聚丙烯表面的计算机模拟

用计算机模拟的方法详细研究了聚丙烯薄膜表面分子级别的结构 .采用无定形本体聚丙烯产生初始的随机父链 ,将一条随机父链在二维边界条件下进行塌陷 ,研究薄膜在真空中的构型 .用 10 0个重复单元的父链生成厚度为 3 5nm的薄膜 .发现薄膜内部密度等于聚丙烯的本体密度 ,而离自由表面 0 8nm处薄膜的密度开始跌落 .主链键在内部随机取向 ,在自由表面附近则明显沿薄膜表面平面取向 ,键开始有序取向的程度大致与质量密度相对于本体密度的减小一致 .与聚丙烯本体相比 ,薄膜表面中CH2 CH 的反式结构和旁式结构是增加的 ,这是因为分子链能更好的沿薄膜平面舒展 .同时通过聚丙烯无定形本体 (3D周期性 )和薄膜 (2D周期性 )中的链的能量的差异计算了薄膜内部能量对表面能量的贡献 .     

Epitaxial growth of isotactic polypropylene on oriented polyethylene from solution

Oriented polyethylene (PE) films with surfaces bounded by the (100) plane were prepared. On the film surfaces, isotactic polypropylene (iPP) was crystallized epitaxially from solution as quadrits with their sides parallel and perpendicular to the polyethylene chain axis. In the through wide-angle x-ray diffraction pattern (taken with incident x-rays normal to the polyethylene film surface), the 111 iPP reflections was observed on the meridian (Parallel to the polyethylene chain axis). In the edge patterns (taken with x-rays incident on the edge of the polyethylene film), 040 and 060 reflections were observed on the equator. From the diffraction patterns, the following lattice coincidence was observed between polyethylene and isotactic polypropylene: (010)iPP//(100) PE, [101]iPP//[001] PE. The Small-angle x-ray scattering patterns showed that edge-on isotactic polypropylene lamellae 9 nm thick were arranged with their long axes inclined at an angle of 40° from the polyethylene axis. Molecular chains were oriented within the lamellae normal to the surfaces.     

Simulation of an amorphous polyethylene nanofiber on a high coordination lattice

Monte Carlo simulations of polyethylene (PE) melts and thin films have previously been performed on the second nearest neighbor diamond (2nnd) lattice by including short and long range interactions. A fiber can be obtained from equilibrated thin film snapshots by increasing another (normal to thin film plane) periodic side to infinity. There is only one effective periodic boundary condition in the simulation. The presence of attractive long range interactions gives cohesion to the fiber. PE fibers, which contain up to 72 chains of C₉₉ and have the radius ≈ 5.0 nm, have been produced and equilibrated on the 2nnd lattice. In these fibers, the density profiles are hyperbolic, with end beads being more abundant than the middle beads at the surface. There are orientational preferences at the surface on the scale of individual bonds and whole chains. Comparison of fibers with different thickness, which contain different number of chains, does not indicate any significant differences in local and global equilibrium properties – for thickness in the range 5.6 to 7.6 nm. Surface energies are calculated directly from the on‐lattice energetics and presented as a function of the fiber radius     

Relation between packing density and thermal transitions of alkyl chains on layered silicate and metal surfaces

Self-assembled layers of alkyl chains grafted onto the surfaces of layered silicates, metal, and oxidic nanoparticles are utilized to control interactions with external media by tuning the packing density of the chains on the surface, head group functionality, and chain length. Characterization through experiment and simulation shows that the orientation of the alkyl layers and reversible phase transitions on heating are a function of the cross-sectional area of the alkyl chains in relation to the available surface area per alkyl chain. On even surfaces, a packing density less than 0.2 leads to nearly parallel orientation of the alkyl chains on the surface, a high degree of conformational disorder, and no reversible melting transitions. A packing density between 0.2 and 0.75 leads to intermediate inclination angles, semicrystalline order, and reversible melting transitions on heating. A packing density above 0.75 results in nearly vertical alignment of the surfactants on the surface, a high degree of crystalline character, and absence of reversible melting transitions. Curved surfaces can be understood by the same principle, taking into account a local radius of curvature and a distance-dependent packing density on the surface. In good approximation, this simple model is independent from the length of the alkyl chains (a minimum length of C10 is required to form sufficiently distinctive patterns), the chemical nature of the surface, and of the surfactant head group. These structural details primarily determine the functionality of alkyl modified surfaces and the temperature of thermal transitions.     

Molecular and Supramolecular Deformations and Disclinations in a Liquid Crystalline Copolyether Thin Films under an Electrostatic Field

An alignment study of a liquid crystalline copolyether TPP‐7/11(5/5) thin films has been carried out in a 10 kV·cm^–1 electrostatic field parallel to the thin film surface normal. This copolyether possesses a negative dielectric anisotropy. The chain molecules are homogeneously aligned in the electric field and they form two‐dimensionally ordered lamellae in a tilted columnar phase when the samples were cooled to room temperature. It is observed that the chain molecules are splayed to form bent lamellae and the chain direction is perpendicular to the tangential direction of the lamellar surfaces. These lamellae thus become replicas of the chain orientation. Due to the flexoelectric effect and density fluctuation on the thin film free surface, disclinations having topological strength s = 1, c = π/4 and defect walls form. These s = 1 disclinations possesses both left‐ and right‐handednesses. Discussion of the defect formations have been attempted.     

Similarities and Differences in the Rapid Crystallization Induced in n‐Tetracontane by an Instantaneous Deep Quench of the Free‐Standing Nanofiber and Free‐Standing Thin Film

The crystallization of a confined short polyethylene chain, n‐tetracontane, quenched from the melt has been investigated by a dynamic Monte Carlo method on a high coordination lattice. The periodic boundary conditions force the formation of a free‐standing nanofiber exposed to a vacuum. After the deep quench, the nanofiber adopts a configuration dominated by extended chains aligned parallel to the fiber axis. The vicinity of the fiber axis is less dense, and less well ordered, than portions of the fiber located further from the fiber axis. Annealing finds that this low‐density region inside the fiber is not as easily removed as is the grain boundary that usually develops inside a free‐standing thin film upon rapid crystallization.     

Internal Architecture of Zwitterionic Polymer Brushes Regulates Nonfouling Properties

In this work, we study how film thickness and chain packing density affect the protein‐resistant properties of polymer brushes in complex media. Polymer brushes based on dual‐functional poly(carboxybetaine acrylamide) (pCB) were prepared via surface‐initiated photoiniferter‐mediated polymerization. By adjusting UV radiation time and solvent polarity, pCB films with different thicknesses can be achieved and characterized using an ellipsometer. The packing density of pCB polymer chains is directly related to the swelling ratio of swollen to collapsed film thicknesses. Results showed that the dry film thickness alone, used often in the literature, is not sufficient to correlate with nonfouling properties and the chain packing density must be considered for the design of nonfouling surface coatings.     

Controllable superhydrophobic and lipophobic properties of ordered pore indium oxide array films

Using the polystyrene (PS) colloidal monolayers as templates, ordered indium oxide pore array films with different morphologies were prepared by sol-dipping method. These porous films took on hydrophilicity, however, after chemical modification, such pore array films displayed both superhydrophobicity and lipophobicity due to rough surface and low surface free energy materials on their surfaces. Interestingly, with increase of the pore size in the films, the superhydrophobicity could be controlled and was gradually enhanced due to the corresponding increase of roughness caused by nanogaps produced by the thermal stress in the annealing process with increase of film thickness.     

Surface roughness and hydrophilicity enhancement of polyolefin‐based membranes by three kinds of plasma methods

The introduction of antibacterial property, conductivity, wettability and antithrombogenicity into polyolefin‐based membranes has evoked much attention, which can be achieved by coating hydrophilic polymers. Therefore, it is necessary to modify the roughness and hydrophilicity of polyolefin‐based membranes to enhance the coating ability. In this paper, three kinds of plasma methods, including inductively coupled (ICP) plasma, radio frequency low pressure (RFP) plasma and atmospheric dielectric barrier discharge (DBD) plasma, were used to modify the surface of the polyethylene (PE), polypropylene (PP) and polyester‐polypropylene (PET–PP) membranes. The surface roughness of the plasma‐modified PE, PP and PET–PP films was investigated by scanning electron microscopy (SEM) and atomic force microscope (AFM). The polar functional groups of films were observed by energy dispersive spectrometer (EDX) and X‐ray photoelectron spectroscopy (XPS). Besides, the hydrophilicity of the plasma‐modified PE, PP and PET–PP films was evaluated by water contact angle measurement. It was found that the surface roughness and hydrophilicity of plasma‐modified PE, PP and PET–PP films increased with the generation of oxygen‐containing functional groups (i.e. C―O, and C?O). The PET–PP membranes were treated by RFP plasma at different processing powers and times. These results indicated that plasma is an effective way to modify films, and the treatment time and power of plasma had a certain accumulation effect on the membranes' hydrophilicity. As for the roughness and hydrophilicity, the DBD plasma modifies the PE film, which is the optimum way to get the ideal roughness and hydrophilicity. Copyright © 2015 John Wiley & Sons, Ltd.     

Efficient Sensing of Explosives by Using Fluorescent Nonporous Films of Oligophenyleneethynylene Derivatives Thanks to Optimal Structure Orientation and Exciton Migration

The fluorescence of thin films of a diimine‐substituted phenyleneethynylene compound can be efficiently quenched by nitroaromatic vapors, which is not the case for the unsubstituted parent compound. Thin‐film porosity is usually considered to be an essential factor for efficient quenching, but in the present case the origin of the quenching is completely different, as both films are nonporous and hermetic to 2,4‐dinitrotoluene (DNT) molecules. The molecular organization in the two crystallized thin films offers a low level of π stacking for both compounds, but the orientation of the phenylenethynylene fluorophore differs markedly with respect to the surface of the films. For the substituted compound, the fluorophore is almost parallel to the surface, thus making it readily available to molecules of a nitroaromatic quencher. This rationale is also observed in the case of a related compound bearing methoxy side chains instead of the long octyloxy moieties. Fluorescence‐lifetime experiments show that the efficient quenching process in the nonporous crystallized films of the substituted compound is due to a fast (<70 ps) diffusion of excitons from the bulk of the film toward the surface where they are quenched, thus providing evidence of antenna effects.     

Strategies toward biocompatible artificial implants: Grafting of functionalized poly(ethylene glycol)s to poly(ethylene terephthalate) surfaces

Epoxide and aldehyde end‐functionalized poly(ethylene glycol)s (PEGs) (M_w = 400, 1000, 3400, 5000, and 20,000) were grafted to poly(ethylene terephthalate) (PET) film substrates that contained amine or alcohol groups. PET‐PAH and PET‐PEI were prepared by reacting poly(allylamine) (PAH) and polyethylenimine (PEI) with PET substrates, respectively; PET‐PVOH was prepared by the adsorption of poly(vinyl alcohol) (PVOH) to PET substrates. Grafting was characterized and quantified by the increase of the intensity of the PEG carbon peak in the X‐ray photoelectron spectra. Grafting yield was optimized by controlling reaction parameters and was found to be substrate‐independent in general. Graft density consistently decreased as PEG chain length was increased. This is likely due to the higher steric requirement of higher molecular weight PEG molecules. Water contact angles of surfaces containing long PEG chains (3400, 5000, and 20,000) are much lower than those containing shorter PEG chains (400 and 1000). This indicates that longer PEG chains are more effective in rendering surfaces hydrophilic. Protein adsorption experiments were carried out on PET‐ and PEG‐modified derivatives using collagen, lysozyme, and albumin. After PEG grafting, the amount of protein adsorbed was reduced in all cases. Trends in surface requirements for protein resistance are: surfaces with longer PEG chains and higher chain density, especially the former, are more protein resistant; PEG grafted to surfaces containing branched or network polymers is not effective at covering the underlying substrate, and thus does not protect the entire surface from protein adsorption; and substrates containing surface charge are less protein‐resistant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5389–5400, 2004     

Monte Carlo Simulation of the Structures and Dynamics of Amorphous Polyethylene Nanoparticles

Monte Carlo simulations of amorphous polyethylene (PE) nanoparticle have been performed on the second nearest neighbor diamond lattice by including short and long‐range interactions. A droplet can be either obtained from equilibrated PE bulk or from nanofiber snapshots by modifying periodic boundary conditions. The presence of attractive long‐range interactions gives cohesion to the nanoparticle. PE nanoparticles, which contain up to 72 chains of C₁₀₀ and have the radius ˜5.0 nm, have been produced and equilibrated on the 2nnd lattice. In these droplets, the density profiles are hyperbolic, with end beads being more abundant than middle beads at the surface. There are orientational preferences at the surface on the scale of individual bonds and whole chains. Comparison of nanoparticles with different sizes, which contain different numbers of chains, does not indicate any significant differences in local and global equilibrium properties – for thickness in the range 5.8 to 7.4 nm. Surface energies are calculated directly from the on‐lattice energetics. The mobility of the chain in the droplet at the level of individual chords or an entire chain is greater than in the bulk, and the mobility increases as the size of the droplet decreases.     

Nanofold‐decorated surfaces from the electrodeposition of di‐alkyl‐cyclopentadithiophenes

This work describes the synthesis and subsequent electrodeposition of 4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene (cyclopentadithiophene) monomers di‐substituted with alkyl chains. Each monomer was electropolymerized in solution to observe their capacity at creating well‐structured, rough surfaces. The length of the alkyl chain substituent has a significant influence on the overall surface morphology and wetting behavior after electropolymerization. In the case of nonsubstituted cyclopentadithiophene monomers or those with short alkyl (methyl and ethyl) substituents, the polymerization proceeds readily, forming rough surfaces that follow the Wenzel regime of wetting. In these cases, the surfaces were decorated with globular agglomerates and woven mat features. The measured surface roughness decreases with alkyl chain length as steric hindrance caused by the alkyl substituents limits electropolymerization. As the alkyl chain substituent increases to propyl chain length and beyond, the increase in steric hindrance is so significant that the surface morphology formed during electrodeposition is primarily due to π‐stacking interactions between very short oligomers formed in solution. With propyl and butyl substituents, nanofold morphology is observed, leading to surfaces with much higher contact angles with water (~132°) that follow the Cassie‐Baxter regime of wetting. This type of surface morphology has only been demonstrated one other time and with the use of fluorinated constituents. This work exposes a mild, fluorine‐free synthetic route to creating nanofold‐decorated surfaces.     

Templating α-helical poly(L-lysine)/polyanion complexes by nanostructured uniaxially oriented ultrathin polyethylene films

We report a templating effect of uniaxially oriented melt-drawn polyethylene (MD-PE) films on α-helical poly(L-lysine)/poly(styrenesulfonate) (α-PLL/PSS) complexes deposited by the layer-by-layer (LBL) method. The melt-drawing process induced an MD-PE fiber texture consisting of nanoscale lamellar crystals embedded in amorphous regions on the MD-PE film surface whereby the common crystallographic c axis is the PE molecular chain direction parallel to the uniaxial melt-drawing direction. The MD-PE film and the α-PLL/PSS deposit were analyzed by atomic force microscopy (AFM) and in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) using polarized light as a complementary method. Both methods revealed that α-PLL/PSS complexes adsorbed at the MD-PE surface were anisotropic and preferentially oriented perpendicular to the crystallographic c direction of the MD-PE film. Quantitatively, from AFM image analysis and ATR-FTIR dichroism of the amide II band of the α-PLL, mean cone opening angles of 12-18° for both rodlike α-PLL and the anisotropic α-PLL/PSS complexes with respect to the PE lamellae width direction were obtained. A model for the preferred alignment of α-PLL along the protruding PE lamellae is discussed, which is based on possible hydrophobic driving forces for the minimization of surface free energy at molecular and supermolecular topographic steps of the PE surface followed by electrostatic interactions between the interconnecting PSS and the α-PLL during layer-by-layer adsorption. This study elucidates the requirements and mechanisms involved in orienting biomolecules and may open up a path for designing templates to induce directed protein adsorption and cell growth by oriented polypeptide- or protein-modified PE surfaces.     

A careful examination of the adsorption step in the alternate layer-by-layer assembly of linear polyanion and polycation

In order to elaborate alternate layer-by-layer assembly as a means to prepare ultrathin films, details of conventional polyion assemblies have been quantitatively analyzed by quartz crystal microbalance (QCM) technique with the aid of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The alternate adsorption of poly(styrenesulfonate) (PSS) and poly(allylamine) (PAM) onto oppositely-charged surfaces displayed the pseudo first-order kinetics and was saturated within 10–20 min at pH 3 and 22°C. It was revealed that drying at every step increased the thickness of adsorbed films due to enhanced surface roughness of the films. Therefore, frequent drying is not profitable for preparing films in a good quality. Non-contact AFM observation revealed that drying of the film with nitrogen stream, forced polymer chains to align to one direction with increasing surface roughness. In contrast, water washing between the consecutive adsorptions was effective for successful alternate adsorption. About 10% of an adsorbed polyion layer was removed by 5-min water washing probably due to removal of the loosely-attached materials.     

Migration and surface modification in polypropylene (PP)/polyhedral oligomeric silsequioxane (POSS) nanocomposites

This paper reports on the migration of POSS‐based nanocomposites both by annealing the melt and by heating the solid blend in the microwave oven. The migration proceeds to all surfaces of the sample as verified by ATR‐FTIR spectra of the bottom and top surfaces. Concentrations of POSS on the surface, exceeding 50%, are obtained. Polarity of the matrix increases POSS migration. During annealing at 190°C, a sublimation of POSS from the upper surface occurs. In air, sublimation is decreased by oxidizing the organic side groups of POSS and the PP to non‐volatile moieties. No sublimation occurs below 100°C. The AFM and SEM‐EDAX verified the high POSS concentration on the surface and indicated very pronounced roughness of the surface of the sample. The static contact angle measurements reveal very high hydrophobicity as well as low surface free energy (SFE) of the surface of the sample, which is close to that of Teflon and of pristine POSS. The migration of POSS is due to its lower surface tension, the entropy considerations, its lower cohesive energy with the matrix chains as compared to the cohesion energy between the chains, and the density and temperature fluctuations of the matrix chains which upon relaxation repulse and propel POSS to the surfaces. Copyright © 2008 John Wiley & Sons, Ltd.     

Accelerated brush growth on nanoparticle surfaces by reversible addition‐fragmentation chain transfer polymerization

It is now well established that controlling the grafted chain lengths and densities on nanoparticle surfaces determines the effective interactions between particles, and their assembly. Here, we present unusual kinetic results for achieving grafted chain lengths longer than the free chains using reversible addition‐fragmentation chain transfer (RAFT) polymerization and discuss the limitations to obtaining polymer grafting density higher than ～0.06 chains/nm². We observe that surface initiated polymerization grows faster than the free chains in solution with high RAFT agent coverage (1.95 agents/nm²) on nanoparticles. The time‐dependence of graft density suggests that activation of the anchored chain transfer agent (CTA) is limited by the diffusion of macro‐radicals within growing grafts. Thus, radical transfer and exchange reactions become inefficient between grafts and free polymer, and convert the surface‐initiated RAFT mechanism to a free radical polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1700–1705     

Thickness dependence of the structural,mechanical and electrical properties of Ni films deposited on polyimide by ion beam‐assisted deposition (IBAD)

Ni thin films with different thicknesses were deposited on pre‐treated polyimide substrates by ion beam‐assisted deposition. Dependence of structural, mechanical and electrical properties of the Ni films on their thickness was investigated. The results showed a clear correlation between film properties and film thickness. The inter‐diffusion at the interface regions of the films with different deposition time were demonstrated by transmission electron microscopy and X‐ray photoelectron spectroscopy. With increasing film thickness, surface roughness of the Ni films firstly decreased and then increased, while the grain size gradually increased. Residual stress of the Ni thin films decreased with increasing Ni film thickness up to 202 nm and then slightly increased as the film thickness further increased. Resistivity decreased, and temperature coefficient of resistivity (TCR) increased with increasing film thickness due to the enhancement of crystallization degree and the increase in grain size. The decrease in surface roughness and residual stress also contributed to the decrease of resistivity and the increase of TCR of the films. An optimal film thickness is suggested, which yielded a relatively high TCR value and low levels of both surface roughness and residual stress. Copyright © 2012 John Wiley & Sons, Ltd.     

Molecular simulation of crystallization in n-alkane ultrathin films: effects of film thickness and substrate attraction

Crystallization in n-alkane ultrathin films supported by solid substrates is investigated by molecular dynamics simulation. We consider a relatively short n-alkane, undecane C11H24, on a flat substrate of varied degree of attraction. By the use of the united atom model for n-alkane, we reveal several characteristics of the thin film crystallization. It is found that the crystalline films consist of thin crystalline lamellae where chains are either parallel or perpendicular to the substrate. The relative amount of both types of lamellae changes systematically with film thickness, substrate attraction, and crystallization temperature; thicker films on substrates of higher attraction comprise dominant parallel lamellae, while thinner films on substrates of weaker attraction prefer the perpendicular lamellae. A clue to the morphogenesis is suggested to be the marked preference of the chain ends to locate on the free surface and on the effectively repulsive substrate. It is also shown that the perpendicular crystals, both on the free surface and on the solid substrate, have melting points higher than that of the bulk.     

Intercation spacing and side chain effects on phosphonium polymers: Thermal,supramolecular, and bactericidal properties

The properties of phosphonium polyelectrolytes (PELs) were evaluated in an effort to assess the influence of both side chain and main chain composition. The influence of side chain was examined by comparing properties of a series of PELs having hydrophobic octyloxy side chains to those of structural analogues lacking the side chains. The influence exerted by backbone flexibility/length of spacer between charges was revealed by comparing properties of two series of polymers with a variable number of methylene units between phosphonium charge‐bearing sites. Side chain composition and spacing between phosphonium units lead to noteworthy influence on thermal stability, glass transition, and crystallinity. The molecular structure of PELs also correlates with trends in film morphology and critical surface energy of PEL dip‐cast films. Sensitivity of morphology to humidity or water in the casting solvent was observed. Supramolecular assembly of films via layer‐by‐layer deposition of PELs alternating with anionic polythiophene derivative layers was also undertaken. The linearity of film growth, amount of material deposited in each bilayer, polycation:polyanion ratio, and film roughness all show noteworthy trends that depend on both the presence/absence of side chains and on spacing between ionic centers. The relationship between side chain and spacer on bactericidal activity against Staphylococcus aureus and Escherichia coli was assessed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 24–34