微波固相反应前驱体热分解法制备纳米氧化铜粉体

将固体CuSO4·5H2O和Na2CO3混合均匀后溶于适量乙醇中,然后进行微波辐照,立即反应生成泥浆状固体,将该泥浆状固体洗涤后干燥即可得到粉状前驱体.然后在600 ℃加热1 h分解该前驱体,即可制得纳米氧化铜粉体.在加热速率为10 ℃/min的条件下,对该前驱体进行表征,发现其热分解和晶体化温度约为550 ℃.对制得的纳米氧化铜粉体进行XRD、SEM、TEM和IR分析,结果表明制得的产物为纳米氧化铜粉体,其粉体粒径在30～50 nm,平均粒径约为40 nm.     

Precipitation and characterization of hollow calcite nanoparticles

A method for preparation of significant amount of hollow rhombohedral calcite nanoparticles, based on carbonation of calcium hydroxide suspension, is described. The mineralogical and morphological analyses of the precipitate confirmed the existence of exclusively stable polymorphic modification, calcite, with the mean particle size of about 100 nm and the diameter of the holes observed at the surfaces that are about 50 nm. The analysis of carbonation kinetics pointed out to a complex mechanism of hollow particles formation at high initial supersaturation, that assumed nucleation of amorphous precursor calcium carbonate phase and its solution mediated transformation into nanosized crystalline calcite. The holes obtained at the calcite surfaces are most probably the imprints remained after the dissolution of amorphous calcium carbonate particles.     

Influence of size on the supercooling in the crystallization of small particles in Bismuth island films

There has been measured the crystallization temperature of supercooled Bi particles versus their size in the 3–100 nm range in island films on amorphous carbon substrates. Crystallization temperature is found to decrease with particle size decreasing and the supercooling vanishes for particles of 2–3 nm in diameter. The results obtained are analyzed in the frame of the classic theory of crystallization.     

CdS纳米棒的水热法制备及形成机理研究

采用水热法以Na2S· 9H2O为硫源,Cd3O12S3·8H2O为镉源,PVP为表面活性剂,成功制备了CdS纳米棒.并利用X射线衍射(XRD)、透射电子显微镜(TEM)和相应选区电子衍射(SAED)、高分辨透射电子显微镜(HRTEM)、X射线能量色散分析谱仪(XEDS)和紫外可见(UV-vis)分光光度计等测试手段对样品的晶体结构、形貌、微观结构和光学特性等特征进行了表征分析,实验结果表明本方法所制备的CdS纳米棒为纤锌矿结构,沿[001]方向择优生长,平均直径大约为50 nm,棒宽均匀、分散性好,带隙为2.43 eV.同时也对CdS纳米棒的形成机理进行了初步探讨,提出了CdS纳米棒的生长模型,其形貌从三角形到阶梯形棒晶,最后再到完整的棒状晶体的一个定向团聚的自组装过程.     

热处理对共沉淀法制备YAG纳米粉体性能的影响

以Al(NO3)3和Y(NO3)3为原料,采用共沉淀法制备出粒度大小为60～100nm,颗粒呈球形的纯相YAG纳米粉.研究了前驱物在不同条件下热处理对YAG纳米粉体性能的影响,并对前驱物在焙烧过程中的物相变化进行了观察,发现延长前驱物在低温下的干燥时间会导致晶粒尺寸增大,而采用在晶化温度前后分别进行保温的方法可在较低的温度获得纯相的YAG粉体.对比了焙烧温度和保温时间对产物粒度的影响,结果表明:在保证粉体晶化完全的前提下,升高焙烧温度比延长保温时间对晶粒尺寸有更显著的影响.     

Synthesis,structural and optical properties of well dispersed anatase TiO2 nanoparticles by non‐hydrothermal method

The formation of nanocrystalline TiO₂ particles has been investigated via a surfactant‐free synthetic non‐hydrothermal method. Titanium isopropoxide and toluene were used as the starting materials. At a low temperature of 250 °C for 6 h, the reaction mixture turned in to a white precipitate (TiO₂) as a result of the thermal decomposition of metal alkoxide. The obtained product was found to crystallize purely in the anatase phase with well defined morphology. The powder XRD study confirms that the average size of the particle is close to ∼15 nm. The TEM analysis indicates the sizes of the primary and secondary particles in the range between 8‐10 nm and 15‐20 nm respectively. The quantum size confinement of the crystallites is evident from the blue shift of the absorption edge in the UV‐Visible absorption spectrum. The luminescence property of the TiO₂ nanoparticles studied by the emission spectrum confirms the presence of defect levels caused by the oxygen vacancies. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A possible new approach to the better understanding of crystallization kinetics

Literature data dealing with the structure of solutions, solubility of tiny particles, and the organization of small colloidal particles in solutions were summarized to support the evidence that the growth units in the crystallization by precipitation are identical with clusters or primary particles. These growth units may self-organize themselves in a kind of a three-dimensional network surrounding the growing crystals or secondary particles. This colloidal concept was used to explain qualitatively some experimental facts observed in the controlled double jet precipitation of sparingly soluble salts.     

Synthesis of GaN nanospindles via a facile solid-state reaction route

Gallium nitride (GaN) nanospindles have been synthesized via a solid-state reaction at a low-temperature condition. X-ray powder diffraction (XRD), Raman spectrum and high-resolution transmission electron microscopy (HRTEM) revealed that the synthesized GaN crystallized in a hexagonal structure and displaying spindly particles morphology has an average diameter of 100 nm and length of 400 nm X-ray photoelectron spectroscopy (XPS) of the sample gave the atomic ratio of Ga and N of 1.04:1. Room-temperature photoluminescence (PL) spectrum showed that the as-prepared product had a peak emission at 372 nm. The possible formation mechanism of the wurtzite GaN is briefly discussed.     

A direct suppression of green band emission of ZnO particles by adjusting the volume fraction of ethanol in reaction solutions

ZnO particles were successfully prepared by one step CTAB‐assisted hydrothermal method with different volume fraction of ethanol‐water mixture solution. The formed thorn‐ball like ZnO particles have an average size of 1 ∼ 2 μm in diameter. XRD result shows a hexagonal wurtzite structure and higher crystallinity. Room‐temperature photoluminescence shows a strong and dominated peak at ∼383 nm with a green emission at ∼510 nm. The intensity ratio between the UV and green emission increased from 1.31 to 7.53 when the volume fraction of ethanol was changed from 0% to 50%, which shows a direct suppression of structural defects just by adjusting the ethanol fraction in reaction solutions. The possible growth and luminescence mechanisms for thorn‐ball like ZnO particles are discussed.     

离子交换树脂均匀沉淀法制备MgO纳米粒子

以(Mg(NO3)2·6H2O, (NH4)2CO3 和NH3·H2O为原料,采用两种离子交换树脂均匀沉淀法分别制备MgO纳米粒子.用热分析、X射线粉末衍射(XRD)、透射电子显微镜(TEM)、高分辨电子显微镜(HR TEM)、选区电子衍射(SAED)和BET等对所制备的MgO粒子进行了表征.结果表明:经700 ℃焙烧后制备的MgO纳米晶体属六方晶系,样品分散性较好,平均粒径约为25 nm;MgO纳米晶体清晰、有序的电子衍射点阵,表明晶体的结晶度较好;纳米粒子a和b的比表面积分别为31 m2/g and 32 m2/g.     

合成条件对尿素沉淀法制备氧化钇纳米微球的影响

本文采用尿素沉淀法合成了粒径约160 nm的激光陶瓷用氧化钇粉微球.颗粒呈较规则球形,单分散性良好.通过对反应过程的系统研究,探讨了粉体前驱体微球的生长机理,并研究了硫酸铵对前驱体微球生长习性的影响.对前驱体微球的热力学性质进行了研究.采用X射线衍射仪,扫描电镜,透射电镜,TG-DTA等仪器对实验过程及实验结果进行表征和分析.得出了溶液升温速率和硫酸铵对于氧化钇粉体制备的影响.较高的升温速率有助于前驱体颗粒在较短的时间内聚集.5;硫酸铵的加入明显减小前驱体尺寸,且硫酸根在1000℃煅烧时分解防止氧化钇微球之间出现烧结颈.从而形成外形规则、单分散的氧化钇微球.     

Homogeneity of a ZrF4-based glass at the nano-scale

A glass of composition 53ZrF₄–20BaF₂–4LaF₃–3AlF₃–20NaF (T_g=260°C) was prepared by careful crucible melting. High-resolution atomic force microscopy of fracture surfaces displayed the presence of nano-pores with diameters of 20–50 nm, being 4–10 nm deep, in all glasses. It was further found that only glasses without annealing and glasses with an annealing step considerably below T_g showed a distinct pattern, i.e. ripples of ≈20 nm in diameter and an rms roughness of ≈0.6 nm. Glasses annealed either near T_g or at the temperatures of maximum nucleation or maximum crystal growth rates showed both regions with the ripple pattern and regions with nano-hillocks, growing in size with increasing annealing temperature and time. Thus these hillocks nearly reach micro-dimensions of ≈270 nm in diameter and ≈65 nm in height following a 90 min annealing step at 343°C, the temperature of maximum crystal growth. These findings give evidence that the glass system, which is thought to be one of the most suitable for fiber drawing, is much less stable against nucleation and crystallization than anticipated.     

Formation of structure in small lead clusters under thermal effect

The thermal effect on lead clusters with radii up to 5.5 nm has been investigated by the molecular dynamics method using a modified tight-binding potential TB-SMA. The melting of Pb nanoparticles of these sizes is strictly homogeneous, without the formation of a surface liquidlike layer. The primary fcc phase in the particles is retained upon heating in the overwhelming majority of model experiments. An analysis of the structure formation during crystallization has shown that structures with pentagonal symmetry are preferred for lead clusters in this case. It is noted that an increase in the nanoparticle size leads to the dominance of the dodecahedral structure over the icosahedral one.     

Formation of nanoparticles in soda-lime glasses by single and double ion implantation

Structural characteristics and optical properties of monometallic and bimetallic Ag and Au nanoparticles in the surface region of soda-lime glass fabricated by ion implantation have been studied by transmission electron microscopy and optical spectroscopy. As a result it has been found that both, implantation dose and process temperature, strongly influence the metal nanoparticle formation governed by ion diffusion and metal precipitation as well as the involved stress generation around the particles. Thus, the mean size of metal nanoparticles and the width of the particle containing region beneath the glass surface increase with increasing temperature as well as implanted dose. Upon sequential high-dose double implantation to form bimetallic Ag–Au nanoparticles a rather complex configuration has been obtained. Particles of sizes above a threshold of 5–10 nm exhibit distinct image contrast features indicating the development of central voids whose sizes are proportional to the outer particle diameter.     

Influence of UV-exposure on the crystallization and optical properties of photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a photosensitive multi-component silicate glass. Photoinduced crystalline phase precipitation results in refractive index variations in UV exposed areas of PTR glass. The precipitation of silver containing particles which occurs during photo-thermo-refractive process increases the optical absorption of the samples in the range 350 nm to NIR wavelengths and the growth of sodium fluoride crystals and their aggregation increases light scattering in visible and NIR regions. We show that one effect of the UV-exposure is a decrease in the crystallization temperature by ～50 °C compared to the unexposed areas as measured by differential scanning calorimetry, which we attribute to an increase in nucleation rate. Using spectro-photometric measurements, a linear function is fitted to the changes in the amplitude of the absorption band of the silver containing particles versus the UV-dosage. The root mean square scatter of the data from the linear function is better than 0.99 and the slope of the function is 0.32 ± 0.01 cm/J. The IR absorption of PTR sample, measured by laser calorimetry shows that the increase of the absorption in infrared region at 1.1 μm, is due to the tail of the absorption band of silver containing particles having maximum at 465 nm. We finally show that after hyper-development, one effect of UV-exposure at 325 nm on the crystallization kinetics of PTR glasses is a decrease in particle sizes from micron size to nanometers size. But additional investigations demonstrate that smaller dosage UV-exposures (a few tens of milliwatts) increase the optical scattering by one order of magnitude. Optical micrographs taken after UV-exposure and hyper-development reveal the use of smaller dosages enhances nucleation rate without preventing the growth of large crystals and therefore induces higher scattering.     

微波辅助水热合成条件对直接合成纳米HZSM-5晶体性质的影响

利用微波辅助水热合成法直接制备了纳米HZSM-5晶体.采用XRD、FT-IR、SEM、BET和NH3-TPD等手段对合成样品进行了分析表征,研究了晶化温度和时间对合成产物晶体性质的影响.结果表明,晶化温度和时间对微波辅助水热直接合成产物微观形貌、晶粒尺寸和分散度影响明显.较低的晶化温度和较短的晶化时间均难以形成形貌规则的HZSM-5晶体.随着晶化温度的升高,合成样品逐渐变为球形晶粒、晶粒尺寸逐渐增大、分散度逐渐提高,继续提高晶化温度达180 ℃时,晶粒长大使比表面积稍有降低;随着晶化时间的延长,样品的微孔和介孔增多,比表面积和孔容逐渐增大,继续延长晶化时间,晶体内微孔可能的收缩和晶粒的长大使得样品孔容和比表面积减小.160 ℃和1.5 h条件下制备的HZSM-5分子筛晶体形貌呈球形,晶粒尺寸约为60 nm,分散程度较好;其比表面积、孔容和平均孔径分别为398.45 m2·g-1、0.63 cm3·g-1和6.27 nm;晶体表面具有弱酸特征.     

Semi-Batch Precipitation of Calcium Oxalate Monohydrate

Calcium oxalate monohydrate (COM) formation on the semi-batch precipitation of CaCl₂ and Na₂C₂O₄ solutions in the stoichiometric ratio carried out at pH = 6 and 37 or 70°C, respectively, was studied. When a certain level of supersaturation in the system is reached, individual COM crystals of a rather uniform size are formed. These crystals then grown and form ‘loose’ agglomerates that later develop into compact and spherical particles. The particle size distribution (PSD) rapidly shifts during early stages of precipitation towards larger sizes as a result of crystal growth and agglomeration. Later the PSD reaches a shape and position on the size axis that remain virtually constant with progressing precipitation. COM agglomerates consisting of mainly intergrown crystals are formed by mechanism of primary and secondary agglomeration. The primary agglomeration can constitute an important factor in urolithiasis.     

Formation and ageing of L‐glutamic acid spherulites

Polycrystalline spherulites of L‐glutamic acid have been crystallized by pH‐shift precipitation from stirred aqueous solutions. The time dependent behaviour of the spherulites has been studied during the crystallization process and batch filtration tests have been performed. It has been shown that the FBRM mean chord length of the investigated spherulites decreases in the course of time. The fact that the size reduction progresses faster at higher temperature and the solubility of resuspended polycrystalline particles decreasing with time, implies an ageing mechanism to be responsible for the observed changes in the particle size. It has been shown that the surface area decreases with time, ruling out particle breakage as a possible explanation for the decrease in particle size. XRD and Raman studies of L‐glutamic acid, however, show only marginal differences in the crystalline structure of particles obtained from different time stages. The ageing may occur due to several different mechanisms like phase transformation and Ostwald ripening. L‐glutamic acid spherulites after 3 h exhibit a 3‐fold higher value for the cake resistance as compared to particles after 0.5 h. However, particles obtained after 22 h exhibit an 8‐fold lower cake resistance as compared to the initially obtained spherulites, The increase in the cake resistance is attributed to the appearance of small plate‐like crystals and a change in the interaction between the crystal surface and the solution. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Al nano-crystallization process in amorphous Al85Ni8Y5Co2

The primary nano-crystallization of fcc Al in initially amorphous Al₈₅Ni₈Y₅Co₂ has been studied by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) in combination with energy electron loss spectroscopy (EELS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffractometry (XRD). TEM in combination with EELS after both isochronal and isothermal annealing allowed the determination of the change of the crystalline particle density and particle density/size distribution. The crystallization in Al₈₅Ni₈Y₅Co₂ was found to take place in three sequences. In the first step of the first sequence spherical fcc Al nano-particles develop with a very high particle density. In the second step of the first sequence the more or less spherical Al particles develop protrusions without significant further nucleation of fcc Al particles. In the second sequence nucleation of new fcc Al particles takes place. Comparing the crystallization behavior of Al₈₅Ni₈Y₅Co₂ with that of Al₈₅Ni₅Y₈Co₂ it follows that the yttrium solute level has a strong influence on the nucleation and growth behavior during the fcc Al primary nano-crystallization.     

溶胶凝胶法制备氧化石墨烯/氧化铝复合材料

将不同配比的异丙醇铝(AlIP)和氧化石墨烯(GO)水分散液,通过溶胶凝胶法制备了氧化石墨烯/氧化铝复合材料.通过SEM和TEM分析,氧化石墨烯被纳米颗粒包裹.XRD分析显示纳米颗粒的成分是Al2O3,通过原子力显微镜(AFM)分析,纳米颗粒的平均粒径为50 nm.复合材料的生长机理是:首先GO和AlIP分子结合,AlIP水解后在GO表面生成AlOOH的小颗粒,随着反应的继续进行颗粒逐渐长大,通过高温处理,AlOOH转变为Al2O3.