A novel nucleation apparatus for regime separated granulation

A novel nucleation apparatus is presented for the production of narrow sized nuclei from various powder and binder liquid combinations. Mono-sized binder liquid droplets are produced by a specially designed mono-disperse droplet generator. The droplet generator is positioned above a conveyor belt, transporting a powder bed through the spray zone of the droplet generator. By nucleating powder on a conveyer belt, the nucleation mechanism is completely separated from all other granulation mechanisms due to the lack of relative motion between primary particles and/or formed nuclei. Nucleation tests were performed using chalcopyrite and limestone powders with water as the binder liquid. At all operating conditions, the formed nuclei were found to originate from multiplicities of drops that merged on the powder bed surface. Investigation of the dynamics of nuclei formation showed that powder-binder liquid combinations with fast penetration dynamics result in less variation in the number of droplets from which nuclei originate. Smaller and more narrowly distributed nuclei were also achieved by increasing powder speed through the spray zone.

Growth regime map for liquid-bound granules: further development and experimental validation

An attempt was made to quantify the boundaries and validate the granule growth regime map for liquid-bound granules recently proposed by Iveson and Litster (AlChE J. 44 (1998) 1510). This regime map postulates that the type of granule growth behaviour is a function of only two dimensionless groups: the amount of granule deformation during collision (characterised by a Stokes deformation number, St(def)) and the maximum granule pore saturation, s(max). The results of experiments performed with a range of materials (glass ballotini, iron ore fines, copper chalcopyrite powder and a sodium sulphate and cellulose mixture) using both drum and high shear mixer granulators were examined. The drum granulation results gave good agreement with the proposed regime map. The boundary between crumb and steady growth occurs at St(def) of order 0.1 and the boundary between steady and induction growth occurs at St(def) of order 0.001. The nucleation only boundary occurs at pore saturations that increase from 70% to 80% with decreasing St(def). However, the high shear mixer results all had St(def) numbers which were too large. This is most likely to be because the chopper tip-speed is an over-estimate of the average impact velocity granules experience and possibly also due to the dynamic yield strength of the materials being significantly greater than the yield strengths measured at low strain rates. Hence, the map is only a useful tool for comparing the granulation behaviour of different materials in the same device. Until we have a better understanding of the flow patterns and impact velocities in granulators, it cannot be used to compare different types of equipment. Theoretical considerations also revealed that several of the regime boundaries are also functions of additional parameters not explicitly contained on the map, such as binder viscosity. (C) 2001 Elsevier Science B.V. All rights reserved.

Recoupled separated-local-field experiments and applications to study intermediate-regime molecular motions

A specific separated-local-field NMR experiment, dubbed Dipolar-Chemical-Shift Correlation (DIPSHIFT) is frequently used to study molecular motions by probing reorientations through the changes in XH dipolar coupling and T-2. In systems where the coupling is weak or the reorientation angle is small, a recoupled variant of the DIPSHIFT experiment is applied, where the effective dipolar coupling is amplified by a REDOR-like pi-pulse train. However, a previously described constant-time variant of this experiment is not sensitive to the motion-induced T-2 effect, which precludes the observation of motions over a large range of rates ranging from hundreds of Hz to around a MHz. We present a DIPSHIFT implementation which amplifies the dipolar couplings and is still sensitive to T-2 effects. Spin dynamics simulations, analytical calculations and experiments demonstrate the sensitivity of the technique to molecular motions, and suggest the best experimental conditions to avoid imperfections. Furthermore, an in-depth theoretical analysis of the interplay of REDOR-like recoupling and proton decoupling based on Average-Hamiltonian Theory was performed, which allowed explaining the origin of many artifacts found in literature data. (C) 2012 Elsevier Inc. All rights reserved.

Intermediate motions as studied by solid-state separated local field NMR experiments

In this report, the application of a class of separated local field NMR experiments named dipolar chemical shift correlation (DIPSHIFT) for probing motions in the intermediate regime is discussed. Simple analytical procedures based on the Anderson-Weiss (AW) approximation are presented. In order to establish limits of validity of the AW based formulas, a comparison with spin dynamics simulations based on the solution of the stochastic Liouville-von-Neumann equation is presented. It is shown that at short evolution times (less than 30% of the rotor period), the AW based formulas are suitable for fitting the DIPSHIFT curves and extracting kinetic parameters even in the case of jumplike motions. However, full spin dynamics simulations provide a more reliable treatment and extend the frequency range of the molecular motions accessible by DIPSHIFT experiments. As an experimental test, molecular jumps of imidazol methyl sulfonate and trimethylsulfoxonium iodide, as well as the side-chain motions in the photoluminescent polymer poly[2-methoxy-5-(2(')-ethylhexyloxy)-1,4-phenylenevinylene], were characterized. Possible extensions are also discussed. (c) 2008 American Institute of Physics.

Liquid distribution in wet granulation: dimensionless spray flux

This study investigates binder distribution in wet granulation and focuses on the nucleation zone, which is the area where the liquid binder and powder surface come into contact and form the initial nuclei. An equipment independent parameter, dimensionless spray flux Psi (a), is defined to characterise the most important process parameters in the nucleation process: solution flowrate, powder flux, and binder drop size. Ex-granulator experiments are used to study the relationship between dimensionless spray flux, process variables and the coverage of binder fluid on the powder surface. Lactose monohydrate powder on a variable speed riffler passed under a flat spray once only. Water and 7% HPC solution at two spray pressures were used as binders. Experiments with red dye and image analysis demonstrate that changes in dimensionless spray flux correlate with a measurable difference in powder surface coverage. Nucleation experiments show that spray flux controls the size and shape of the nuclei size distribution. At low Psi (a), the system operates in the drop controlled regime, where one drop forms one nucleus and the nuclei size distribution is narrow. At higher Psi (a), the powder surface cakes creating a broader size distribution. For controlled nucleation with the narrowest possible size distribution, it is recommended that the dimensionless spray flux be less than 0.1 to be in the drop-controlled regime. (C) 2001 Elsevier Science S.A. All rights reserved.

Seed maturation and effect of temperature regime on Trema micrantha (L.) Blume seed germination

T. micrantha (L.) Blume (Ulmaceae), a common pioneer tree species in Brazil, is used in the restoration of degraded areas. The fruits are fleshy and indehiscent, with only one water impermeable seed. During the fruiting period, fruits of different colours are found at the same time on the same branch. This research aimed to correlate fruit colour with other physical indicators of seed maturity and to Verify the effect of temperature regime on seed germination. Collected fruits were separated in to green, green-red and red colour and for each of these maturation stages, size, moisture content and dry matter of both fruits and seeds were determined. Seeds were scarified with sulphuric acid and submitted to a germination test conducted at constant (20 degreesC, 30 degreesC and 40 degreesC) and alternating (20-30 degreesC, 30-40 degreesC and 20-40 degreesC) temperatures for 15 weeks. Seed germination percentage and speed were analysed after five weeks and the fmal percentage of germinated and Viable seeds after 15 weeks. Seed maturity is attained when the fruits are green-red. At this stage, moisture content was about 64% for fruits and 10% for seeds. Alternating temperature was required for seed germination and 20-30 degreesC was the best option. Most seeds had germinated after five weeks, providing mature seeds, acid scarification and alternating temperature were used.

Nucleation regime map for liquid bound granules

Nucleation is the first step in granulation where the powder and liquid first contact. Two types of nucleation in wet granulation processes are proposed. Drop controlled nucleation, where one drop forms one nucleus, occurs when drops hitting the powder surface do not overlap (low spray flux Psi(a)) and the drop must wet quickly into the bed (short drop penetration time t(p)). If either criterion is not met, powder mixing characteristics will dominate (mechanical dispersion regime). Granulation experiments were performed with lactose powder, water, PEG200, and 7% HPC solution in a 6 L and a 25 L mixer granulator. Size distributions were measured as the drop penetration time and spray flux were varied. At short penetration times, decreasing Psi(a) caused the nuclei distribution to become narrower. When drop penetration time was high, the nuclei size distribution was broad independent of changes in dimensionless spray flux. Nucleation regime maps were plotted for each set of experiments in each mixer as a function of the dimensionless distribution width delta. The nucleation regime map demonstrates the interaction between drop penetration time and spray flux in nucleation. The narrowest distribution consistently occurred at low spray flux and low penetration time, proving the existence of the drop controlled regime. The nucleation regime map provides a rational basis for design and scale-up of nucleation and wetting in wet granulation.

Modelling nucleation in wet granulation

Nucleation is the first stage in any granulation process where binder liquid first comes into contact with the powder. This paper investigates the nucleation process where binder liquid is added to a fine powder with a spray nozzle. The dimensionless spray flux approach of Hapgood et al. (Powder Technol. 141 (2004) 20) is extended to account for nonuniform spray patterns and allow for overlap of nuclei granules rather than spray drops. A dimensionless nuclei distribution function which describes the effects of the design and operating parameters of the nucleation process (binder spray characteristics, the nucleation area ratio between droplets and nuclei and the powder bed velocity) on the fractional surface area coverage of nuclei on a moving powder bed is developed. From this starting point, a Monte Carlo nucleation model that simulates full nuclei size distributions as a function of the design and operating parameters that were implemented in the dimensionless nuclei distribution function is developed. The nucleation model was then used to investigate the effects of the design and operating parameters on the formed nuclei size distributions and to correlate these effects to changes of the dimensionless nuclei distribution function. Model simulations also showed that it is possible to predict nuclei size distributions beyond the drop controlled nucleation regime in Hapgood's nucleation regime map. Qualitative comparison of model simulations and experimental nucleation data showed similar shapes of the nuclei size distributions. In its current form, the nucleation model can replace the nucleation term in one-dimensional population balance models describing wet granulation processes. Implementation of more sophisticated nucleation kinetics can make the model applicable to multi-dimensional population balance models.

Scaleup of wet granulation processes: science not art

Significant advances have been made in the last decade to quantify the process of wet granulation. The attributes of product granules from the granulation process are controlled by a combination of three groups of processes occurring in the granulator: (1) wetting and nucleation, (2) growth and consolidation and (3) breakage and attrition. For the first two of these processes, the key controlling dimensionless groups are defined and regime maps are presented and validated with data from tumbling and mixer granulators. Granulation is an example of particle design. For quantitative analysis, both careful characterisation of the feed formulation and knowledge of operating parameters are required. A key thesis of this paper is that the design, scaleup and operation of granulation processes can now be considered as quantitative engineering rather than a black art. Résumé

Fluidodinâmica de sementes de brócolos em leito fluizado e leito de jorro

The spouted and fluidized bed technologies are usually employed in operations of drying, coating and granulation of particles by the chemical and pharmaceutical industries. The use of these techniques in agronomy is limited to the treatment of some species of seeds. In this work, the objective was to analyse the fluid-dynamics of fluidized and spouted beds when broccoli (Brassica oleracea L. var. Italica) seeds are used and also to verify the influence on seed germination after 60 min of seed exposition to spouting or fluidization, at room temperature. The fluid-dynamics was defined by the measurements of the bed pressure drop as a function of the air flow rate for different seeds loads. The experimental conditions were based on the physical properties of the seeds and were limited by the apparatus dimensions. The cone-cylindrical bed was constructed in plexyglass to permit flow visualization. The values of the parameters: maximum pressure drop, minimum spouting flow rate and pressure drop, and stable spout pressure drop were experimentally obtained from the fluid-dynamic analysis and were compared with the values calculated by empirical equations found in the literature. The same procedure was carried out with the fluidized bed and the important parameters for this regime were the air velocity and the bed pressure drop at minimum fluidization. The analysis of seed germination indicated that no damage was caused to the seeds by the spout or fluidization processes.

Variabilidade do regime de monções sobre o Brasil: o clima presente e projeções para um cenário com 2xCO2 usando o modelo MIROC

Este trabalho investiga a variabilidade do Sistema de Monções da América do Sul (SMAS) sobre o Brasil com particular interesse na região do cerrado brasileiro. O início, final e total de precipitação durante as monções de verão são examinados utilizando estimativas de precipitação por satélite (pêntadas) do Global Precipitation Climatology Project (GPCP) entre 1979-2004. Analogamente, as características do regime de monção simuladas pelo modelo climático global acoplado MIROC (Model for interdisciplinary Research on Climate) do IPCC (Intergovernmental Panel for Climate Change) são examinadas em dois cenários distintos: o clima do século XX (1981-2000) e o clima em uma condição com o dobro da concentração atual de CO2 (2xCO2) na atmosfera (2061-2080). Mostra-se que a variabilidade espacial do início da monção de verão sobre o cerrado na simulação do clima do século XX pelo MIROC corresponde bem às observações. Além disso, há indicação de uma mudança das caudas da distribuição sazonal da precipitação no Cerrado para um cenário com 2xCO2, comparativamente com o clima presente. Este resultado sugere uma mudança na probabilidade de ocorrência de eventos extremos (secos ou úmidos) em um cenário com 2xCO2 sobre o cerrado, o que de acordo com o MIROC, indica uma maior exposição da região às conseqüências de possíveis mudanças climáticas resultantes do aumento de gases de efeito estufa.

Brasil e brasileiros: notas sobre modelagem de significados políticos na crise do Antigo Regime português na América

Partindo da análise do significado político de Brasil e de brasileiro em documentos escritos por colonos em meados dos setecentos, o artigo aponta para a importância analítica do caráter desviante de variantes americanas da matriz societária portuguesa de tipo Ancien Régime. Trabalhando com os conceitos de memória e experiência, sustenta-se nele a idéia de que, por se tornarem assimétricas, as estruturas nacionais portuguesas dos dois hemisférios também se tornaram irredutíveis a um mesmo enquadramento constitucional quando da instauração da conjuntura revolucionária do final dos anos vinte do século XIX.

Pernambuco, Rio da Prata e a crise do antigo regime na América ibérica: o “caso” de Félix José Tavares Lira

The aim of this article is to discuss conexions between Pernambuco and Rio de la Plata around the year 1817. In a more general sense, it offers a large pattern of comprehension of the indepdendences of Luso and Spanish America in terms of its mutual relationships.

Beyond the Fragmentation Threshold Hypothesis: Regime Shifts in Biodiversity Across Fragmented Landscapes

Ecological systems are vulnerable to irreversible change when key system properties are pushed over thresholds, resulting in the loss of resilience and the precipitation of a regime shift. Perhaps the most important of such properties in human-modified landscapes is the total amount of remnant native vegetation. In a seminal study Andren proposed the existence of a fragmentation threshold in the total amount of remnant vegetation, below which landscape-scale connectivity is eroded and local species richness and abundance become dependent on patch size. Despite the fact that species patch-area effects have been a mainstay of conservation science there has yet to be a robust empirical evaluation of this hypothesis. Here we present and test a new conceptual model describing the mechanisms and consequences of biodiversity change in fragmented landscapes, identifying the fragmentation threshold as a first step in a positive feedback mechanism that has the capacity to impair ecological resilience, and drive a regime shift in biodiversity. The model considers that local extinction risk is defined by patch size, and immigration rates by landscape vegetation cover, and that the recovery from local species losses depends upon the landscape species pool. Using a unique dataset on the distribution of non-volant small mammals across replicate landscapes in the Atlantic forest of Brazil, we found strong evidence for our model predictions - that patch-area effects are evident only at intermediate levels of total forest cover, where landscape diversity is still high and opportunities for enhancing biodiversity through local management are greatest. Furthermore, high levels of forest loss can push native biota through an extinction filter, and result in the abrupt, landscape-wide loss of forest-specialist taxa, ecological resilience and management effectiveness. The proposed model links hitherto distinct theoretical approaches within a single framework, providing a powerful tool for analysing the potential effectiveness of management interventions.