Temperature stability of the interfacial structure between a sulfonated crystalline alkyl side-chain polymer and a soft adhesive

The fracture toughness of interfaces between a sulfonated alkyl side-chain graft copolymer and a soft acrylic random copolymer containing acrylic acid monomers was investigated with a probe test method. Interfaces between a thin (100 nm) layer of the block copolymer and a thick (100 microm) layer of the acrylic copolymer were prepared at room temperature and subsequently annealed for 7 h at different temperatures. After the annealing step, the interface was quenched to room temperature and tested, a strategy that provides the advantage of keeping constant the mechanical properties of the materials on both sides of the interface so that any major difference in adhesive behavior can only be attributed to a change in the interfacial structure. For annealing temperatures below the crystalline to liquid crystalline transition temperature (86 degrees C), the adhesion energy remained very low and failure occurred by interfacial crack propagation. However when the interface was annealed above that temperature, a much higher adhesion energy was observed at room temperature because of the formation of a fibrillar structure upon debonding. The results indicate that the crystalline order at low temperature is very stable presumably because of the strong interactions between the sulfone groups in the side chains. However, when these interactions weaken and the side chains become liquid crystalline, the surface reconstruction mechanism cannot be prevented and strong interactions formed between the polar parts of the copolymer and the acrylic acid. These strong interactions remain during the cooling step, and a mechanism of surface reconstruction is proposed.     

Confinement effect of polystyrene on the relaxation behavior of polyisobutylene

The dynamic mechanical loss tangent (tan δ) peak of polyisobutylene (PIB) reveals an asymmetrical broad structure with a maximum on the high‐temperature side and a shoulder on the low‐temperature side. By comparing with the literature results, it is suggested that the shoulder and the maximum originate from local segmental motion and Rouse modes, respectively. Blending polystyrene (PS) with PIB has two effects on the relaxation behavior of PIB. One effect is that the maximum and the shoulder are both suppressed, but the maximum is suppressed to a higher extent. After PS forms the continuous phase, the maximum becomes lower than the shoulder, and even almost disappears when the weight ratio of PIB/PS is under 20/80. The other effect is that, before PS forms the continuous phase, the temperature position of the maximum (T_s) and that of the shoulder (T_α) remains constant, but after PS forms the continuous phase, both of them are reduced with decreasing particle size of the PIB phase, in a way similar to nano‐confinement effect on the depression of glass transition temperature. The depression amplitude of T_s is larger than that of T_α. The aforementioned two effects can be interpreted in terms of the limited expansion of free volume of the PIB phase exerted by the PS phase, which affects the maximum to a higher extent than the shoulder because Rouse modes are more sensitive to the free volume than local segments. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Large-amplitude motion in polymer crystals and mesophases

Large-amplitude motion of macromolecules involves mainly rotation about bonds (conformational motion). In the liquid phases, the large-amplitude motion is coupled with disorder and accounts for the flow and viscoelastic behavior. Perfectly ordered crystals, in contrast, permit only little large-amplitude motion. The mesophases are intermediate in order and mobility. In crystals, large-amplitude motion leads initially to gauche defects and kinks (conformational defects), and ultimately may produce conformationally disordered crystals (condis crystals). Molecular dynamics simulations of crystals with up to 30 000 atoms have been carried out. They show the mechanism of defect formation, permit the study of the distribution of defects, and lead to a visualization of the hexagonal crystal phase. The main-chain liquid-crystalline macromolecules and condis crystals, the two mesophases of polymers, can be distinguished on the basis of an analysis of the phase separation (partial crystallinity), present in condis crystals and not in liquid crystals. Solid state NMR is the tool of choice for the detection of mobile and rigid phases. In highly drawn fibers one can find four different states of order and mobility. Besides the (defect) crystalline phase and the isotropic amorphous phase, an intermediate oriented phase and a rigid amorphous phase exist.     

Influence of deformation on irreversible and reversible crystallization of poly(ethylene‐co‐1‐octene)

The effect of uniaxial deformation and subsequent relaxation at ambient temperature on irreversible and reversible crystallization of homogeneous poly(ethylene‐co‐1‐octene) with 38 mol % 1‐octene melt‐crystallized at 10 K min was explored by calorimetry, X‐ray scattering, and Fourier transform infrared spectroscopy. At 298 K, the enthalpy‐based crystallinity of annealed specimens increased irreversibly by stress‐induced crystallization from initially 15% to a maximum of, at least, 19% when a permanent set of more than 200% was attained. The crystallinity increased by formation of crystals of pseudohexagonal structure at the expense of the amorphous polymer, and as a result of destruction of orthorhombic crystals. The stress‐induced increase of crystallinity was accompanied by an increase in the apparent specific heat capacity from 2.44 to about 2.59 J g^?1 K^?1, which corresponds to an increase of the total reversibility of crystallization from, at least, 0.10 to 0.17% K^?1. The specific reversibility calculated for 100% crystallinity increased from 0.67 to 0.89% K^?1 and points to a changed local equilibrium at the interface between the crystal and amorphous phases. The deformation resulted in typical changes of the phase structure and crystal morphology that involve orientation and destruction of crystals as well as the formation of fibrils. The effect of the decrease of the entropy of the strained melt on the reversibility of crystallization and melting is discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1223–1235, 2002     

Effect of crystallization time on the properties of melt-crystallized linear polyethylene

Linear polyethylene was crystallized isothermally from the melt. Specimens were removed at different crystallization times and quenched to room temperature. The density, static mechanical properties, and small-angle x-ray scattering (SAXS) behavior of these specimens were measured at room temperature. The density and Young's modulus increased with crystallization time, whereas the upper yield point decreased with crystallization time. SAXS data showed that a zero-angle peak gradually disappeared as crystallization time increased. Concurrently, the breadth of the SAXS peaks, the Bragg angle, and the integrated intensity decreased. Changes in the ratio of second- and first-order peak intensities were also noted. On the basis of the SAXS and density data, it was concluded that a competition exists between the thickening of existing crystals and the creation of new crystallites between the older ones. At relatively low crystallization times, numerous new crystals can form during quenching to room temperature, whereas quenching after prolonged crystallization primarily results in the additional thickening of existing crystals. No change in the density of the amorphous material is found. A model is given whereby the upper yield stress is coupled to these morphological changes through a stress concentration effect caused by a decreased population of chains connecting adjacent crystallites. The tie-chain population change occurs by their elimination as crystallites disappear.     

Molecular understanding of the adhesive interactions between silica surface and epoxy resin: Effects of interfacial water

The molecular mechanism of the adhesion between silica surface and epoxy resin under atmospheric conditions is investigated by periodic density-functional-theory (DFT) calculations. Slab models of the adhesion interface were built by integrating a fragment of epoxy resin and hydroxylated (0 0 1) surface of α-cristobalite in the presence of adsorbed water molecules. Effects of adsorbed water on the adhesion interaction are evaluated on the basis of geometry-optimized structures, adhesion energies, and forces. Calculated results demonstrate that adsorbed water molecules significantly reduce both the adhesion energies and forces of the silica surface–epoxy resin interface. The reduction of adhesion properties can be associated with structural deformation of water molecules confined in the tight space between the adhesive and adherend as well as structural flexibility of the hydrogen-bonding network in the interfacial region during detachment of the epoxy resin from the hydrophilic silica surface. © 2018 Wiley Periodicals, Inc.     

Reversibly Thermosecreting Organogels with Switchable Lubrication and Anti-Icing Performance

Synthetic gels with switchable interfacial properties have great potential in smart devices and controllable transport. Herein, we design an organogel by incorporating a binary liquid mixture with an upper critical solution temperature (UCST) into a polymer network, resulting in reversible modulation of lubrication and adhesion properties. As the temperature changes, the lubricating mechanism changes reversibly from boundary lubrication to hydrodynamic lubrication due to phase separation within the binary solution permeating the gel (friction coefficient 0.4–0.03). Droplets appear on the gel surface at low temperature and disappear with temperature higher than the critical phase separation temperature (T_ps) of the organogel. The organogel possesses a relatively low ice adhesive strength (less than 1 kPa). This material has potential applications in anti-icing and smart devices, and we believe that this design strategy can be expanded to other systems such as aqueous solutions and hydrogels.     

Electric and adhesion properties of an interface between Sn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis> </Subscript>Mn<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>Te single crystals and Bi–Sn alloys

The adhesion and electric properties of an interface between Sn_{1 ? x}Mn_xTe single crystals and a 57 wt % Bi and 43 wt % Sn alloy in a temperature range of ～77–300 K are studied. It is shown that the Bi–Sn alloy and the above single crystals form an ohmic contact that exhibits fairly high work of adhesion and strength of adhesion, along with low contact resistance. The deposition of the Bi–Sn alloy on the end faces of the crystals results in the formation of such intermediate phases as Bi₂Te₃ and SnTe at the interface, the doping of the near-contact region of the crystal, and the filling of vacancies in the tin sublattice in this region with diffusing atoms of the contact alloy components.     

Reversibly Thermosecreting Organogels with Switchable Lubrication and Anti‐Icing Performance

Synthetic gels with switchable interfacial properties have great potential in smart devices and controllable transport. Herein, we design an organogel by incorporating a binary liquid mixture with an upper critical solution temperature (UCST) into a polymer network, resulting in reversible modulation of lubrication and adhesion properties. As the temperature changes, the lubricating mechanism changes reversibly from boundary lubrication to hydrodynamic lubrication due to phase separation within the binary solution permeating the gel (friction coefficient 0.4–0.03). Droplets appear on the gel surface at low temperature and disappear with temperature higher than the critical phase separation temperature (T_ps) of the organogel. The organogel possesses a relatively low ice adhesive strength (less than 1 kPa). This material has potential applications in anti‐icing and smart devices, and we believe that this design strategy can be expanded to other systems such as aqueous solutions and hydrogels.     

Mechanism of adhesion between polymer fibers at nanoscale contacts

Adhesive force exists between polymer nano/microfibers. An elaborate experiment was performed to investigate the adhesion between polymer nano/microfibers using a nanoforce tensile tester. Electrospun polycaprolactone (PCL) fibers with diameters ranging from 0.4-2.2 μm were studied. The response of surface property of electrospun fiber to the environmental conditions was tracked by FTIR and atomic force microscopy (AFM) measurements. The effect of temperature on molecular orientation was examined by wide angle X-ray diffraction (WAXD). The adhesive force was found to increase with temperature and pull-off speed but insensitive to the change of relative humidity, and the abrupt increase of adhesion energy with temperature accompanied by a reduced molecular orientation in the amorphous part of fiber was observed. Results show that adhesion is mainly driven by van der Waals interactions between interdiffusion chain segments across the interface.     

Molecular mobility and structuring in textured films of the ferroelectric copolymer of vinylidene fluoride with tetrafluoroethylene

The processes of molecular mobility in vinylidene fluoride–tetrafluoroethylene ferroelectric copolymer–based films textured via uniaxial drawing are studied. It is found that the cooperative mobility in the amorphous regions of the copolymer is described by the Vogel–Fulcher equation, whose parameters are sensitive to the drawing conditions. It is shown that a decrease in the drawing temperature causes a reduction in the effective activation energy of the above-mentioned motion. In accordance with the X-ray diffraction data, this circumstance may be explained by an increase in the packing density of chains in interlamellar spaces. This effect is partially provided by deformation-induced processes of formation of small and defective crystals of the paraelectric or antiferroelectric phase in spaces between neighboring lamellar crystals at the primary stage of crystallization. The relationship between the value of the orientational polarization in oriented films and the topology of structure formation in microfibrils is discussed. It is observed that enlargement of the interlamellar space (filled with a liquidlike amorphous phase) between neighboring crystals in microfibrils promotes an increase in the orientational polarization of chains in the amorphous phase.     

Adhesive and electrical properties of the interface between Pb1 − x Mn x Te Crystals and In-Ag-Au alloy

The effect of annealing of Pb_{1 ? x} Mn _x Te crystals at ～690 K and structures on their basis at ～383 K on the adhesive and electric properties of the interface in the Pb_{1 ? x} Mn _x Te-(In-Ag-Au) structure was studied over the temperature range ～77–300 K. The contacts possessed high adhesive strength. The effect of annealing on contact resistance r _c was determined by a change in the specific resistance of crystals, diffusion of Ag atoms into the near-contact area of crystals, and the formation of intermediate phases of the Ag₂Te type at the interface.     

Structural evolution in microbial polyesters

The crystallization behavior of microbially synthesized poly(3-hydroxybutyrate) (PHB) and its copolymers [P(HB-co-HHx)] containing 2.5, 3.4, and 12 mol % 3-hydroxyhexanoate (HHx) comonomer and the melting of the resultant crystals were studied in detail using time-resolved small-angle X-ray scattering and differential scanning calorimetry. The polyesters were found to undergo primary crystallization as well as secondary crystallization. In the primary crystallization, the thicknesses of the lamellar crystals were sensitive to the crystallization temperature, but no thickening was observed throughout the entire crystallization at a given temperature. The thickness of the lamellar crystals in the PHB homopolymer was always larger than that of the amorphous layers. In the copolymers, by contrast, the randomly distributed HHx comonomer units were found to be excluded from the lamellar crystals into the amorphous regions during the isothermal crystallization process. This interrupted the crystallization of the copolymer chains, resulting in the formation of lamellar crystals with thicknesses smaller than those of the amorphous layers. The lamellar crystals in the copolymers had lower electron densities compared to those formed in the PHB homopolymer. On the other hand, secondary crystallization favorably occurred during the later stage of isothermal crystallization in competition with the continuous primary crystallization, forming secondary crystals in amorphous regions, in particular in the amorphous layers between the primarily formed lamellar crystal stacks. Compared to the primarily formed lamellar crystals, the secondary crystals had short-range-ordered structures of smaller size, a broader size distribution, and a lower electron density.     

热历史对尼龙1212熔融行为的影响

利用DSC方法研究了不同热历史条件对尼龙1212熔融行为的影响.不同的热历史条件下,在DSC曲线上,观察到尼龙1212产生2个或3个熔融峰,依据聚合物结晶理论,对各峰的来源进行了分析.在160℃下不同温度退火120 min的尼龙1212样品DSC曲线上,低温结晶熔融峰主要由低温结晶形成的一些微晶体或者片晶熔融产生,其晶体完善程度较差,熔融峰值较低,峰面积较小;主熔融峰是由样品在淬火过程中形成的晶体和升温过程中低温结晶形成的晶体的熔融重结晶形成较为完善的晶体熔融所产生,熔融峰值较高,峰面积较大.在不同的升温速率条件下,熔融峰温度有所移动,表明不同升温速率条件下产生的熔融峰的结晶晶型是相同的.在不同结晶时间下结晶,延长结晶时间对较高完善程度晶体的生长有利.在不同温度下依次退火处理的样品,熔融产生两个附加峰,这两个附加峰的峰温都比它们相应的退火温度高,而峰高和峰面积随退火温度降低而减小.根据等温结晶结果,由Hoffman方法确定了尼龙1212的平衡熔融温度为202.8℃.     

DTA and x-ray studies on extended-chain crystals of polyethylene under high pressure

The relation between the thermal behavior of extended-chain crystals (ECCs) of polyethylene and the phase transitions, i.e., orthorhombic ? hexagonal ? melt, of polyethylene at high pressures above about 400 MPa has been studied by high-pressure differential thermal analysis (DTA), and with a high-pressure and high-temperature x-ray diffraction apparatus equipped with a position-sensitive proportional counter measuring system. The original sample used in this study consists mainly of two kinds of ECC, which we designate as “ordinary extended-chain” crystals (OECCs) and “highly-extended-chain” crystals (HECCs). Experimental results at pressures below 300 MPa substantiate the results previously reported: i.e., the phase diagram indicating the relation between the melting temperatures and pressure for the OECCs and HECCs can be determined for pressures up to 500 MPa. In heating at pressures above about 500 MPa, the peak intensity of the (100) reflection of the hexagonal structure decreases in two stages with increasing temperature. The phenomenon corresponds to the thermal behavior determined by high-pressure DTA in which two small endothermic peaks can be observed at temperatures above that of the crystal transition evidenced by the strong peak. This phenomenon suggests melting in two stages of hexagonal structures with different thermal stabilities, and that the change at higher temperature may be due to fusion of the hexagonal phase annealed either below or above the transition temperature.     

剪切场下两亲性棒状粒子对聚异丁烯/聚二甲基硅氧烷共混物相形态的影响

合成了具有两亲表面性质的棒状SiO₂粒子,借助共聚焦激光扫描显微镜研究了两亲性棒状SiO₂粒子在共混物中的选择性分布,并通过在线剪切-显微技术和流变技术研究了其对聚异丁烯/聚二甲基硅氧烷（PIB/PDMS）不相容共混物形态结构的影响.研究表明,两亲性棒状SiO₂粒子倾向于分布在两相界面处及PIB相中.分散相的剪切诱导凝聚行为强烈依赖于粒子的含量和共混物的组成比.少量两亲性SiO₂粒子会促进分散相的凝聚,而加入足够量的粒子则能抑制分散相凝聚.     

Structure evolution of α′‐phase poly(lactic acid)

Poly(lactic acid) films consisting of α′‐forms were prepared and uniaxially drawn. The effects of the draw rate at temperatures above the glass transition temperature on chain conformation, degree of crystallinity, and crystalline phase transformation were investigated by a combination of vibrational spectroscopy (infrared and Raman), differential scanning calorimetry, and wide‐angle X‐ray diffraction (WAXD). It was established that the α′‐crystal's phase of poly(lactic acid) films does not transform into either an α or β crystals on uniaxial drawing at a fixed draw ratio of 4. However, the degree of crystallinity was significantly increased on deformation. The structural change as a function of deformation also promotes an increase in the strain‐induced enthalpic relaxation endothermic peak appearing near the glass transition region. While the overall changes in physical properties can be attributed to the changes in the degree of crystallinity as a function of strain rate, polarized Raman spectra, and WAXD clearly illustrated changes and the differences in the amorphous and crystalline orientation as a function of processing conditions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1446–1454, 2011     

Micromechanisms involved in the atypical tensile behavior observed in polyamide 11 at high temperature

Even far above the glass transition temperature, the amorphous phase in semicrystalline polymers is known to be constrained by crystals and less mobile than a pure amorphous polymer close to its equilibrium rubbery state. The aim of this paper devoted to Polyamide 11 was to investigate the existence and significance of a relaxed state in the amorphous phase of a semicrystalline polymer far above T_g. It focuses on the high temperatures, low strain‐rates, and small deformation ranges. A nonstrain‐rate dependent tensile curve (called “asymptotic curve”) was evidenced below a critical strain‐rate, consistently with reaching a fully relaxed state of the rubbery amorphous phase. Nevertheless, paradoxical mechanical features were observed at the same time (nonstrain‐rate dependent but hysteretic unloading, relaxation, and creep involving same strain‐rates as the asymptotic loading regime). Micromechanisms (orientation of primary crystals, creation of local hexagonal arrangements, orientation, and relaxation of the amorphous phase) were analyzed from DSC and X‐ray experiments. It suggested distinct amorphous and crystalline contributions depending on the loading path and therefore highlighted paradox of the mechanical behavior. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3046–3059, 2007     

Adhesion characteristics of aromatic thermosetting copolyester and glass fiber laminates with copper foils for improved circuit boards

Copper foils are the vital elements used in microelectronic devices. Adequate adhesion between copper foils to various substrates, such as Si, SiO₂ and polyimide, is crucial to functional electronic devices. Liquid‐crystalline polymers (LCPs) can be used as substrates for these modules as well as the adhesive to copper foils. The adhesion between aromatic thermosetting copolyester (ATSP)/fiberglass fabric (GF) laminates and copper foils was characterized by peel strength tests. It was found that ATSP/GF laminates with copper foil using ATSP oligomers as adhesive showed a highest average peel strength of 711 N · m^?1. Scanning electron microscope (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed an excellent bond between the composite and the copper foil interface. Failure occurred between the backside of the copper foil and the ATSP/GF laminates in the peeling test and the mechanism is discussed. Thermogravimetic analyzer (TGA) indicated a thermal stability up to 371°C for ATSP/GF composite substrate and a glass transition temperature of over 400°C as determined by peak in tan δ during Dynamic Mechanical Analysis (DMA). Copyright © 2016 John Wiley & Sons, Ltd.     

Surface films and metallurgy related to lubrication and wear

The nature of the tribological surface is identified and characterized with respect to adhesion, friction, wear, and lubricating properties. Surface analysis is used to identify the role of environmental constituents on tribological behavior. The effect of solid to solid interactions for metals in contact with metals, ceramics, semiconductors, carbons, and polymers is discussed. The data presented indicate that the tribological surface is markedly different than an ideal solid surface. The environment is shown to affect strongly the behavior of two solids in contact. In certain instances, the environment can dominate surface characteristics. With metals in contact with metals, adhesion is found to be related to the cohesive binding energy. Strong adhesive bonding occurs for metals in contact with ceramics, semiconductors, carbons, and polymers. Bond strength at the interface is, with some exceptions, stronger than the bond strength of the cohesively weaker of the two materials. Many different surface properties of metals and alloys influence tribological performance. These include (1) surface energy, (2) crystallographic orientation, (3) amorphous versus the crystalline state, (4) grain boundaries, (5) texturing of the surface, (6) crystal structure, and (7) order-disorder transformations. At sufficiently high loads or sliding velocities, metals or alloy surfaces are shown to undergo recrystallization effecting tribological properties. The chemical valency, d-valence-bond characteristics, of metal surfaces affect adhesion, friction, and wear. The greater the percent d-bond character, the lower the friction and wear. The ideal tensile and shear strengths of simple transition metals correlate with friction coefficients. Results presented also show that small amounts of alloying elements in base metals can alter markedly adhesion, friction, and wear by segregating to the solid surface.