Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications.     

直立在金膜表面的单壁碳纳米管的研究

用水溶胶体将单壁碳纳米管（ＳＷＣＮＴｓ）组装在晶态金膜表面,用扫描隧道显微镜（ＳＴＭ）研究了表面单壁碳纳米管直立于金膜表面,单根碳管的长度约在１０－１５ｎｍ之间。     

Adsorption of nonpolar benzene derivatives on single-walled carbon nanotubes

The adsorption of benzene, toluene, and chlorobenzene on single-walled carbon nanotubes (SWCNTs) with and without acid oxidation was conducted to investigate the influences of derivative groups on benzene rings and functional groups from SWCNTs on adsorption by SWCNTs. The SWCNTs of high purity were chosen and moderate acid oxidation was performed so that the surface physical properties remained unchanged after acid oxidation and the influences of acid oxidation on adsorption were only contributed from the modification of the surface chemistry of SWCNTs. The oxygen-containing surface groups introduced by acid oxidation obstructed the interactions between functional groups of nonpolar benzene derivatives and C-rings of SWCNTs significantly. The dispersive interaction between the partially positive H⁺ of the methyl group and the oxygen-containing surface groups slightly increased the adsorption of toluene on oxidized SWCNTs at high solution pH. The thermodynamic of adsorption was also studied at different temperatures.     

RAFT “grafting-through” approach to surface-anchored polymers: Electrodeposition of an electroactive methacrylate monomer

The synthesis of homopolymer and diblock copolymers on surfaces was demonstrated using electrodeposition of a methacrylate-functionalized carbazole dendron and subsequent reversible addition-fragmentation chain transfer (RAFT) “grafting-through” polymerization. First, the anodically electroactive carbazole dendron with methacrylate moiety (G1CzMA) was electrodeposited over a conducting surface (i.e. gold or indium tin oxide (ITO)) using cyclic voltammetry (CV). The electrodeposition process formed a crosslinked layer of carbazole units bearing exposed methacrylate moieties. This film was then used as the surface for RAFT polymerization process of methyl methacrylate (MMA), styrene (S), and tert-butyl acrylate (TBA) in the presence of a free RAFT agent and a free radical initiator, resulting in grafted polymer chains. The molecular weights and the polydispersity indices (PDI) of the sacrificial polymers were determined by gel permeation chromatography (GPC). The stages of surface modification were investigated using X-ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM) to confirm the surface composition, thickness, and film morphology, respectively. UV-Vis spectroscopy also confirmed the formation of an electro-optically active crosslinked carbazole film with a p \pi - p^* \pi^{{\ast}}_{} absorption band from 450-650nm. Static water contact angle measurements confirmed the changes in surface energy of the ultrathin films with each modification step. The controlled polymer growth from the conducting polymer-modified surface suggests the viability of combining electrodeposition and grafting-through approach to form functional polymer ultrathin films.     

Hydrophilic modification of microporous polysulfone membrane via surface-initiated atom transfer radical polymerization of acrylamide

Polyacrylamide (PAM) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surface by surface-initiated atom transfer radical polymerization (SI-ATRP) to improve the membrane's hydrophilic property. In order to anchor the initiator onto polysulfone (PSF) membrane surface, CMPSF was used to prepare the microporous membrane by phase-inversion process. Attachment of the PAM chains on membrane surface was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The grafted density of PAM was calculated to be 0.08 chains nm⁻². Field emission scanning electron microscopy (FESEM) and atomic force microscope (AFM) were used to characterize the surface morphology of the CMPSF membrane and modified membrane. The number-average molecular weight (M_n) of PAM linearly increased with the polymerization time, while the static water contact angle (θ) of the membrane grafted with PAM linearly decreased. This indicated the hydrophilic property of the membrane was linearly correlated with the chain length of graft polymer. Therefore linear control of PSF membrane's hydrophilic property was realized through adjusting polymerization time.     

Microbial degradation of lignin: Role of lignin peroxidase,manganese peroxidase,and laccase

Lignin peroxidase (LiP), laccase (LA) and manganese peroxidase (MnP) of white-rot basidiomycetes such as Phanerochaete chrysosporium, Coliorus versicolor, Phlebia radiata and Pleurotus eryngii catalyze oxidative degradation of lignin substructure model compounds and synthetic lignins (DHPs). Side chain- and aromatic ring cleavage products of both phenolic and non-phenolic substrates oxidized by LiP were isolated and characterized by NMR and MS. The cleavage mechanism was elucidated by using ¹⁸O, ²H, and ¹³C labeled lignin substructure dimers with ¹⁸O₂ and H₂ ¹⁸O. Recent studies suggested that LiP is capable of oxidizing lignin directly at the protein surface via a long-range electron transfer process. LA and MnP, which oxidize phenolic but not non-phenolic moieties, generally degrade lignin stepwise from phenolic moieties. However, recent studies indicated that MnP and LA can degrade both phenolic and non-phenolic aromatic moieties of lignin with some special mediators.     

Study of tribochemical decomposition of ionic liquids on a nascent steel surface

Tribological properties and the decomposition process of ionic liquids (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide) on a nascent surface of bearing steel 52100 were investigated by a ball-on-disk friction tester in a vacuum chamber equipped with a quadrupole mass spectrometer (Q-MS). Ionic liquids exhibited better tribological properties than synthetic hydrocarbon oil (multialkylated cyclopentane (MAC)) in high vacuum conditions. The induction period for decomposition of MAC was about 10 km, while no obvious gaseous products were observed for ionic liquids even after a sliding distance of 22 km under the same mechanical conditions. The mass spectra indicated that both the anionic and cationic moieties of ionic liquids decomposed on the nascent steel surface during friction processes. The cationic moiety with a longer alkyl chain was more difficult to decompose on the nascent steel surface than that with a shorter alkyl chain. XPS analysis revealed that the tribofilm formed by ionic liquid was mainly composed of FeF₂ and FeS, which deactivated the nascent surface. As a result, desorption rate of gaseous products decreased appreciably comparing with MAC. The critical load for the mechanical activation of the decomposition correspondingly increased from 1.1 N of MAC to 8 N of ionic liquids.     

Modification of cycloolefin copolymer and poly(vinyl chloride) surfaces by superimposition of nano- and microstructures

Cycloolefin copolymer (COC) and poly(vinyl chloride) (PVC) surfaces were patterned with nanopillars or with microbumps on which nanopillars were superimposed. The area of patterned surfaces was several square centimeters. Patterning was achieved by applying nanoporous anodized aluminum oxide (AAO) membrane as a mask in injection molding or imprinting. Nanostructures superimposed on microstructures were achieved by patterning the AAO mask with microstructures before anodization. Micro- and nanometer-sized structures could then be transferred simultaneously to polymer surfaces. Structures were characterized by SEM, AFM, and contact profilometry. The effect of different-sized structures on properties of the polymer surface was studied by contact angle measurements. Relative to the smooth surface, the increase in water contact angle on a COC surface with nanostructures superimposed on microstructures was up to 50°.     

Visible-light photochromism of phosphomolybdic acid and polyvinyl alcohol by inorganic-organic nanocomposite multilayer films

A novel visible-light photochromic inorganic-organic multilayer was constructed based on phosphomolybdic acid (PMoA) and polyvinyl alcohol (PVA) which was prepared using the layer-by-layer (LbL) assembly technique to form the multilayer film. The structures of the multilayer films were characterized via Fourier transform infrared spectra (FT-IR) and atomic force microscopy (AFM). The grown process, internal interaction, the surface topography and photochromic properties could be obviously studied through ultraviolet–visible (UV–vis) spectra and X-ray photoelectron spectra (XPS). The advantage of the structure and performance of the multilayer films prepared by layer-by-layer method could be found. It was suggested that the nearly linear growth process in peak-top absorbance in multilayer assembly. The PVA polymer substrate could disperse PMoA particles and changed the surface morphology. The polymer skeleton and PMoA particles were with strong interfacial interactions. The PMoA/PVA LbL film had wonderful visible light response. The oxygen acted a significant part during the bleaching process. According to XPS resoults, 51% of Mo⁶⁺ in the PMoA turned into Mo⁵⁺, obvious photoinduce oxidation and reduction reactions happened from PVA and PMoA through the proton transfer mechanism.     

Tip-surface interactions at redox responsive poly(ferrocenylsilane) (PFS) interface by AFM-based force spectroscopy

Poly(ferrocenylsilanes) (PFS) belong to the class of redox responsive organometallic polymers. Atomic force microscopy (AFM)-based single molecule force spectroscopy (SMFS) was used earlier to study single chain PFS response and redox energy driven single chain PFS molecular motors. Here we present further AFM investigations of force interactions between tip and a grafted PFS surface under potential control in electrochemical redox cycles. Typical tip-Au interaction is considered as reference in the force measurements. First the electrostatic component in the diffused double layer (DL) in NaClO₄ electrolyte environment was considered for a “grafted to” PFS, which dominated the interplay between the tip and sample surface. The DL forces can also hinder the physisorption of PFS chain onto the tip when the voltage was applied at −0.1 V. On the other hand, if the tip contacted the PFS surface prior to the electrochemical process, physisorption of PFS chains governed the overall interaction regardless of subsequently applied surface potential. In addition, prolonged contact time, t_c, may also contribute to the stability of tip-PFS bridging and detection of electrostatic forces between the tip-PFS interface. The results showed that tip-substrate interaction forces without PFS grafts have negligibly small force contributions under similar, electrochemically controlled, conditions used in single PFS chain based molecular motors.     

Surface modification of polypropylene using argon plasma: Statistical optimization of the process variables

Low pressure plasma treatment using radiofrequency (rf) discharge of argon gas was employed to improve the hydrophilicity of polypropylene. The effects of argon plasma on the wettability, surface chemistry and surface morphology of polypropylene were studied using static contact angle measurements, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Increase in surface energy of polypropylene was observed as a result of argon plasma treatment. SEM and AFM images revealed the increased surface roughness. A set of identified process variables (rf power, pressure, argon flow rate and time) were used in this study and were optimized using central composite design (CCD) of response surface methodology (RSM). A statistical model was developed to represent the surface energy in terms of the process variables mentioned above. Accuracy of the model was verified and found to be high.     

Thiolated poly(ε-caprolactone) macroligand with vacant coordination sites on gold substrate: Synthesis and surface characterization

Surface-confined telechelic poly(ε-caprolactone) macroligand with two distinct functional groups per polymeric chain has been synthesized and characterized. The molecular microstructure of the macroligand with regard to the properties of the end-capped functionalities and with those on surface substrate has been studied by solution and surface analytical methods (i.e., X-ray photoelectron spectroscopy (XPS), grazing angle reflectance-Fourier transform IR spectroscopy (GA-FTIR), water contact angle measurements, and atomic force microscopy (AFM)) to elucidate the structure and properties of such multifunctional polymer on gold (1 1 1) substrate.     

Surface analysis for LiBq4 growing on ITO and CuPc film using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

We have investigated the morphology and surface electron states of LiBq₄ deposited on ITO and CuPc/ITO, using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The AFM observations indicate that LiBq₄ can form a much more uniform film on CuPc than that on ITO. Furthermore, X-ray photoelectron spectroscopy (XPS) is utilized to further demonstrate the AFM results. From the analysis of XPS, we found that LiBq₄ molecules have poor thermal stability, they are seriously oxidized during depositing; but when a CuPc layer is inserted between LiBq₄ and ITO film, the oxidation and surface contamination of LiBq₄ are significantly reduced. It is then concluded that the introduction of a CuPc buffer layer under the LiBq₄ film can improve the film quality of LiBq₄.The XPS results also testified the fact that no coordination bonds between N atoms and B atoms are formed in LiBq₄ molecules, which make LiBq₄ to be potential blue organic light-emitting material.     

Surface modification of polyethylene film by acrylamide graft and alcoholysis for improvement of antithrombogenicity

To improve antithrombogenicity of polyethylene (PE) films, the films pretreated by Ar plasma were radiated by ultraviolet light to initiate grafting polymerization with acrylamide (AAm) in absence of photo-initiator, then the AAm-grafted PE films (PE-g-AAm) were alcoholized with octadecyl alcohol. Effects of Ar plasma composite parameter (W/FM), pretreated time, AAm monomer concentration, and UV irradiation time on grafting rate were investigated systematically. AAm-grafted PE film and alcoholized PE film (PE-g-SAAm) were characterized by contact angle, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transfer infrared (ATR-FT-IR) spectroscopy and atomic force microscope (AFM), respectively. The results indicated that the moieties of AAm and stearyl were successively immobilized onto the PE surface. The platelet adhesion experiment showed that antithrombogenicity of the modified PE films was improved in comparison with PE films. The change in antithrombogenicity is attributed to the surface of the modified film in presence of tail-like structure which consists of polyacrylamide as spacer and stearyl as end groups.     

Investigation into layers formed by selective transfer CMP mechanisms with atomic force microscope

To understand mechanisms of chemical mechanical planarization (CMP), an atomic force microscope (AFM) was used to characterize polished layer surfaces formed by selective transfer after a set of polishing experiments. It is know that in the process of friction of two materials and in the presence of own lubricants, wear phenomenon itself manifests as a transfer of material from an element of a friction couple on the other, this phenomenon being characteristic to the selective transfer process. A selective transfer can be safely achieved in a friction couple, if there is a favorable energy, and in the presence of relative movement, if in the friction area is a material made by copper and the lubricant is adequate (glycerin or special lubricant). The forming selective layer on the contact surfaces makes that the friction force to be very low because of the structure formed by selective transfer. To optimize the CMP process, one needs to obtain information on the interaction between the slurry abrasive particles (with the size range of about 30–70 nm) and the polished surface. To study such interactions, we used AFM. Surface analysis of selective layer using the AFM revealed detailed surface characteristics obtained by CMP. Studying the selective layer CMP, of which the predominated one is copper (in proportion of over 85%), we found that the AFM scanning removes the surface oxide layer in different rates depending on the depth of removal and the pH of the solution. Oxide removal happens considerably faster than the copper CMP removal from the selective layer. This is in agreement with generally accepted models of copper CMP. It was found that removal mechanisms depend on the slurry chemistry, potential per cent of oxidizer, and the applied load. This presentation discusses these findings. Both load force and the friction forces acting between the AFM tip and surface during the polishing process were measured. One big advantage of using the AFM tip (of radius about 50 nm) as abrasive silica particle is that we can measure forces acting between the particle-tip and the surface being polished. Here, we report measurement of the friction force while scratching and polishing. The correlation between those forces and removal rate is discussed.     

Strain-induced metal to semiconductor transition in ultra-small diameter single-wall carbon nanotubes

Under a large tensile strain near fracture limit, the band structures of single-wall carbon nanotubes (SWCNTs) with diameter less than 0.5 nm begin a metal to semiconductor transition and these ultra-small SWCNTs can normally maintain their metallicities. The band gap behavior of these SWCNTs intrinsically originates from the long axial direct bond lengths and the severe curvature. The gap opening comes mainly from the transfer of pπ electrons. And the localized π and σ states can result in a lower electrical conductivity. This band gap behavior suggests that it has potential to find applications in nano-electromechanical system.     

单壁BN纳米管和碳纳米管物理吸附储氢性能的理论对比研究

采用巨正则蒙特卡罗方法(GCMC)研究了单壁氮化硼纳米管(SWBNNTs)和单壁碳纳米管(SWCNTs)的物理吸附储氢性能,主要对比研究了纳米管的管径、温度和手性对二者物理吸附储氢量的影响. 研究结果表明：在低温下,SWBNNTs的物理吸附储氢性能优于相应的SWCNTs;但是随着温度的升高,二者的物理吸附储氢性能差别越来越小,在常温下,SWBNNTs不具备有比SWCNTs更强的物理吸附储氢性能,而是和相同条件下的SWCNTs相差不大,只是在高压下的物理吸附储氢量稍稍大于SWCNTs,并给出了合理的理论解释 关键词： 巨正则蒙特卡罗方法(GCMC) 单壁氮化硼纳米管(SWBNNTs) 单壁碳纳米管(SWCNTs) 储氢     

Fabrication of superhydrophobic silica-based surfaces with high transmittance by using tetraethoxysilane precursor and different polymeric species

The preparation of superhydrophobic silica-based surfaces via the sol-gel process through the addition of different polymeric species into the precursor solution was done in this study. The surface roughness of the films was obtained by removing the organic polymer at a high temperature, and then the hydrophobic groups were bonded onto the films with a monolayer by chemical reaction with hexamethyldisilazane (HMDS). The characteristic properties of the as-prepared films were analyzed by contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), nitrogen adsorption/desorption, and UV-vis scanning spectrophotometer. The experimental results revealed that the superhydrophobic thin films with high transmittance could easily be prepared using polypropylene (PPG), polyethylene (PEG), and poly(vinylpyrrolidone) (PVP). Surface roughness and pore size were enhanced using PPG polymeric species. The distribution of pore size was from the microporous to the mesoporous and marcoporous regions. In addition, the contact angles of the rough surfaces prepared at 500 °C without modification of HMDS were smaller than 5° but larger than 156° after modified by HMDS.     

Thermally oxidized aluminum as catalyst-support layer for vertically aligned single-walled carbon nanotube growth using ethanol

Characteristics and role of Al oxide (Al-O) films used as catalyst-support layer for vertical growth of single-walled carbon nanotubes (SWCNTs) were studied. EB-deposited Al films (20 nm) were thermally oxidized at 400 °C (10 min, static air) to produce the most appropriate surface structure of Al-O. Al-O catalyst-support layers were characterized using various analytical measurements, i.e., atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and spectroscopy ellipsometry (SE). The thermally oxidized Al-O has a highly roughened surface, and also has the most suitable surface chemical states compared to other type of Al-O support layers. We suggest that the surface of thermally oxidized Al-O characterized in this work enhanced Co catalyst activity to promote the vertically aligned SWCNT growth.     

Surface properties of UV-irradiated poly(vinyl alcohol) films containing small amount of collagen

The surface properties of poly(vinyl alcohol) (PVA) films in the presence of 1%, 3% and 5% of collagen before and after UV-irradiation have been studied by atomic force microscopy (AFM) and by contact angle measurements. PVA films have been obtained by solvent evaporation from water solution of PVA and PVA containing small amount of collagen. After drying, the samples were irradiated with UV light wavelength λ = 254 nm in air. Surface properties before and after UV-irradiation were observed using AFM. Contact angles of two liquids: diiodomethane (D) and glycerol (G) on polymeric films were measured at constant temperature using goniometer.The results have shown that the contact angle and the surface free energy for PVA films were altered by UV-irradiation. These alterations indicate photooxidation and an increase of polarity of the surface. The comparison of surface properties of PVA films and PVA containing collagen points out that collagen is more sensitive to photooxidation than PVA and PVA/collagen blends. PVA films containing collagen easier undergo photooxidation process with formation of new polar groups than pure PVA films.