Graft copolymerization to cellulose. Effect of sodium thiosulfate on hydrogen peroxide initiator system

The effect of sodium thiosulfate on the graft copolymerization of methyl methacrylate to cellulose in the hydrogen peroxide initiator system was investigated. The addition of sodium thiosulfate in general was effective for decreasing the per cent grafting and the average molecular weight of grafts and increasing the formation of homopolymer, and the effects became pronounced with increasing hydrogen peroxide concentration. Moreover, the addition of sodium thiosulfate slightly suppressed the formation of grafts at a hydrogen peroxide concentration of 3 mmole/l., but greatly promoted it at 20 mmole/l. Traces of metallic ions present in cellulose could not be eliminated sufficiently by treatment with 3N hydrochloric acid. Such ions were found to interact with hydrogen peroxide and thus participate directly in the initiation and termination of the polymerization reaction. EDTA, the chelating agent, was highly effective for suppressing such participation of metallic ions. In the hydrogen peroxide initiator system applied to the EDTA-treated samples, sodium thiosulfate caused an effective initiation of graft formation.     

Microstructural Analysis and Photocatalytic Activity of Plasma-Sprayed Titania-Hydroxyapatite Coatings

Hydroxyapatite (HAp Ca₁₀(PO₄)₆(OH)₂) is known to be a biomaterial and an adsorbent for chromatography. In this study, HAp was agglomerated with anatase TiO₂ to manufacture thermal-spray powders to improve the adsorption activity of TiO₂, and then to improve its photocatalytic activity. The microstructures, compositions and photocatalytic activity of plasma-sprayed TiO₂, TiO₂-10%HAp, TiO₂-30%HAp, and HAp coatings were investigated. Due to the low thermal conductivity of HAp compound, not all HAp particles fully melted even under the arc current of 800 A. The addition of HAp inhibited the phase transformation of anatase TiO₂ to rutile. Under the arc current of 600 A, the anatase content in the TiO₂, TiO₂-10%HAp and TiO₂-30%HAp coatings was 11, 20 and 42%, respectively. With the increasing of the spraying distance from 70 to 110 mm, the anatase content in the TiO₂-30%HAp coatings decreased from 34 to 17% under arc current of 700 A. Furthermore, a slight decomposition of HAp to α-Ca₃(PO₄)₂ was found in the TiO₂-30%HAp coatings, it did not decompose to CaO and P₂O₅ according to the XRD and EDAX analysis. The addition of the secondary gas of helium had no significant influence on the melting state of the TiO₂-HAp feedstock powders. Moreover, the HAp in the TiO₂-10%HAp and TiO₂-30%HAp coatings had adsorption characteristic to acetaldehyde. The photocatalytic activity of TiO₂-10%HAp coating was highest among TiO₂, TiO₂-10%HAp, and TiO₂-30%HAp coatings sprayed under the arc current of 600 A for the optimum adsorption property and anatase content. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Penetration treatment of plasma-sprayed ZrO2 coating by liquid Mn alloys

The penetration phenomena of liquid manganese (Mn) alloy into porous ZrO₂ (8 vvt % Y₂O₃) coating plasma sprayed on SS400 steel substrate was studied by heating in a vacuum atmosphere. The improvement in mechanical properties of the coating by heat treatment with liquid Mn alloys was examined. Liquid Mn alloys, such as Mn-Cu, Mn-Sn, and Mn-In, rapidly penetrated the coating and formed a chemical bond between the coating and the substrate. The densification of the ZrO₂ coating occurred when ZrO₂ particles were sintered with liquid Mn alloys that penetrated the porous coating. The dense coating was free of porosity, and its hardness increased after heat treatment with Mn alloys, compared with assprayed ZrO₂ coating. Moreover, the fracture toughness of the coating reached the same levels as those of sintered yttria-stabilized PSZ.     

低气压等离子喷涂TiO2涂层结构的研究

本研究分析了在低气压等离子喷涂条件下,TiO_2涂层的结构受等离子弧喷涂过程中氧分解量所影响。氧分解量很大程度上依赖于离子气中氢流量的大小,此外喷涂室压力也有一定影响。而等离子弧功率和喷涂距离对TiO_2涂层的氧分解量没有多大影响。在离子气中氢流量不变的条件下,涂层中Ti_3O_5量随喷涂室压力(从100×133.322Pa至400×133.322Pa)增加而增加。     

Impedancemetric gas sensor based on Pt and WO3 co-loaded TiO2 and ZrO2 as total NOx sensing materials

Pt-loaded metal oxides [WO₃/ZrO₂, MO_x/TiO₂ (MO_x = WO₃, MoO₃, V₂O₅), WO₃ and TiO₂] equipped with interdigital Au electrodes have been tested as a NO_x (NO and NO₂) gas sensor at 500 °C. The impedance value at 4 Hz was used as a sensing signal. Among the samples tested, Pt-WO₃/TiO₂ showed the highest sensor response magnitude to NO. The sensor was found to respond consistently and rapidly to change in concentration of NO and NO₂ in the oxygen rich and moist gas mixture at 500 °C. The 90% response and 90% recovery times were as short as less than 5–10 s. The impedance at 4 Hz of the present device was found to vary almost linearly with the logarithm of NO_x (NO or NO₂) concentration from 10 to 570 ppm. Pt-WO₃/TiO₂ showed responses to NO and NO₂ of the same algebraic sign and nearly the same magnitude, while Pt/WO₃ and WO₃/TiO₂ showed higher response to NO than NO₂. The impedance at 4 Hz in the presence of NO for Pt-WO₃/TiO₂ was almost equal at any O₂ concentration examined (1–99%), while in the case of Pt/WO₃ and WO₃/TiO₂ the impedance increased with the oxygen concentration. The features of Pt-WO₃/TiO₂ are favorable as a NO_x sensor that can monitor and control the NO_x concentration in automotive exhaust. The effect of WO₃ loading of Pt-WO₃/ZrO₂-based sensor is studied to discuss the role of surface W-OH sites on the NO_x sensing.     

A bio-inspired predictive sensory-motor coordination scheme for robot reaching and preshaping

This paper presents a sensory-motor coordination scheme for a robot hand-arm-head system that provides the robot with the capability to reach an object while pre-shaping the fingers to the required grasp configuration and while predicting the tactile image that will be perceived after grasping. A model for sensory-motor coordination derived from studies in humans inspired the development of this scheme. A peculiar feature of this model is the prediction of the tactile image. The implementation of the proposed scheme is based on a neuro-fuzzy module that, after a learning phase, starting from visual data, calculates the position and orientation of the hand for reaching, selects the best-suited hand configuration, and predicts the tactile feedback. The implementation of the scheme on a humanoid robot allowed experimental validation of its effectiveness in robotics and provided perspectives on applications of sensory predictions in robot motor control.     

Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Oxygen-redox-based-layered cathode materials are of great importance in realizing high-energy-density sodium-ion batteries (SIBs) that can satisfy the demands of next-generation energy storage technologies. However, Mn-based-layered materials (P2-type Na-poor Na_y[A_xMn_1−x]O₂, where A = alkali ions) still suffer from poor reversibility during oxygen-redox reactions and low conductivity. In this work, the dual Li and Co replacement is investigated in P2-type-layered Na_xMnO₂. Experimentally and theoretically, it is demonstrated that the efficacy of the dual Li and Co replacement in Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂ is that it improves the structural and cycling stability despite the reversible Li migration from the transition metal layer during de-/sodiation. Operando X-ray diffraction and ex situ neutron diffraction analysis prove that the material maintains a P2-type structure during the entire range of Na⁺ extraction and insertion with a small volume change of ≈4.3%. In Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂, the reversible electrochemical activity of Co³⁺/Co⁴⁺, Mn³⁺/Mn⁴⁺, and O^2-/(O₂)^n- redox is identified as a reliable mechanism for the remarkable stable electrochemical performance. From a broader perspective, this study highlights a possible design roadmap for developing cathode materials with optimized cationic and anionic activities and excellent structural stabilities for SIBs.     

Observers and output feedback stabilising controllers for nonlinear strict-feedback systems with sampled observation

The design of observers and output feedback stabilising controllers for continuous-time strict-feedback systems with sampled observation is considered. First two types of observers are designed. One is a discrete-time semiglobal and practical reduced-order observer for the exact model and the other is a continuous-time semiglobal and practical full-order observer for continuous-time strict feedback systems with sampled observation. Then by combining the designed continuous-time observers and continuous-time state feedback laws that are continuous, zero at the origin, and uniformly globally asymptotically stabilise continuous-time systems, output feedback semiglobally practically uniformly asymptotically stabilising controllers are constructed. Numerical examples are given to illustrate the proposed design of observers and output feedback controllers.     

Output intersampling approach to direct closed-loop identification

A new direct closed-loop identification method, which uses the output intersampling technique, is proposed in this note. By using the intersampled plant input-output data, the proposed method removes the traditional restrictive identifiability condition, and does not require an external persistently exciting (PE) test signal     

Dual frequency open-loop electric potential microscopy for local potential measurements in electrolyte solution with high ionic strength

Recent development of open-loop electric potential microscopy (OL-EPM) has enabled to measure local potential distribution at a solid/liquid interface. However, the operating environment of OL-EPM has been limited to a weak electrolyte solution (<1 mM). This has significantly limited its application range in biology and chemistry. To overcome this limitation, we have developed dual frequency (DF) mode OL-EPM. In the method, an ac bias voltage consisting of two frequency components at f(1) and f(2) is applied between a tip and sample. The local potential is calculated from the amplitudes of the f(1) and |f(1) - f(2)| components of the electrostatic force. In contrast to the conventional single frequency (SF) mode OL-EPM, the detection of the 2f(1) component is not required in DF mode. Thus, the maximum bias modulation frequency in DF mode is twice as high as that in SF mode. The high bias modulation frequency used in DF mode prevents the generation of electrochemical reactions and redistribution of ions and water, which enables to operate OL-EPM even in a strong electrolyte solution. In this study, we have performed potential measurements of nanoparticles on a graphite surface in 1 and 10 mM NaCl solution. The results demonstrate that DF mode OL-EPM allows measurements of local potential distribution in 10 mM electrolyte solution.