Manipulating the surface properties of polyacrylamide with nitrogen plasma

Polyacrylamide (PAL) was physically adsorbed onto a hydroxylated silicon surface to form a uniform PAL film and the up-top PAL thin film was treated by nitrogen (N₂) plasma for surface modification. The atomic composition of the modified surface of the PAL film adsorbed on silicon substrate was analyzed with Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The surface energy of PAL film was calculated from the data of contact angle of three-probe liquid. The FTIR results show an increase of peak intensity at 1214 cm⁻¹ (NH₂ stretch vibration) after the nitrogen plasma treatment, which confirms that the nitrogen was grafted to the PAL surface in the process of N₂-plasma treatment. The XPS results show that the ratio of relative intensity of N1s to O1s increases with increasing the plasma treatment time, which further affirms the formation of the amine groups on the PAL surface after the nitrogen plasma treatment. The surface tension increases with increasing the plasma grafting time. However, the surface energy decreases rapidly at the early stage when stored in air and approaches to an equilibrium value. It suggests that some physically-adsorbed ions and alkyl radicals on PAL surface can rapidly lose their activities. The increase of the surface tension of the plasma treated PLA films is due to the amine groups covalently grafted to PAL surface.     

Growth of Anodic Films on Compound Semiconductor Electrodes: InP in Aqueous (NH4)2S

 Film formation on compound semiconductors under anodic conditions is discussed. The surface properties of InP electrodes were examined following anodization in an (NH₄)₂S electrolyte. The observation of a current peak in the cyclic voltammetric curve was attributed to selective etching of the substrate and a film formation process. AFM images of samples anodized in the sulfide solution revealed surface pitting. Thicker films formed at higher potentials exhibited extensive cracking as observed by optical and electron microscopy, and this was explicitly demonstrated to occur ex situ rather than during the electrochemical treatment. The composition of the thick film was identified as In₂S₃ by EDX and XPS. The measured film thickness varies linearly with the charge passed, and comparison between experimental thickness measurements and theoretical estimates for the thickness indicate a porosity of over 70%. Cracking is attributed to shrinkage during drying of the highly porous film and does not necessarily imply stress in the wet film as grown. During the growth of the thick porous film, spontaneous current oscillations have been observed. The frequency of oscillation was found to be proportional to the current density, regardless of whether the measurements were carried out during a potential sweep or at constant potential. Thus, the charge passed per oscillation remained constant. A characteristic value of approximately 0.3 C · cm⁻² was measured under potential sweep conditions, and a similar value was obtained at constant potential.     

Ultrathin CuF2-Rich Solid-Electrolyte Interphase Induced by Cation-Tailored Double Electrical Layer toward Durable Sodium Storage

Solid-electrolyte interphase (SEI) seriously affects battery's cycling life, especially for high-capacity anode due to excessive electrolyte decomposition from particle fracture. Herein, we report an ultrathin SEI (3–4 nm) induced by Cu⁺-tailored double electrical layer (EDL) to suppress electrolyte consumption and enhance cycling stability of CuS anode in sodium-ion batteries. Unique EDL with SO₃CF₃-Cu complex absorbing on CuS in NaSO₃CF₃/diglyme electrolyte is demonstrated by in situ surface-enhanced Raman, Cyro-TEM and theoretical calculation, in which SO₃CF₃-Cu could be reduced to CuF₂-rich SEI. Dispersed CuF₂ and F-containing compound can provide good interfacial contact for formation of ultrathin and stable SEI film to minimize electrolyte consumption and reduce activation energy of Na⁺ transport. As a result, the modified CuS delivers high capacity of 402.8 mAh g⁻¹ after 7000 cycles without capacity decay. The insights of SEI construction pave a way for high-stability electrode.     

Growth of Anodic Films on Compound Semiconductor Electrodes: InP in Aqueous (NH4)2S

Summary.  Film formation on compound semiconductors under anodic conditions is discussed. The surface properties of InP electrodes were examined following anodization in an (NH₄)₂S electrolyte. The observation of a current peak in the cyclic voltammetric curve was attributed to selective etching of the substrate and a film formation process. AFM images of samples anodized in the sulfide solution revealed surface pitting. Thicker films formed at higher potentials exhibited extensive cracking as observed by optical and electron microscopy, and this was explicitly demonstrated to occur ex situ rather than during the electrochemical treatment. The composition of the thick film was identified as In₂S₃ by EDX and XPS. The measured film thickness varies linearly with the charge passed, and comparison between experimental thickness measurements and theoretical estimates for the thickness indicate a porosity of over 70%. Cracking is attributed to shrinkage during drying of the highly porous film and does not necessarily imply stress in the wet film as grown. During the growth of the thick porous film, spontaneous current oscillations have been observed. The frequency of oscillation was found to be proportional to the current density, regardless of whether the measurements were carried out during a potential sweep or at constant potential. Thus, the charge passed per oscillation remained constant. A characteristic value of approximately 0.3 C · cm⁻² was measured under potential sweep conditions, and a similar value was obtained at constant potential. Received October 16, 2001. Accepted (revised) December 21, 2001     

Surface characterization of plasma‐modified poly(ethylene terephthalate) film surfaces

Poly(ethylene terephthalate) (PET) film surfaces were modified by argon (Ar), oxygen (O₂), hydrogen (H₂), nitrogen (N₂), and ammonia (NH₃) plasmas, and the plasma‐modified PET surfaces were investigated with scanning probe microscopy, contact‐angle measurements, and X‐ray photoelectron spectroscopy to characterize the surfaces. The exposure of the PET film surfaces to the plasmas led to the etching process on the surfaces and to changes in the topography of the surfaces. The etching rate and surface roughness were closely related to what kind of plasma was used and how high the radio frequency (RF) power was that was input into the plasmas. The etching rate was in the order of O₂ plasma > H₂ plasma > N₂ plasma > Ar plasma > NH₃ plasma, and the surface roughness was in the order of NH₃ plasma > N₂ plasma > H₂ plasma > Ar plasma > O₂ plasma. Heavy etching reactions did not always lead to large increases in the surface roughness. The plasmas also led to changes in the surface properties of the PET surfaces from hydrophobic to hydrophilic; and the contact angle of water on the surfaces decreased. Modification reactions occurring on the PET surfaces depended on what plasma had been used for the modification. The O₂, Ar, H₂, and N₂ plasmas modified mainly CH₂ or phenyl rings rather than ester groups in the PET polymer chains to form C? O groups. On the other hand, the NH₃ plasma modified ester groups to form C? O groups. Aging effects of the plasma‐modified PET film surfaces continued as long as 15 days after the modification was finished. The aging effects were related to the movement of C?O groups in ester residues toward the topmost layer and to the movement of C? O groups away from the topmost layer. Such movement of the C?O groups could occur within at least 3 nm from the surface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3727–3740, 2004     

Surface characteristics of AZ91D alloy anodized with various conditions

Anodic oxidation of an AZ91D magnesium alloy was carried out in an attempt to increase the corrosion resistance. The alloy was placed in an electrolyte containing 0.1 M sodium silicate (Na₂SiO₃), 2.0 M sodium hydroxide (NaOH) and 0.1 M sodium phosphate (Na₃PO₄), and treated with a current density of 100–400 mA/cm² for 1 to 4 min. After the anodic oxidation treatment, the surface characteristics were analyzed by SEM, X‐ray diffraction (XRD) and a surface roughness tester. The corrosion resistance was determined by measuring the corrosion potential and corrosion current density using potentiodynamic polarization in a 3.5 wt% NaCl electrolyte solution. Although the anodic oxidation treatment with the base electrolyte resulted in an arrival voltage ranging from 60 to 70 V, the addition of silicate tended to reduce this arrival voltage by approximately 10–20 V and decrease the critical voltage required for the formation of a porous oxide film. The pore size and film thickness increased with increasing applied current and treatment time. The addition of silicate to the electrolyte resulted in films with a homogeneous pore size and a film thickness increasing with the increasing applied current and treatment time. XRD showed the formation of a new MgO and Mg₂SiO₄ phase. The formation of Mg₂SiO₄ was attributed to the presence of SiO₄^4? in the film. After the addition of silicate, the corrosion potential increased and corrosion current decreased, resulting in improved corrosion resistance. Copyright © 2008 John Wiley & Sons, Ltd.     

Quartz crystal microbalance monitoring of density changes in mesoporous TiO2 phytate films during redox and ion exchange processes

Nanofilm deposits of TiO₂ nanoparticle phytates are formed on gold electrode surfaces by ‘directed assembly’ methods. Alternate exposure of a 3-mercapto-propionic acid modified gold surface to (i) a TiO₂ sol and (ii) an aqueous phytic acid solution (pH 3) results in layer-by-layer formation of a mesoporous film. Ru(NH₃)₆³⁺ is shown to strongly adsorb/accumulate into the mesoporous structure whilst remaining electrochemically active. Scanning the electrode potential into a sufficiently negative potential range allows the Ru(NH₃)₆³⁺ complex to be reduced to Ru(NH₃)₆²⁺ which undergoes immediate desorption. When applied to a gold coated quartz crystal microbalance (QCM) sensor, electrochemically driven adsorption and desorption processes in the mesoporous structure become directly detectable as a frequency response, which corresponds directly to a mass or density change in the membrane. The frequency response (at least for thin films) is proportional to the thickness of the mass-responsive film, which suggests good mechanical coupling between electrode and film. Based on this observation, a method for the amplified QCM detection of small mass/density changes is proposed by conducting measurements in rigid mesoporous structures.     

Introduction of Primary Amino Groups on Poly(ethylene terephthalate) Surfaces by Ammonia and a Mix of Nitrogen and Hydrogen Plasma

With the aim of introducing primary amino groups on the surface of poly(ethylene terephthalate) (PET), two methods were compared—the use of ammonia or a combination of nitrogen and hydrogen low-pressure microwave plasma. Several plasma parameters were optimized on the reactor to increase the –NH₂ surface density, which was estimated by colorimetric titration and X-ray photoelectron spectroscopy (XPS). These techniques show that whatever the plasma treatment, almost 2 –NH₂/nm2 are incorporated on PET films. Emission spectroscopy highlighted a correlation between the density of primary amino groups and the ratio between an NH peak intensity and an Ar peak intensity (I_NH/I_Ar). Variation in surface hydrophilicity with aging in air after plasma treatment was monitored with contact angle measurements and showed a hydrophobic recovery. This was confirmed by XPS, which suggests also that surfaces treated by NH₃ plasma are more stable than surfaces treated by N₂/H₂.     

Preparation of Silica Microspheres Containing Ag Nanoparticles

Two sol-gel fabrication processes were investigated to make silica spheres containing Ag nanoparticles: (1) a modified Stöber method for silica spheres below 1 m size, and (2) a SiO₂-film formation method on spheres of 3–;7 m size. The spheres were designed to incorporate silver nanoparticles of high ⁽³⁾ in a spherical optical cavity structure for the resonance effect. For the incorporation, interaction between [Ag(NH₃)₂]⁺ ion and Si-OH was important. In the Stöber method, the size of the silica spheres was determined by a charge balance of plus and minus ions on the silica surface. In the film formation method, the capture of Ag complex ion on the silica surface depended on whether the surface was covered with OH groups or not. After doping [Ag(NH₃)₂]⁺ into silica particles or SiO₂ films on the spheres, these ions w ere reduced by NaBH₄ to form silver nanoparticles. From plasma absorption at around 420 nm wavelength and TEM photographs of nanometer-sized silver particles, their formation inside the spherical cavity structures was confirmed.     

Isoelectric points of plasma‐modified and aged silicon oxynitride surfaces measured using contact angle titrations

Acid‐base properties of metal oxides and polymers can control adhesion properties between materials, electrical properties, the physical structure of the material and gas adsorption behavior. To determine the relationships between surface isoelectric point, chemical composition and aging effects, plasma‐surface treatment of amorphous silicon oxynitride (SiO_xN_y) substrates was explored using Ar, H₂O vapor, and NH₃ inductively coupled rf plasmas. Overall, the Ar plasma treatment resulted in nonpermanent changes to the surface properties, whereas the H₂O and NH₃ plasmas introduced permanent chemical changes to the SiO_xN_y surfaces. In particular, the H₂O plasma treatments resulted in formation of a more ordered SiO₂ surface, whereas the NH₃ plasma created a nitrogen‐rich surface. The trends in isoelectric point and chemical changes upon aging for one month suggest that contact angle and composition are closely related, whereas the relationship between IEP and composition is not as directly correlated. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of current densities on the formation of LiCoO<Subscript>2</Subscript>/graphite lithium ion battery

The activation characteristics and the effects of current densities on the formation of a separate LiCoO₂ and graphite electrode were investigated and the behavior also was compared with that of the full LiCoO₂/graphite batteries using various electrochemical techniques. The results showed that the formation current densities obviously influenced the electrochemical impedance spectrum of Li/graphite, LiCoO₂/Li, and LiCoO₂/graphite cells. The electrolyte was reduced on the surface of graphite anode between 2.5 and 3.6 V to form a preliminary solid electrolyte interphase (SEI) film of anode during the formation of the LiCoO₂/graphite batteries. The electrolyte was oxidized from 3.95 V vs Li⁺/Li on the surface of LiCoO₂ to form a SEI film of cathode. A highly conducting SEI film could be formed gradually on the surface of graphite anode, whereas the SEI film of LiCoO₂ cathode had high resistance. The LiCoO₂ cathode could be activated completely at the first cycle, while the activation of the graphite anode needed several cycles. The columbic efficiency of the first cycle increased, but that of the second decreased with the increase in the formation current of LiCoO₂/graphite batteries. The formation current influenced the cycling performance of batteries, especially the high-temperature cycling performance. Therefore, the batteries should be activated with proper current densities to ensure an excellent formation of SEI film on the anode surface.     

Preparation, characterization, and application of electrodes modified with electropolymerized one-dimensional Magnus' green salts: Pt(NH3)4 · PtCl4 and Pt(NH3)4 · PtCl6

We report the modification of various electrode surfaces with electropolymerized Magnus' green salts, [Pt(NH₃)₄ · PtCl₄] _n and [Pt(NH₃)₄ · PtCl₆] _n . The modified electrodes were prepared by cyclic scanning of the electrode potential in an aqueous solution containing Pt(NH₃)₄ ²⁺ and PtCl₄ ²⁻ or PtCl₆ ²⁻ and the supporting electrolyte. The conditions for the film deposition were studied in detail. Several surface analytical techniques, including micro-Raman scattering and X-ray diffraction, were employed to characterize the modifier film. The electrochemical behavior of the modified electrode was studied in detail and the modified electrodes display very good electrocatalytic activity in the oxidation of ascorbic acid, hydrogen peroxide, thiosulfate, and especially nitric oxide. Received: 22 April 1999 / Accepted: 30 June 1999     

Investigation of the Ionic Conduction Mechanism in Carboxymethyl Cellulose/Chitosan Biopolymer Blend Electrolyte Impregnated with Ammonium Nitrate

In the present work, an attempt has been made to prepare a new natural biopolymer blend electrolyte of carboxymethyl cellulose/chitosan impregnated with NH₄NO₃ by the solution casting technique. The conductivity for the system was measured by impedance spectroscopy. The incorporation of 40 wt.% NH₄NO₃ optimized the ambient temperature conductivity of the electrolyte up to 1.03 × 10^?5 S cm^?1. All electrolytes were found to follow the Arrhenius relationship. Dielectric studies confirmed that the electrolytes obey non-Debye behavior. The temperature dependence of the power law exponent s for the highest conducting film can be represented by the correlated barrier hopping model.     

Surface Synergistic Protections on Red Phosphorus Anode Material by Poly(3, 4-ethylenedioxythiophene) Coating and Electrolyte Strategy in Sodium Ion Batteries

Red phosphorus has attracted more attention as a promising sodium storage material due to its ultra-high theoretical capacity and suitable sodiation potential. However, the low intrinsic electrical conductivity and large volume change of pristine red phosphorus lead to high polarization and fast capacity fading during cycling. Herein, surface synergistic protections on red phosphorus composite are successfully proposed by conductive poly(3, 4-ethylenedioxythiophene) (PEDOT) coating and electrolyte strategy. Nanoscale red phosphorus is confined in porous carbon skeleton and the outside is packaged by PEDOT coating via in-situ polymerization. Porous carbon provides rich pathways for rapid Na⁺ diffusion and empty spaces accommodate the volume expansion of red phosphorus, PEDOT coating isolates the direct contact between electrolyte and active materials to form a stable solid electrolyte interphase. In addition, the reformulated electrolyte with 3 wt% SbF₃ additives can stabilize the electrode surface and thus enhance the electrochemical performance, especially cycling stability and rate capability (433 mA·h·g^-1 at high current density of 10 A/g).     

Effect of fluoride and hydroxyl group on bioactivity of the anodized films prepared by two-step anodization at low current density

Titanium and its alloys are promising dental implant materials. In order to improve the bioactivity of the anodized films, the two-step anodization was performed to produce the films. The steps were performed at 0.2 mA/cm² for 30 min in electrolytes containing H₃PO₄/C₂H₅OH and H₃PO₄/C₂H₅OH/NH₄F, respectively. The anodized films were soaked in a simulated body fluid (SBF). The effects of surface roughness, hydroxyl groups, fluoride, and hydrophilicity groups on the bioactivity were investigated and were found on the anodized films formed under two-step anodization using 1 M H₃PO₄ + 80% V/V C₂H₅OH + 0.75 wt% NH₄F. The bioactivity evaluation showed that the combination of two-step anodization in NH₄F as an electrolyte induced a formation of apatite on the anodized films. The surface roughness, hydroxyl groups, and fluoride formed on the hydrophilic anodized films are found to be responsible for the rapid formation of hydroxyapatite during SBF soaking. This will be useful in various biomedical applications especially in dental implant procedures.     

Wetting films on a hydrophilic silica surface obtained from aqueous solutions of hydrophobically modified inulin polymeric surfactant

The thickness of wetting films on a hydrophilic silica surface was investigated using a microinterferometric technique. Aqueous solutions of hydrophobically modified inulin (INUTEC^®SP1) at various concentrations, in the presence or absence of NaCl or Na₂SO₄, were studied. The equilibrium film thickness (h _eq) showed a complex dependence on INUTEC^®SP1 concentration. At low electrolyte concentrations, h _eq decreased with an increase in INUTEC^®SP1 concentration, reaching a minimum at 10^?6 mol dm^?3. However, at high electrolyte concentrations, this dependence became less pronounced. At any given INUTEC^®SP1 concentration, the equilibrium film thickness decreased with an increase in electrolyte concentration as a result of the compression of the electrical double layer reaching a minimum value. After that, the film thickness showed a small decrease with further increase in electrolyte concentration. This indicates that the electrostatic component of disjoining pressure can be neglected, and the steric repulsion of the loops and tails of INUTEC^®SP1 determined the film thickness.     

Effect of water and fluoride content on morphology and barrier layer properties of TiO2 nanotubes grown in ethylene glycol-based electrolytes

This paper studies the effect of H₂O and NH₄F content on morphology and barrier layer properties of TiO₂ nanotubes grown by potentiostatic anodization in ethylene glycol-based electrolytes. The increase in these two variables leads to an increase in the chemical attack of the formed oxide. However, each of these variables plays a different role in the formation of TiO₂ nanotubes. On the one hand, a higher percentage of H₂O in the electrolyte leads to a transition from a nanoporous to a nanotubular structure, as well as to a greater diameter of the tubes and a decrease in their length and barrier layer thickness. In contrast, a higher NH₄F concentration decreases nanotube diameter and increases their length modifying barrier layer properties due to insertion of F^? ions into the lattice. This diminishes the barrier layer resistance, but increases both the adsorption and the diffusion coefficient of F^? ions. The different roles of H₂O and NH₄F in film formation are also associated with the presence of sub-oxides detected by XPS.     

Evaluating the electrochemical properties of PEO‐based nanofibrous electrolytes incorporated with TiO2 nanofiller applicable in lithium‐ion batteries

In the present work, nanofibrous composite polymer electrolytes consist of polyethylene oxide (PEO), ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate (LiClO₄), and titanium dioxide (TiO₂) were designed using response surface method (RSM) and synthesized via an electrospinning process. Morphological properties of the as‐prepared electrolytes were studied using SEM. FTIR spectroscopy was conducted to investigate the interaction between the components of the composites. The highest room temperature ionic conductivity of 0.085 mS.cm^?1 was obtained with incorporation of 0.175 wt. % TiO₂ filler into the plasticized nanofibrous electrolyte by EC. Moreover, the optimum structure was compared with a film polymeric electrolyte prepared using a film casting method. Despite more amorphous structure of the film electrolyte, the nanofibrous electrolyte showed superior ion conductivity possibly due to the highly porous structure of the nanofibrous membranes. Furthermore, the mechanical properties illustrated slight deterioration with incorporation of the TiO₂ nanoparticles into the electrospun electrolytes. This investigation indicated the great potential of the electrospun structures as all‐solid‐state polymeric electrolytes applicable in lithium ion batteries.     

Air-gap sulfide sensor with super-nernstian response in the low concentration range

An air-gap sulfide sensor is presented which operates on the basis of selective extraction of H₂S from an acidified sample into a small alkaline electrolyte film containing the dicyanoargentate (I) complex. This complex is partly decomposed during the measurement by the absorbed sulfide, and the potential of a silver sulfide-based indicator electrode which is in direct contact only with the electrolyte, then depends on the sulfide concentration of the sample. Because of the extraction and dissociation equilibria, the sensor responds in the low sulfide concentration range with a slope four times larger than that of a normal sulfide electrode. The lower limit of linearity is 10^?8 mol l^?1, because sulfide accumulates in the electrolyte film.     

Bi基化合物膜包覆ZnO的制备和电化学性能

为提高锌镍电池ZnO的循环充放电性能,采用Bi(NO3)3水解沉积法对ZnO包覆Bi基化合物膜,系统研究了包覆ZnO的微结构和电化学性能。TEM,XRD和EDS表明由Bi6(NO3)4(OH)2O6·2H2O,BiO和Bi2O3组成的Bi基化合物膜包覆在ZnO表面。表面包覆能提高ZnO的循环性能和放电容量,含5.1wt%Bi的包覆ZnO循环性能稳定,平均放电容量为509mAh·g-1,利用率为78%,性能有较大改善。充放电曲线和循环伏安结果均表明包覆Bi基化合物膜能降低锌镍电池的充电平台,加宽放电平台,提高ZnO的电化学活性。包覆Bi基化合物膜能有效减小活性材料与碱性电解液的接触,抑制ZnO的溶解,提高循环稳定性;而包覆膜的微孔结构又可使活性材料接触到电化学反应必须的H2O和OH-,保证了高的放电容量。