Low-temperature elastic moduli and internal dilational and shear friction of polymethyl methacrylate

Longitudinal and transverse wave velocity, five kinds of elastic parameters (young, shear and bulk moduli, Lamér; parameter. Poisson's ratio) and dilational and shear internal friction of polymethyl methacrylate were simultaneously measured over a temperature range 68–400K, using the ultrasonic pulse method. All elastic moduli decrease with increasing temperature, suggesting lowering of molecular bonding strength. From dilational and shear internal frictions, the 139, 382, and 385K peaks are interpreted as rotation of x-methyl estel groups, micro Brownian motion of main chains and stress relaxation, and abrupt increases from 242 and 395K are regarded as free motion of side chains and glass transition, respectively. ©1995 John Wiley & Sons, Inc.     

A nanoscopic view of structure and deformation of hard elastic polypropylene with scanning force microscopy

Scanning force microscopy (SFM) was used to visualize the surface of hard elastic polypropylene (HEPP) film. The surface morphology of unstrained HEPP shows crystalline and noncrystalline rows oriented parallel to the extrusion direction. The crystalline rows are composed of lamellar blocks. The dimensions of crystalline and noncrystalline regions are determined. The structural surface changes induced by stepwise elongation of the film with a home-built stretching device are documented by SFM. Stretching of HEPP perpendicular to the extrusion direction causes cracks advancing through several crystalline rows. During elongation parallel to the extrusion direction the separation of adjacent lamellae by their translatory displacement occurs. Deformation-induced structural changes of HEPP on the nanometer scale are compared with proposed deformation models. Nanostructural changes are correlated with characteristic variations in the force-elongation curve. © 1996 John Wiley & Sons, Inc.     

Unique plastic and recovery behavior of nanofilled elastomers and thermoplastic elastomers (Payne and Mullins effects)

We have proposed recently that the mechanical properties of nano-filled elastomers are governed by the kinetics of rupture and re-birth of glassy bridges which link neighboring nanoparticles and allow for building large rigid clusters of finite life-times. The latter depend on parameters such as the temperature, the nanoparticle-matrix interaction, and the distance between neighboring fillers. Most importantly these life-times depend on the history of deformation of the samples. We show that this death and re-birth process allows for predicting unusual non-linear and plastic behavior for these systems. We study in particular the behavior after large deformation amplitude cycles. At some point we put the systems at rest under large deformation, and let the stress relax in this new deformed state. During this relaxation process the life-time of glassy bridges increases progressively, even for large deformation states. The systems thus acquire a new reference state, which corresponds to a plastic deformation. The stretching energy of the polymer strands of the rubbery matrix is larger than in the initial undeformed state, but this effect is compensated by a new configuration of glassy bridges, which are much stiffer. For plastic deformations of less than about 10%, the new system acquires mechanical properties around this new reference state which are very close to those of the initial system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1495–1508, 2010     

Pressure relaxation of polystyrene and its comparison to the shear response

Isothermal pressure relaxation as a function of temperature in two pressure ranges has been measured for polystyrene using a self-built pressurizable dilatometer. A master curve for pressure relaxation in each pressure regime is obtained based on the time–temperature superposition principle, and time–pressure superposition of the two master curves is found to be applicable when the master curves are referenced to their pressure-dependent T_g. The pressure relaxation master curves, the shift factors, and retardation spectra obtained from these curves are compared with those obtained from shear creep compliance measurements for the same material. The shift factors for the bulk and shear responses have the same temperature dependence, and the retardation spectra overlap at short times. Our results suggest that the bulk and shear response have similar molecular origin, but that long-time chain mechanisms available to shear are lost in the bulk response. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3375–3385, 2007     

The friction coefficient on polycarbonate as a function of the contact pressure and nanoscale roughness

During dry friction the rheological behavior at the interface between a polymer surface and a rigid indenter is linked to the local pressure and the roughness of the surface of the indenter. This study on polycarbonate reports experimental results obtained at ambient temperature using rigid, spherical glass indenters of various radii. In a first step, a plot of the experimental friction coefficient μ versus the mean contact pressure p_mean showed that below the yield stress (p_mean < 100 MPa) the intrinsic friction coefficient follows a master curve for smooth indenters. In a second step, roughened indenters were prepared by chemical etching, which allowed the monitoring of nanoscale roughness parameters. From 5.5 to 140 nm Rrms, the friction coefficient μ progressively fell to a plastic‐like constant value, indicating that the nanoroughness mediates the friction. These results form the basis for a study of the rheology of confined polymer layers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Mechanical properties of unsaturated polyester resins in relation to their chemical structure. I. Secondary relaxations and local motions

Dynamic mechanical spectroscopy has been combined with high-resolution solid-state ¹³C NMR to characterize the molecular motions responsible for the γ and β secondary relaxations in unsaturated polyester networks. In DEG networks the 7γ transition is assigned to restricted phenyl group rotation in the styrene cross-links whereas the motion of molecular groups in the vicinity of the residual maleic double bonds account for the β transition. © 1994 John Wiley & Sons, Inc.     

Relaxation spectra of polymers and phenomena of electrical and hydrophobic recovery: Interplay between bulk and surface properties of polymers

Low‐density polyethylene, polypropylene, and polycarbonate were exposed to cold air plasma treatment. The decay of electret response, hydrophobic recovery, and mechanical relaxation of polymers were studied experimentally. The three‐exponential decay kinetic model was used for the treatment of mechanical and electret responses. The characteristic time scales of mechanical and electret responses turned out to be very close. The “longest” relaxation time, extracted from the experimental study of the hydrophobic recovery, was also close to the corresponding characteristic time spans of electret and mechanical responses. The kinetics of surface processes taking place in polymers is controlled by the mobility of their functional groups, represented by the bulk relaxation spectra. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 198–205     

Studies on the mechanical and friction properties of polyamide 6-Cu/Si nanocomposites

Polyamide 6 nanocomposites reinforced with Cu/Si nanoparticles (PA6-Cu/Si) were prepared by the in-situ ring-opening polymerization of ?-caprolactam. The in-situ polymerization was critical for preventing the aggregation of Cu/Si nanoparticles. The Cu/Si nanoparticles in the nanocomposite retained their nano characteristics and were not oxidized by the amino groups in PA6. The structure of the as-fabricated PA6-Cu/Si nanocomposite was evaluated by transmission electron microscopy (TEM), X-ray diffraction (XRD), and ultraviolet-visible absorption spectroscopy (UV-vis). The friction and wear resistance, mechanical strength, and antistatic performance of PA6-Cu/Si were also evaluated. The PA6 polymer chains prevent the Cu/Si nanoparticles from aggregation by coating the surface of the Cu/Si nanoparticles via physical adsorption or an electrostatic effect. The mass fraction of the Cu/Si nanoparticles also had a significant effect on the crystalline form of PA6. The γ crystalline form of PA6 was predominant at a high mass fraction of Cu/Si to PA6. Moreover, PA6-Cu/Si with improved mechanical properties and wear resistance was generated by tuning the amount of nano-Cu/Si filler added during the polymerization. PA6-Cu/Si with a nano-Cu/Si content of 0.5% possesses the highest tensile strength and wear resistance and shows promise in applications as a functional polymer-matrix composite.     

Ageing effects and internal stresses in quenched unfilled and clay-filled high density polyethylene

The stress relaxation and creep behaviour of high density polyethylene (HDPE), unfilled or filled with clay particles, were measured after different ageing times after quenching from 120 °C. The measurements were performed at room temperature in the uniaxial extension mode. Ageing time had a pronounced influence on the viscoelastic properties, e.g. the creep curves shifted to longer times with increasing ageing time. The internal stresses, as evaluated from stress relaxation data, were found to increase markedly when the ageing period was extended, and it was suggested that this behaviour may be associated with relaxation of thermal residual stresses. It was furthermore suggested that the change in residual stresses, in addition to the physical ageing process, could also affect the ageing behaviour of HDPE, i.e. the change in viscoelastic properties with ageing time. Clay addition changes the ageing behaviour of HDPE, which could be attributed to a change in the internal stress dependence of the ageing time and/or to a difference in the physical ageing process. The effects of a surface treatment on the ageing of HDPE-clay composites are also evaluated and discussed.     

乙醇和环己烷液体混合物的内压

测定了25-65℃温度范围内乙醇和环己烷液体混合物的热压力系数, 它们都很好地遵守我们先前提出的修正van der Waals模型。从模型参数B/A^2, 可以得到乙醇自缔合的破坏与浓度间的定量关系。混合物的内压不仅取决于两个组分的内压, 而且还与相互作用参数A12有关。     

1H NMR study of internal motions and quantum rotational tunneling in (CH3)4NGeCl3

(CH3)4NGeCl3 is prepared, characterized and studied using 1H NMR spin lattice relaxation time and second moment to understand the internal motions and quantum rotational tunneling. Proton second moment is measured at 7 MHz as function of temperature in the range 300-77 K and spin lattice relaxation time (T1) is measured at two Larmor frequencies, as a function of temperature in the range 270-17 K employing a homemade wide-line/pulsed NMR spectrometers. T1 data are analyzed in two temperature regions using relevant theoretical models. The relaxation in the higher temperatures (270-115 K) is attributed to the hindered reorientations of symmetric groups (CH3 and (CH3)4N). Broad asymmetric T1 minima observed below 115 K down to 17 K are attributed to quantum rotational tunneling of the inequivalent methyl groups.     

Modeling of Shape Memory Induction and Recovery in Heat‐Shrinkable Polymers

Summary: A mechanical model was developed to describe qualitatively and quantitatively the stress‐strain‐time behavior of a prepared shape memory crosslinked polyethylene during hot stretching, stress relaxation under 200% strain at high temperature and strain recovery of the heat shrinkable polymer. The stress‐strain, the stress relaxation and the irrecoverable strain behavior of the model were established by driving the constitutive equation, which could qualitatively represent the behavior of the real material. By choosing significant values for the parameters of the proposed model, an excellent fit was obtained between the experimental behavior of the polymer and that predicted by the model. It was also revealed that the main source responsible for the imperfect recovery of the induced strain observed was the stress relaxation occurring during the stretch holding‐cooling time step.

Stress relaxation of crosslinked polyethylene under 200% strain at 160 °C.     

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin‐lattice relaxation time (T₁) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T₁ values. The method is applicable for measuring a range of T₁ values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross‐correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright © 2015 John Wiley & Sons, Ltd.     

Scaling of the segmental relaxation times of polymers and its relation to the thermal expansivity

Segmental relaxation times of polymers measured at various temperatures and pressures can be superposed as a function of temperature, using a shift factor equal to the specific volume raised to a power. The material-specific scaling exponent can be linked to the nature of the intermolecular repulsive potential for the material. We show the relationship of this scaling exponent to the thermal expansivity of the material, and how it can be used to sort out the different contributions to the temperature dependence of the local dynamics.     

External and internal plasticization of cellulose acetate with caprolactone: Structure and properties

Cellulose acetate was modified with caprolactone in an internal mixer at temperatures between 120 and 220 °C, and reaction times between 5 and 45 min in the presence of tinoctoate catalyst. The effect of plasticization on the properties of the polymer was studied by dynamic mechanical analysis and tensile testing. The dynamic mechanical spectrum of cellulose acetate exhibits three main relaxation transitions. These can be assigned to segments (α), to smaller structural units of the main chain, probably individual glucose rings (β), and to hydroxyl or hydroxylmethyl groups (γ). Plasticization by caprolactone leads to the decrease of the glass transition temperature of CA, but also to the breakdown of relatively large segments to smaller structural units. Free hydroxyl groups interact with the plasticizer forming larger units with higher transition temperature. Grafting decreases the intensity of the γ‐transition peak. External plasticization creates a larger number of small structural units, but the external plasticizer is less efficient in the decrease of stiffness than grafted polycaprolactone chains. Internal plasticization is more advantageous because it leads to higher flexibility at larger strength than external plasticization, and the migration of the plasticizer is prevented at the same time. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 873–883, 2007     

Application of the model‐free approach to low molecular weight systems with hindered internal rotation: cinnamoylmesitylene

We investigated the molecular dynamics of the molecule of cinnamoylmesitylene, a substituted chalcone. Known rotation barriers for the O?C‐4—C‐3?C‐2 bond of substituted chalcones are in the range of values accessible to modern NMR techniques. The internal rotation about the C‐3—C‐4 bond is found to be fast relative to the complete lineshape analysis (CLSA) time‐scale. To determine the activation parameters of overall and internal motions of the molecule, the Lipari–Szabo model‐free analysis of the relaxation times and heteronuclear NOE data was used instead. Simultaneous analysis of both heteronuclear spin–lattice relaxation times and NOE data for the two carbon atoms C‐2 and C‐7 in the O?C‐4—C‐3?C‐2 and mesitylene fragments at different temperatures was performed. The correlation times and activation energies of overall and internal motions and the generalized order parameter, which are measures of the molecular mobility, were thus determined. The standard enthalpies of activation, ΔH^≠, calculated from the experimental data for C‐2 and C‐7, are 5.6 and 6.6 kcal mol^?1, respectively. Theoretical estimates of the barriers to internal rotations by ab initio MO calculations were made to verify the experimental results. The agreement between the NMR and theoretical results was good. Copyright © 2003 John Wiley & Sons, Ltd.     

Mittag-Leffler函数及其在粘弹性应力松弛中的应用

Mittag-Leffler函数在分数阶粘弹理论中起着重要作用. 我们对该函数的计算及收敛性进行了分析; 利用遗传算法结合共轭梯度法, 提出了对广义函数进行非线性参数拟合的方法. 用分数Maxwell模型对强弱、硬柔具有显著差别的塑料、玻璃态合金及聚合物近熔体的应力松弛过程进行了研究.     

Integration of scale-down experimentation and general rate modelling to predict manufacturing scale chromatographic separations

Chromatography is an essential downstream processing step in the production of biopharmaceuticals. Here we present an approach to chromatography scale-up using scale-down experimentation integrated with general rate modelling. This type of modelling takes account all contributions to the mass transfer kinetics providing process understanding. The model is calibrated using a 2.5 cm height, 1 ml column and used to predict chromatograms for 20 cm height columns from 40 ml to 160 L volume. Simulations were found to be in good agreement with experimental results. The envisaged approach could potentially reduce the number of experiments, shorten development time and reduce costs.