Tribological properties of perfluoralkylethyl methacrylate-polymethyl methacrylate copolymer thin films

Perfluoroalkylethyl methacrylate and polymethyl methacrylate copolymers (FMA/MMA) were synthesized by the atom transfer radical polymerization at various FMA/MMA mole ratios. 5 wt% copolymer solutions were spun cast onto PMMA sheet substrates. The effects of monomer ratio on tribological properties were investigated in terms of the surface energy calculated from contact angles, the dynamic friction, and the wear obtained from multiple scratchings. There is a range of optimum FMA/MMA ratios between (1–5)×10⁻³ in which we attain a minimum dynamic friction. The results obtained are discussed in terms of connections between friction, surface tension, and wear mechanisms.     

Laser ablation of Ga-Sb-Te thin films monitored with quadrupole ion trap time-of-flight mass spectrometry

Laser ablation of Ga-Sb-Te chalcogenide thin films prepared by radiofrequency magnetron co-sputtering was monitored with quadrupole ion trap time-of-flight mass spectrometry (QIT-TOF-MS). The mass spectra of 11 thin films of various compositions (Ga: 0–53.1, Sb: 0–52.0, and Te: 0–100.0 at. %) were recorded. Several series of unary (Ga_x, Sb_y, and Te_z) binary (Ga_xSb_y, Ga_xTe_z, and Sb_yTe_z), and ternary Ga_xSb_yTe_z clusters were identified in both positive and negative ion modes. Stoichiometry of observed clusters was determined. Up to 18 binary clusters (positively and negatively charged) were detected for thin film with low Sb content of 6.5 at. %. The highest number (4) of ternary clusters was observed for thin film with high Te content of 66.7 at. %. The number of generated clusters and their peaks intensity varied according to the chemical composition of thin films. Altogether, 41 clusters were detected. The laser ablation monitoring shows laser-induced fragmentation of thin film structure. The relation of clusters stoichiometries to the chemical composition of thin films is discussed. The fragmentation can be diminished by covering a surface of thin films with paraffin's, glycerol, or trehalose sugar thin layers. The stoichiometry of generated clusters shows partial structural characterization of thin films.     

Tris(trimethylsilyl)methyl functionalized 4‐chloromethyl styrene polymers: Effects of side chain modification on polymer structure and glass transition temperature

4‐Chloromethyl styrene was copolymerized with various molar ratio of methyl methacrylate or ethyl methacrylate by solution free radical polymerization method, at 70 ± 1°C using α,α′‐azobis(isobutyronitrile) as an initiator. Then, very highly sterically hindered tris(trimethylsilyl)methyl substituent was covalently linked to the obtained copolymers with liberation of chlorine atoms. The structure of all polymers was characterized and confirmed by FT‐IR, ¹H and ¹³C NMR spectroscopy techniques. The average molecular weight and glass transition temperature of polymers were determined using gel permeation chromatograph and differential scanning calorimeter instruments, respectively. Study of differential scanning calorimetry analyses showed that chemical modification of 4‐chloromethyl styrene copolymers with tris(trimethylsilyl)methyl substituents leads to an increase in the rigidity and glass transition temperature of polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 633–639, 2006     

Surface Structuring of Synthetic Fibres by UV Laser Irradiation,Part I: Phenomenological Report

A modern technique for a controlled surface modification of synthetic fibres consists of irradiation with a pulsed UV laser, which can be used to execute submicrometre surface treatment on polymers. Many types of synthetic fibres, e.g. poly(ethylene terephthalate), polyamides and aramides, show a characteristic surface modification when irradiated by ArF and KrF lasers. The originally smooth surface of these fibres changes its morphology to a rather regular roll-like structure perpendicular to the fibre axis after this treatment. A phenomenological report on the dependence of structure formation on polymer and laser conditions is given. © 1997 SCI.     

Synthesis of phthalocyanines functionalized by 4-fluorophenoxy moieties and their linear optical properties

Four kinds of phthalocyanines with 4-fluorophenoxy group (H₂Pc, CuPc, Li₂Pc, and FePc) are synthesized by the microwave-assisted method under 15 min. The synthesized phthalocyanines have good solubility in aprotic polar solvents and do not form any new aggregation state with a concentration increase. The phthalocyanine coordinated with Li⁺ ion has a more stable and stronger absorption property in aprotic polar solvents than the phthalocyanine with Cu²⁺ or Fe²⁺ ion. The phthalocyanine coordinated with Fe²⁺ ion is more subject to H-aggregation than other phthalocyanines, especially in polar solvents.     

Pulsed Laser Deposition of zeolitic thin films: Novel structures for molecular recognition

Pulsed Laser Deposition is used to deposit zeolitic films onto a substrate. Using this technique, thin films are formed using both mordenite and faujasite targets. The target application for the films was the development of gas-selective sensors. These films are comprised of small crystallites embedded in an amorphous matrix. The amorphous material is microporous having pore sizes on the order of those in the parent zeolites. These pores are oriented perpendicular to the substrate. Pore orientation coupled with the high porosity provides a thin film with a potential for high gas throughputs. Quartz crystal microbalances coated with the material have been tested for gas uptake and have shown to discriminate between isomers of small molecules. Beyond sensors, the zeolitic films may hold promise for such applications as membranes.     

Germanium-antimony-selenium-tellurium thin films: Clusters formation by laser ablation and comparison with clusters from mixtures of elements

Quaternary germanium-antimony-selenium-tellurium (Ge-Sb-Se-Te) thin films deposited from Ge_19.4Sb_16.7Se_63.9−xTe_x (x = 5, 10, 15, and 20) glass-ceramics targets by radio frequency magnetron sputtering were studied using laser ablation quadrupole ion trap time of flight mass spectrometry. Binary, ternary, and quaternary Ge_aSb_bSe_cTe_d clusters were formed and their stoichiometry was determined. By comparison of the clusters obtained from quaternary Ge-Sb-Se-Te thin films and those from ternary Ge-Sb-Te materials, we found that Ge-Te species are not detected from the quaternary system. Furthermore, Ge-Se and Se-Te species are missing in mass spectra generated from Ge-Sb-Se-Te thin films. From the Ge-Sb-Se-Te thin films, 16 clusters were detected while ternary Ge-Sb-Se glasses yielded 26 species. This might be considered as a signal of higher stability of Ge-Sb-Se-Te thin films which is increasing with a higher content of Te. The missing (Se₂⁺, Ge_aSb⁺ (a = 1–4), and GeSe_c⁺ (c = 1, 2)) and new (Ge⁺ and Sb_bTe⁺ (b = 1–3)) clusters may indicate that some of the structural features of the films (Ge₂Se_6/2 and Se₂Sb-SbSe₂) were replaced by (GeSe_4−xTe_x and SbSe_3−xTe_x) ones. In addition, when comparing the stoichiometry of clusters formed from Ge-Sb-Se-Te thin films with those from the mixtures of the elements, only Sb₃⁺ and SbSe⁺ were observed in both cases. The knowledge gained concerning clusters stoichiometry contributes to the elucidation of the processes proceeding during plasma formation used for the chalcogenide thin films deposition.     

Impact of oxygen partial pressure on resistive switching characteristics of PLD deposited ZnFe2O4 thin films for RRAM devices

In this paper we show resistive switching characteristics of ZnFe₂O₄ thin films grown by pulsed laser deposition at various oxygen partial pressures. We discuss how the microstructure, surface roughness, oxidation condition, and resistive switching properties of ZnFe₂O₄ thin films are influenced by the oxygen partial pressure prevalent in the chamber during the deposition process. The films were deposited at oxygen partial pressure (pO₂) of 0.0013, 0.013, 0.13 and 1.3 mbar. The ZnFe₂O₄ thin film deposited at the lowest pO₂ (0.0013 mbar) did not display a resistive switching characteristic. The ZnFe₂O₄ device deposited at 0.13 mbar yielded the best results. These devices have a low SET variance and a large memory window (more than 2 orders of magnitude) due to an optimum amount of oxygen vacancies/ions contained in the ZnFe₂O₄ film, which is helpful for better resistive switching, than devices deposited at other oxygen pressures. We also find that the migration of oxygen vacancies is linked to the resistive switching process.     

Comparison of tris(dimethylphenylsilyl)methyllithium and tris(trimethylsilyl)methyllithium reactions with carbon disulfide: a new route for the synthesis of some 1,1-bis(benzylthio)- and bis(allylthio)-2,2-bis(dimethylphenylsilyl)ethenes

A series of bis(benzylthio)- and bis(allylthio)-2,2-bis(dimethylphenylsilyl) ethenes has been obtained by the reaction of (PhMe₂Si)₃CLi and CS₂ with benzyl and allyl bromides. A plausible mechanism for the formation of these compounds has been proposed. The reactivity of (PhMe₂Si)₃CLi toward CS₂ has been compared with that of (Me₃Si)₃CLi. The reaction of (PhMe₂Si)₃CLi with CS₂ and 2-methyloxirane gave a cyclic thiocarbonate.     

Properties of SiO2 thin films prepared by anodic oxidation under UV illumination and rapid photothermal processing

Anodic oxidation under ultraviolet (UV) illumination and rapid photothermal processing technique used for high quality oxide preparation in terms of device surface passivation and gate or tunnel dielectrics are reported. A number of samples of SiO₂ thin films were prepared using this technique. It is shown that anodic oxidation under UV illumination followed by rapid photothermal processing (450 °C, 15 s) in the inert ambient yields the best optimization of the SiO₂ thin films properties. Avoiding high temperature process should result in a better performance of the semiconductor devices. Anodic oxidation under UV illumination at low temperature and post-oxidation photothermal processing can be a possible alternative to the furnace growth silicon oxide; not only because of the low temperature process, but also because this technology essential improves the oxides properties.     

Surface properties of polymer films including multiblock copolymer

B(AB)_n multiblock copolymers of which the A block and the B block are hydrophobic and hydrophilic, respectively, were blended into crosslinkable coating compositions for preparing a hydrophilic surface, and compared with the graft copolymers including A and B as the pendant groups. The main constituent of A was polydimethyl-siloxane and that of B was poly(ethylene oxide). While the block copolymer slightly increased the hydrophobicity of the surface, it quickly became hydrophilic on contact with water. On the contrary, the graft copolymer increased the hydrophobicity even after its contact with water. Elementary analysis with ESCA demonstrated that both the silicon atoms and ether groups were concentrated on the very top of the surface in the films including the block copolymers but only silicon atoms were concentrated on the film surface which included the graft copolymers. In spite of their propensity to remain in the bulk due to their high surface energy, hydrophilic poly(ethylene oxide) moieties in the block copolymers migrated onto the near surface accompanying the movement of the hydrophobic polydimethyl-siloxane. because their mobility would be restricted by the bonding of both sides. Inclusion of the block copolymers significantly improved soil resistance. The advantage of the block copolymers as a surface modifier was further developed as an adhesion promoter. The introduction of a larger amount of the hydroxyl group into the hydrophilic block was effective for this purpose. This was discussed with respect to the change in the γ_p parameter.     

Solution‐derived ferroelectric vinylidene fluoride oligomer thin films with large polarization

Dense and uniform vinylidene fluoride (VDF) oligomer thin films with a highly polar β phase were prepared for the first time by a low‐cost and scalable solution casting approach, after treatments of substrate surface functionalization and hot‐pressing. Introducing hydrated salt in the precursor solution effectively promoted the ferroelectric β phase. The VDF oligomer thin films obtained with short molecular chains exhibited high crystallinity and high remnant polarization (91 mC m^?2), which is larger than both the polymer and copolymer counterpart films. The reasons for the observed low dielectric constant at low electric field, despite its larger polarization at high field, and the relatively high coercive field are discussed on the basis of the distinct structural characteristics of VDF oligomers. The low polar bulky end‐groups and difficulties in kink formation and propagation may result in the observed low dielectric constant at low electric field and the high coercive field. Copyright © 2011 Society of Chemical Industry     

Laser protection with optical limiting by combination of polymers with dyes

Lasers are becoming more and more common and can damage eyes and sensors, so arise the need for efficient protection. A possibility is the use of filters with optical limiting abilities. Optical limiting leads to a reduced transmittance of these filters above a certain light energy. Solid-state optical limiting filters consist frequently of poly(methyl methacrylate) (PMMA). Using dyes is an often used way to provide optical limiting qualities to polymers. PMMA does not offer the possibility to attach the dye covalently to the polymer chain. Poly(lactide), also a transparent polymer, has so far not been used for filters for optical limiting. Its polymerization mechanism offers a simple possibility to a covalent binding of the dyes, by using them as initiator. This should be, like the attaching of big side groups to dyes, a possibility to increase stability of dyes against aggregation. Hybrids out of polymers and dyes and filters thereof could be produced. The polymers were analyzed by nuclear magnetic resonance, gel permeation chromatography, and nonlinear optical measurements. Including azophloxine leads to an attenuation of the laser beam in the range of 10⁻³ and Eosin B even to 10⁻⁵. The eosin sample shows a two magnitudes better attenuation then usual guest–host systems like poly(methyl acrylate) with carbon nanotubes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47150.     

Controlled local organization of lyotropic liquid crystalline polymer thin films with electric fields

The ability of electric fields to induce the controlled alignment of lyotropic liquid crystalline polymer thin films on microfabricated substrates is demonstrated. These devices allow for variations in electric field geometry on the polymer alignment to be examined systematically. The polymers studied included poly(hexyl isocyanate) (PHIC) and poly(benzyl l-glutamate). The polymers were oriented by the electric field while in solution and solidified into a stable, oriented structure by solvent evaporation. Optical microscopy and transmission electron microscopy experiments make it possible to directly image the disclinations that mediate molecular alignment. The defect type and density in the solidified films are a function of the electric field geometry.     

Characterization of photo‐ and thermoresponsible amphiphilic copolymers having azobenzene moieties as side groups

Two series of amphiphilic copolymers, poly(HPMA‐co‐MPAP) I–V with n = 0.05–0.29 of the molar ratio of MPAP and poly(HPMA‐co‐MPAH)‐I–V with n = 0.05–0.23 of the molar ratio of MPAH, were prepared by radical copolymerization of N‐(2‐hydroxypropyl) methacrylamide (HPMA) with azo‐monomers such as 4‐(4‐methoxyphenylazo) phenyl methacrylate (MPAP) and 6‐[4‐(4‐methoxyphenylazo) phenoxy] hexyl methacrylate (MPAH) using 2,2′‐azobisisobutyronitrile as an initiator. Self‐organization of these copolymers in water was confirmed by disappearance of the proton signal of the methoxyazobenzene in ¹H‐NMR spectra measured in the solvent system of D₂O and CD₃OD. It was also found from the λ_max, located near 344 nm, that azobenzene groups self‐organized to form the dimeric chromophore type of aggregate. The aqueous solutions of poly(HPMA‐co‐MPAP) and poly(HPMA‐co‐MPAH) exhibited the lower critical solution temperature (LCST) from at 68 to 40°C and from at 70 to 52°C in the dark state, respectively, with increasing the molar ratios of azo‐monomers. On the other hand, the LCST measured in the photostationary state showed the higher temperature by 2–4°C compared with that in the dark state. It was found that the adsorption of poly(HPMA‐co‐MPAP)‐V (n = 0.29) on polystyrene microspheres was photoregulated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3056–3063, 2001     

不同金属离子掺杂TiO2薄膜的制备及光催化活性的研究

以溶胶-凝胶法制备了分别用Ag^+、Cu²⁺、Fe³⁺、La³⁺、Ce³⁺和Eu³⁺等离子掺杂的纳米TiO₂薄膜，经XRD和UV-Vis对薄膜样品进行表征并研究了其光催化活性。XRD结果证明，掺镧TiO₂薄膜与未掺杂薄膜的X射线衍射图基本一致，实验条件下主要为锐钛矿型，且掺入La^3+离子使得TiO₂薄膜的晶粒变小。UV-Vis吸收光谱说明当λ＞380 nm时，其吸光度低于0.15。薄膜光催化降解亚甲基蓝的实验表明,La³⁺或Fe^3+掺杂薄膜的光催化降解率远高于未掺杂TiO₂薄膜，而Ce^3+或Cu^2+离子掺杂薄膜与未掺杂薄膜的光催化活性相似，掺Ag⁺或Eu³⁺离子则降低了活性。当最佳掺杂量La³⁺为0.6%或Fe³⁺为1.5%时，光催化降解率分别高达92%和82%。     

Electron transfer rate of redox ion controlled by electrostatic interaction with bilayer films assembled using thiolate-copper ion-carboxylate bridges

11-mercaptoundecanoic acid (MUA) monolayer and MUA-copper ion-MUA bilayer assembled using thiolate-coppcr ion-carboxylate bridges on MUA monolayer electrode were prepared, and tried to control electron transfer rate of redox ions. The soaking solution to assemble MUA on gold electrode changed from ethanolic MUA solution to 1-butanolic one, then the differential interfacial capacitance decreased from 2.5±0.1 μF cm⁻² to 1.6±0.2 μF cm⁻², and electron rate constant, k⁰ of [Co(phen)₃]³⁺ decreased from 20×10⁻⁶ cm s⁻¹ to 8.3×10⁻⁶ cm s⁻¹. These results show that highly ordered MUA monolayer can be obtained only changing soaking solvent to assemble MUA, Obtained highly ordered MUA monolayer electrode was block off completely redox anion by electrostatic repulsion and MUA film thickness. Moreover using MUA-copper ion-MUA bilayer electrode, k⁰ of [Co(phen)₃]³⁺ decreased under 1/400 against using MUA monolayer electrode, that value become to under 0.02×10⁻⁶ cm s⁻¹. This study shows that the combination of electrode surface charge and length of insulating spacers is able to control electron transfer rate of various electroactive ions.     

A feasible method of preparation of block copolymer latex films with stable microphase separation structures

RAFT (reversible addition–fragmentation chain transfer) miniemulsion polymerization was engaged to engineer latex particle morphology. With this approach, a macromolecular amphiphilic RAFT agent with epoxy groups was synthesized that assembled onto the surface of monomer mini-droplets. It caused the polymer chains to grow inwards gradually in particles as polymerization proceeded. The batch polymerization of n-butyl acrylate (BA) followed by addition of styrene (St) led to the formation of PBA-b-PSt diblock copolymer shell–core latex, where epoxy groups were enriched on the particle surface. The shell–core ratio was varied feasibly by changing the mass of St. When the structured latexes were dried, epoxy groups underwent efficient curing reactions triggered by a thermal-latent curing agent (dicyandiamide) in a controlled manner, leading to the formation of bonded PBA blocks connecting the PSt blocks in adjacent particles. Mechanical tests show that the films behaved like ductile materials, whose modulus and elongation at break were functions of copolymer compositions. Furthermore, curing reaction was a very robust method of preserving film morphology which correlated well with that observed for the latex particles. The results demonstrated a feasible method of preparation of latex films with stable microphase separation structures and thus improved mechanical properties.     

Optical and electrical properties of (111)-oriented epitaxial SrVO3 thin films

Perovskite oxide SrVO₃ (SVO) is a transparent conductor with excellent optical and electrical properties. Most of the previous works have focused on (001)-oriented SVO thin films. As an alternative to tin-doped indium oxide (ITO), the other orientations of SVO thin films are important to be considered as well. In the present work, the optical and electrical properties of (111)-oriented SVO epitaxial films have been investigated. Excellent electrical conductivity (2.92?×?10⁴?S?cm^?1) and optical transparency (56.6%) have been demonstrated, which are comparable to those of ITO and expand the applications of epitaxial SVO thin films in other orientations as transparent conducting oxide.     

Synthesis and properties of novel flame‐retardant poly(amide‐imide)s containing phosphine oxide moieties in main chain by microwave irradiation

Eight new flame‐retardant poly(amide‐imide)s with high inherent viscosities containing phosphine oxide moieties in main chain were synthesized from the polycondensation reaction of N,N′‐(3,3′‐diphenylphenylphosphine oxide) bistrimellitimide diacid chloride 7, with eight ;aromatic diamine 8a–h by two different methods such as solution and microwave‐assisted polycondensation. Results showed that the microwave‐assisted polycondensation by using a domestic microwave oven proceeded rapidly, compared with solution polycondensation and were completed within about 10–12 min. The resulting poly(amide‐imide)s 9a–h showed high thermal stability and flame‐retardant properties. All of the obtained polymers were fully characterized by means of elemental analysis, viscosity measurements, solubility test, and FTIR spectroscopy. Thermal properties of the PAIs 9a–h were investigated by using thermal gravimetric analysis (TGA), derivative thermogravimetric analysis (DTG), and differential scanning calorimetry (DSC). Char yield measurements at 600°C demonstrated that incorporating phosphine oxide moieties in polymer backbone markedly improves their flame retardancy. All of the earlier polymers were soluble at room temperature in various organic solvents such as NMP, DMF, DMSO, DMAc, and concentrated sulfuric acid. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4263–4269, 2006