Soluble organic additive effects on stress development during drying of calcium carbonate suspensions

The effect of polymer, plasticizer, and surfactant additives on stress development during drying of calcium carbonate particulate coatings was studied using a controlled-environment apparatus that simultaneously monitors drying stress, weight loss, and relative humidity. We found that the calcium carbonate coatings display a drying stress evolution typical of granular films, which is characterized by a sharp capillary-induced stress rise followed by a rapid stress relaxation. The addition of a soluble polymer to the CaCO3 suspension resulted in a two-stage stress evolution process. The initial stress rise stems from capillary-pressure-induced stresses within the film, while the second, larger stress rise occurs due to solidification and shrinkage of the polymeric species. Measurements on the corresponding pure polymer solutions established a clear correlation between the magnitude of residual stress in both the polymer and CaCO3-polymer films to the physical properties of the polymer phase, i.e. its glass transition temperature, T(g), and Young's modulus. The addition of small organic molecules can reduce the residual stress observed in the CaCO3-polymer films; e.g., glycerol, which acts as a plasticizer, reduces the drying stress by lowering T(g), while surfactant additions reduce the surface tension of the liquid phase, and, hence, the magnitude of the capillary pressure within the film.     

Shear response of concentrated calcium carbonate suspensions

The rheology of concentrated calcium carbonate suspensions is investigated with respect to addition of solution and dispersion polymers. System materials and composition are chosen to be similar, generically, to those in use in the coating of paper. Specifically, we investigate the particle volume fraction dependence of the relative viscosity, using both capillary and steady-shear concentric cylinder measurement methods to cover a broad range of concentrations. The results are interpreted in terms of semi-empirical models, such as the Krieger-Dougherty model. Oscillatory shear measurements are also employed to investigate the viscoelastic behavior of the concentrated suspensions. The measurements indicate that a common solution polymer thickener, carboxymethyl cellulose (CMC), causes depletion flocculation of calcium carbonate suspensions.     

Dynamics of shear-thinning suspensions of core-shell structured latex particles

The rheological behavior and microstructure of shear-thinning suspensions of core-shell structured carboxylated latex particles were examined. The steady shear viscosity of the suspension increased with increasing dissociation of the carboxyl groups or increasing particle concentration, however the critical shear stress sigma(c) and inter-particle distance xi of the microstructure did not change. With increasing particle diameter, sigma(c) increased and xi decreased. These results were consistent with a Brownian hard sphere model, in which competition exists between the bulk mass transfer due to the applied field and diffusion of the particles. We confirmed that sigma(c) depends on xi, as expressed by sigma(c) = 3kT/4pi xi3. This relationship is consistent with the dynamics of a Brownian hard sphere model with particle diameter xi. Thus the dynamics of shear-thinning suspensions of core-shell particles can be explained by a Brownian thermodynamic model.     

Preparation of pure monodisperse calcium carbonate particles

The non-template synthesis of monodisperse spherical particles of calcium carbonate is reported. Particles of a 3.5–4.5 μm size were produced by precipitation of calcium carbonate from alcohol solution at subzero temperatures.     

Microcrystalline composite particles of carbon nanotubes and calcium carbonate

Coprecipitation of urea-melt modified carbon nanotubes and calcium carbonate from an aqueous solution by two methods yielded microcrystalline composite particles. Powders obtained by colloidal crystallization from a supersaturated solution that were isolated and dried soon after precipitation were a mixture of raspberry-shaped and rhombohedral particles. These were shown by infrared and X-ray diffraction analyses to be mainly calcite. Particles that were kept wet for 1 day or longer before being isolated were typically entirely rhombohedral with edge lengths in the range of 5-30 microm. Scanning electron microscopy investigations revealed that the nanotubes were adsorbed on the particle surface and also incorporated into the interior matrix. Removal of the calcium carbonate component by treating the particles with acid yielded nanotube shells whose size and shape reflected those of the original particles.     

Elaboration of hydrophilic aminodextran containing submicron magnetic latex particles

Aminodextran containing submicron magnetic latex particles were prepared in two steps: (a) transformation of oil-in-water magnetic emulsion into structured magnetic latex particles via combination of seed and miniemulsion-like polymerization process and (b) immobilization (adsorption and chemical grafting) of prepared aminodextran onto negatively charged seed magnetic latex particles. The elaborated magnetic latex particles were characterized in terms of particle size, size distribution, morphology, surface charge density, chemical composition, magnetic properties, and also colloidal stability. The results showed that the morphology of the prepared seed magnetic latex is core–shell like and the cationic latex particles are hydrophilic and of high colloidal stability, irrespective of the aminodextran immobilization process.     

Shape changes during the drying of droplets of suspensions

During drying of droplets of suspensions, several flow regimes contribute to the radial flow of powder to the periphery to leave a pile-up of powder at the rim. It is shown that the shape of the droplet residues can be controlled both by restricting evaporation and by combining high and low boiling point solvents which modify particle flows and produce a range of droplet residues varying from a concave "doughnut" shape, sometimes with a central hole, to a convex dome shape. Addition of formamide to aqueous suspensions is shown to affect powder deposition by setting up a Marangoni flow rather than by reducing evaporation at the periphery. The results find direct application in thick-film combinatorial printing of ceramics to form small disks by droplet drying.     

Flocculation of starch-coated solidified emulsion droplets and calcium carbonate particles

Zirconium phosphate (ZrP) has recently been demonstrated as an excellent sorbent for heavy metals due to its high selectivity, high thermal stability, and absolute insolubility in water. However, it cannot be readily adopted in fixed beds or any other flowthrough system due to the excessive pressure drop and poor mechanical strength resulting from its fine submicrometer particle sizes. In the present study a hybrid sorbent, i.e., polymer-supported ZrP, was prepared by dispersing ZrP within a strongly acidic cation exchanger D-001 and used for enhanced lead removal from contaminated waters. D-001 was selected as a host material for sorbent preparation mainly because of the Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid group on the exchanger surface, which would enhance permeation of the targeted metal ions. The hybrid sorbent (hereafter denoted ZrP-001) was characterized using a nitrogen adsorption technique, scanning electron microscope (SEM), and X-ray diffraction (XRD). Lead sorption onto ZrP-001 was found to be pH dependent due to the ion-exchange mechanism, and its sorption kinetics onto ZrP-001 followed the pseudo-first-order model. Compared to D-001, ZrP-001 exhibited more favorable lead sorption particularly in terms of high selectivity, as indicated by its substantially larger distribution coefficients when other competing cations Na(+), Ca(2+), and Mg(2+) coexisted at a high level in solution. Fixed-bed column runs showed that lead sorption on ZrP-001 resulted in a conspicuous decrease of this toxic metal from 40 mg/L to below 0.05 mg/L. By comparison with D-001 and ZrP-CP (ZrP dispersion within a neutrally charged polymer CP), enhanced removal efficiency of ZrP-001 resulted from the Donnan membrane effect of the host material D-001. Moreover, its feasible regeneration by diluted acid solution and negligible ZrP loss during operation also helps ZrP-001 to be a potential candidate for lead removal from water. Thus, all the results suggested that ZrP-001 offers excellent potential for lead removal from contaminated water.     

Effect of cationic Praestols on sedimentation of concentrated suspensions of calcium carbonate

Using photosedimentation procedure, the sedimentation stability of 60% suspension of calcium carbonate was studied in relation to the concentration, molecular weight, chemical composition, and conformation of macromolecules of cationic Praestol and to the concentration and nature of mineral coagulants (NaCl and CaCl₂).     

An investigation of electrorheological properties of calcium carbonate suspensions in silicone oil

In this study, electrorheological behavior of suspensions prepared from 0.9 and 5.0 µm calcium carbonate particulates, dispersed in insulating silicone oil medium was investigated. Sedimentation stabilities of suspensions (c = 5 wt %) prepared using these calcium carbonate powders were determined to be 6 and 4 days, respectively. Electrorheological activity of all the suspensions was observed to increase with increasing electric field strength, concentration and decreasing shear rate. Shear stress of calcium carbonate suspensions increased linearly with increasing concentrations of the particles and with the applied electric field strength. Electric field viscosity of all the suspensions was decreased sharply with increasing shear rate and particle size, showing a typical shear thinning non-Newtonian visco-elastic behavior. Effects of elevated temperature and polar promoter onto electrorheological activity of calcium carbonate/silicone oil system were also investigated.__________From Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 268–273.Original English Text Copyright © 2005 by Yilmaz, Ünal, Yavuz.This article was submitted by the authors in English.     

pH-dependent release from ethylcellulose microparticles containing alginate and calcium carbonate

Ethylcellulose microparticles containing alginate and calcium carbonate nanoparticles were prepared by spray drying water-in-oil emulsion. Alginate solution (3%) in distilled water was used as an aqueous phase, ethylcellulose solution (5%) in dichloromethane as an oil phase, and sorbitan sesquioleate as an emulsifier. The nanoparticles of calcium carbonate were dispersed into the emulsion. By spray-drying the emulsion, ethylcellulose microparticles containing alginate and calcium carbonate were obtained. When the ratios of alginate to calcium carbonate were 4:1 and 2:1, the pH dependency of the release was marked and the degree of release was suppressed in acidic conditions. When the ratio increased to 1:2, the degree of release increased while the pH-dependent release profiles were maintained. Cavities created by the dissolution of calcium carbonate could account for the increased release.     

Aspects on the interaction between sodium carboxymethylcellulose and calcium carbonate and the relationship to specific site adsorption

The mechanisms of adsorption and association for sodium carboxymethylcellulose (NaCMC) in calcium carbonate suspensions have been determined from isothermal calorimetry and adsorption measurements. The equilibrium adsorption isotherms were determined by two different methods of separation; a depletion method and a serum exchange method. The enthalpy of dilution for NaCMC was determined on supernatants obtained from the calcium carbonate suspensions in order to investigate the interaction between NaCMC and dissolved species from the mineral. For comparison, NaCMC was injected into CaCl(2) solutions in order to determine the role of calcium ions in the adsorption process. The initial part of the adsorption isotherm showed a quasi-infinite slope indicating a high affinity for the NaCMC to the calcium carbonate surface, which was significantly reduced when anionic sodium polyacrylate was preadsorbed onto the calcium carbonate implying competitive adsorption. An endothermic enthalpy change was observed between the NaCMC and the calcium carbonate surface, suggesting attachment of the carboxylic acid groups onto the hydrated calcium sites. A similar endothermic enthalpy was observed when NaCMC was injected into CaCl(2) solutions or supernatants obtained from the calcium carbonate suspensions, indicating a complexation of carboxylic acid groups and hydrated calcium ions. It was concluded that the mechanisms of interaction of NaCMC in calcium carbonate suspensions are primarily an association between NaCMC and Lewis acid sites on the calcium carbonate surface and the formation of NaCMC-Ca(2+) complexes in the bulk solution, both of which will be affected by the amount of anionic sodium polyacrylate present.     

Poly(methyl methacrylate) encapsulation of calcium carbonate particles

Dispersed calcium carbonate particles are encapsulated with poly(methyl methacrylate). The optimum condition for the polymerization is investigated; and the encapsulated particles are characterized by spectrophotometric analysis, acid decomposition, thermal analysis, and microscopic observation. From the conversion comparison of the MMA monomer it is found that the optimum concentration of polymerization initiator is 1.58 × 10^?3 mol/L. The highest yield of encapsulation is obtained at 250 rpm with a concentration of 0.5 wt % surfactant (sodium dodecyl benzene sulfonate). A comparison of the Fourier transform IR spectra distinctly indicates the formation of PMMA on the surface of the calcium carbonate particles. The outcome of an acid decomposition test proves that the PMMA coating protects the particles. In addition, thermal analyses and microscopic observation characterize the PMMA on the surface of encapsulated particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4063–4073, 2004     

Healing and photon diffusion during sintering of high-T latex particles

A steady-state fluorescence technique was used to examine the annealing of films formed from high-T latex particles above the glass transition temperature. The films were prepared by sintering pyrene-labeled poly(methyl methacrylate) latex particles. During the annealing processes, the transparency of the film changed considerably. Direct fluorescence emission from excited pyrene was monitored as a function of annealing temperature to detect these changes. Scanning electron microscopy in conjunction with Monte Carlo simulations of photon diffusion in latex film were used to interpret the fluorescence results. Healing temperature and time were measured at the point where the fluorescence emission intensity becomes maximum. This was associated with the longest optical path of a photon in latex film during healing of particle(SINGLEBOND)particle boundaries. Healing activation energy was measured and found to be 10 kcal/mol. © 1996 John Wiley & Sons, Inc.     

Effects of PAA additive and temperature on morphology of calcium carbonate particles

Calcium carbonate particles with various shapes were prepared by the reaction of sodium carbonate with calcium chloride in the absence and presence of a polyacrylic acid (PAA) at 25°C and 80°C, respectively. The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The effects of pH, temperatures, aging time and concentration of PAA and CaCO₃ on the crystal form and morphologies of the as-prepared CaCO₃ were investigated. The results show that pH, temperatures, concentration of PAA and CaCO₃ are important parameters for the control of morphologies of CaCO₃. Various crystal morphologies of calcite, such as, plates, rhombohedras, rectangles, ellipsoids, cubes, etc. can be obtained depending on the experimental conditions. Especially, the monodispersed cubic calcite particles can be produced by PAA addition at 80°C. Moreover, higher temperature is beneficial to the formation of monodispersed cubic or rectangular calcite particles. This research may provide new insight into the control of morphologies of calcium carbonate and the biomimetic synthesis of novel inorganic materials.     

Heterogeneous reactions of gaseous methanesulfonic acid with calcium carbonate and kaolinite particles

Heterogeneous reactions of gaseous methanesulfonic acid (MSA) with calcium carbonate (CaCO₃) and kaolinite particles at room temperature were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatography (IC). Methanesulfonate (MS^?) was identified as the product in the condensed phase, in accordance with the product of the reaction of gaseous MSA with NaCl and sea salt particles. When the concentration of gaseous MSA was 1.34 × 10¹³ molecules cm^?3, the uptake coefficient was (1.21 ± 0.06) × 10^?8 (1σ) for the reaction of gaseous MSA with CaCO₃ and (4.10 ± 0.65) × 10^?10 (1σ) for the reaction with kaolinite. Both uptake coefficients were significantly smaller than those of the reactions of gaseous MSA with NaCl and sea salt particles.     

Photocatalytic degradation of aniline at the interface of TiO2 suspensions containing carbonate ions

The degradation of aniline has been investigated using aqueous TiO2 suspensions containing carbonate ions as photocatalyst. The addition of carbonate to Degussa P-25 increased the number of active adsorption sites at its surface. For the TiO2 suspensions containing carbonate ions the intensity of adsorption of aniline increased to 6.9 x 10(2) from 5.5 x 10(2) mol(-1) dm(3) in case of bare TiO2 suspensions. This in turn results in the increased interfacial interaction of the photogenerated charge carriers with the adsorbed aniline and thus enhancing the rate of its photodecomposition to 6.5 x 10(-6) mol dm(-3) s(-1) compared to 2.7 x 10(-6) mol dm(-3) s(-1) in the absence of Na(2)CO(3). The maximum efficiency of this photocatalyst has been obtained upon addition of 0.11 mol dm(-3) of Na(2)CO(3) at pH 10.8. The photocatalytic action is understood by the simultaneous interaction of intermediates, *OH and CO*-(3), and their reactivity with aniline. Azobenzene, p-benzoquinone, nitrobenzene, and NH(3) have been identified as the major products of the photooxidation of aniline. Both the reactant and products have been followed kinetically. The photodegradation follows Langmuir-Hinshelwood Model. The mechanism of the occurring reactions has been analyzed and discussed. In the presence of Na(2)CO(3), 3 x 10(-3) mol dm(-3) of aniline could be photodegraded completely in about 6 h while all organic intermediates decomposed completely within about 10 h.     

Aerobic biodegradation of calcium carbonate filled polyethylene film containing pro-oxidant additives

Two low density polyethylene films, which contained pro-oxidant additives, where investigated, one of them containing micro-milled calcium carbonate filler. Both materials were subjected to controlled thermal oxidation, the oxidation was obviously retarded in the filler-containing sample. Following this, the biodegradability of samples pre-oxidized for 40 and 80 days was investigated. The levels of carbon mineralization reached 13% and 16% for the 40 and 80 days pre-oxidized polyethylene containing filler, respectively, after approximately 16 months in a soil environment at 25 °C, and both types of sample were mineralized to about 19% in compost environment at 58 °C during the same period. The sample not containing filler was mineralized to about 7% in soil after 13 months, and about 23%, after 8 months in compost. Scanning electron microscopy revealed dense colonization of the sample surfaces in both soil and compost. The data presented here provide clear quantitative evidence that part of the polyethylene material was biodegraded.     

Dynamics of fracture in drying suspensions

We investigate the dynamics of fracture in drying films of colloidal silica. Water loss quenches the nanoparticle dispersions to form a liquid-saturated elastic network of particles that relieves drying-induced strain by cracking. These cracks display intriguing intermittent motion originating from the deformation of arrested crack tips and aging of the elastic network. The dynamics of a single crack exhibits a universal evolution, described by a balance of the driving elastic power with the sum of interfacial power and the viscous dissipation rate of flowing interstitial fluid.     

Rapid gel-like latex film formation through controlled ionic coacervation of latex polymer particles containing strong cationic and protonated weak acid functionalities

We introduce a controlled ionic coacervation (CIC) process that rapidly forms uniform, gel-like latex films with significant mechanical integrity without loss of water from the film. This process uses latex particles that contain both strong cationic charges and weak protonated acid groups. An increase in pH ionizes the weak acid and triggers the rapid setting of the latex films. The necessary increase in pH can be achieved by coating the latex onto an alkaline surface (such as concrete) or by controlled release of a fugitive acid (such as carbon dioxide). We explore the effect of latex composition and concentration on this process. We show that the CIC process does not require a water-soluble polymer to obtain the rapid-set film properties. Our proposed mechanism for CIC process is consistent with models for rapid, irreversible, particle-particle aggregation.