Rheology of silica-filled polystyrene: From microcomposites to nanocomposites

Rheology and viscoelastic behavior of polystyrene (PS)/silica microcomposites and nanocomposites were studied. The apparent viscosity, transient shear stress growth after startup shear flow and stress relaxation after cessation of flow at various shear rates, the complex dynamic viscosity, the storage and loss moduli at small and large strain amplitudes and various frequencies were performed. The effect of size, shape and volume concentration of silica was discussed. The maximum volume concentration, corresponding to the concentration at which the relative viscosity of mixtures goes to infinity, with respect to the hydrodynamic contribution of the particles and to polymer-filler interactions was obtained. The difference between the yield stress and residual stress is shown. The domain of equivalence between the apparent viscosity as a function of the shear rate in steady state flow and the complex dynamic viscosity as a function of the strain rate amplitude in highly nonlinear region of oscillatory flow was established. The viscoelastic behavior was interpreted based on the morphology of microcomposites and nanocomposites observed by SEM.     

Effects of the degree of surface modification on the rheological responses of precipitated silica suspensions in benzyl alcohol

Two types of precipitated silica powders modified by poly (dimethylsiloxane) (PDMS) were suspended in benzyl alcohol and their rheological properties were investigated as a function of silica volume fraction, φ. The suspensions were classified into sol, pre-gel, and gel states based on the increase in φ. An increase in the degree of surface modification by PDMS caused gelation at higher φ. Plots of apparent shear viscosity against shear rate in the sol and pre-gel states of highly modified silica suspensions showed weak shear thickening behavior, while the same plots for silica suspensions with a low modification level exhibited shear thinning behavior. The dynamic moduli of hydrophobic suspensions in the pre-gel and gel states were dependent on the surface modification: the storage modulus G′ was larger than the loss modulus G″ in the linear region and these moduli increased with increasing φ, irrespective of the silica powder. The linear region of the φ range for the precipitated silica suspensions was wider than that for the fumed silica powders modified by PDMS suspended in benzyl alcohol, while the G′ value in the linear region for the precipitated silica suspensions was less than those for the fumed silica suspensions.     

Modification of the rheological properties of polyurethanes by adding fumed silica: influence of the preparation procedure

The way of addition of fumed silica determined the rheological properties of polyurethane (PU) adhesives. The higher the shear rate during preparation of fumed silica containingPU adhesives, the higher viscosity and improved plasticity and thixotropy in the solutions. The improved properties of these adhesive solutions were ascribed to the creation of interactions between the silanol groups on the fumed silica, the polar groups in the soft segments of the polyurethane and/or the solvent. However, the way of incorporate the fumed silica in the polyurethane did not affect the rheological properties of fumed silica-PU composites (obtained by solvent removal from the solutions), indicating the key role of the solvent in the rheology of PU adhesive solutions.     

Dynamic and steady-shear melt rheology of and ethylene-methacrylic acid copolymer and its salts

Studies have been made on the dynamic and steady-shear melt rheology of an ethylene–methacrylic acid copolymer and two of its salts obtained by partial neutralization with sodium and with calcium bases. Measurements were made with a Weissenberg rheogoniometer over a broad range of shear rates and frequency in the temperature interval mainly from 100 to 160°C. The temperature coefficients of dynamic and steady shear viscosity are evaluated at both constant shear rate and constant stress. Likewise, complex dynamic viscosities and apparent high steady-flow viscosities and intercompared at equivalent frequencies and shear rates. The un-ionized acid copolymer shows good correlation between the frequency dependence of the complex viscosity and the shear rate dependence of the apparent viscosity. This is not true for either the sodium salt or the calcium salt. These results are consistent with the two-phase structural model for these materials, i.e., a matrix of hydrocarbon in which are embedded ionic domains.     

Viscoelastic behavior of an amorphous polymer under oscillations of large amplitude

The influence of periodic shear deformation and steady flow on a typical amorphous polymer is discussed. Forced sinusoidal vibrations were applied and the complex viscosity was determined. The action of a vibration of finite amplitude is equivalent to steady flow with a definite finite shear rate. Both processes cause truncation of the long-time part of the relaxation specturm. It may be accepted to a first approximation that the long-time boundary of the remaining part of the relaxation spectrum conforms to the long-time part of the initial spectrum, even if the plateau region of the spectrum is truncated. The concept of limiting truncation of the short-time part of the spectrum is introduced, this corresponding to the minimum absolute value of the complex viscosity versus reduced frequency and the lowest values of the dynamic and apparent viscosities. With an approximate representation of the relaxation spectrum, calculations were made of the maximum values of the viscosity and the coefficient relating the first difference of normal stresses to the square of the shear rate, and also of the apparent viscosity and normal stresses as functions of the shear rate. The calculated values are compared with experimental measurements, and it is shown that the correlation of the apparent viscosity and the absolute value of the complex viscosity is distributed at high frequencies, being superseded by a correlation between the apparent and dynamic viscosities.     

Rheological Properties of Silica Particle Suspensions in Mineral Oil

The rheological properties of particles suspended in a non‐polar mineral oil have been investigated as a function of volume fraction of particles, particle size, surface properties and shear rate. Three different types of particles were investigated; glass microspheres, monodisperse silica particles and fumed silica. The suspensions showed shear thinning behavior at higher volume fractions, and the viscosity increased with decreasing particle size. The hydrophobic particles display lass shear thinning effects. The relative viscosity of all the suspensions was well fitted to the Krieger and Dougherty model.     

Structure of fumed silica gels in dodecane: enhanced network by oscillatory shear

The structure and viscoelastic properties of fumed silica gels in dodecane were studied by means of dynamic rheology. With increasing the specific surface area of fumed silica nanoparticles, the plateau elastic modulus (G′), which is frequency-independent and shows the characteristic of a network of the fumed silica gels, decreases. Such networks of fumed silica gels show a significant temperature-dependent behavior and a transition temperature (T _c) related with the restructuring of nanoparticle chain aggregates of fumed silica in gels. Under oscillatory shear, the fumed silica gels experience disorganization and reorganization and present strong structural recovery ability after adjusting oscillatory shear (AOS) at small strain amplitudes (1–10%), and a more perfect network structure than that in origin gels can be induced. Elevated temperature (above T _c) improves the network structure to be more compact and stronger than that at a lower temperature, as a result, the deformation resistance during the AOS period and the structural recovery after AOS are enhanced. These results indicate that the network structure and viscoelastic properties of fumed silica gels can be tailored and optimized by performing small-amplitude oscillatory shear at a properly selected temperature.     

SiO_2表面性质对LBG丙酮溶液体系粘度的影响

本文讨论了增塑剂、剪切速率、不同含量和不同表面性质的二氧化硅对LBG(一种偏氟乙烯和六氟丙烯共聚物 )的丙酮溶液粘度的影响机理     

Time dependent viscosity of concentrated alumina suspensions

Viscometric investigations of concentrated aqueous alumina suspensions with particles smaller than 5 μm have been performed. Experimental flow curves indicate thixotropy in the shear rate interval between =20 and 640 s⁻¹. In the range smaller than =200 s⁻¹ we found pseudoplastic flow behavior, in the higher range the material shows dilatancy. The non-Newtonian behavior results from a small content of sodium aluminum oxide in the alumina suspension. This gives rise to interparticle forces that can drive the suspension into a gel-like state. The time scale of this process is some days. On the short-time scale of some hours the material ages slowly increasing moderately the apparent viscosity. Studying the relaxation process after a shear rate jump, the shear stress time dependency at constant shear rate follows an exponential law. There is a single particular relaxation time for each shear rate. The relaxation towards a steady state occurs asymptotically over some 10³ s. Flow curves calculated from steady state data after relaxation processes are below the experimental flow curves which were measured during some 100 s. The flow curves follow the Herschel–Bulkley formula. The shape of the viscosity curves indicates changes of suspension structure at ca. =200 and 400 s⁻¹. At constant shear rates in the interval between =400 and 450 s⁻¹ the apparent viscosity of the alumina suspension fluctuates periodically in time in the same manner found for other suspensions. This effect is interpreted as periodic organization of agglomeration and deglomeration processes. Supposing, that the stabilisation energy of agglomerates is of the order of the energy introduced by the mechanical shear field, the observation of oscillations at =400 s⁻¹ is in agreement with the drastic slope change in the viscosity curves.     

Effect of composition and structure on rheological properties of styrene-butadiene block copolymers

Styrene-butadiene copolymers of the S-B-S and S-B-S-B-S types, both unmodified and extended with paraffinic-naphthenic oil, were studied by dynamic mechanical spectroscopy and capillary rheometry. In the triblocks at low deformation rates, an increase in 1-vinylethylene unit content leads to an increase in complex dynamic viscosity |η*|. This may be explained by their different supermolecular structure with a higher proportion of long relaxation times. The pentablocks show a considerable effect of molecular parameters on their flow behaviour at low deformation rates. In all the systems, steady viscosity η shows no significant differences at higher shear rates. Obviously the supermolecular structure is disintegrated in these conditions and the effect of chemical structure is negligible. An expected decrease in viscosity in the whole range of deformation rates was observed with the oil-extended copolymer. The dependences of complex dynamic viscosity on angular frequency were compared with those of steady viscosity on shear rate but no unequivocal conclusion as regards the validity of the Cox-Merz rule could be reached.     

Effect of silica content on thermal stability of fumed silica/epoxy composites

Composites of a fumed silica industrial residue and an epoxy resin were prepared and their thermal stability and thermal degradation behaviour were studied by TGA in air. Classical thermal stability parameters, based on the initial decomposition temperature (IDT), temperature of maximum rate of mass loss (T_max) and integral procedure decomposition temperature (IPDT) were calculated before and after subtraction of the filler mass from the TGA curves. Without filler mass subtraction, the thermal stability of the epoxy resin seems to be improved and the mass loss rate was reduced by the addition of fumed silica. Nevertheless, after subtraction of the filler mass, the thermal degradation behaviour of the resin was only slightly affected by the silica content. A possible negative effect of the silica content on the cure was also found.     

振荡剪切流场下PS/PVME/SiO2复合物的相行为

利用光学显微镜-剪切台联用系统研究了振荡剪切流场下聚苯乙烯（PS）/聚甲基乙烯基醚（PVME）/二氧化硅（SiO₂）纳米粒子复合物的热力学稳定性. 结果表明,小振幅振荡剪切可导致PS/PVME共混物出现类似在稳态流场下的剪切诱导相容及剪切诱导相分离现象. 共混体系存在临界振荡频率ω_c,当振荡频率低于ω_c时,发生剪切诱导相分离（SID）行为,反之发生剪切诱导相容（SIM）行为. SiO₂纳米粒子的加入使复合体系的相容性提高. 存在一个临界SiO₂纳米粒子含量φ_c,当SiO₂纳米粒子含量高于φ_c时,复合体系中不存在临界振荡频率ω_c,低振荡频率下的剪切诱导相分离得到抑制. 此外,复合体系的上述行为与升温速率和共混物组成密切相关.     

Stress jumps on weakly flocculated dispersions: steady state and transient results

Weakly flocculated, thixotropic suspensions have been investigated by means of fast stress jump experiments. With a suitable procedure, reliable stress relaxation data could be collected starting 20 ms after cessation of flow. This technique has been used to determine the elastic and hydrodynamic contributions to the shear stress. Steady state as well as transient flows have been studied for suspensions containing either fumed silica or carbon black particles in a Newtonian medium. In both systems, the elastic stress totally dominates the response at low shear rates and consequently also the apparent yield stress. This stress contribution becomes negligibly small at high shear rates. The hydrodynamic contribution to the viscosity has finite limits at both the low and high shear rate ends. The data are relevant for testing rheological models. As an illustration, it is shown that the data agree qualitatively with the model proposed by Potanin et al. (J. Chem. Phys. 102 (14) (1995) 5845-5853).     

在(TPA)2O-Na2O-SiO2-H2O系统中MFI型硅沸石的结晶行为(Ⅰ)──结晶动力学的研究

以四丙基溴化按作模板剂,以白炭黑(Ⅰ)、硅溶胶(Ⅱ)和水玻璃(Ⅲ)为不同硅源在140～180℃合成MFI型硅佛石(Silicalite－1).反应物配比相同,其结晶动力学曲线有明显差异.从它们的成核诱导期及生长速度计算出各体系硅佛石晶核形成活化能与生长活化能,在体系(Ⅰ)中为46/76kJ/mol,体系(Ⅱ)中为41/43kJ/mol,体系(Ⅲ)中为38/78kJ/mol.产物结晶粒径的大小由各体系成核活化能与生长活化能的差值决定.合成产物的结晶度以白炭黑为硅源时最高.提高温度有利于提高产物结晶度.     

Dynamic yielding, shear thinning, and stress rheology of polymer-particle suspensions and gels

The nonlinear rheological version of our barrier hopping theory for particle-polymer suspensions and gels has been employed to study the effect of steady shear and constant stress on the alpha relaxation time, yielding process, viscosity, and non-Newtonian flow curves. The role of particle volume fraction, polymer-particle size asymmetry ratio, and polymer concentration have been systematically explored. The dynamic yield stress decreases in a polymer-concentration- and volume-fraction-dependent manner that can be described as apparent power laws with effective exponents that monotonically increase with observation time. Stress- or shear-induced thinning of the viscosity becomes more abrupt with increasing magnitude of the quiescent viscosity. Flow curves show an intermediate shear rate dependence of an effective power-law form, becoming more solidlike with increasing depletion attraction. The influence of polymer concentration, particle volume fraction, and polymer-particle size asymmetry ratio on all properties is controlled to a first approximation by how far the system is from the gelation boundary of ideal mode-coupling theory (MCT). This emphasizes the importance of the MCT nonergodicity transition despite its ultimate destruction by activated barrier hopping processes. Comparison of the theoretical results with limited experimental studies is encouraging.     

Shear-Induced Changes in Rheological Reponses and Neutron Scattering Properties of Hydrophobic Silica Suspensions at Low Silica Concentrations

Rheological responses of hydrophobic fumed silica powders, whose surface silanol groups were modified by hexadecane, suspended in 1,4-dioxane at lower silica concentrations than 6.8 vol% have been investigated as a function of the silica concentration. Transient shear stress behavior before attaining the steady-state shear stress could be classified into three regimes as follows, irrespective of the silica concentration: at the lower shear rates than ca. 0.3 s^?1 a stress overshoot was observed, at the shear rate ranges from 0.3 to 30 s^?1 sustained oscillations in shear stresses were exhibited and these oscillations were first observed for the suspensions at the low particle concentrations, and beyond the shear rate of 30 s^?1 a sigmoid decrease of the shear stress with increasing time, that is, structural breakdown, was observed. At the steady state the silica suspensions showed shear thickening. Small angle neutron scattering (SANS) measurements of the silica suspension under shear flow provided that changes in the SANS intensities were well correlated with the shear thickening behavior. However, shear thinning behavior at higher shear rates did not cause any changes in the SANS intensities.     

孪尾疏水缔合三元共聚物的粘度行为:水解度的影响

以十二烷基硫酸钠(SDS)为表面活性剂,利用氧化还原体系、采用前加碱共聚-共水解的方法制备了孪尾疏水缔合水溶性三元共聚物聚(丙烯酰胺／丙烯酸钠／N,N-二己基丙烯酰胺)[P(AM/NaAA／DiC6AM)],研究了P(AM／NaAA／DiC6AM)稀溶液及亚浓溶液的性能。随理论水解度的增加,P(AM／NaAA／DiC6AM)水溶液的特性粘数[η]增加,Huggins常数KH减小。P(AM／NaAA／DiC6AM)水溶液的表现粘度随理论水解度的增加而增加,随温度、剪切速率的增加而降低,随剪切速率的增加开始时降低较快而后变化较小。P(AM／NaAA/DiC6AM)在盐溶液中随NaCl、CaCl2质量浓度的增加,出现盐增粘现象;理论水解度不同的P(AM／NaAA／DiC6AM)与SDS水溶液的表现粘度在wSDS=0．050～0．400g／L范围内随SDS质量浓度的变化差别不大。     

轻度磺化聚苯乙烯与聚苯乙烯共混物的流变性能表征

采用DSR-200动态应力流变仪研究了磺化度为0.98%(摩尔分数)的轻度磺化聚苯乙烯(SPS)离聚物及其锌盐(ZnSPS)与聚苯乙烯(PS)的共混物(PS/SPS,PS/ZnSPS)的流变性能.由于离聚物中离子聚集的物理交联作用,使其流变性能与PS相比有明显差别.动态频率实验结果表明,所有样品均可采用时温等效处理.另外,在与分子链运动相关的低频区,由于离子聚集的作用使得离聚物的模量远大于PS的模量.离聚物在稳态剪切作用下,由于离子聚集的破坏而表现出明显的屈服现象,并能用Utracki的屈服应力公式表征其屈服应力和零切粘度.此外,离聚物的屈服现象还与温度相关.由于动态和稳态实验分别测试离子聚集存在和破坏的不同材料状态,因此对离聚物无法应用Cox-Merz规则.动态和稳态实验结果均表明,PS/SPS和PS/ZnSPS的性能与组成的变化规律不同,意味着二者之间存在不同的离子聚集结构或相互作用.     

Viscometric behavior of mesomorphic ethyl cellulose solution in chloroform

A simple modification of the viscometer used to determine the viscosity of concentrated solutions is described which permits the ready measurement of viscosity versus shear rate behavior above room temperature. Basic experimental viscometry was performed on the ethyl cellulose–chloroform system using a B-type (Brookfield-like) rotating-cylinder viscometer. Data are compared with theoretical predictions. The flow curves exhibit yield stress at low shear rate. The yield stress is dependent on concentration and temperature. The viscosity versus concentration curves show typical mesomorphic behavior. The concentration dependences of viscosity and yield stress are similar. The critical concentration increases with temperature. In the single-phase region (isotropic or anisotropic state) the viscosity decreases with temperature and the apparent activation energy (E_a) for flow is positive, but in the biphasic range the viscosity increases with temperature and E_a is negative. The experimental results for the critical concentration appear to agree with Flory's theory of rodlike molecules when the ratio of persistence length to diameter of the chain is taken as the aspect ratio.     

Rheological and Interfacial Properties of Colloidal Electrolytes

Electric conductivity and rheological responses of colloidal electrolytes consisting of lithium bis(trifluoromethanesulfon)imide, polyethylene glycol(PEG) oligomer, and fumed silica have been investigated. Incorporating silica could improve ionic conductivity of the electrolytes at the same lithium/oxygen ratios. The colloidal electrolytes demonstrate a sol to gel transition with increasing silica content while they exhibit shear thickening behaviors during steady flow at intermediate range of strain rate. The presence of lithium salt, on the one hand, could lower the crystallinity of PEG or forbid the crystallization and on the other hand, interferes the chain adsorption on the surface of silica. Furthermore, lithium salt strongly retards the segmental relaxation of PEG in the colloidal electrolytes.