毛细上升现象的热力学解释*

从热力学的角度讨论毛细上升平衡高度以及毛细上升现象中的能量转换与守恒。在毛细上升的始终态之间设计了可逆途径,计算了可逆毛细上升过程中系统的赫姆霍兹自由能减少值,系统克服重力以及外压做功的值,并根据能量守恒定律推导出了毛细上升平衡高度和球形曲面的拉普拉斯方程。该方法拓展了热力学在表面现象中的应用,并有利于学生理解毛细上升现象的能量来源。     

诱导成膜聚合与IPN界面

本文简要介绍了一种新颖的聚合物/聚合物复合薄膜的制备方法——诱导成膜聚合法。即用一种高分子溶液作某一能溶于该溶液的单体的诱导成膜剂,诱导单体成膜。经聚合后,便得到具有IPN界面的聚合物/聚合物层状复合薄膜。     

Monte Carlo Simulation of Polymer Reactions at Interfaces

Adhesion of immiscible polymers during two‐component injection moulding may be improved by transreactions of properly functionalised components. We performed MC simulations based on the three‐dimensional coarse‐grained bond fluctuation model (BFM) including a thermal interaction potential in with energy to characterise the behaviour of several selected types of chemical reactions, which are governed by activation energies of E_A = 0, 1, 3 and 5 k_BT. The consumption of reactive monomers for all the reactions in the time interval below the Rouse time τ_R exhibits a typical crossover from a kinetic‐controlled to a diffusion‐controlled behaviour and can be described by a bimolecular kinetic ansatz.

     

Polymer and Mesoporous Silica Microspheres with Chiral Nematic Order from Cellulose Nanocrystals

Polymer microspheres with chiral nematic order were obtained from an emulsion polymerization technique using cellulose nanocrystals (CNCs) as the template. The growth of the liquid crystals from tiny tactoids to droplets with spherical symmetry was captured and investigated by both optical and electron microscopy for the first time. The size of the microspheres could be tuned between tens and hundreds of micrometers; to obtain single, integrated chiral nematic kernels, the size of water droplets in the emulsion should be similar to that of CNC tactoids. Through a double‐matrix templating method, novel silica microspheres with chiral nematic order were fabricated, which showed a high surface area and mesoporosity. The methods developed here may help to reveal the evolution of other self‐assembling systems, and these materials have potential applications in optical devices and chiral separations.     

A Ten-Year Perspective on Twist-Bend Nematic Materials

The discovery of the twist-bend nematic phase (N_TB) is a milestone within the field of liquid crystals. The N_TB phase has a helical structure, with a repeat length of a few nanometres, and is therefore chiral, even when formed by achiral molecules. The discovery and rush to understand the rich physics of the N_TB phase has provided a fresh impetus to the design and characterisation of dimeric and oligomeric liquid crystalline materials. Now, ten years after the discovery of the N_TB phase, we review developments in this area, focusing on how molecular features relate to the incidence of this phase, noting the progression from simple symmetrical dimeric materials towards complex oligomers, non-covalently bonded supramolecular systems.     

Study of Adhesion and Fracture of Polymer Laminates by Imaging of Interfaces

The adhesion and fracture of styrene‐acrylonitrile random copolymer and poly(methyl methacrylate) (PMMA/SAN) laminates were studied. They showed a drastic transition from brittle to ductile on varying the acrylonitrile (AN) content in SAN, with changes in the fracture mode from interfacial failure to cohesive fracture. Energy‐filtering transmission electron microscopy (EFTEM) and scanning electron microscopy (SEM) with an in‐lens detector system were employed to study the interface and adhesion of the laminates. The effect of the AN content in SAN on the PMMA/SAN interfacial structures could be revealed by imaging of the interfaces using elemental mapping and electron energy loss spectroscopy (EELS). The in‐lens detector system in the SEM enabled the differentiation of thin interfaces with poor adhesion strength, yielding smooth and flat fracture surfaces, where numerous nanosized fibrils were formed normal to the surfaces.

     

Bacterial Imprinting at Pickering Emulsion Interfaces

The tendency of bacteria to assemble at oil–water interfaces can be utilized to create microbial recognition sites on the surface of polymer beads. In this work, two different groups of bacteria were first treated with acryloyl‐functionalized chitosan and then used to stabilize an oil‐in‐water emulsion composed of cross‐linking monomers that were dispersed in aqueous buffer. Polymerization of the oil phase followed by removal of the bacterial template resulted in well‐defined polymer beads bearing bacterial imprints. Chemical passivation of chitosan and cell displacement assays indicate that the bacterial recognition on the polymer beads was dependent on the nature of the pre‐polymer and the target bacteria. The functional materials for microbial recognition show great potential for constructing cell–cell communication networks, biosensors, and new platforms for testing antibiotic drugs.     

Thermodynamics of polymer systems

This work gives an introduction into the thermodynamic modeling of polymer systems. After a short overview about the different basics of thermodynamic models, results obtained with the recently proposed PC-SAFT equation of state are discussed exemplarily for systems containing polymers as well as copolymers.     

On the Uniaxial–Biaxial Nematic Phase Transition in Liquid‐Crystalline Polymers and Elastomers

We study how the uniaxial–biaxial nematic phase transition changes its nature when going from a low‐molecular‐weight liquid crystal to a liquid‐crystalline elastomer or polymer (the latter above the Maxwell frequency) and find a qualitative change due to the presence of a coupling to the strain field in these materials. While this phase transition can be of second‐order in low‐molecular‐weight materials, as is also experimentally observed, we show here that the order of this phase transition is changed generically to no phase transition at all or to a first‐order phase transition in mean‐field approximation. We analyze the influence of an external mechanical stress field above the uniaxial–biaxial nematic phase transition and find that either biaxial nematic order is induced, which is linear or quadratic in the stress intensity, or no response to an external stress results at all, depending on the relative orientation of the applied shear with respect to the director of the uniaxial nematic phase.     

Interfacial Thermodynamics of Polymeric Mesophases

Summary: A complete mechanical‐thermodynamical formulation for multicomponent nematic polymer‐isotropic fluid interfaces is derived, validated, and used to derive the structure and shape equations for these soft anisotropic polymer interfaces. The fundamental role of liquid crystalline order and long range effects in coupling bulk and interfacial effects, and in coupling thermodynamical/liquid crystalline order/geometrical variables is demonstrated, discussed, and validated. The Gibbs‐Duhem nemato‐thermodynamics equation emerges from an interfacial tension γ = γ(Θ, μ, Q , ∇_s Q , k ) that depends on temperature (Θ), chemical potential (μ), nematic tensor order parameter Q , surface gradients of Q , and geometry k , and leads to new couplings in these enhanced phase spaces. The role of entropy and adsorption, and long range effects on interfacial shape and structure selection is revealed. For flat interfaces the preferred structure emerges from a competition between energy, entropy, and adsorption.     

Hydrogen‐Bond‐Selective Phase Transfer of Nanoparticles across Liquid/Gel Interfaces

In the swim : Colloidal nanoparticles coated with polylactide (PLA, red) and poly(ethylene glycol) brushes (PEG, black) can transfer from organic to aqueous phases across liquid/liquid or liquid/gel interfaces during degradation of the PLA coating (see picture: first step), which is driven selectively by the hydrogen bonding of the PEG coating with the aqueous phase (second step).

     

Soft Polymer Janus Nanoparticles at Liquid–Liquid Interfaces

Soft polymeric Janus nanoparticles (JNPs), made from polystyrene‐b‐poly(butadiene)‐b‐poly(methylmethacrylate), PS‐PB‐PMMA, triblock terpolymers, assemble into a monolayer at the water–oil interface to reduce interfacial tension. The extent to which the polymer chains can deform influences the packing density of the JNPs at the interface. The longer the polymer chains are relative to the core, the softer are the JNPs, resulting in a JNPs assembly with a lower initial lateral packing density. The interfacial activity of JNPs can be further tuned by complexation of the PMMA chains with lithium ions that are introduced into the water phase. This work provides a fundamental understanding of soft JNPs packing at the water–oil interface and provides a strategy to tailor the areal density of soft JNPs at liquid–liquid interface, enabling the design of smart responsive structured‐liquid systems.     

Entropic Sampling of Free and Ring Polymer Chains

Summary: We extend Monte Carlo (MC) methods developed in our previous paper (J. Phys. A, Math. Gen. 2004 , 37, 1573) and based on entropic sampling within Wang‐Landau (WL) algorithm to the simulation of lattice and continuous models of ring polymers. For a continuous freely joined ring chain (an equilateral polygon) with hard sphere monomer units, the excess entropy of rings relative to the corresponding reference system, a phantom ring chain, is obtained. The excess specific entropy is calculated for a set of various diameters of monomer units d and chain lengths N. Its limiting values for ( ) are estimated for each d and coincidence with those for corresponding free chains is demonstrated. We also develop a WL approach to calculate thermal properties of free and ring continuous chains with an Lennard‐Jones attraction between nonbonded beads being added to hard core repulsion at fixed d. The obtained energy distributions provide calculation of canonical properties such as conformational energy, heat capacity, entropy, and mean square radius of inertia. Thermal results for free and ring chains are being finally compared. Analogous calculations are performed for lattice‐free chains and rings.

     

Synthesis of Polymer Nanoparticles via Vapor Phase Deposition onto Liquid Substrates

In this article, the growth of polymer nanoparticles formed at the liquid–vapor interface via vapor phase polymerization is studied. The particles grow by polymer aggregation, which is driven by the surface tension interaction between the liquid and polymer. It is demonstrated that the mechanism of particle growth is determined by whether polymer particles remain at the liquid–vapor interface or submerge into the liquid. The position of the particles depends on the interaction between the polymer and the liquid. For example, the deposition of poly(n‐butyl acrylate) onto poly(dimethyl siloxane) and Krytox liquids leads to the formation of nanoparticles that remain at the liquid–vapor interface. The size of these particles increases as a function of deposition time. The deposition of poly(4‐vinylpyridine) onto poly(dimethyl siloxane) and Krytox leads to the formation of nanoparticles that submerge into the liquid. The size of these particles does not significantly change with deposition time. Our study offers a new rapid, one‐step synthetic approach for fabricating functional polymer nanoparticles for applications in catalysis, photonics, and drug delivery.

     

On the Physical Parameters and Relaxation Processes in Nematic Azobenzene Polymers for Optical Nanowriting

The possibility of achieving devices for rewritable optical storage is provided by liquid-crystalline polymers with azobenzene side groups, because they undergo photochemically induced trans-cis reversible isomerization. In this work we overview our investigations into a nematic azobenzene-polymethacrylate (PMA4) as a suitable material for optical nanowriting. Relaxation processes over different time-length scales are discussed with particular reference to understanding the interplay between homogeneity at the molecular level, bit stability and working temperature range.     

APplication of Continuous Thermodynamics to the Stability of Polymer Systems. II

A determinant criterion for the critical state in solutions and mixtures of polydisperse polymers is established within the general framework of Gibbs theory. The treatment continues an earlier paper by considering more general Gibbs free energy relations: The function replacing the x-term in the classic Flory-Huggins equation is permitted to depend on a finite number of moments of the polymer distribution(s) so as to embrace most Gibbs free energy relations of practical use. The new criterion leads to a very large reduction of computer time and of needed storage capacity compared to the traditional Gibbs determinant criterion. Some relations known from the literature are shown to be special cases of the established new criterion.     

Nonequilibrium Statistical Thermodynamics of Interfaces

Using Zubarev's theory of the operator, nonequilibrium linear quasithermodynamics is presented. Laws connecting generalized fluxes with generalized forces are formulated. The components of the kinetic transfer coefficients are determined. These are rank 0-4 tensors. Copyright 2000 Academic Press.