The role of poly(methacrylic acid) conformation on dispersion behavior of nano TiO2 powder

To exploit the advantages of nanoparticles for various applications, controlling the dispersion and agglomeration is of paramount importance. Agglomeration and dispersion behavior of titanium dioxide (TiO₂) nanoparticles was investigated using electrokinetic and surface chemical properties. Nanoparticles are generally stabilized by the adsorption of a dispersant (polyelectrolyte) layer around the particle surface and in this connection ammonium salt of polymethacrylic acid (Darvan C) was used as dispersant to stabilize the suspension. The dosages of polyelectrolyte were optimized to get best dispersion stability by techniques namely particle charge detector (13.75 mg/g) and adsorption (14.57 mg/g). The surface charge of TiO₂ particles changed significantly in presence of dispersant Darvan C and isoelectric point (iep) shifted significantly towards lower pH from 5.99 to 3.37. The shift in iep has been quantified in terms of free energy of interaction between the surface sites of TiO₂ and the adsorbing dispersant Darvan C. Free energies of adsorption were calculated by electrokinetic data (−9.8 RT unit) and adsorption isotherms (−10.56 RT unit), which corroborated well. The adsorption isotherms are of typical Langmuir type and employed for calculation of free energy. The results indicated that adsorption occurs mainly through electrostatic interactions between the dispersant molecule and the TiO₂ surface apart from hydrophobic interactions.     

FTIR，XPS和SEM研究聚羧酸盐分散剂在吡唑醚菌酯颗粒表面的吸附性能

采用傅里叶变换红外光谱、X射线光电子能谱和扫描电子显微镜相结合的方式，从微观角度研究梳状聚羧酸盐分散剂在吡唑醚菌酯颗粒表面的吸附性能，为聚羧酸盐分散剂在吡唑醚菌酯悬浮剂中的应用提供理论依据。研究结果表明：吡唑醚菌酯吸附聚羧酸盐分散剂后，红外谱图未出现新的吸收峰，聚羧酸盐分散剂与吡唑醚菌酯之间主要是物理吸附，范德华力是聚羧酸盐分散剂与吡唑醚菌酯颗粒表面结合的主要作用力。吡唑醚菌酯颗粒吸附聚羧酸盐分散剂后，吡唑醚菌酯颗粒界面的N和Cl电子峰强度减弱，C和O电子峰强度明显增强，还出现了Na的电子峰，这主要是聚羧酸盐分散剂中C，O和Na的贡献，说明聚羧酸盐分散剂在吡唑醚菌酯颗粒表面形成了良好的吸附。并以Cl元素为特征元素，计算出聚羧酸盐分散剂在吡唑醚菌酯颗粒表面的吸附层厚度约为1.22 nm。用扫描电子显微镜研究了样品的形貌，吸附聚羧酸盐分散剂后，原本光滑的吡唑醚菌酯颗粒表面吸附了很多细小的颗粒，且有序分布，这是由于分散剂疏水集团对吡唑醚菌酯颗粒形成了包覆，亲水基团充分外露，从而有效阻止吡唑醚菌酯颗粒间的团聚，提高了吡唑醚菌酯悬浮剂的物理稳定性。     

Adsorption of a semiflexible wormlike chain

Adsorption of ideal polymers with stiff backbone onto a flat surface is considered theoretically. Both scaling approach and quantitative theory are developed. We predict a self-similar monomer concentration profile c(x) ∼ x ^-4/3 near the surface (when the distance to the surface x is much smaller than the chain persistence length l /2). The typical conformation of a weakly adsorbed chain can be viewed as a sequence of alternating flat (2-dimensional) trains of wormlike short loops (flat blobs) and coil-like (3-dimensional) loops forming a triple-layer structure: contact layer (x < Δ) of adsorbed fragments virtually laid on the surface, proximal layer (Δ < x < l) of flat blobs, and more dilute distal corona layer (x > l). Here Δ defines the range of monomer/surface attraction, Δ ≪ l. The adsorption transition is continuous. However, its relative width is small (T ^* is the adsorption temperature, ΔT is the relevant temperature interval): ∼ , i.e. a discontinuous transition in the limit Δ/l↦ 0. Received 10 October 2002 and Received in final form 22 November 2002 RID="a" ID="a"Permanent address: Physics Department, Moscow State University, Moscow 119992, Russia. e-mail: semenov@polly.phys.msu.ru     

Electrodeposition of nickel/SiC composites in the presence of cetyltrimethylammonium bromide

Electrodeposition of SiC particles with nickel matrix in the presence of cetyltrimethylammonium bromide (CTAB) at two current densities was carried out. Surface chemistry (amount of acidic and basic superficial groups, surface charge, Ni²⁺ and Br⁻ adsorption) of the SiC powder in the presence of various CTAB amounts (0-1.1 mM) was studied. Cationic surfactant inhibited adsorption of cations and enhanced adsorption of anions on the positive charged carbide surface, but Br⁻/Ni²⁺ molar ratios for adsorbed ions were higher than in the bath. It was attributed to the CTAB adsorption realized predominantly by hydrophobic interactions between aliphatic chain of the molecule and SiC surface with the positive head group of CTA⁺ pointed toward the bulk solution. Increased SiC incorporation to the composite coating with CTAB addition was observed. Correlation between current efficiency and Br⁻/Ni²⁺ molar ratios for ions adsorbed on SiC was found. The influence of CTAB concentration on the cathodic polarization curves was also determined. Structure of the composite coatings was studied by microscopic observations. Microhardness of the fine-grained metal matrix composites was also determined.     

SMA-g-MPEG comb-like polymer as a dispersant for Al2O3 suspensions

SMA-g-MPEG comb-like polymer is first employed as the dispersant of Al₂O₃ suspensions in this paper. The comb-like polymer has anionic polycarboxylate backbone, which makes the polymer easily absorbed on the cationic surface of Al₂O₃ particles; on the other hand, the comb-like polymer has hydrophilic MPEG side chains, which extend into the solution to provide steric repulsion after the comb-like polymer is absorbed on the surface of Al₂O₃ particles. The adsorption behavior, zeta potential, apparent viscosity, granularity and TEM images of the Al₂O₃ suspensions using SMA-g-MPEG as dispersant are investigated. The addition of SMA-g-MPEG improves the dispersibility and decreases the apparent viscosity of the Al₂O₃ suspension observably. The impacts of the length of side chains on the dispersion of Al₂O₃ suspensions are particularly discussed. The adsorbed molecular number of the dispersant decreased by increasing the length of side chains. The zeta potential of Al₂O₃ suspension is more negative by using comb-like polymer with shorter side chains. Based on the steric repulsion and adsorbed molecular number, SMA-g-MPEG with moderate length of side chain is found to have the best dispersibility for Al₂O₃ suspension.     

EPR Equilibration Study of the O–H Bond Dissociation Enthalpy in a Benzyl Phenolic Antioxidant

The equilibrium of the reaction galvinoxyl radical + 4,4′-methylene-bis(2,6-di-tert-butyl-phenol) (IOH) ⇆ hydrogalvinoxyl + 4,4′-methylene-bis(2,6-di-tert-butyl-phenoxyl radical) was monitored by electron paramagnetic resonance spectroscopy between 213 and 293 K. The equilibrium constant was calculated for each temperature point and correlated to T ⁻¹ applying the Van't Hoff relationship lnK _R = (−ΔH _R ⁰/RT) + (ΔS _R ⁰/R). The reaction enthalpy was found to be 12.0 ± 0.9 kJ/mol and the bond strength in IOH (BDE_(O–H)) = 340.7 ± 3.0 kJ/mol. The thermochemical stabilization of the involved phenoxyls is discussed. Authors' address: Sara N. Mendiara, Departamento de Química, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Funes 3350, Mar del Plata 7600, Argentina     

Josephson and single-particle currents between partially dielectricized superconductors with charge-density waves

The amplitudes of the nonstationary Josephson current I ¹, the interference current I ², and the quasiparticle current J through symmetric and asymmetric tunnel junctions, including superconductors with charge density waves, are calculated. In the symmetric (s) case the dependence of the Josephson current I _s ¹ on the voltage V on the junction has a logarithmic singularity at |eV|=2Δ, Δ+D, and 2D, where , Δ and Σ are the superconducting and dielectric order parameters, and e is the unit charge. At temperatures T≠0 jumps appear in the current-voltage characteristics I _s ¹ (V) at |eV|=D−Δ. Jumps and singularities are observed in the currents I _s ² and J _s at the same voltages at which singularities and jumps appear in I _s ¹ , respectively. In the nonsymmetric (ns) junctions which include an ordinary superconductor, singularities and jumps occur at |eV|=D+Δ_BCS, Δ+Δ_BCS, and (for T≠0) |D−Δ_BCS| and |Δ−Δ_BCS|, where Δ_BCS is the order parameter of an ordinary superconductor. The quasiparticle current J _ns is an asymmetric function of the voltage V and does not depend on the sign of Σ. The results are compared with experiment. Fiz. Tverd. Tela (St. Petersburg) 39, 991–999 (June 1997)     

Mechanism of catalytic reduction of NO by H2 or CO on a Pd foil; Role of chemisorbed nitrogen on Pd

The adsorption of NO and its reaction with H₂ over polycrystalline Pd were investigated using flash desorption technique and ultraviolet photoelectron spectroscopy under 10^?5 Pa pressure range of reactants and surface temperatures between 300 and 900 K. NO was adsorbed dissociatively onto the Pd surface above 500 K, and the heat of dissociative adsorption was ca. 126 kJ/mol. Atomic nitrogen was observed to accumulate on the Pd surface during the NO-H₂ reaction, whose desorption rate exhibited second order kinetics and is expressed as follows: V_d = 10^{?9.8 ± 0.3}exp(?67(kJ/mol)/RT) (cm²/atom·s). Hydrogenation of the adsorbed nitrogen proceeded rapidly at 485 K. It was confirmed from these results that formation of N₂ and NH₃ in the NO-H₂ reaction proceeds through this atomically adsorbed nitrogen. Pd-N bond energy and enthalpies of some intermediate states of the NO-H₂ reaction were estimated.     

Use of surface acoustic waves for analysis of gases and surface processes induced by them

An analytical expression for the magnitude of the “response” of surface acoustic waves (SAWs) to gases is obtained. It is tested experimentally. The main features of the detection of gases by means of SAWs are predicted theoretically and confirmed experimentally. The SAWs in coated and uncoated gas sensors are compared. A technique for using SAWs to determine the relative changes in the density (Δρ/ρ) and the elastic moduli (ΔC ₁₁/C ₁₁ and ΔC ₄₄/C ₄₄) of films upon the adsorption (desorption) of gases is proposed. The possibility of using this technique to analyze adsorption and desorption processes is demonstrated. The adsorption properties of polycrystalline, thermally deposited palladium films before and after low-temperature vacuum annealing, as well as unannealed Pd and Pd:Ni films, are compared. The prospects of using SAWs to detect gases and to study surface processes induced by them are discussed. Zh. Tekh. Fiz. 68, 73–81 (February 1998)     

Charge density waves in partially dielectrized <Emphasis Type="Italic">d</Emphasis>-pairing superconductors

A self-consistent theory has been constructed for describing a superconductor with a d _x ²−y ² charge density wave caused by the appearance of a dielectric gap in antinodal sections of the two-dimensional Fermi surface. The theory explains some key features of high-temperature oxides. In particular, it has been shown that the observed large values of the ratio 2Δ(T = 0)/T _c are associated with the stronger suppression of the critical temperature T _c of the superconducting transition rather than the superconducting gap Δ at low temperatures T under the action of charge density waves. It has been predicted that there can exist two critical temperatures of the appearance and disappearance of the dielectric order parameter Σ(T) in a specific range of bare parameters of the model.     

Adsorption effect in non-reaction wetting: In–Ti on CaF2

The experiments show that the alloying liquid In with only (0.1–0.5) at% Ti dramatically reduces the equilibrium contact angle Θ _∞ formed by In on the surface of CaF₂. The aim of this paper is to clarify whether this practically important and conceptually challenging effect can be explained solely by Ti adsorption at the F-terminated solid–liquid interface without resorting to any other Ti-induced effect. The combination of ab initio calculations and regular solution approximation was proposed for finding the binding energy, ΔE _Ti of Ti adatom with the interface “CaF₂/liquid solutions In–Ti.” With thus obtained ΔE _Ti=1.16 eV, we calculated from the Shishkovsky isotherm the reduction in the solid–liquid interface energy, Δγ _SL induced by Ti adsorption from liquid In with various Ti concentration, C. It was found that Δγ _SL(C) dependence demonstrated close inverse correspondence with Θ _∞(C) and that the theory fitted very well all available experimental data on the concentration and temperature dependence of Δγ _SL. It was concluded that the Ti adsorption effect is large enough to account for the observed wetting improvement. The proposed multiscale modeling approach to the role of adsorption in wetting can be applied also to other nonreactive systems “liquid metal–ceramics” where the substrate determines the surface density of the adsorption sites for the active element.     

N-doped graphene as a nanostructure adsorbent for carbon monoxide: DFT calculations

ABSTRACT

This work reports the physisorption of carbon monoxide (CO) on the surface of N-doped graphene. To study the adsorption of CO on N-doped graphene, some quantum chemical calculations were used through density functional theory. Based on our results, it can be found that the CO molecule could be adsorbed on the surface of N-doped graphene physically with the adsorption energies (E_ads) of ?2.9 and ?0.8 kcal mol^?1 (depends on the kind of configuration) while positive adsorption energies were calculated upon adsorption of CO on pristine graphene. We used the charge analysis for calculation of the net transferred charge of adsorbed CO on pristine and N-doped graphene sheets to evaluate the sensing ability of surface. The global indices of reactivity were calculated from the differences of the lowest unoccupied molecular orbital and highest occupied molecular orbital energies. Graphs for density of states point to some orbital hybridisation between CO molecule and N-doped graphene. Consequently, the N-doped graphene transforms the existence of CO molecules into electrical signal, and it may be potentially used as a sensor for CO.     

Lysine adsorption on the silanized SiO2-surface for immobilization of the estrogen receptor hERα

We investigated the adsorption of the l-lysine (200 mmol) molecule to a silanized SiO₂ surface as a function of the pH value. The SSC (Spraying Spin Coating) method [Cherkouk et al., J. Colloid Interf. Sci. 337 (2009) 375-380] was applied to functionalize the SiO₂ surface by using the (3-aminopropyl)trimethoxysilane (APMS) as coupling agent with a NH₂ functional group. We adsorbed lysine molecules to the silane film for pH-values of 2.5, 7.5, 8.7, 9.5 and 13, which correspond to the di-cationic, cationic, zwitterinonic (pH 8.7 and 9.5) and the anionic charge state of lysine, respectively. The infrared spectroscopy is not suitable to investigate the system because the NH³⁺ signal at 1600 cm⁻¹ originating from the silane film overlaps with the infrared signal of the deprotonated carboxyl group of the lysine molecule. X-ray photoelectron spectroscopy (XPS) was used to measure the binding energies C 1s and N 1s as function of the pH value. This pH change affects the charge state which was fitted in the XPS spectra to obtain the optimal adsorption conditions at pH 7.5 of the lysine to the functionalized SiO₂ surface.     

Luminescence detection of multiphoton ionization-fragmentation of the molecular CrO 4 2− anions adsorbed on the surface of dispersed SiO2

It is shown that luminescence detection of multiphoton ionization-fragmentation of the molecular CrO ₄ ²⁻ anions adsorbed on the surface of dispersed SiO₂ is possible under excitation with the fundamental frequency of a Nd:YAG pulsed laser (λ=1.064 μm). The structure and the process of formation of the adsorbed complexes under thermal activation of the surface and the nature of luminescence transitions in CrO ₄ ²⁻ anions are studied in detail. It is shown that luminescence is excited as a result of the recombination of photoelectrons and ionized chromate ions. Multiphoton ionization of the ions occurs under three-photon resonance conditions. The resonance level is an antibonding state of the adsorption complex formed with the participation of an oxygen vacancy on the SiO₂ surface. The dynamics of the multiphoton luminescence excitation process includes autoionization (stimulated by intercomplex electronic excitation) in superexcited states, fragmentation of chromate anions, and annealing of surface oxygen vacancies. The rate equations for three-photon-resonance multiphoton ionization are studied. The cross sections for two-and one-photon transitions on the nonresonance steps of multiphoton absorption are obtained. It is concluded that the nonlinear polarizability of the donor-acceptor adsorption bond in “chromate anion-oxygen vacancy” complexes is very important. Zh. éksp. Teor. Fiz. 111, 1748–1774 (May 1997)     

Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

Infrared (IR) spectroscopy of chemisorbed C₆₀ on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm^-1 per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C₆₀/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules. Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C₆₀ molecules, which results in rather small values (∼2×10⁹ s^-1 for Ag and Au, and ∼1.6×10⁹ s^-1for Cu), consistent with a marked metallic character of the adsorbed molecules. Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C₆₀ deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron–phonon coupling with induced surface states. Received: 6 June 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002     

Monitoring of the Proton Electrochemical Gradient in Reconstituted Vesicles: Quantitative Measurements of Both Transmembrane Potential and Intravesicular pH by Ratiometric Fluorescent Probes

Proteoliposomes carrying reconstituted yeast plasma membrane H⁺-ATPase in their lipid membrane or plasma membrane vesicles are model systems convenient for studying basic electrochemical processes involved in formation of the proton electrochemical gradient (Δμ_H ⁺) across the microbial or plant cell membrane. Δψ- and pH-sensitive fluorescent probes were used to monitor the gradients formed between inner and outer volume of the reconstituted vesicles. The Δψ-sensitive fluorescent ratiometric probe oxonol VI is suitable for quantitative measurements of inside-positive Δψ generated by the reconstituted H⁺-ATPase. Its Δψ response can be calibrated by the K⁺/valinomycin method and ratiometric mode of fluorescence measurements reduces undesirable artefacts. In situ pH-sensitive fluorescent probe pyranine was used for quantitative measurements of pH inside the proteoliposomes. Calibration of pH-sensitive fluorescence response of pyranine entrapped inside proteoliposomes was performed with several ionophores combined in order to deplete the gradients passively formed across the membrane. Presented model system offers a suitable tool for simultaneous monitoring of both components of the proton electrochemical gradient, Δψ and ΔpH. This approach should help in further understanding how their formation is interconnected on biomembranes and even how transport of other ions is combined to it.     

密度泛函理论研究Hg与Auqn(n=1—6, q=0,+1,-1) 团簇的相互作用

采用密度泛函理论中的广义梯度近似对Hg与小团簇Au ^q_n (n=1—6, q=0, +1, -1)的相互作用进行了系统研究. 结果表明,除Au₅^+,-团簇外,前线分子轨道理论可以成功预测大部分Au _n Hg ^q 复合物的最低能量结构. Au_n团簇对Hg的吸附受团簇尺寸大小和团簇所携带电荷的影 关键词： 密度泛函理论 汞 金团簇 吸附能     

Role of pH and calcium ions in the adsorption of an alkyl N-aminodimethylphosphonate on steel: An XPS study

The role of pH and calcium ions in the adsorption of an alkyl N-aminodimethylphosphonate on mild steel (E24) surfaces was investigated by XPS. Fe 2p_3/2 and O 1s spectra show that the oxide/hydroxide layer developed on the steel surface, immersed in the diphosphonate solution (7 ≤ pH ≤ 13, without Ca²⁺) or in a filtered cement solution (pH 13, 15.38 mmol l⁻¹ of Ca²⁺), consists of Fe₂O₃, covered by a very thin layer of FeOOH (goethite). The total thickness of the oxide/hydroxide layer is ∼3 nm and is independent of the pH and the presence/absence of Ca²⁺. In the absence of Ca²⁺ ions, the N 1s and P 2p spectra reveal that the adsorption of the diphosphonate on the outer layer of FeOOH takes place only for pH lower than the zero charge pH of goethite (7.55). At pH 7, the adsorbed diphosphonate layer is continuous and its equivalent thickness is ∼24 Å (monolayer). In the presence of Ca²⁺ ions, the C 1s and Ca 2p signals indicate that calcium is present on the steel surface as calcium phosphonate (and Ca(OH)₂, in very small amount). The adsorption of the diphosphonate molecules on the steel surface is promoted in alkaline solution (pH > 7.55) by the doubly charged Ca²⁺ ions that bridge the O⁻ of goethite and the P-O⁻ groups of the diphosphonate molecules. The measured values for the Ca/P intensity ratio are in the range 0.75-1, which suggests that the diphosphonate molecules are adsorbed on steel forming a polymer cross-linked by calcium ions through their phosphono groups. In the presence of Ca²⁺ ions in alkaline solution, the adsorbed diphosphonate layer is discontinuous and the surface coverage is found to be ∼34%.     

Study on Adsorption States by Surface-Enhanced Raman Spectroscopy

Abstract

SERS has been used as a state-resolving probe to study the adsorption states. in the case of pyridine (Py) adsorbed on the Ag electrode surface, the equilibrium and transition between two adsorbed states, i.e., the perpendicular mode adsorbed through the nitrogen lone-pair electrons and the flat mode through the π electrons of the aromatic ring, were studied. It was found that in the low pyridine concentration or the initial stage of adsorption, the flat mode was favored. While the concentration became higher and the adsorption tended to equilibrium, the adsorbed molecules would transit to the perpendicular mode. The similar phenomenon was also observed when changing the applied electric potential and the pH value of the solution. In the case of the adsorption of Methylene Blue (MB) on the HNO₃-etched silver surface, the influence of Cl^? ions on the adsorption states of MB was investigated. It showed that MB molecules adsorbed on the silver surface tended to transform from the “lying-down” state to the “end-on” state while adding Cl^? ions.     

Confrontation of nucleus deformation and multipole mixture parameters in (2+0 n ?2+01) transitions with rotational band structure for K π = 0 2+ and 0 3+

The difference of the energies of levels Δ _n = E _lev(2⁺0 _n ) − E _lev(0⁺0 _n ) at n = 1, 2, and 3 and the multipole-mixture parameter δ for (2⁺0₂−2⁺0₁) and (2⁺0₃−2⁺0₁) transitions are contrasted against the structure of the K ^π = 0₂⁺ and 0₃⁺ rotational bands that was calculated on the basis of the quasiparticle-phonon model. The values of (Δ₂ − Δ₁), (Δ₃ − Δ₁), and (Δ₂ − Δ₃) are found to correlate with the sign of the parameter δ and with the calculated structure of the K ^π = 0₂⁺ and 0₃⁺ bands. Original Russian Text ? A.M. Demidov, L.I. Govor, V.A. Kurkin, I.V. Mikhailov, 2009, published in Yadernaya Fizika, 2009, Vol. 72, No. 2, pp. 236–240.