The hydration of reactive cement-in-polymer dispersions studied by nuclear magnetic resonance

The behaviour of two novel cement-in-polymer (c/p) dispersions, namely cement-in-poly(vinyl acetate) and cement-in-poly(vinyl alcohol) upon exposure to water at room temperature was investigated by a combination of various NMR methods. The swelling, cracking, and the water ingress were monitored non-destructively using ¹H single point imaging. The hydration of the cement matrix was investigated using ²⁹Si NMR whilst ¹³C CPMAS NMR spectra allowed the quantification of the kinetics of the hydrolysis reaction of poly(vinyl acetate) into poly(vinyl alcohol). The polymer controls the rate of water ingress and swelling which in turn determines the behaviour of the c/p dispersions upon exposure to water. For the cement-in-poly(vinyl alcohol), the rates of water ingress and swelling are much faster than the hydration of the clinker whilst for the cement-in-poly(vinyl acetate) the slow rates of the two processes allow the formation of a cementious matrix which assures the stability of the sample.     

良好分散尼龙6/多壁碳纳米管复合材料的研究

采用柔和混合法制备纳米粒子良好分散的尼龙-6/多壁碳纳米管(PA6/MWNTs)复合材料,采用差示扫描量热仪(DSC)和广角X射线衍射法(XRD)研究了MWNTs对PA6基体结晶熔融行为的影响。DSC结果表明,MWNTs的加入大幅度地提高了PA6的结晶温度(最高提高约20℃),基体的结晶度也有所提高,说明良好分散的MWNTs在PA6结晶过程中呈现明显的异相成核作用;XRD结果证实,分散良好的MWNT促进PA6形成α晶型,抑制γ晶型的形成。同时,MWNT的加入导致复合材料出现熔融双峰现象,其形状随MWNT含量的变化而改变,双峰结构可能是由于熔融过程中伴随着重结晶而引起的。     

Polymer particles with a pomegranate-like internal structure via micro-dispersive polymerization in a geometrically confined reaction space I. Experimental study

The synthesis of micron-sized polymer particles with a core-shell pomegranate-like morphology is presented. The proposed polymerization technique takes advantage of a reaction-induced micro-phase separation within a suspended organic liquid droplet containing monomer, a chemical initiator, a steric stabilizer, and a poor solvent for the polymer. With an increase in monomer conversion, the monomer droplet suspended in a continuous aqueous medium is transformed first into a micro-capsule with a thick pericellular membrane, and eventually into a polymer particle packed with 300-500 nm polymer sub-particles. The experimentally observed evolution of particle morphology indicates that the reaction pathway is strongly influenced by micro-phase separation and transport phenomena. In the first stage of polymerization, a pseudo-homogeneous polymerization takes place at the droplet surface, followed by a starved macro-dispersive polymerization in the inner region where polymer precipitates out from the solvent phase as nano-sized sub-particles.     

Influences of polymer matrix melt viscosity and molecular weight on MWCNT agglomerate dispersion

In order to study the influence of melt viscosity and molecular weight on nanotube dispersion and electrical volume resistivity, three different polycarbonates (PCs) varying in molecular weight were melt compounded with 1 wt% multiwalled carbon nanotubes (MWCNTs, Baytubes^® 150 HP) using a small-scale compounder. The experiments were performed at constant melt temperature but at varying mixing speeds, thereby applying different magnitudes of shear stress. Light transmission microscopy was used to access the state of agglomerate dispersion, and electrical resistivities of the composites were measured on pressed plates. The results indicate that with increasing matrix viscosity the agglomerate dispersion gets better when using constant mixing conditions but worse considering comparable shear stress values. To study the effect of molecular weight, in a second set of experiments melt temperatures were adjusted so that all PCs had similar viscosity and mixing was performed at constant mixing speed. As investigated on two viscosity levels, the composites based on the low molecular weight matrix showed smaller sized un-dispersed primary agglomerates as compared to composites with higher molecular weight matrices, highlighting the role of matrix infiltration into primary nanotube agglomerates as the first step of dispersion. The resistivity values of composites prepared using low viscosity matrices were lower than those of composites from high viscosity matrix.     

Effect of montmorillonite dispersion on flammability properties of poly(styrene-co-acrylonitrile) nanocomposites

Poly(styrene-co-acrylonitrile)/Cloisite 20A (95/5) nanocomposites, having various spatial dispersion levels of the clay, were prepared with controlling clay concentrations in a solvent by the coagulation method. X-ray diffraction, transmission electron microscopy and laser scanning confocal microscopy were used to characterize the structure and morphology of the nanocomposites on a nano-scale and on a micro-scale. Quantitative analysis of clay spatial dispersion in the nanocomposites based on the laser scanning confocal microscopy images was conducted from three different perspectives: 1) clay spatial distribution; 2) the non-clay-occupied domain size; and 3) the relationship between the frequency and intensity of pixels in the images. The results from these quantitative methods indicate that nanocomposites with different spatial dispersion levels of clay in the poly(styrene-co-acrylonitrile) matrix were obtained. Evidently, the ?d₀₀₁ data from the X-ray diffraction was found to be not useful in measuring the clay dispersion in the nanocomposites. The effect of clay dispersion on the flammability properties of the nanocomposites and relevant mechanism of the clay dispersion having influence on flammability were also investigated. In radiant gasification experiments at 50 kW/m², the best clay dispersion yielded a 32% reduction in peak mass loss rate, as compared to the nanocomposites with the worst dispersion.     

The synthesis and characterization of lanthanide-encoded poly(styrene-co-methacrylic acid) microspheres

Lanthanide-encoded polystyrene microspheres with methacrylic acid (MAA) as a co-monomer and with diameters on the order of 2 μm and a very narrow size distribution were synthesized by two-stage dispersion polymerization (2-DisP). These microspheres were designed as a platform for mass cytometry-based bioassays. Different lanthanides (Ln) were loaded into these microspheres during the synthesis, through the addition of LnCl₃ salts and excess MAA to the reaction after about 10% conversion of styrene, i.e., well after the microsphere nucleation stage was complete. Different levels of MAA were employed to investigate the relationship between the number of carboxyl group on the particle surface and the amount of MAA used. The reaction remained well controlled with both 2 and 4 wt % MAA. As monitored by inductively coupled plasma (ICP) mass spectrometry, we found high incorporation efficiency (>95%) of Ln ions into the particles when the total amount of LnCl₃ salts in the reaction mixture was sufficiently small. The Ln incorporation efficiency decreased with the increasing amount of LnCl₃ salts. Mass cytometry analysis shows that individual microspheres contain ca. 10⁵-10⁸ chelated lanthanide ions, either a single element or a mixture of elements. This method of incorporating lanthanide into P(S-MAA) particles through the second stage of two-stage dispersion polymerization yields microspheres suitable for the highly multiplexed detection of biomolecules.     

New vinyl ester copolymers as stabilisers for dispersion polymerisation in scCO2

In this paper we demonstrate new poly vinyl alkylate homopolymers and copolymers with excellent solubility in scCO₂ that can be used as stabilisers for dispersion polymerisation in scCO₂. Poly (vinyl acetate) (PVAc) was combined in various ratios with poly (vinyl butyrate) (PVBu) and poly (vinyl octanoate) (PVOc) to both tune the scCO₂-solubility and provide adequate steric stabilisation. The polymer cloud points observed were found to be dependent on the ratio of the different blocks and the molecular weights and polydispersities (PDI) of the polymers. The effectiveness of these new polymeric stabilisers for dispersion polymerisation of N-vinyl pyrrolidone (N-VP) in scCO₂ is presented.     

Continued self-similar breakup of drops in viscous continuous phase in agitated vessels

Drop breakup in viscous liquids in agitated vessels occurs in elongational flow around impeller blade edges. The drop size distributions measured over extended periods for impellers of different sizes show that breakup process continues up to 15–20 h, before a steady state is reached. The size distributions evolve in a self-similar way till the steady state is reached. The scaled size distributions vary with impeller size and impeller speed, in contrast with the near universal scaling known for drop breakup in turbulent flows. The steady state size of the largest drop follows inverse scaling with impeller tip velocity. The breadth of the scaled size distributions also shows a monotonic relationship with impeller tip velocity only.     

CFD Prediction of the Critical Agitation Speed for Complete Dispersion in Liquid‐Liquid Stirred Reactors

A computational fluid dynamics (CFD) model is adopted to simulate the turbulent immiscible liquid‐liquid flow in a stirred vessel based on a two‐fluid model with a k‐ϵ‐A_P turbulence model. An improved inner‐outer iterative procedure is adopted to deal with the impeller rotation in a fully baffled stirred tank. Different drag formulations are examined, and the effect of the droplet size on both the dispersed phase holdup distribution and the velocity field is analyzed. Two different numerical criteria are tested for determining the critical impeller speed for complete dispersion. The simulated critical impeller speeds are generally in good agreement with the correlations in the literature when the fixed droplet size is properly selected. This demonstrates that the modeling approach and the numerical criteria proposed in this work are promising for predicting the dispersion characteristics in liquid‐liquid stirred tanks.     

Optimierte Beschreibung von Dispersionsschichten an einem vertikalen Abscheider

The image analysis of dispersion layers in a vertical separator is realized by the development of an evaluation routine. The influence on the dispersion layer of the volume flow and hydrostatic pressure is investigated in continuous and discontinuous settling tests. A direct relationship between volumetric flow / hydrostatic pressure and dispersion layer height can be determined. The observed properties of the dispersion layer are explained by the underlying coalescence and sedimentation processes. The modeling of the dispersion layer is analyzed using four different model approaches.