剪切速率和静置时间对Fe-Al-Mg-MMH/钠质蒙脱土复合触变性体系触变性的影响

研究了测定条件对R=0.051的Fe-Al-Mg型混合金属氢氧化物(简称MMH)/钠质蒙脱土(简称MT)复合触变性悬浮体性质的影响.主要考察了高速剪切分散后,测定粘度(η)随时间(t)变化时采用的剪切速率(DL)和测定η前的静置时间(ts)的影响发现DL和ts的影响很复杂,ts=0,低DL时(10和170s-1)呈现复合触变性的体系,在高DL时(340、511和1022s-1)可呈现正触变性;DL增加,体系η逐渐降低.在所研究的ts范围内(0～2h),随ts的增加,体系分别由低DL时(10和170s-1)的复合触变性和高DL时(340、511和1022s-1)的正触变性皆转变为负触变性.低DL时(10和170s-1),η随ts逐渐降低;高DL时(340、511和1022s-1),η随t逐渐增高.对影响机理进行了初步探讨.     

Tailoring HASE rheology through polymer design: Effects of hydrophobe size, acid content, and molecular weight

Hydrophobically modified alkali-soluble emulsion (HASE) polymers are an important class of rheology modifiers for waterborne coatings applications. They are typically prepared as terpolymers by emulsion polymerization of ethyl acrylate (EA), methacrylic acid (MAA), and an associative macromonomer. The viscosity development and shear responses of HASE solutions depend on a number of factors. This article presents rheological data reflecting the impacts of three key variables: hydrophobe size, acid content, and molecular weight, on model HASE thickening and rheological performance. The relative contributions of hydrophobic association, chain expansion, and polymer chain length are discussed. In steady shear flow, all thickener solutions approached some constant low-shear viscosity at small deformation rates. At the same molar composition, larger hydrophobe size resulted in higher viscosity development and greater shear thinning behavior. The amount of acid monomer in HASE polymers can influence the balance between hydrophobic attraction and electrostatic repulsion forces. It was found that a minimum of 15 wt% MAA was required to effect dissolution and thickening of the model HASE polymers. Increasing the MAA level yielded higher zero-shear viscosity and storage modulus G’ with maximal values being obtained at 40% MAA. The molecular weight of the model thickeners was controlled by the amount of chain transfer agent (CTA) added during polymerization. When the CTA level was below 0.1 wt% based on total monomers, the polymer solutions displayed shear-thinning behavior. A small increase in CTA concentration beyond 0.1% resulted in a dramatic change to Newtonian flow, and the solution viscosity was nearly two orders of magnitude lower. The model thickeners were also tested in a vinyl acrylic architectural paint formulation. The effects of each individual factor on paint thickener efficiency, high-shear, and low-shear properties are discussed and compared with solution rheology for predictive relationships. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 11–12, 2003, in Philadelphia, PA.     

Styrene-butadiene branched star-shaped asphalt modifiers: Synthesis and mechanical characterization

Abstract

The synthesis and the corresponding characterization of styrene-butadiene (SB), branched, star-shaped copolymers was investigated as part of a research project on asphalt modification using polymers with precise molecular structures. The method of anionic polymerization was followed to prepare samples of block copolymers of SB, a synthesis method that controls chain-architecture, molecular weight distribution, monomer distribution, and the average molecular weight. The research studies are the synthesis of block copolymers including linear, three- and four-arms constructs, depending on the coupling agent used. The techniques of nuclear magnetic resonance (1NMR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology were carried out to characterize the copolymers. From the results of the 1NMR, DSC, and GPC analyses, all star-shaped copolymers investigated showed a similar block copolymer composition. Furthermore, the rheological behavior of one of the synthesized star-shaped copolymers was nearly the same as a four-branched commercial copolymer. Rheologically, the four-arm block copolymer sample had the largest storage modulus (G′) among the branched copolymers synthetized, indicating that such architecture produces a highly structured material. In regard to polymer-modified asphalt formulations, the three-branched copolymer architecture yielded better elastic behavior than the four-branch version. In summary, the findings of this investigation provide new insight about a polymer system that may offer advantages in industrial asphalt paving applications.     

Estimation of rheological parameters using velocity measurements

In the present investigation, we develop a method for estimating rheological parameters of viscoelastic fluids using velocity measurement in a square straight channel. It is believed that a somewhat complicated patterns of secondary flows due to the non-zero second normal stress difference are more useful than the simple viscometric flows traditionally adopted in the determination of rheological parameters. The inverse problem of determining the rheological parameters from a set of velocity measurements is solved using a conjugate gradient method. When applied to a general constitutive equation encompassing the UCM model, the Oldroyd-B model and the PTT model, the present method is found to yield a reasonably accurate estimation of five rheological parameters simultaneously even with noisy velocity measurements.     

Preparation and rheology of polyamide-6/attapulgite nanocomposites and studies on their percolated structure

The polyamide-6/attapulgite nanocomposites were prepared via an in situ polymerization route with attapulgites pre-modified with cetyltrimethylammonium bromide (CTAB) and toluene-2,4-diisocyanate (TDI). Morphology observation showed that the exfoliated attapulgite fibers were well dispersed in the polyamide-6 matrix on a nanometer scale and formed a percolation network structure. The rheological behaviors of such polymer/fibrous clay nanocompostie samples were investigated by an ARES rheometer with parallel plate geometry. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of these samples increased monotonically with attapulgite content at low frequencies. The presence of attapulgites caused these nanocomposite melts to have solid-like behaviors and slower relaxation. This behavior can be explained in terms of the development of a grafting-percolated fibrous-silicate network structure. Monte Carlo simulations were performed to determine the critical threshold for attapulgites fibers in 3D. The calculated critical threshold from simulations fitted the results of our rheological experiments very well.     

Time and shear dependent rheology of maleated polyethylene and its nanocomposites

Dipole-dipole and/or hydrogen-bonding interactions between the pendant functional groups within maleated high-density polyethylene (PE-g-MAn) establish a physical polymer network, whose formation kinetics and shear-sensitivity are revealed by dynamic oscillatory testing. The pronounced time and shear dependent viscoelastic properties of PE-g-MAn were not observed for a corresponding imide derivative, PE-g-imide, presumably due to weakened functional group associations in the latter material.The melt compounding of PE-g-MAn with onium-ion exchanged montmorillonite clay (NR₄⁺-MM) resulted in a partially exfoliated hybrid nanocomposite structure, whose viscoelastic behaviour differed significantly from that of the unfilled polymer. The presence of dispersed clay platelets altered the extent of functional group associations, thereby changing the dynamics of network formation.     

HDPE/LLDPE reactor blends with bimodal microstructures—Part II: rheological properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components.     

Optimising the dewatering behaviour of clay tailings through interfacial chemistry, orthokinetic flocculation and controlled shear

The effect of shear on dewatering behaviour and particle interactions of Na-exchanged smectite and kaolinite clay dispersions has been investigated at pH 7.5, using hydrolysable Ca(II) and Mn(II) ions as coagulants and high molecular weight anionic and non-ionic polyacrylamide (PAM A and PAM N, respectively) and polyethylene oxide (PEO) flocculants. Metal ion addition enhanced the flocculation performance by dramatically reducing the magnitude of the particle zeta potential and, in the case of smectite pulp, suppressing osmotic swelling. Under optimum orthokinetic flocculation conditions of controlled agitation rate and duration, PAM A and PEO-based flocs settled faster than those of PAM N whilst kaolinite pulps produced higher sedimentation rates than smectite pulps. The settling rates are nearly an order of magnitude greater than those observed under standard flocculant-pulp mixing/flocculation methods of inversion and plunging. The difference in the flocculant behaviour is attributed to the more expanded conformation of PAM A and PEO polymer chains in contrast to PAM N, whilst the lower yield stresses, reflecting inter-particle bridging and floc network structure strength that are conducive to faster clarification, were displayed by kaolinite pulps. Following shear, similar consolidation enhancement of ≈ 5-7 wt.% solid for both pulps was achieved at an optimum agitation range of 100-200 rpm. This was accompanied by decreased yield stress in the case of PAM A-based pulps, indicating non-reversible disruption of polymer mediated particle and floc network structure. In contrast, the yield stresses of PAM N and PEO flocculated dispersions indicated similar and stronger particle interactions, respectively, upon consolidation following shear. The findings show clear links between effect of shear, interfacial chemistry and polymer structure on pulp particle interactions and dewaterability.     

The rheodynamics and combustion of coal-water mixtures

Investigation methods for characteristics of movement along the tubes, combustion dynamics and gasification of separate drops were developed for the coal-water mixtures (CWM). The following parameters were determined on the basis of laser heating: thermometric, pyrometric and concentration dynamics of single-drop combustion, complete combustion times, duration of temperature phases of combustion, as well as the moment and temperature of ignition. Information on the combustion mass velocity and gasification products was also obtained using laser heating.     

甘油三酸脂对硅溶胶的分散作用

通过对硅溶胶泥浆的流变性实验确定了硅溶胶泥浆的流变模型，验证并分析了加入少量经过低温氧化过的甘油三酸脂（ＧＴＯ）不改变硅溶胶泥浆的流变模型，但能有效地改善其流变性能。因此，ＧＴＯ可作为硅溶胶结合浇注料的高效减水剂。