机械力化学合成CaTiO3纳米晶的研究

研究了采用高能球磨机混合粉磨CaO,TiO2的机械力化学变化过程，发现在一定操作参数（行星磨公转转速300r/min，自转200r/min)条件下，粉磨初期（2h)为无定形形成期，混合物颗粒粒度减小，晶格畸变，转变为无定形，并形成CaTiO3晶核；粉磨中期（2－10h)为晶粒生长期，CaTiO3晶粒长大；粉磨后期（10h以后）为动态平衡期，晶粒生长与粉磨引起的晶粒减小处于动态平衡，锐钛矿型TiO2能够转变为金红石型TiO2，具有较好的反应活性，XRD，TEM，FT－IR研究表明：混合粉磨CaO,TiO2可机械力化学合成CaTiO3纳米晶体，晶粒尺寸为20－30nm。     

机械力化学法制备金红石型TiO_2纳米晶体

研究了高能球磨机粉磨锐钛矿型TiO2 的机械力化学变化过程。发现在一定操作参数 (行星磨公转转速30 0r/min、自转 2 0 0r/min)条件下 ,粉磨初期 (5h)为无定形形成期 ,颗粒粒度减小 ,晶格畸变 ,转变为无定形 ,并形成金红石型TiO2 晶核 ;粉磨中期 (5～ 15h)为晶粒长大期 ,金红石型TiO2 晶粒长大 ;粉磨后期 (15h以后 )为动态平衡期 ,晶粒长大与粉磨引起的晶粒减小处于动态平衡 ;XRD、TEM、FT IR研究表明 :行星磨粉磨锐钛矿型TiO2 可使晶型转变为金红石型TiO2 ,晶粒尺寸为 14 .1nm ,颗粒尺寸为 2 0～ 4 0nm。     

机械力化学合成纳米晶PZT的研究

通过研究PbO-ZrO2-TiO2机械力化学过程,探明了机械力化学法制备PZT纳米粉体的工艺条件。在一定操作参数的条件下(公转转速250 r/min,自转转速为62.5 r/min)粉磨60 b,能够制备出10～30 nm PZT纳米粉体。采用XRD,DTA,SEM,TEM对不同粉磨时间的混合粉体进行表征分析。发现机械力化学合成纳米粉体经过颗粒细化、晶粒尺寸减小、晶格畸变、混合物粉体无定形化、固相反应等阶段。铅黄型PbO经高能球磨晶型转变为密陀僧型PbO,混合物粉体保持化学计量。     

机械力化学合成BaTiO3纳米晶TEM及HR-TEM研究

采用XRD，TEM及高分辨电子显微镜（HR－TEM），研究了高能球磨BaO,锐钛矿型TiO2混合粉体，机械力学法合成BaTiO3纳米晶的反应机制。研究表明：机械力的作用使混合物粉体粒度减小，晶格畸变，转变为无定形，具有较高的反应活性，提高固相反应的扩散系数，降低了活化能，从而使本该在较高温度进行的反应也可在较低的温度下进行，晶体形成经过成核和生长两个阶段，但生长到一定程度时达到动态平衡，合成的BaTiO3纳米晶体颗粒尺寸为10－30nm。     

钢渣助磨剂的助磨效果研究

以南京梅山钢铁厂钢渣为研究对象,对一种新型钢渣助磨剂的助磨效果进行了研究.结果表明:钢渣的主要化学成分为CaO、SiO2、Al2O3和MgO等,其中CaO含量高达36.8%.钢渣中只存在无定形类玻璃态物质,无矿物晶体相.助磨剂对粉磨的促进效果主要体现在粉磨前期(30 min以内).粉磨20 min时,加助磨剂的钢渣粉磨...     

机械力化学作用对CaO-B2O3-SiO2系陶瓷微观结构及相组成和相变规律的影响

采用X射线衍射、扫描电镜和差热热重分析等手段研究了机械力化学作用对CaO-B_2O_3-SiO_2(CBS)混合粉末及其陶瓷的微观结构、相组成和相变过程的影响。结果表明:高能球磨中的机械力化学作用能够细化晶粒、提高球磨混合粉体的反应活性和诱导室温化学反应。CBS混合粉末高能球磨120 h可合成出C_2B(2CaO·B_2O_3)中间相,该球磨粉末950℃烧成后的主晶相为CB(CaO·B_2O_3),C_6S_4(6CaO·4SiO_2)和CS(CaO·SiO_2)。该种材料的介电常数ε≈5,介电损耗<2×10~(-3)(1 MHz),有望用于低介高频电子元件领域。     

PbO和TiO2混合粉磨的机械力化学反应和化学变化

本实验首次发现,在振动磨中混合粉磨PbO和TiO_2化学配比的粉体,能合成PbTiO_2化合物。这种机械力化学反应是以表面能为扩散的主要推动力,使PbO扩散至TiO_2颗粒内并在TiO_2颗粒表面形成PbTiO_2,实验证明在PbTiO_2形成以前,PbO及TiO_2二者受机械力的作用,晶型均已发生了变化,锐钛矿转变为金红石,铅黄转变为密陀僧。由铅黄向密陀僧转变的过程中,当密陀僧的容积成分达到75％时即达平衡状态,然而这种机械化学平衡是亚稳的,继续粉磨超过75h后,平衡即遭破坏,密陀僧又重新转变为铅黄。     

机械力化学法制备单相莫来石的机理研究

以高岭土和氢氧化铝为原料,采用机械力化学法制备出了单相莫来石。用热重-差示扫描分析研究了混合粉体经高能球磨后的结构变化,并讨论了单相莫来石的形成机理。结果表明：高能球磨破坏了混合物的晶体结构;随着粉磨的进行,混合物的比表面积会增加,无序程度也会增加,键能会减小,从而导致了内部贮能的增加,反应活化能的减小,并可得到均匀混合物。粉磨30h混合物制成的烧结体的热膨胀系数要比未粉磨的低约20％。     

TiO2对烧成镁钙砖烧结性能的影响

研究了两种晶型的TiO2(锐钛矿型和金红石型)作为添加剂对烧成镁钙砖烧结性的影响.结果表明,两种晶型的TiO2都能显著促进镁钙砖的烧结,其中以锐钛矿晶型为添加剂的效果好于金红石型的.XRD分析结果表明,TiO2与CaO反应生成了CaTiO3,这是加入TiO2使镁钙砖烧结性变好的主要原因.     

机械激活对固态反应合成Al2TiO5的作用分析

采用行星式球磨机机械激活处理α-Al2O3和锐钛矿型TiO2混合粉体.在相对低下的条件下合成了高纯度Al2TiO5块体材料,分析了机械激活作用所导致的混合粉体变化过程、产物及对合成Al2TiO5的影响作用.研究表明,机械激活作用是具有时间依赖性的累积过程,而激活过程中所发生的诸如相变、细化、畸变以及磨介杂质的引入对于反应合成Al2TiO5具有有益的作用.     

纳米TiO_2的制备及其在处理含DNBA废水中的应用研究

在室温条件下,以钛酸四丁酯水解制备了无定形Ti(OH)4胶体,然后在酸性条件下,加入分散剂,搅拌、老化16h,加入甲苯,用油水分离器除去水和大部分甲苯,60℃真空干燥,得到纳米TiO2粉末。在400℃煅烧3h即得到锐钛矿晶型TiO2;500℃煅烧3h即有部分锐钛矿晶型TiO2转化为金红石晶型TiO2;700℃煅烧3h主要以金红石晶型存在;在800℃煅烧3h完全转化为金红石晶型,粒径20～50nm。室温条件下,金红石晶型的纳米TiO2粒子,能够使3,5 二硝基苯甲酸(DNBA)发生光催化降解反应,DNBA经光催化反应160min后,其浓度由原来的2×10-4mol/L降为9 7×10-6mol/L。表明金红石晶型的纳米TiO2粒子对DNBA具有很高的光催化活性。H2O2能显著提高DNBA的光催化降解速率。     

Coating of Silica and Titania Aerosol Nanoparticles by Silver Vapor Condensation

Silica and titania aerosol nanoparticles are coated with silver through a physical coating process. The silver is evaporated in a tubular furnace flow system and condensed on the ceramic carrier particles with diameters of approximately 100?nm. The temperature gradient in the furnace system is optimized in order to avoid homogeneous nucleation of the silver. The generated ceramic–silver composite nanoparticles are characterized with aerosol measurements and analytical transmission electron microscopy. Two completely different particle morphologies are clearly observed, silver-decoration and composite doublet, with amorphous silica and crystalline rutile titania as the carrier particles, respectively. The former morphology consists of multiple silver nanodots with diameters of 1–10?nm, while in the latter morphology the silver had formed a larger structure with a size comparable to that of the carrier particle. Different shapes are observed in these larger silver structures, such as triangular, rodlike, and hexagonal. Differences in the silver particle migration on the surface of the silica and titania particles is proposed to be the key factor resulting into the two distinct particle morphologies.

Copyright 2015 American Association for Aerosol Research     

The influence of concentration on the formation of BaTiO3 by direct reaction of TiCl4 with Ba(OH)2 in aqueous solution

The formation of fine BaTiO₃ particles by reaction between liquid TiCl₄ and Ba(OH)₂ in aqueous solution at 85 °C and pH⩾13 has been studied for 0.062⩽[Ba²⁺]⩽0.51 mol l⁻¹. The concentration of Ba²⁺ ions has a strong influence on reaction kinetics, particle size and crystallite size. When [Ba²⁺]>≈0.12 mol l⁻¹, the precipitate consists of nanosized (≈30 nm) to submicron (100–300 nm) particles of crystalline BaTiO₃. At lower concentrations, the final product is a mixture of crystalline BaTiO₃ and a Ti-rich amorphous phase even for very long reaction times. A two-steps precipitation mechanism is proposed. Initially, a Ti-rich amorphous precipitate is rapidly produced. Reaction between the amorphous phase and the Ba²⁺ ions left in solution then leads to crystallisation of BaTiO₃. In addition to nucleation and growth of nanocrystals, the final size and morphology of BaTiO₃ particles obtained at low concentration can be determined by aggregation of nanocrystals and heterogeneous nucleation on existing crystal surfaces.     

Ca-α SiAlON hollow spheres prepared by carbothermal reduction–nitridation from different SiO2 powders

The formation process of hollow spheres composed of nanosized Ca-α SiAlON particles was investigated using SiO₂ starting powders with different characteristics in particle size, shape and crystalline state. TEM observations showed Ca-α SiAlON hollow spheres composed of a large number of nanosized particles in the products prepared at 1450 °C for 120 min in nitrogen. In all systems, the Ca-α SiAlON hollow spheres were always produced through an intermediate Si–Al–Ca–O liquid phase in the same mechanism, regardless of the characteristics of SiO₂ starting powders used. Spherical solid particles consisted of amorphous phase containing Si, Al, Ca, O and a small amount of N were generated at the initial stage of carbothermal reduction–nitridation. These spherical solid particles changed into hollow particles with the progression of the reaction from the liquid phase to the crystalline Ca-α SiAlON with increasing temperature.     

Influence of temperature schedules on particle size and crystallinity of titania synthesized by vapor-phase oxidation route

Crystalline TiO₂ particles were produced in a tubular flow reactor by chemical vapor synthesis using titanium tetrachloride as a starting material in oxygen containing atmospheres. The dependence of particle size, morphology and crystalline phase of titania on temperature schedules including the reactor temperature, the oxygen preheated temperature and the product cooling measure were explored. It is found that there are two opposite effects of temperature on particle size and crystalline phase content. The particle size distribution, SEM and TEM of resulting powders show that the grain size is controlled by the relative magnitudes of the nucleation rate and growth rate, both of them being subject to the temperature schedules. XRD indicates that particles crystalline phase is predominately anatase and the rutile content increment is not consistent with temperature increase. Anatase titania can be converted to rutile by addition of crystal modifier AlCl₃. The element analysis by EDS shows that Al enriches on the particle outer surface.     

INFLUENCE OF CALCINATION ON MICROSTRUCTURES AND PHOTOACTIVITIES OF ALKOXIDE-DERIVED TiO2 NANOPARTICLES PREPARED IN W/O MICROEMULSIONS

Ultrafine titania particles were synthesized by hydrolysis of titanium tetraisoproxide (TTIP) in the nanodroplets of water/NP-5/cyclohexane microemulsions. The as-prepared particles were amorphous, transformed into the anatase phase at 450°C, and completely into the rutile phase at 700°C. The amorphous-to-anatase phase transition temperature decreased with increasing water/surfactant molar ratio. With increasing temperature from 500 to 900°C, the crystallite size increased about twice from 11.7 to 24.4 nm, while the size of the secondary particles, agglomerates of the primary panicles, increased by a factor of about 10. The particles grew largely by intra-agglomerate densification below 700°C, whereas they grew by interagglomerate densification above 700°C. The anatase phase formed at 500-600°C showed considerable photoactivity for the degradation of phenol, whereas both the amorphous phase at 300°C and the rutile phase at 700°C were almost inactive for this reaction.     

Evolution of Microstructures and Nitrogen Sorption during High-Energy Milling of Silicon in Ammonia

The structural transformation, microstructural changes, and nitrogen sorption of crystalline Si induced by high-energy ball milling in ammonia have been investigated. It is found that significant refinement of particles and crystallites occurs at the early stage of milling (within ∼10 h of milling), after which the average particle size and crystallite size decrease gradually and approach a lower limit of ∼100 and 6.0 nm, respectively. It is proposed that refinement of particle sizes is dominated by the fragmentation process, whereas refinement of crystallite sizes is dictated by plastic deformation. Substantial amorphization does not occur until most of the crystallites have reached the average size of 6.5–6.0 nm. The crystallite-refinement-induced amorphization has been identified as the major mechanism for the nanocrystalline-to-amorphous transformation. A substantial amount of nitrogen is sorbed by Si powders and primarily dissolved in the amorphous Si phase.     

Processing and Characterization of Porous TiO2 Coatings

Titania coatings were prepared by spin coating anhydrous titanium ethoxide solutions onto Si substrates. During deposition, Ti ethoxide in the solution layer reacted with atmospheric moisture to form precipitated particles. The resulting microstructures were composed of a network of particles and particle clusters. The induction time for precipitation, the particle diameter, and the size and packing of particle clusters were influenced by the Ti concentration in the sol and the spinning rate used for deposition. Individual particle sizes ranged from ∼150 to 250 nm. Smaller particles and more compact particle clusters were characteristic of coatings prepared from solutions with lower Ti concentrations and those prepared using faster spinning rates. Asdeposited coatings were amorphous and crystallized into the anatase phase at ∼400°C. Transformation to the rutile phase began at ∼850°C, and the transformation rate was influenced by the microstructure.