vapour deposition. In this work we demonstrate the growth behaviour of carbon nanotubes (CNTs) grown on pure Fe-film and Ag–Fe films. We find that using Ag film beneath Fe film significantly abate the catalyst–substrate interactions by acting as a barrier layer as well as enhances the nucleation sites for the growth of CNTs due to the limited solubility with Fe and silicon. Scanning electron microscopy and transmission electron microscopy studies were carried out to image the microstructures of the samples. It was observed that the length of Fe catalyzed CNTs was ∼500 nm and Ag–Fe catalyzed CNTs varied from ∼600 nm to 1.7 μm. Micro Raman spectroscopy confirmed the improved crystalline nature of Ag–Fe CNTs. It was found that I_D/I_G ratio for Fe catalyzed CNTs was ∼1.08 and for Ag–Fe catalyzed CNTs was ∼0.7. The Ag–Fe catalyzed CNTs were found to be less defective as compared to Fe catalyzed CNTs. Field emission measurements using diode configuration, showed that electron emission from Ag–Fe catalyzed CNTs was much stronger as compared to Fe catalyzed CNTs. The threshold field for Ag–Fe catalyzed CNTs was (2.6 V μm⁻¹) smaller as compared to Fe catalyzed CNTs (3.8 V μm⁻¹) and thus shows better emission properties. This enhancement in electron emission mechanism as a result of introduction of Ag underlayer is attributed to the increased emitter sites and improved crystallinity.     

The emission effect of metal-tip removal in carbon nanotubes by bias-assisted ICPHFCVD

This paper presents a technique for the preparation of vertically grown carbon nanotubes (CNTs) by bias-assisted inductively coupled plasma hot-filament chemical vapor deposition. Purification of the CNTs using r.f. plasma in a one-step process, based on the different etching property of the metal tip is also discussed. The Ni at the tip of the CNTs was effectively removed by using r.f. plasma based on the different etching property. After purification CNTs show the multi-walled and hollow-type structure. The measured critical current density on CNTs with a Ni tip was 3.52×10^–7 A cm^–2 at 2.47 V m^–1 turn-on field and 6.6×10^–4 A cm^–2 at 4.8 V m^–1 of the critical field. On the other hand, the critical current density on purified CNTs after Ni removal by an r.f. source was 1.36×10^–7 A cm^–2 at 2.1 V m^–1 turn-on field and 1.5×10^–3 A cm^–2 at 6 V m^–1 of the critical field, respectively.     

Aligning Solution‐Derived Carbon Nanotube Film with Full Surface Coverage for High‐Performance Electronics Applications

The main challenge for application of solution‐derived carbon nanotubes (CNTs) in high performance field‐effect transistor (FET) is how to align CNTs into an array with high density and full surface coverage. A directional shrinking transfer method is developed to realize high density aligned array based on randomly orientated CNT network film. Through transferring a solution‐derived CNT network film onto a stretched retractable film followed by a shrinking process, alignment degree and density of CNT film increase with the shrinking multiple. The quadruply shrunk CNT films present well alignment, which is identified by the polarized Raman spectroscopy and electrical transport measurements. Based on the high quality and high density aligned CNT array, the fabricated FETs with channel length of 300 nm present ultrahigh performance including on‐state current I_on of 290 µA µm^?1 (V_ds = ?1.5 V and V_gs = ?2 V) and peak transconductance g_m of 150 µS µm^?1, which are, respectively, among the highest corresponding values in the reported CNT array FETs. High quality and high semiconducting purity CNT arrays with high density and full coverage obtained through this method promote the development of high performance CNT‐based electronics.     

Plasma treatment effects on surface morphology and field emission characteristics of carbon nanotubes

In this study, electron field-emission properties of carbon nanotube films (CNTs) grown on silicon substrate before and after tetrafluoromethane (CF₄), hydrogen (H₂) and argon (Ar) plasma etchings were investigated. The CNTs were synthesized by thermal decomposition of methane in the presence of nickel catalyst. Our research results reveal that plasma treatment can modify the surface morphology and enhance the field-emission characteristics of CNTs regardless of the plasma used. The CNTs treated by both non-reactive and reactive plasmas have a higher density of defect and a smaller average diameter reflecting the etching effects of plasma treatments. In addition, higher emission currents and lower turn-on electric fields are also obtained for the CNTs after plasma treatment. As expected, reactive plasma treatment has a more pronounced effect on the surface morphology and field-emission characteristics of the synthesized CNTs than non-reactive plasma treatment. In particular, a huge increase in emission current (more than three orders of magnitude at high electric fields) and a substantial lower turn-on electric field are found for the CNTs after H₂ plasma treatment. This huge increase in the emitted current is primarily caused by the increase in the density of field-emission sites resulting from the change of surface morphology and the –CH _x nanoparticles redeposited on the CNTs.     

Calcium and titanium release in simulated body fluid from plasma electrolytically oxidized titanium

The release of titanium and calcium species to a simulated body fluid (SBF) at 37°C has been investigated for titanium treated by dc plasma electrolytic oxidation (PEO) in three different electrolytes, namely phosphate, silicate and calcium- and phosphorus-containing. The average rate of release of titanium over a 30 day period in immersion tests, determined by solution analysis, was in the range ~1.5–2.0 pg cm⁻² s⁻¹. Calcium was released at an average rate of ~11 pg cm⁻² s⁻¹. The passive current densities, determined from potentiodynamic polarization measurements, suggested titanium losses of a similar order to those determined from immersion tests. However, the possibility of film formation does not allow for discrimination between the metal releases due to electrochemical oxidation of titanium and chemical dissolution of the coating.     

Novel ring structure for minimisation of screening effect in carbon nanotube based field emitters

Carbon Nanotubes (CNTs) are promising candidates for cold cathodes because of their high aspect ratio and robustness. However, the major hindrance in cold cathode based applications is the screening effect, which reduces the effective field at the tip and thereby the current density. The emission current can be improved by minimising the screening effect. The adverse effect of screening can be addressed by either controlling the growth density or by optimising the patterns of CNT cathodes. Here, novel patterns have been used to increase edge length per unit area in planar vertically aligned CNT bundles. Our motive was to increase the number of effective emitters, since the CNT at the edges are less screened by the proximal CNTs. By varying geometry and spacing of solid CNT dot patterns and by introducing the square ring structures; we could successfully enhance the effective emitters at the edges. It has been observed that an enhancement of edge length from 0.032 per micron to 0.2 per micron increases the current density from 0.71mA/cm² to 16.2 mA/cm² at a field of 4.5 V/μm. CNTs in dotted structure with high value of edge length per unit area emit very high current density as compared to other dotted structures with low value of edge length per unit area Simulation studies confirms our argument that CNTs at the corners are the least screened and have the maximum local electric field.     

CNTs增强Cr基复合电刷镀层的性能

以45号钢为基体,采用电刷镀制备了Cr-CNTs复合镀层。通过X射线衍射仪(XRD)、扫描电镜(SEM)、扫描电子显微镜附带能谱仪(EDS)等技术对镀层的晶粒尺寸,截面与表面形貌及CNTs在镀层表面的分布进行了表征。此外,利用显微硬度计、电化学工作站、磨损试验机等仪器对镀层的硬度、抗腐蚀性、耐磨性等进行了测试。研究结果表明:Cr-CNTs复合镀层组织致密无明显缺陷,CNTs弥散分布于镀层中,在胞状组织的交界处出现了富集;适量CNTs的加入在一定程度上细化了镀层的晶粒;在CNTs弥散强化和细晶强化等作用下,复合镀层的硬度提高了23.8%,腐蚀速率降低了49.2%,而且耐磨性能也得到了显著的改善。     

Fullerene C60 coated silicon nanowires as anode materials for lithium secondary batteries

A Fullerene C60 film was introduced as a coating layer for silicon nanowires (Si NWs) by a plasma assisted thermal evaporation technique. The morphology and structural characteristics of the materials were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM observations showed that the shape of the nanowire structure was maintained after the C60 coating and the XPS analysis confirmed the presence of the carbon coating layer. The electrochemical characteristics of C60 coated Si NWs as anode materials were examined by charge-discharge tests and electrochemical impedance measurements. With the C60 film coating, Si NW electrodes exhibited a higher initial coulombic efficiency of 77% and a higher specific capacity of 2020 mA h g(-1) after the 30th cycle at a current density of 100 microA cm(-2) with cut-off voltage between 0-1.5 V. These improved electrochemical characteristics are attributed to the presence of the C60 coating layer which suppresses side reaction with the electrolyte and maintains the structural integrity of the Si NW electrodes during cycle tests.