Surface analysis of long-distance oxygen plasma sterilized PTFE film

The influence of long-distance oxygen plasma sterilization on surface properties of substrate material, i.e., medical poly(tetrafluoroethylene) (PTFE), and aging effect of these sterilized PTFE film surfaces were investigated by contact angle measurement, mass loss determination, scanning electron microscopy (SEM) as well as bacterial adhesion and platelet adhesion measurements in vitro, respectively. The changes in chemical structure of sterilized PTFE film were followed using X-ray photoelectron spectroscopy (XPS). As a result of plasma sterilization oxygen-containing functional groups (such as CO and CO), especially the CO group are introduced into PTFE surfaces, and thus pronounced increases of surface free energy and surface wettability are presented when the sample positions are within 0-40 cm. The film surface wettability degrades little as the aging time continued as long as 190 days. At the same time, the minimal surface degradation and damage occur on the sterilized PTFE when the sample position is at 40 cm. Moreover, the antibacterial adhesion and blood compatibility of sterilized PTFE surface are enhanced and the optimal effects are also obtained at 40 cm. The essential reason may be due to the optimal equilibrium between surface wettability and surface damage, which is achieved at 40 cm. Overall, of the surface properties of long-distance oxygen plasma sterilized PTFE analyzed, the sterilization at 40 cm is optimal.     

Mössbauer spectroscopy study on the hydrothermal transformation α-FeOOH→α-Fe2O3

The reaction kinetics of the hydrothermal transformation -FeOOH-Fe₂O₃ was studied by means of Mössbauer spectroscopy. From the reaction isotherms, a monomolecular, first order reaction was found to characterise the hydrothermal transformation of alpha oxihydroxide to the alpha iron oxide. The rate constant as well as the activation energy of this process were determined. No intermediate phases were identified in the hydrothermal samples. The thermodynamic properties of the hydrothermal system -FeOOH-Fe₂O₃ in correlation with Mössbauer spectroscopy data are discussed.     

Unitary Correlations and the Fejér Kernel

Let M be a unitary matrix with eigenvalues t _j , and let f be a function on the unit circle. Define X _f (M)=f(t _j ). We derive exact and asymptotic formulae for the covariance of X _f and X _g with respect to the measures |(M)|²dM where dM is Haar measure and an irreducible character. The asymptotic results include an analysis of the Fejér kernel which may be of independent interest.     

Formation of a high hydrophilic/hydrophobic contrast surface on PET substrates by ECR generated sulfur hexafluoride plasma

High hydrophilic/hydrophobic contrast surfaces on polyethylene terephthalate (PET) substrates were formed by shadow mask technique in electron cyclotron resonance generated sulfur hexafluoride plasma atmosphere. The X-ray photoelectron spectroscopy (XPS) analyses indicate that the unmasked PET surfaces contained a high proportion of the CF₂-CF₂ groups, and therefore were hydrophobic with large water contact angle. However, the surface wettability was found to increase drastically on the masked PET surfaces. This could be resulted from a mass of COF (acid fluoride) compounds observed by XPS on the masked film surfaces. The COF compounds could react with atmospheric moisture to form -COOH groups, which in turn increased the surface wettability. In addition, the surface wetting property of the masked areas was found to change significantly with the plasma treatment time, the mask-to-substrate distance and the storage time after the treatment. The best contract in water contact angle obtained from the treated PET samples was larger than 100° after 168 h of storage.     

Invariants of 3-manifolds and projective representations of mapping class groups via quantum groups at roots of unity

An example of a finite dimensional factorizable ribbon Hopf -algebra is given by a quotientH=u _q (g) of the quantized universal enveloping algebraU _q (g) at a root of unityq of odd degree. The mapping class groupM _g,1 of a surface of genusg with one hole projectively acts by automorphisms in theH-moduleH ^*g , ifH ^* is endowed with the coadjointH-module structure. There exists a projective representation of the mapping class groupM _g,n of a surface of genusg withn holes labeled by finite dimensionalH-modulesX ₁, ...,X _n in the vector space Hom _H (X ₁ ... X _n ,H ^*g ). An invariant of closed oriented 3-manifolds is constructed. Modifications of these constructions for a class of ribbon Hopf algebras satisfying weaker conditions than factorizability (including most ofu _q (g) at roots of unityq of even degree) are described.This work was supported in part by the EPSRC research grant GR/G 42976.     

A simple formula for low-energy sputtering yields

A simple formula for low-energy sputtering yields of elemental targets is presented. The formula follows directly from Sigmund's theory but includes a modified form of the function(M _t /M _p ) and an accurate expression for the nuclear stopping cross section. Good agreement with experimental results is obtained for the projectiles Ne, Ar, Kr sputtering not too reactive surfaces at energies 1 keV. Further experiments are suggested as well as theoretical work concerning the meaning of the surface binding energy and the effect of the surface on the sputtering process in general.     

Modification of wetting properties of CR39 by plasma source ion implantation

Plasma source ion implantation (PSII), a hybrid implantation technique between ion beams and immersion plasmas has been used to modify CR39 surfaces for improved wettability providing both advancing (θ_a) and receding (θ_r) contact angles below 5°. The modifications brought to the polymer surface structure have been characterized by X-ray photoelectron spectroscopy (XPS) and its combination with chemical derivatization (CD-XPS). Oxygen desorption has been observed in spite of the very hydrophilic surfaces. C_1s XPS peak has been displaced toward greater energies, while the opposite has been found for O_1s, both involving new components and strong modifications after ion implantation treatment. Strong evidences about the formation of new chemical functions, like OOH, COOH and CC, have been found and have provided an explanation for the increased wettability.     

Chemical reactions as dynamical systems on the interval

We consider the most general chemical reaction of the typen ₁ A ₁+...+n _N A _N m ₁ B ₁+...+m _M B _M whereN,M1,n ₁,...,n _N andm ₁,...,m _M are positive integers defining the stoichiometry, andA ₁,...,A _N andB ₁,...,B _M are the names of chemicals or ions. We assume that _i=1 ^N n_i= _j=1 ^M m_j. The time evolution of the concentrations is given by the law of mass action and leads to a dynamical system (with discrete or continuous time) which is governed by a polynomial map of the interval [B, C], where B0 and C1. We define the physically meaningful range for the parameters of the map, and we show that, within such a range, the map has a unique fixed point, which is stable and a global attractor, with the exception of one particular case, where bifurcation is observed.     

Coupled Hamiltonians and three-dimensional short-range wetting transitions

We address three problems faced by effective interfacial Hamiltonian models of wetting based on a single collective coordinate

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(y) representing the position of the unbinding fluid interface. Problems (P1) and (P2) refer to the predictions of non-universality at the upper critical dimension d = 3 at critical and complete wetting, respectively, which are not borne out by Ising model simulation studies. (P3) relates to mean-field correlation function structure in the underlying continuum Landau model. Building on earlier work by Parry and Boulter we investigate the hypothesis that these concerns arise due to the coupling of order parameter fluctuations near the unbinding interface and wall. For quite general choices of collective coordinates X_i(y) we show that arbitrary two-field models H[X₁,X₂] can recover the required anomalous structure of mean-field correlation functions (P3). To go beyond mean-field theory we introduce a set

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of Hamiltonians based on proper collective coordinates s(y) near the wall which have both interfacial and spin-like components. We argue that an optimum model H[s,

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]

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, in which the degree of coupling is controlled by an angle like variable δ^*, best describes the non-universality of the Ising model and investigate its critical behaviour. For critical wetting the appropriate Ginzburg criterion shows that the true asymptotic critical regime for the local susceptibility χ₁ is dramatically reduced consistent with observations of mean-field behaviour in simulations (P1). For complete wetting the model yields a precise expression for the temperature dependence of the renormalised critical amplitude θ in good agreement with simulations (P2). We highlight the importance of a new wetting parameter which describes the physics that emerges due to the coupling effects.     

Studies on radiation effects of PTFE. I. Changes in crystallizing behavior and number average molecular weight of PTFE irradiated at different temperatures

The present work deals with changes in the number average molecular weight (M _n) of PTFE irradiated at different temperatures. A decrease in M _n was observed and attributed to the scission of polymer chains. On the other hand, it was also observed that M _n decreased to a minimum value with increasing irradiation dose and then increased; the doses at which the minimum value of M _n occurs are temperature dependent. The increase is explained as being due to crosslinking reactions occurring during the irradiation of PTFE.     

Surface modification of porous poly(tetrafluoraethylene) film by a simple chemical oxidation treatment

A simple, inexpensive and environmental chemical treatment process, i.e., treating porous poly(tetrafluoroethylene) (PTFE) films by a mixture of potassium permanganate solution and nitric acid, was proposed to improve the hydrophilicity of PTFE. To evaluate the effectiveness of this strong oxidation treatment, contact angle measurement was performed. The effects of treatment time and temperature on the contact angle of PTFE were studied as well. The results showed that the chemical modification decreased contact angle of as-received PTFE film from 133 ± 3° to 30 ± 4° treated at 100 °C for 3 h, effectively converting the hydrophobic PTFE to a hydrophilic PTFE matrix. The changes in chemical structure, surface compositions and crystal structure of PTFE were examined by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), respectively. It was found that the F/C atomic ratio decreased from untreated 1.65-0.10 treated by the mixture at 100 °C for 3 h. Hydrophilic groups such as carbonyl (CO) and hydroxyl (OH) were introduced on the surface of PTFE after treatment. Furthermore, hydrophilic compounds K_0.27MnO₂·0.54H₂O was absorbed on the surface of porous PTFE film. Both the introduction of hydrophilic groups and absorption of hydrophilic compounds contribute to the significantly decreased contact angle of PTFE.     

Determination of the Breakage and Wetting Parameters of Calcite and Their Correlations

This paper presents the breakage and wetting parameters of calcite mineral obtained experimentally and establishes a correlation between these characteristic parameters. The breakage parameter obtained from the different feed sizes of grinding is the specific rate of breakage (S_i). The wettability parameter, obtained from surface chemistry‐based processes such as contact angle measurements or flotation methods, is the critical surface tension of wetting of a solid or mineral (γ_c). Calcite mineral, studied for the determination of the above parameters and their correlations, was ground in a laboratory‐size ceramic ball mill with dry, wet and chemically aided grindings and tested extensively to determine the γ_c values by using a contact angle goniometer and a newly designed micro‐column flotation cell. The highest S_i value obtained was 0.35 min^?1 for sodium dodecyl sulfate (SDDS)‐aided grinding, and the lowest S_i value was 0.26 min^?1 for dry grinding of the ?600+425 feed in the mill. The γ_c values for calcite were obtained as 34.0–34.9 mN/m for SDDS‐treated calcite surfaces, 29.9–31.4 mN/m for sodium oleate‐treated surfaces and >72 mN/m for both dry and wet ground products whose surfaces were not treated chemically. Some correlations were established between the S_i and γ_c parameters; as the S_i increases, γ_c decreases, indicating that relatively more hydrophobic surfaces are broken faster for the largest sizes, resulting in higher S_i values with more fines (lower γ of B_{i, j}) in the finer size distribution region (i.e. ?150 μm).     

Controlling wettability by light: illuminating the molecular mechanism

The functionalisation of a surface with an organic monolayer containing photoactive moieties such as the azobenzene chromophore opens an elegant route for controlling its wettability by light. In this paper we investigate the microscopic origin of the macroscopic change in wettability upon photo-induced cis-trans isomerization of a copolymeric diphenyl-diazene Langmuir-Blodgett monolayer. Polarised UV-Vis and FTIR spectroscopy have been used to monitor the orientational order of various functional groups, Atomic Force Microscopy and Imaging Ellipsometry is employed for the quantification of the surface roughness and morphology, contact angle and surface potential measurements are carried out for a characterisation of the polar ordering. The data analysis is further supported by semi-empirical and ab-initio calculations of the molecular dipole moments and the normal IR-modes of the fluorinated chromophore. The combination of all these techniques provides a detailed molecular picture. The data suggest that changes in the projection of the dipole moment onto the surface normal caused by isomerization of the azobenzene are responsible for the observed changes in the surface energy. This knowledge allowed us to predict guidelines for the synthesis of molecules in order to maximize the wetting contrast upon photo-irradiation. Received 5 September 2002 Published online: 16 April 2003 RID="a" ID="a"e-mail: hubert.motschmann@mpikg-golm.mpg.de     

Calabi-Yau manifolds of some special forms

Let M=M ₁×...×M _m be a product of Kähler C-spaces with second Betti numbers b ₂(M _i )=1 (1im). The work establishes that the complete intersections X of M produce a finite number of N-dimensional Calabi-Yau manifolds. Moreover, if b ₄(M _i )=1, then the complete intersections with vanishing first Pontrjagin classes are finitely many, as well.On the other hand, we consider hypersurfaces of weighted projective spaces and give an explicit formula for their Euler characteristics. As in the previous case, it turns out that only a finite number of these are Calabi-Yau manifolds.     

Distribution of Vacancies in a Hybrid M<Subscript>(5–11/18)</Subscript>X<Subscript>(5–11/18)</Subscript> Superstructure of a High-Temperature Ordered β-TiO Phase

A new structural model of the high-temperature ordered β-TiO phase of titanium monoxide with vacancies in metallic and nonmetallic sublattices has been proposed. The model suggests that the vacancies are simultaneously distributed over sites of two partially disordered superstructures: monoclinic M₅X_5(mon) (space group C2/m (A2/m)) and cubic M₅X_5(cub) (space group Pm\(\overline 3 \)m). The hybrid superstructure belongs to space group P1m1 of the monoclinic system. The proposed notation M_(5–11/18)X_(5–11/18) of the hybrid superstructure takes into account an expansion of the vacancy sublattice due to the superposition of initial \({M_5}{X_{{5^ - }}}\) type superstructures. It is shown that the arrangements of the superstructure reflections in the diffraction spectra of the M_(5–11/18)X_(5–11/18) and M₅X_5(cub) superstructures are identical.     

正癸烷纳米液滴润湿特性的分子动力学研究

流体液滴在固体表面的浸润性对其润滑性能至关重要.本文利用分子动力学方法研究了正癸烷纳米液滴在铜表面上的润湿特性.结果表明：在平坦光滑表面上,壁面的厚度和分子数目对润湿效果影响不大.随着壁面能量势阱参数εs 增大,接触角线性减小.随着温度升高,液滴的接触角减小.在沟槽粗糙表面上,随着粗糙度因子增大,对于疏液表面,接触角增大到一定值后基本保持不变,符合Cassie理论;中性和亲液表面接触角则会减小,为Wenzel润湿模式.当表面分数增大时,疏液与亲液表面接触角整体呈减小的趋势,对中性表面影响不大.当温度升高时,粗糙疏液表面接触角会增大,润湿效果更差,而粗糙中性和亲液表面液滴润湿性会更好.     

Electrostatic properties of PE and PTFE subjected to atmospheric pressure plasma treatment; correlation of experimental results with atomistic modeling

The use of an atmospheric pressure glow discharge (APGD) plasma was used at Kennedy Space Center (KSC) to increase the hydrophilicity of spaceport materials to enhance their surface charge dissipation and prevent possible electrostatic discharge (ESD) in spaceport operations. Significant decreases in charge decay times were observed after tribocharging the materials using the standard KSC tribocharging test. The polarity and amount of charge transferred was dependant upon the effective work function differences between the respective materials. In this study, PE and PTFE were exposed to a He+O₂ APGD. The pre and post-treatment surface chemistries were analyzed by X-ray photoelectron spectroscopy and contact angle measurements. Semi-empirical and ab initio calculations were performed to correlate the experimental results with some plausible molecular and electronic structure features of the oxidation process. For the PE, significant surface oxidation was observed, as indicated by XPS showing C–O, CO, and O–CO bonding, and a decrease in the surface contact angle from 98.9° to 61.2°. For the PTFE, no C–O bonding appeared and the surface contact angle increased indicating the APGD only succeeded in cleaning the PTFE surface without affecting the surface structure.The calculations using the Parametric Method 3 (PM3) and Density Function Theory (DFT) methods were performed on single and multiple oligomers to simulate a wide variety of oxidation scenarios. Calculated work function results suggest that regardless of oxidation mechanism, e.g. –OH, O or a combination thereof, the experimentally observed levels of surface oxidation are unlikely to lead to a significant change in the electronic structure of PE and that its increased hydrophilic properties are the primary reason for the observed changes in its electrostatic behavior. The calculations for PTFE argue strongly against significant oxidation of that material, as confirmed by the XPS results.     

Adjustable wettability of paperboard by liquid flame spray nanoparticle deposition

Liquid flame spray process (LFS) was used for depositing TiO_x and SiO_x nanoparticles on paperboard to control wetting properties of the surface. By the LFS process it is possible to create either superhydrophobic or superhydrophilic surfaces. Changes in the wettability are related to structural properties of the surface, which were characterized using scanning electron microscope (SEM) and atomic force microscope (AFM). The surface properties can be ascribed as a correlation between wetting properties of the paperboard and the surface texture created by nanoparticles. Surfaces can be produced inline in a one step roll-to-roll process without need for additional modifications. Furthermore, functional surfaces with adjustable hydrophilicity or hydrophobicity can be fabricated simply by choosing appropriate liquid precursors.     

Diffraction spectra of order–order transition structural states in titanium monoxide

A new class of M_(n?i)X_(n?i) superstructures (n is an integer constant and i is a rational variable) that are formed after incomplete equilibrium second-order order–order phase transitions in solid solutions and in compounds with atom–vacancy ordering is proposed. New superstructures are superpositions of partially disordered M _n ?X _n superstructures of various symmetries in the matrix of the basic crystal structure. The model parameters affecting the positions and intensities of superstructure reflections on diffraction patterns have been studied by example of the high-temperature ordered phase β-TiO of titanium monoxide. It has been shown that the diffraction spectra of the low-symmetric M_(5-i)X_(5-i) superstructure (space group P1m1) and the high-symmetric M₅X₅ superstructure (space group Pm3?m) at certain parameters are identical in the positions of superstructure reflections.