Precipitation of calcium carbonate in the presence of citrate and EDTA

The influence of process conditions such as feed rate, calcium/carbonate ratio, pH, complexing agents [ethylenediaminetetraacetic acid (EDTA), citrate (CIT)] and their concentration on the average particle size and shape of precipitated calcium carbonate was studied. The precipitation was performed in a semi-batch operated agitated vessel at constant pH by adding sodium hydrogen carbonate to a solution containing calcium chloride. In the absence of a complexing agent, agglomerates of needle-shaped crystals, probably aragonite, are obtained. Increasing feed time and the calcium/carbonate ratio increases the average particle size, whereas the opposite effect is observed for increasing pH. The observations can be related to the level of supersaturation. In the presence of complexing agents and at a concentration ratio of calcium vs. a complexing agent of 6, differently shaped and smaller particles were obtained. Furthermore, the effect of the other parameters on particle size becomes much weaker in the presence of complexing agents. In the presence of EDTA mostly spherical particles were obtained, and in the presence of citrate mainly rhombic particles corresponding to calcite were obtained. The effect on particle shape and size is attributed to interactions of the complexing agents with the faces of the crystalline calcium carbonate.     

Investigations of spherulitic growth in industrial crystallization

The discrimination between crystal growth and aggregation is of crucial importance for the control of morphology and particle size in crystallization processes, as they are influenced in very different ways by the industrial processing environment. A collection of resembling solution-grown polycrystalline particles that differ widely in chemical nature, like elemental nickel, calcium and sodium carbonate, l-glutamic acid and an aromatic amine have been identified to grow by a spherulitic growth mechanism usually only associated with the crystallization of polymers or melts. The particles are not growing by agglomeration of small individual crystals, as often claimed in the literature. The effect of initial supersaturation, temperature and solvent composition on the spherulitic growth of calcium carbonate (vaterite) has been used to demonstrate how spherulites can grow from solution both by central multidirectional growth (in water) and by unidirectional growth followed by low angle branching (in 90 wt% ethylene glycol). The progression of non-crystallographic branching could be monitored as a function of time at intermediate initial supersaturation values, supplying direct visual evidence for spherulitic growth in this system. A reduction in initial supersaturation and temperature resulted in insufficient branching and dumbbell particles, whereas increased levels of supersaturation rapidly produced fully grown spherulites.     

超细碳酸钙的合成与形状控制

采用气体分布板控制碳化速度,通过加入不同形状的控制剂,合成了链状、片状、立方体状、纺锤状、球形、针状六种不同形状的超细碳酸钙．研究了碳化过程中的粘度变化及机理和碳化速率对碳酸钙晶体成核生长过程的影响．基本实现了链状碳酸钙的粒度控制．     

Study on Preparation of Insensitive and Spherical High Bulk Density Nitroguanidine with Controllable Particle Size

In this study, the solventing‐out recrystallization method was applied to prepare insensitive and spherical high bulk density nitroguanidine (NQ). Experiments were performed at various operating conditions by using N‐methyl‐pyrrolidone (NMP) and acetone as solvent and antisolvent, respectively. The effects of different operating parameters such as NQ/NMP ratio, amount of acetone used, crystallization temperature, stirring speed and stirring time were investigated. The particle size and morphology of the prepared NQ crystals were observed by scanning electron microscopy (SEM), the bulk density was measured by the Archimedes’ method and the impact sensitivity was determined by fall hammer method. The experimental results showed that the solventing‐out recrystallization method could be used to prepare spherical high bulk density NQ with a narrow particle size distribution and the particle size could be controlled by changing the operating conditions. The bulk density of these spherical NQ particles was found to be in the range of 0.94–0.97 g cm⁻³, which is higher than that of needle‐shaped NQ particles, and they became less sensitive towards impact.     

球形碳酸钙的控制合成研究

以硼酸为控制剂,氯化钙和碳酸钠为原料,采用共沉淀法制备了方解石型碳酸钙球形晶体。研究了控制剂浓度、反应温度、反应时间、反应物浓度等因素对碳酸钙粒径和形貌的影响。结果表明：在硼酸浓度为0.4 mol/L、氯化钙浓度为0.1 mol/L、20 ℃饱和碳酸钠溶液滴速为4.9 mL/min、反应时间为60 min、陈化时间为60 min、反应温度为50 ℃、氯化钙与碳酸钠物质的量比为1∶1条件下,制备的球形碳酸钙颗粒大小均匀,平均粒径为1.57 μm。     

羟基乙叉二膦酸(HEDP)对碳酸钙晶体生长过程影响的原子力显微镜(AFM)研究

用原子力显微镜 (AFM)观测了添加羟基乙叉二膦酸 (HEDP)后的碳酸钙晶粒的表面形貌变化。纯碳酸钙过饱和溶液析出的碳酸钙晶体有两种主要的形态 :薄片状菱形晶体和类似立方体的菱方体晶体。AFM图像显示添加HEDP后菱方体晶体的形貌发生了根本性的变化 ,呈现一种类似多晶的表面结构 ;而薄片状菱形晶体在添加HEDP前后测量不到生长变化。实验结果表明HEDP对薄片状菱形晶体有阻垢效果 ,而对菱方体晶体的生长无抑制作用或较差     

Continuous precipitation of calcium sulfate dihydrate from waste sulfuric acid and lime

Precipitation of calcium sulfate dihydrate, gypsum, from (i) a pure sulfuric acid/lime suspension and (ii) a waste sulfuric acid/lime suspension in a continuous pilot plant in the temperature range from 40 °C to 80 °C was studied. It was observed that in the case of waste sulfuric acid with a high content of Mg²⁺ and Fe²⁺ ions, several hours after the beginning of the precipitation, partial dissolution of the product and modification of the crystals from needle‐ and plate‐like to agglomerated structures occurred. It is suggested that the secondary changes occur due to the increased concentration of Mg²⁺ and Fe²⁺ ions in the reactor. Below 60 °C, and above 70 °C plate‐like and needle‐like single crystals respectively were formed. The mean size (d₅₀) of the crystals was found to increase with increasing temperature and decrease with the initial concentration of lime. Gypsum produced between 70 °C and 80 °C is suitable for further processing for construction plaster. In a precipitation process with pure sulfuric acid only single perfect needle‐like crystals occurred. Copyright © 2005 Society of Chemical Industry     

棕榈酸改性纳米碳酸钙的工艺研究

采用从漆蜡中提取的棕榈酸作为表面改性剂,以活化度作为改性效果主要评价指标,对纳米碳酸钙粉体进行表面改性处理,确定了最佳改性工艺条件。对改性前后碳酸钙粉体的接触角、吸油率、石蜡糊粘度、粒度分布、分散性等性能进行了比较。结果表明,经棕榈酸表面改性处理后的纳米碳酸钙粒度分布均匀,分散性、亲油性好。     

The Influence of Shear Stress on Crystallization in an Ultrasound Levitator

Industrial precipitation processes often use chemical agents to influence crystal morphology and size distribution. This experimental study deals with the investigation of physical parameters including an alternative method to affect crystal growth, thus, avoiding the presence of additives as intrinsic impurities. The influence of shear stress acting on growing crystals within a droplet is investigated in an ultrasound levitator. An ultrasound levitator enables the suspension of a single droplet against gravity and the study of containerless precipitation with specific mechanical forces acting on crystals. The levitator is used as a three‐phase reactor with precipitation from the gas and liquid, and as a reactor for precipitation from two different solutions. Calcium carbonate is used as a model system. The variation of temperature and the amount of applied shear stress leads to different amounts of calcium carbonate morphologies. An increase in the shear stress results in more rounded or spherical crystals. The intensity of the shear stress also influences the particle size distributions of the precipitated crystals, i.e., with increasing shear stress, particle size distributions are shifted to smaller sizes.     

Influence of Particle Characteristics on Filter Ripening

Abstract

To investigate the dependence of filter ripening on particle size and surface charge, multiple experiments were conducted under different particle destabilization conditions including pH control, alum, and polymer destabilization. Laboratory‐scale filtration experiments were performed at a filtration velocity of 5 m/h using spherical glass beads with mean diameter of 0.55 mm as collectors. Particle suspensions with a broad size distribution and a 1.7 µm mean particle size were filtered through a 10 cm depth filter column. Better initial solids removal was confirmed under favorable particle and collector conditions (i.e., under smaller surface charge), but better initial particle removal does not necessarily mean better overall particle removal efficiency. It was shown that changes of the particle size distribution (PSD) in the effluent can significantly influence overall particle removal efficiency. Chemical parameters such as zeta potential can be important during the initial stage of filtration, but their importance can decrease over time depending on the specific chemical conditions. The influent PSD and the removal of certain size particles during the initial stage of filtration can significantly influence ripening, which in turn, can influence the overall particle removal efficiency.     

Investigation of different crystal habits without chemical additives in a three-phase reactor

A lot of powders with fine particle sizes and specific crystal habits are produced by precipitation processes, in which growth and morphology of the particles are controlled by a wide range of chemical agents. This study investigates alternative ways to limit crystal growth and influence crystal morphology. Experiments are carried out in an ultrasound levitator, where a single droplet can be suspended against gravity by an acoustic levitation force. The ultrasound leviator is a three-phase reactor, which allows the investigation of precipitation with applying specific shear forces at growing crystals within the droplet. The investigated system is calcium carbonate. By variation of physical reaction parameters as temperature and level of applied shear forces it is possible to obtain different crystal habits and morphologies. The morphology of calcium carbonate produced in the leviator can vary between prismatic, shell-like and spherical shape. Also the particle size distribution of the precipitated product is influenced. Increasing mechanical stress leads to a shift of the particle size distribution to smaller sizes.     

Preparation of L-PLA submicron particles by a continuous supercritical antisolvent precipitation process

Submicron particles of L-polylactic acid (L-PLA) without residual solvent were prepared by a continuous supercritical antisolvent (SAS) recrystallization process. Methylene chloride (CH₂C1₂) was used as a carrier solvent of L-PLA. Experiments were performed with changing process parameters such as pressure and temperature at constant concentration. Also, L-PLA initial concentrations in methylene chloride were varied from 0.3 to 4 wt%. The flow rates of CO₂ and solution, which were introduced into the precipitator, and nozzle diameter were kept unchanged in all of the experiments. It was found that the SAS process gives fine tuning of particle size and particle size distribution (PSD) by simple manipulations of the process parameters. In all cases of SAS recrystallization experiments, the formed spherical fine particles with a smooth surface were non-agglomerated and free flowing. Mean particle size of the L-PLA microparticles formed was varied from 0.1 to 1 μm by means of adjusting the system pressure and/or temperature.     

Polypropylene/combinational inorganic filler micro‐/nanocomposites: Synergistic effects of micro‐/nanoscale combinational inorganic fillers on their mechanical properties

Polypropylene (PP) has wide applications in various areas, but its low‐temperature brittleness and low moduli have limited its applications in engineering areas. This article reported micro‐/nanoscale combinational inorganic fillers (CIFs) to reinforce PP‐matrix composites as the first example. The CIFs consisted of plate‐like talc (T), needle‐like wollastonite (W), and nano‐Al₂O₃ (N). The PP/CIFs specimens were fabricated via a process of twin‐screw extrusion and screw‐type injection molding. The mechanical properties and thermal deflection temperature (HDT) of the PP/CIF composites were tested according to the corresponding standards, and the morphologies of the tensile‐fractured sections were observed using FE‐SEM. The PP/WT composites had higher mechanical properties and HDTs than those of either PP/W or PP/T. Small amounts of Al₂O₃ nanocrystals together with WT simultaneously strengthened and toughened the PP‐matrix composites. The PP/WTN composite with 2.6% of nano‐Al₂O₃ had well‐balanced properties, enhanced by a large increment when compared with the PP matrix or PP/WT composites. The enhancements should be attributed to the synergistic effects of the CIFs not only in the aspect of various shapes (plate‐like, needle‐like, and spherical) but also in hierarchical size‐levels (microscale and nanoscale). The novel strategy overcame the limitation of conventional rigid modification and solved the problem of uniform dispersion of nanocrystals in polymer matrices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of process conditions on spray dried calcium carbonate powders for thermal spraying

Powder preparation is an important stage in the production of thermal spray coatings with the desired characteristics. An important powder feature is flowability, which can be adjusted through particle morphology, particle size and size distribution. Combined, these features dictate the quality of the coating produced. To increase a powder's flowability, spherical particles within a particular size range are ideal. One way to achieve this is through spray drying. The aim of the present study was to investigate the effect of spray drying process parameters on the physical properties of calcium carbonate powder, with the goal of producing large, spherical particles ranging between 50 and 100 μm in preparation for thermal spray experiments. A key aspect was the use of ethanol to aide in the production of large spheres. A 2³ factorial design of experiments (DoE) was utilised to study the following process parameters: gas flow rate, feed flow rate and solids loading. The resulting powders were characterised in terms of particle size, morphology and production yield. Porous, hollow, spherical particles were produced in a suitable size range for thermal spraying, which was attributed to the rapid evaporation of ethanol. Statistical analysis was utilised to interpret trends between the spray drying parameters and powder characteristics quantitatively.     

氨基酸调控无水碳酸镁晶体结晶试验研究

无水碳酸镁晶体作为一种新型无机功能材料引起了研究者们的广泛关注。以氯化镁为原料,碳酸钠为沉淀剂,合成了无水碳酸镁晶体,再以甘氨酸、组氨酸、丙氨酸及L-天门冬氨酸四种不同种类氨基酸作为添加剂,调控其结晶的粒度及形貌。采用X射线衍射仪、扫描电子显微镜、激光粒度分析仪对合成产物进行表征,分析不同种类氨基酸对合成的无水碳酸镁晶体物相结构和形貌的影响。结果表明:在组氨酸调控下合成的无水碳酸镁结晶纯度高,生成的产物中n(Mg²⁺)∶n(CO^2-₃)为1∶0.94;L-天门冬氨酸调控合成的晶体纯度次之;甘氨酸和丙氨酸调控合成的晶体中掺杂大量碱式碳酸镁晶体。在组氨酸、L-天门冬氨酸、甘氨酸及丙氨酸四种氨基酸调控作用下,晶体结晶形貌依次呈凸面球三角形状、近球状、球状及不规则状,且无水碳酸镁晶体粒径分布均呈先上升后振荡下降最后小粒径拖尾的趋势。以上研究结果为无水碳酸镁晶体的仿生合成提供了参考。     

A Comparative Study on the Separation of Different‐Shape Particles Using a Mini‐Hydrocyclone

The separation efficiency from water of different‐shape particles was studied experimentally using a mini‐hydrocyclone. Spherical and flaky (plate‐like) aluminum particles with the same particle size distributions were employed. Also, the effects of the feed flow rate and the temperature on the separation performance were studied. The results were investigated in terms of slurry recovery, total efficiency, and partition curves. The separation efficiency of the spherical particles increased with increasing particle size, temperature, and feed flow rate, as expected. The fishhook effect, as a noticeable phenomenon, was observed for the spherical particles. In case of the flaky particles, the separation showed an unusual behavior: The separation efficiency decreased with increasing particle size in the largest particle fraction, which has so far not been reported and addressed in this way.     

Crystallization of Cephradine Polymorphs and Hydrates from Mixed Solvents of Methanol and Water

Cephradine monohydrate (CPH) crystallizes with a needle‐like shape which leads to severe agglomeration and slow filtration. Effects of different operating conditions on the particle size and shape as well as the filterability of the crystal products are described. The solubility and stability of one anhydrate of cephradine (CPA1) and CPH as a function of temperature and water activity was investigated in different methanol and water mixtures. A solvent‐mediated transformation from CPH to CPA1 was observed at water mole fractions below 0.2–0.35 depending on the temperature. The crystallization behavior of CPH was studied by linear cooling and antisolvent crystallization. Lowering the cooling rate and addition of seeds led to an increase in particle size and improvement of filterability.     

Effects of the reinforcement and toughening of acrylate resin/CaCO3 nanoparticles on rigid poly(vinyl chloride)

Novel composite particles based on nanoscale calcium carbonate (nano‐CaCO₃) as the core and polyacrylates as the shell were first synthesized by in situ encapsulating emulsion polymerization in the presence of the fresh slush pulp of calcium carbonate (CaCO₃) nanoparticles. Subsequently, these modified nanoparticles were compounded with rigid poly(vinyl chloride) (RPVC) to prepare RPVC/CaCO₃ nanocomposites. At the same time, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were investigated, and the synergistic effect of modified nanoparticles with chlorinated polyethylene (CPE) was also studied. The results showed that in the presence of nano‐CaCO₃ particles, the in situ emulsion polymerization of acrylates was carried out smoothly, and polyacrylates successfully encapsulated on the surface of nano‐CaCO₃ to prepare the modified nanoparticles, breaking down nano‐CaCO₃ particle agglomerates, improving their dispersion in the matrix, and also increasing the particle–matrix interfacial adhesion. Thus, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were very significant, and the cooperative effect of the nanoparticles with CPE occurred in the united modification system. Scanning electron microscopy analyses indicated that large‐fiber drawing and network morphologies coexisted in the system of joint modification of nanoparticles with CPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3940–3949, 2007     

Kinetics, energy characteristics, and intensification of crystallization processes in chemical precipitation of hardness ions

An analysis of the literature data on the solubility and kinetics of the chemical (reagent) precipitation of calcium carbonate and magnesium hydroxide is performed. The possible causes of the significant discrepancy in the available data are considered. The kinetics of the homogeneous and heterogeneous crystallization of calcium carbonate and magnesium hydroxide in reagent precipitation is studied using different methods. It is shown that the use of heterogeneous crystallization on seed particles pretreated in an ultrasonic field raises the rate of crystallization by an order of magnitude. The kinetics of nucleation is studied; the effect of supersaturation and temperature on the induction period in the homogeneous and heterogeneous nucleation of CaCO₃ and Mg(OH)₂ crystals is investigated. The energy characteristics of nucleation, namely, the interfacial tension (surface energy) and activation energy, are determined. The use of fine-dispersed particles activated by ultrasound makes it possible to considerably reduce the energy barrier for nucleation.     

Particle growth of magnesium alkoxide as a carrier material for polypropylene polymerization catalyst

Images from scanning electron microscopy, transmission electron microscopy and X-ray diffraction profiles of typical magnesium diethoxide (MGE) particles obtained by the reaction of ethanol, metal magnesium and iodine showed the round MGE particle (tertiary particle) had a layer structure consisting of many crystalline fragments (secondary particles) comprising many minute crystals (primary particles). It was clearly shown that each precipitated secondary particle had not agglomerated, but had repeatedly grown and combined with others. From the investigation of the course of a reaction, it was suggested the MGE crystals grown on Mg metal exfoliated as “lump-like” seeds, and crystal growth on seeds proceeded such that the shapes of the final MGE particles were more spherical than those of their seeds. It was presumed from a model reaction that the enhancement of MGE solubility by I₂ addition to form the quasi-stable complex nMg(OEt)₂·MgI₂·mEtOH was the key process in the formation of plate crystals. The relationship between the size of crystalline fragments and crystallization rate (reaction rate, MGE solubility) was discussed.The catalyst, when prepared using MGE as the carrier material, exhibited exceptionally high polymerization activity than when it was prepared with MgCl₂ alcohol complex (MgCl₂·ROH). We presume that this is because particles of the MGE-based catalyst are porous, and because the formation of active species of the supported Ti and monomer diffusion progressed adequately from the surface of the particle to its internal parts.