Flocculation kinetics of precipitated calcium carbonate

When the percentage of filler in paper is increased, the optical properties are improved and the production cost lowered. However, fillers weaken paper strength by decreasing the fibre–fibre bonded area. Little is known about the optimum filler floc size or filler floc properties to allow developing optimum paper characteristics. Consequently, the kinetics of aggregation of scalenohedral precipitated calcium carbonate (PCC) filler was studied using various polymers (flocculants, coagulants and dry strength agents). The sodium salt of partially hydrolysed polyvinyl formamide copolymerized with acrylic acid (PVFA/NaAA) or C-starch lead to floc sizes, less sensitive to dosage within a certain range. Results from stability ratios correlate with PCC particle size. The change in particle size measured by photometric dispersion analysis (PDA) correlates well with the change in PCC particle size measured by light scattering/diffraction. Kinetic calculations show the orthokinetic aggregation times to be consistent with the experimental PDA results. The main uncertainty in the orthokinetic times is estimating the effective shear rate. It is proposed that the bridging surface area of PCC particles, the area which can form bonds between PCC particles or aggregates, should be used to study the kinetics of PCC aggregation, and not the total or projected surface area. In polymer induced aggregation, the PCC particle size increases to a plateau value with increasing polymer dosage. Two regions are most pronounced for C-PAM, PVFA/NaAA and A-starch. Region I corresponds to bridging flocculation. Region II is where the particle size reaches a plateau, and not the expected maximum predicted by classical polymer bridging theory or charge neutralisation theory, likely because of a competition between particle aggregation and polymer adsorption.     

The kinetics of the thermal degradation of calcium carbonate

The decomposition of calcium carbonate fine powder in a flowing nitrogen atmosphere has been investigated by non-isothermal thermogravimetry at heating rates in the range, 10–50 deg min^–1. The analog percentage weight change record was digitized at 1 deg intervals. The resulting data, transformed into dimensionless extents of reaction and calculated rates of reaction, was then subjected to the Arrhenius, Friedman and Generalized Kissinger analyses, using a recently developed FORTRAN program system. The value ofn namely 0.39 ±0.04, resulting when the data is analyzed assuming an nth order reaction, strongly indicates that the most probable rate controlling step is a three-dimensional diffusion process (D4 mechanism), withE=172.4 kJ·mol^–1 andA=1.97·10⁴ K^–1·min^–1. Reasons for the wide disparity in previously reported kinetic data are discussed.

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Zusammenfassung Die Zersetzung von feinpulvrigem Calciumcarbonat im Stickstoffstrom wurde durch nicht-isotherme Thermogravimetrie bei Aufheizgeschwindigkeiten von 10–50 °C/min untersucht. Die analoge prozentuale Gewichtsverlustregistrierung wurde in Intervallen von einem Grad digitalisiert. Die erhaltenen, in solche eines dimensionslosen Reaktionsgradcs überführten Daten und berechnete Reaktionsgeschwindigkeiten wurden der Arrhenius-, der Friedmann- und einer verallgemeinerten Kissinger-Analyse unterzogen, wobei ein kürzlich aufgestelltes FORTRAN-Programm benutzt wurde. Der unter der Annahme einer Reaktion n-ter Ordnung fürn erhaltene Wert von 0.39 ±0.04 ist ein nachdrücklicher Hinweis darauf, daß der geschwindigkeitsbestimmende Schritt höchstwahrscheinlich ein dreidimensionaler Diffusionsprozeß (D4-Mechanismus) mitE=172.4 kJ·mol^–1 undA=1.97·10⁴ K^–1·min^–1 ist. Gründe für die weitreichende Verschiedenheit der bisher mitgeteilten kinetischen Daten werden diskutirt.

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10–50° . , , 1. , , , , , . n- , =0,39 ±0,04 , , e (4 ) E=172, 4 · ^–1 =1,97·10^{4 –1}·^–1. .

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To be presented at the 14th North American Thermal Analysis Society Conference, San Francisco, CA, September 15–18, 1985.     

Crystallization of calcium carbonate with the filtration of aqueous solutions through a microporous membrane

It is established that the filtration of water through a microporous membrane does not change the hardness of the water; it does, however, reduce the amount of scale deposit, due to the crystallization of salts in water in the form of aragonite. The effect is consistently observed in water with a hardness of more than 7.0 H, a content of hydrocarbonate ions of more than 500 mg/L, and a pH ≥ 7.3. It is shown that introducing the seeds of calcite crystals into a filtrate results in the precipitation of calcite rather than aragonite. It is concluded that quasi-softening in the case of hard water microfiltration is caused by the removal of calcite micronuclei, and thus by conditions being created for the crystallization of aragonite as a thermodynamically less stable form.     

Determining calcium carbonate neutralization kinetics from experimental laboratory data

In the framework of a research aimed at estimating the performance and lifetime of porous filters filled with marble powder and used to neutralize acid waters, we propose a mathematical model for determining the calcium carbonate reaction kinetics from some experimental data. In particular we show how to determine the order of the reaction and the reaction rate when calcium carbonate is immersed in a HCl solution. These parameters are evaluated by means of a fitting procedure based on least square methods. The experiments are performed using CaCO₃ in the form of a slab and powder and measuring (by means of BET analysis) the specific reaction surface.     

Crystallization of calcium carbonate in magnetic water in the presence of paramagnetic substances

Effect of a paramagnetic substance on the crystallization of calcium carbonate in magnetic water was studied.     

Crystallization of calcium carbonate controlled by Pluronic P123 in room-temperature ionic liquid

The crystallization of calcium carbonate (CaCO₃) controlled by Pluronic P123 in a room-temperature ionic liquid, ethylamine nitrate (EAN), was investigated. The CaCO₃ aggregates were obtained by rapid mixing of ammonium carbonate ((NH₄)₂CO₃) and calcium chloride (CaCl₂). Cubic calcite, spherical vaterite, and bagel-like vaterite were obtained easily by changing P123 concentration and reaction temperature. The morphologies of the as-prepared CaCO₃ aggregates were investigated by transmission electron microscopy and scanning electronic microscopy. The phase change of the obtained crystals was confirmed by X-ray diffraction and Fourier transform infrared spectroscopy. It was shown that higher P123 concentration and higher reaction temperature favor the formation of vaterite in EAN. Unusual bagel-like vaterite was first obtained at 60 °C in the presence of 5 g/L P123 in EAN. Mineralization of CaCO₃ regulated by P123 in EAN is a simple, novel, and environment-friendly strategy for vaterite synthesis.     

The compensation effect in the kinetics of the thermal decomposition of calcium carbonate

The kinetic parameters of the Arrhenius equation for the thermal decomposition of CaCO₃ depending on the values of the sample weight and of the linear heating rate are interrelated by the compensation relationship lgA=a+bH*.     

Crystallization kinetics of amorphous

The active sites of hydrogen-exchanged Y zeolite (HY) and dealuminated (HDY) zeolites are investigated by TPD of carbon monoxide. Only the high temperature TPD spectra of CO (TM»620-690°C) were observed, meaning that CO molecules interact with very strong acid sites. The amounts of CO bonded on these sites are small (less than 1 molecule per unit cell). The strong influence of dealumination on the coverage degree is found. The calculated values for kinetic parameters indicate chemisorption of CO in the investigated systems (Edes»240 kJ mol^-1, A»1011 s^-1).     

Crystallization, mechanical and thermal properties of sorbitol derivatives nucleated polypropylene/calcium carbonate composites

<正>The effect ofαphase nucleating agent(NA) 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol(DMDBS) on crystallization and physical properties of polypropylene/calcium carbonate(PP/CaCO_3) composites has been comparatively investigated.Compared with binary PP/CaCO_3 composites,in which CaCO_3 exhibits weak heterogeneous nucleation, inconspicuous reinforcement and toughening effects for PP,the introduction of a few amounts of DMDBS induces a great increase of the degree of crystallinity.Largely improved tensile properties,fracture toughness at relatively higher temperature and heat deformation temperature(HDT) are observed for DMDBS nucleated PP/CaCO_3 composites.     

Effect of cationic polyacrylamide adsorption kinetics and ionic strength on precipitated calcium carbonate flocculation

The effect of polymer adsorption kinetics and ionic strength on the dynamics of particle flocculation was quantified using a model system consisting of precipitated calcium carbonate (PCC) and cationic polyacrylamide (CPAM) at a low shear rate. All early flocculations detectable by a photodispersion analyzer (PDA) happened in nonequilibrium polymer adsorption regimes. We observed discrepancies in flocculation rates with the surface coverage theory, which is based on a simple monolayer adsorption model, in both early and late flocculation stages. For instance, the same amount of adsorbed CPAM reached at different polymer doses demonstrated different flocculating capabilities. This highlighted the importance of polymer adsorption kinetics upon flocculation. The transient conformation of the adsorbed CPAM during the kinetic process sometimes even superceded the adsorbed amount in the determination of PCC flocculation. Both antagonistic and synergetic effects of increased ionic strength on the CPAM-induced PCC aggregation were observed during early flocculation. However, late-stage PCC flocculation shared some similarities, irrespective of polymer dose and ionic strength. Despite the decreased amount of adsorbed polymer from the increased ionic strength, the combination of CPAM and salt, at certain concentrations, demonstrated a synergy to promote PCC aggregation more efficiently than the same amount of the respective components.     

Crystallization kinetics of metallic glasses

In this study, the temperature-heating rate diagram of the main crystallization process of two metallic glasses, Fe₇₄Ni_3.5Mo₃B₁₆Si_3.5 and Fe₄₁Ni₃₈Mo₃B_18, was obtained from one experimental differential scanning calorimetry (DSC) scan and the knowledge of their activation energy as determined by an isoconversional method. A good concordance was observed between the diagram curves obtained by calculation (isoconversional approach) and the experimental data, which verifies the reliability of the method and the validity of the kinetic approach in these alloys.     

Crystallization kinetics of syndiotactic polypropylene

Melting-point and spherulite growth rate measurements for a sample of syndiotactic polypropylene (S = 0.716 and η = 0.356) were analyzed for the parameters characterizing crystal formation and growth: T_m = 159 ± 2°C, σ_e = 47 erg cm ^?2, σ = 4.4 erg cm^?2, and q = 5.6 kcal per mole of folds. The q and σ_e values place syndiotactic polypropylene in the group of “unhindered” polymers. Failure of the isotactic-polypropylene spherulite growth rate data to follow current theories of crystal growth precluded a comparison of crystal parameters of the two stereoisomers. At comparable degrees of supercooling, the absolute growth rates for the two forms are of the same order of magnitude and exhibit one or more crossover(s) in relative position.     

Crystallization kinetics of amorphous Se

Differential scanning calorimetry was used to study crystallization behavior in selenium glass under non-isothermal conditions. The crystallization kinetics were described in terms of the Johnson–Mehl–Avrami nucleation-growth model; activation energies and kinetic parameter m _JMA were determined. The study was performed in dependence with particle size, so that a novel approach to the evaluation of crystallization kinetics—the advanced interpretation of characteristic kinetic functions—could be employed. Extensive discussion of all aspects of a full-scale kinetic study for a complex crystallization process was performed within the framework of the introduced conception. The complexity of the crystallization process was found to be represented by very closely overlapping consecutive competing surface and bulk nucleation-growth mechanisms. Mutual interactions of both mechanisms as well as all other observed effects were explained in terms of thermal gradients, surface crystallization centers arising from the sample preparation treatments and a changing amount of volume nuclei originating from the combination of the pre-nucleation period and the actual glass preparation phase. The main objective of the study is to demonstrate the extent of so-far neglected information hidden in the characteristic kinetic functions and introduce a convenient tool for its acquisition.     

Crystallization kinetics of stretched natural rubber

Studies of the crystallization kinetics of natural rubber networks held in simple extension are reported. In these experiments the length of the specimen was held constant, and the crystallization process was followed by the decay in stress that occurred. A wide range of extension ratios and crystallization temperatures was encompassed by these experiments. From an analysis of the shapes of the crystallization isotherms, it can be concluded that major changes take place in the nucleation and growth processes as the extension ratio is increased. This conclusion is in accord with reports in the literature of changes in the crystallite morphology with extension ratio. Analysis of the temperature coefficient of crystallization, by means of nucleation theory, indicates a substantial increase in apparent interfacial free energies with increased deformation. This latter observation is interpreted to indicate a departure from a correlated crystallization process to one where isolated crystallites are formed.     

Crystallization kinetics of dilute polyethylene solutions

The crystallization kinetics of a high molecular weight fraction of linear polyethylene was studied in dilute solutions of p-xylene, n-hexadecane, and decalin by dilatometric methods. For all solvents and temperatures, the experimental isotherms could be quantitatively described by the Avrami formulation for the complete transformation. This result is unique in the realm of polymer crystallization, since marked deviations from this theory are usually observed in more concentrated systems. The Avrami exponent is found to be n = 4 in all cases. The temperature coefficients of the rate constants are indicative of a nucleation controlled process. The data fit either a two-dimensional or three-dimensional nucleation mode, and a discrimination can not be made between these two cases. The interfacial free energies are found to be independent of the solvent medium. It is also shown that, irrespective of the type of nucleation control governing the kinetics, the same type governs the crystallite thickness of the lamella-like crystals that are formed.     

Crystallization kinetics of yttrium aluminate glasses

Journal of Thermal Analysis and Calorimetry - Yttrium aluminate glasses with eutectic AY-E and near-eutectic composition AY-NE were prepared in the form of glass microspheres. Their basic...     

Crystallization kinetics of metallocene type polypropylenes

The crystallization kinetics from the melt of metallocene type isotactic poly(propylenes) having the same chain defect concentration and molecular weights ranging from 68480 to 288430 have been studied by differential scanning calorimetry. The crystallization rates and the variation of the rates with crystallization temperature follow a pattern that is basically independent of molecular weight. This result contrasts with the molecular weight dependence on the crystallization rate observed in linear polyethylene, random ethylene copolymers as well as other semicrystalline systems.Most significant is the fact that the metallocene poly(propylenes) show apparently significantly higher _eu products than do the Ziegler type fractions of matched molecular weight and defect concentration. This difference can be interpreted as the metallocene type crystallites having higher effect on surface interfacial free energies than the Ziegler type, or can result from the two different chain types having different sequence propagation probabilities.The work at Florida State University was supported by the Polymer Program, National Science Foundation 94-19508. This support is greatfully acknowledged. MJG wishes to acknowledge support from the National Research Council of Argentina (CONICET).