Specific surface area and chemical reactivity of quartz powders during mechanical processing

The present work focuses on the specific surface area increase, and on the related chemical reactivity enhancement of quartz powders submitted to mechanical processing. The mechanical treatment was carried out in a suitably developed ball mill allowing the control of the frequency and energy of the impacts between ball and reactor. The specific surface area was directly measured by nitrogen physisorption, whereas electron microscopy was used to determine the size distribution of powder particles. Based on the experimental results, a simplified mathematical model was developed to describe the process of specific surface area increase on a phenomenological basis. The model permits to gain valuable information on the amount of powder processed in individual impacts. The density of reactive centers at the surface of powder particles was also estimated by using the neutralization of a free radical as a test reaction. It is shown that the surface density of reactive centers increases with the energy of collisions.     

矿渣粉比表面积及粒度分布对水泥强度的影响

采用勃氏透气仪和激光粒度分析仪,对矿渣粉试样进行比表面积和颗粒群粒度分布的测试,研究矿渣粉比表面积及粒度分布对水泥强度的影响。结果表明:矿渣粉总体颗粒越细,则比表面积越大,特征粒径越小,颗粒群分布越宽;细颗粒含量(小于5μm)越多的矿渣粉,其比表面积越大,水泥砂浆的早期强度就越高。     

Suspension characteristics and rheological properties of mullite/zirconia powder in methyl isobutyl ketone

Particle size and its distribution, sedimentation bulk density and rheology of mullite, zirconia, and mullite/zirconia mixed suspensions have been studied in terms of oxide loading (20, 30 vol%), and types of additives (dispersant, dispersant/plasticizer, dispersant/plasticizer/binder). Polyester/polyamine, dibutyl phthalate, poly(vinyl butyral), and methyl isobutyl ketone have been used as the dispersant, plasticizer, binder, and liquid medium, respectively. Sedimentation density significantly increased upon adding dispersant; the effect was more pronounced with zirconia suspension most likely due to the fine and hence high specific surface area of zirconia. With further addition of plasticizer and plasticizer/binder, the sedimentation density decreased. The suspension viscosity generally behaved in an opposite manner to the sedimentation density, i.e., low sedimentation density gave high low-shear viscosity, indicative of high order structure formation in the suspended particles. High shear rate rheology showed a shear thinning and its onset began at lower shear rate with higher solid loading. Mullite/zirconia mixed suspension gave intermediate sedimentation and rheological behavior, implying the two types of particles are non-interacting.     

低温分相法制备高比表面积微/介孔SiOC陶瓷

以含氢聚硅氧烷(PHMS)、四甲基四乙烯基环四硅氧烷(D₄ ^vi)和铂络合物为原料, 采用热交联合成交联体, 通过水蒸汽辅助热解促进前驱体低温分相及后续HF对SiOC陶瓷侵蚀基础上, 获得高比表面积微/介孔SiOC陶瓷。采用XRD、FT-IR、SEM和BET等测试技术对试样的物相组成、化学键、微观结构、比表面积和孔径分布等进行了表征。实验结果表明, 水蒸气能够促进前驱体低温分相, 使SiOC陶瓷中生成Si-O-Si键、SiO₂纳米畴和SiO₂纳米晶, 这些可以作为造孔剂而被HF侵蚀, 从而提高了SiOC陶瓷的比表面积。在热解温度1300℃条件下, 微/介孔SiOC陶瓷具有最大比表面积1845.5 m²/g, 孔径分布2.0~10 nm。     

Electron microscopy studies of plasma-polymerized organosilicon thin films

Plasma-polymerized thin films of hexamethylcyclotrisilazane were pyrolysed in vacuum and studied by transmission electron microscopy. Examination of the polymer film after various durations of pyrolysis revealed significant changes in their surface structure and a distinct difference in the thermal stability powder and film phases. The number of powder particles in the surface layer and their size increased with pyrolysis time. The observations showed that powder particles embedded in the film matrix were gradually exposed in the surface layer owing to a decrease in the film thickness during pyrolysis. Good agreement was obtained between the experimental and theoretical distribution curves of particle size. The identical properties of powder particles exposed in the surface of the pyrolysed film and those taken from the interelectrode region indicates that they are primarily formed in the gas phase.     

Cohesion of lactose powders at low consolidation stresses

The flow characteristics of a powder system are known to be influenced by particle size distribution, particularly the content of fine particles, and interparticle forces. This paper reports an investigation that has identified and quantified links between physical properties, viz size distribution, bulk density and particle density, and cohesion in compacted beds of powder. An annular shear cell was used in the determination of the cohesion of cohesive and free-flowing milled lactose powders at low consolidation stresses in the range 0.31–4.85 kPa and under ambient conditions. Following consideration of the compaction and shearing processes, it was postulated and confirmed that cohesion could be expressed as a function of powder surface area per unit volume and dimensionless preconsolidation stress. It was shown that care is needed in the measurement of surface–volume mean diameter when applying correlations developed from the experimental data.     

超细六硝基颗粒比表面积测试条件优化

采用热重分析仪、氮气吸附比表面积测定仪,对超细六硝基颗粒比表面积测试前脱气处理温度进行优化,比较分析超细六硝基颗粒在不同温度下的失重现象和比表面积、孔径分布情况。结果表明:55～65℃温度区间为超细六硝基颗粒表面积测试时的最佳脱气温度,可以有效减小超细六硝基颗粒比表面积测试误差。     

Aggregation of CaCO3 particles in PP composites: Effect of surface coating

The occurrence and effect of aggregation in PP composites containing seven different precipitated CaCO₃ fillers coated with stearic acid are described in this study. The particle size and specific surface area of the filler varied in a relatively wide range, the latter changed between 2 and 12 m²/g. The fillers were characterized by various methods including surface area, particle size and bulk density. PP composites were prepared in an internal mixer in the composition range of 0–0.3 volume fraction filler content and their structure was studied by optical microscopy. The tensile and rheological properties of the composites were related to their structure. The results prove that the unambiguous detection of the presence of aggregation is difficult in particulate filled composites. The coating of CaCO₃ fillers with a surfactant changes the behavior of the particles considerably, but does not eliminate aggregation completely. The association of filler particles depends on the relative magnitude of adhesion and separating forces. Although coating decreases the surface free energy of the filler significantly, gravitational forces are much smaller than adhesion between either uncoated or coated fillers thus powder particles always aggregate. Different forces act in suspensions used for the determination of the particle size distribution of the filler; the shape of the distribution may indicate the presence of aggregation. Coated fillers form much looser aggregates with more diffuse interphases, than uncoated particles. Composite stiffness is completely insensitive to changes in structure or interaction, but the direct evaluation of other tensile properties may also lead to erroneous conclusions. Model calculations, oscillatory viscometry, as well as the proper representation of the results allow the unambiguous detection of aggregation.     

Synthesis of mesoporous silica with embedded nickel nanoparticles for catalyst applications

Here we describe a new route for the synthesis of nanometric Ni particles embedded in a mesoporous silica material with excellent potential for catalytic applications. Mesoporous silica with a surface area in the range of 202-280 m2/g, with narrow pore size distribution and Ni nanoparticles (particles in the range of 3-41 nm) were obtained in a direct process. A different approach was adopted to process such a nanocomposite. This new approach is based on the formation of a polymer with the silicon oxianion and nickel cation chelated to the macromolecule structure and on the control of the pyrolysis step. The CO/CO2 atmosphere resulting from the pyrolysis of the organic material promotes the reduction of the Ni citrate.     

Spray-Dried Chitosan as a Direct Compression Tableting Excipient

The objective of this study was to prepare and evaluate a novel spray-dried tableting excipient using a mixture of chitosan and lactose. Three different grades of chitosan (low-, medium-, and high-molecular-weight) were used for this study. Propranolol hydrochloride was used as a model drug. A specific amount of chitosan (1, 1.9, and 2.5 g, respectively) was dissolved in 50 mL of an aqueous solution of citric acid (1%) and later mixed with 50 mL of an aqueous solution containing lactose (20, 19.1, and 18.5 g, respectively) and propanolol (2.2 g). The resultant solution was sprayed through a laboratory spray drier at 1.4 mL/min. The granules were evaluated for bulk density, tap density, Carr index, particle size distribution, surface morphology, thermal properties, and tableting properties. Bulk density of the granules decreased from 0.16 to 0.13 g/mL when the granules were prepared using medium- or high-molecular-weight chitosan compared with the low-molecular-weight chitosan. The relative proportion of chitosan also showed a significant effect on the bulk density. The granules prepared with 1 g of low-molecular-weight chitosan showed the minimum Carr index (11.1%) indicating the best flow properties among all five formulations. All three granules prepared with 1 g chitosan, irrespective of their molecular weight, showed excellent flow properties. Floating tablets prepared by direct compression of these granules with sodium bicarbonate showed 50% drug release between 30 and 35 min. In conclusion, the spray-dried granules prepared with chitosan and lactose showed excellent flow properties and were suitable for tableting.     

Spray-dried chitosan as a direct compression tableting excipient

The objective of this study was to prepare and evaluate a novel spray-dried tableting excipient using a mixture of chitosan and lactose. Three different grades of chitosan (low-, medium-, and high-molecular-weight) were used for this study. Propranolol hydrochloride was used as a model drug. A specific amount of chitosan (1, 1.9, and 2.5 g, respectively) was dissolved in 50 mL of an aqueous solution of citric acid (1%) and later mixed with 50 mL of an aqueous solution containing lactose (20, 19.1, and 18.5 g, respectively) and propanolol (2.2 g). The resultant solution was sprayed through a laboratory spray drier at 1.4 mL/min. The granules were evaluated for bulk density, tap density, Carr index, particle size distribution, surface morphology, thermal properties, and tableting properties. Bulk density of the granules decreased from 0.16 to 0.13 g/mL when the granules were prepared using medium- or high-molecular-weight chitosan compared with the low-molecular-weight chitosan. The relative proportion of chitosan also showed a significant effect on the bulk density. The granules prepared with 1 g of low-molecular-weight chitosan showed the minimum Carr index (11.1%) indicating the best flow properties among all five formulations. All three granules prepared with 1 g chitosan, irrespective of their molecular weight, showed excellent flow properties. Floating tablets prepared by direct compression of these granules with sodium bicarbonate showed 50% drug release between 30 and 35 min. In conclusion, the spray-dried granules prepared with chitosan and lactose showed excellent flow properties and were suitable for tableting.     

Setting time and formability of calcium phosphate cements prepared using modified dicalcium phosphate anhydrous powders

Calcium phosphate cements (CPCs) were prepared using Ca₄(PO₄)₂O (TeCP) and modified CaHPO₄ (DCPA) to evaluate the effects of the powder properties for DCPA particles on the setting time and formability of the resulting CPCs. Two types of modified DCPA were prepared by milling commercially available DCPA with ethanol (to produce E-DCPA) or distilled water (to produce W-DCPA). The E-DCPA samples consisted of well-dispersed, fine primary particles, while the W-DCPA samples contained agglomerated particles, and had a smaller specific surface area. The mean particle size decreased with increased milling time in both cases. The raw CPC powders prepared using W-DCPA had a higher packing density than those prepared using E-DCPA, regardless of the mean particle size. The setting time of the CPC paste after mixing with distilled water decreased with decreases in the mean particle size and specific surface area, for both types of DCPA. The CPCs prepared using W-DCPA showed larger plasticity values compared with those prepared using E-DCPA, which contributed to the superior formability of the W-DCPA samples. The CPCs prepared using W-DCPA showed a short setting time and large plasticity values, despite the fact that only a small amount of liquid was used for the mixing of the raw CPC powders (a liquid-to-powder ratio of 0.25 g g^?1 was used). It is likely that the higher packing density of the raw CPC powders prepared using W-DCPA was responsible for the higher performance of the resulting CPCs.     

高温热处理对活性炭纤维微孔及表面性能的影响

研究了1173K高温改性处理对沥青基活性炭纤维吸附性能、孔径分布、微孔结构和表面化学的影响。低温(77K)N2吸附结果表明热处理后活性炭纤维比表面积略有下降，通过密度函数理论解析活性炭纤维全孔范围的孔分布得出活性炭纤维表面孔径大于1．0nm的微孔明显减少，微孔孔径更加集中于0．5nm～1．0nm，从而提高了活性炭纤维的碘吸附值。X射线衍射分析表明活性炭纤维是乱层石墨结构，热处理使活性炭纤维类石墨微晶碳层面的层间距下降，X光电子能谱分析表明热处理后活性炭纤维表面的含氧官能团C=O和COOH的含量变化不大，而呈碱性酚羟基C—OH含量的明显下降使活性炭纤维表面碱性降低。     

玻璃球宏细观冲击特性的SHPB试验和耦合数值模拟研究

为研究玻璃球的宏细观冲击特性,该文开展了不同相对密实度玻璃球的一维霍普金森杆(SHPB)冲击试验和离散元-有限差分法耦合数值模拟研究。结果表明：一维冲击荷载下玻璃球经历初始弹性、屈服、颗粒间互锁硬化和颗粒破碎硬化四个阶段。基于耦合数值模拟发现,颗粒平均配位数随着冲击荷载时程不断增加,但增加的速率逐渐下降,其原因是配位数变化取决于孔隙压缩和以旋转为主的颗粒重排,随着试样压缩变形的发展,孔隙压缩和颗粒重排需要克服更大的颗粒间互锁效应,因此逐渐变缓。而试样孔隙率在弹性阶段基本不变,在屈服阶段和互锁硬化阶段近似线性下降,其原因是孔隙率变化受控于颗粒整体移动,弹性阶段颗粒整体移动尚未发展,屈服之后颗粒整体移动产生的孔隙压缩随荷载时程呈线性发展。冲击荷载下,颗粒位移以整体移动为主,相对位移为辅,因此,颗粒位移对试样的初始密实度不敏感。颗粒旋转需要克服周围颗粒的互锁效应,互锁效应取决于试样级配和颗粒粒径,对密实度较敏感。     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。     

碳包覆NiO纳米颗粒的制备与性能

采用直流电弧放电等离子体技术成功制备了碳包覆NiO(NiO@C)纳米颗粒,并对样品的形貌、晶体结构、粒度、比表面积和孔结构采用高分辨透射电子显微镜、X射线衍射、X射线能量色散分析谱仪、拉曼散射光谱和N_2吸-脱附等测试手段进行了分析。实验结果表明:直流电弧等离子体技术制备的NiO@C纳米颗粒具有典型的核壳结构,内核为面心立方结构的NiO纳米颗粒,外壳为碳层。颗粒形貌主要为立方体结构,粒度均匀,分散性良好,粒径分布在30~70nm范围,平均粒径为50nm,外壳碳层的厚度为5nm。NiO@C纳米颗粒BET比表面积为28m~2/g,等效直径为46nm,与TEM和XRD测得的结果基本一致。Raman光谱说明样品中碳包覆层的石墨化程度较低,发生了红移现象。     

模板炭化法制备沥青基中孔炭材料

以MgO为模板,采用低软化点(27℃)各向同性沥青为炭材料前驱体,采用程序升温一步炭化法制得了系列中孔炭材料。采用乙酸镁和柠檬酸镁为MgO的前驱体,沥青与MgO前驱体按照不同质量比混合,混合比例以得到的MgO为计算基准。采用低温N2吸附测得炭材料的比表面积和孔径分布,采用透射电镜观察炭材料的内部结构特征。结果表明,两种前驱体与沥青混合得到的炭材料比表面积均随MgO/沥青质量比例的增加呈线性增加趋势,柠檬酸镁体系中MgO/沥青质量比为8/2时最高比表面积达到1295m2/g,随MgO/沥青质量比的不同分别在2.5nm和5nm处有集中的孔分布;乙酸镁体系制得的炭最高比表面积也达到1199m2/g,并且在5nm和12nm处有集中的孔分布。     

Artificial neural network analysis of the effect of matrix size and milling time on the properties of flake Al-Cu-Mg alloy particles synthesized by ball milling

In this study, the effect of matrix size and milling time on the particle size, apparent density, and specific surface area of flake Al-Cu-Mg alloy powders was investigated both by experimental and artificial neural networks model. Four different matrix sizes (28, 60, 100, and 160?µm) and five different milling times (0.5, 1, 1.5, 2, and 2.5?h) were used in the fabrication of the flake Al-Cu-Mg alloy powders. A feed forward back propagation artificial neural network (ANN) system was used to predict the properties of flake Al-Cu-Mg alloy powders. For training process, the ANN models of the flake size, apparent density, and specific surface area have the mean square error of 0.66, 0.004, and 0.01%. For testing process, it was obtained that the R² values were 0.9984, 0.9998, and 0.9932 for the flake size, apparent density, and specific surface area, respectively. The degrees of accuracy of the prediction models were 95.145, 99.705, and 94.25% for the flake size, apparent density, and specific surface area, respectively.     

Synthesis of nanocomposite powders of γ-alumina-carbon nanotube by sol–gel method

The nanocomposite powders of γ-alumina-carbon nanotube were successfully synthesized by a sol–gel process. The homogeneous mixture of carbon nanotubes and alumina particles was obtained by mixing the carbon nanotubes within alumina solution and followed by heating into gel. The resultant gel was dried and calcined at 200 °C into boehmite-carbon nanotubes composite powders. The mean particle size of synthesized boehmite was of the order of 4 nm. The boehmite-carbon nanotubes composite powders were calcined at different temperatures and XRD investigations revealed that as the amount of carbon nanotube increases, γ- to α-alumina phase transformation is completed at higher temperatures. The specific surface area and mean particle size of resultant nanocomposite powders increased and decreased, respectively by increasing the content of carbon nanotubes.     

Scaling of energy dissipation in crushing and fragmentation: a fractal and statistical analysis based on particle size distribution

An extensive experimental investigation on concrete specimens under crushing and fragmentation over a large scale range (1:10) – exploring even very small specimen dimensions (1 cm) – was carried out to evaluate the influence of fragment size distribution on energy density dissipation and related size effect. To obtain a statistically significant fragment production as well as the total energy dissipated in a given specimen, the experimental procedure was unusually carried out up to a strain of approximately –95%, practically corresponding to the initial fragment compaction between the loading platens. The experimental fragment analysis suggests a fractal law for the distribution in particle size; this simply means that fragments derived from a given specimen appear geometrically self-similar at each observation scale. In addition, clear size effects on dissipated energy density are experimentally observed. Fractal concepts permit to quantify the correlation between fragment size distribution and size effect on dissipated energy density, the latter being governed by the total surface area of produced fragments. The experimental results agree with the proposed multi-scale interpretation satisfactorily.