In‐Plane Direct‐Write Assembly of Iridescent Colloidal Crystals

Materials made by directed self‐assembly of colloids can exhibit a rich spectrum of optical phenomena, including photonic bandgaps, coherent scattering, collective plasmonic resonance, and wave guiding. The assembly of colloidal particles with spatial selectivity is critical for studying these phenomena and for practical device fabrication. While there are well‐established techniques for patterning colloidal crystals, these often require multiple steps including the fabrication of a physical template for masking, etching, stamping, or directing dewetting. Here, the direct‐writing of colloidal suspensions is presented as a technique for fabrication of iridescent colloidal crystals in arbitrary 2D patterns. Leveraging the principles of convective assembly, the process can be optimized for high writing speeds (≈600 µm s^?1) at mild process temperature (30 °C) while maintaining long‐range (cm‐scale) order in the colloidal crystals. The crystals exhibit structural color by grating diffraction, and analysis of diffraction allows particle size, relative grain size, and grain orientation to be deduced. The effect of write trajectory on particle ordering is discussed and insights for developing 3D printing techniques for colloidal crystals via layer‐wise printing and sintering are provided.     

Layered double hydroxide using hydrothermal treatment: morphology evolution,intercalation and release kinetics of diclofenac sodium

The present work demonstrates the possibilities of hydrothermal transformation of Zn-Al layered double hydroxide (LDH) nanostructure by varying the synthetic conditions. The manipulation in washing step before hydrothermal treatment allows control over crystal morphologies, size and stability of their aqueous solutions. We examined the crystal growth process in the presence and the absence of extra ions during hydrothermal treatment and its dependence on the drug (diclofenac sodium (Dic-Na)) loading and release processes. Hexagonal plate-like crystals show sustained release with ～90% of the drug from the matrix in a week, suggesting the applicability of LDH nanohybrids in sustained drug delivery systems. The fits to the release kinetics data indicated the drug release as a diffusion-controlled release process. LDH with rod-like morphology shows excellent colloidal stability in aqueous suspension, as studied by photon correlation spectroscopy.     

Fabrication of colloidal crystals with hierarchical structure and its water adhesion properties

A facile fabrication method of colloidal crystals with hierarchical structure has been presented. The colloidal crystals were assembled from latex spheres with various uneven surfaces, which were simply synthesized via emulsion polymerization by varying initiator feeding times. The as-prepared colloidal crystals demonstrated the water adhesion properties, which could be modulated by designing the hierarchical structure of latex surface. The result provided a simple fabrication method for colloidal crystals with hierarchical structure and high water adhesion force. This would greatly extend the applications of colloidal crystals to many other important fields, for instance, microfluidic device.     

Crystalline transformation of colloidal nanoparticles on graphene oxide

Emergence of novel two-dimensional (2-D) templates, e.g., graphene oxide, has signified new intriguing opportunities to couple nanocrystals electronically to the microscopic 2-D contacts. A promising approach to uniform dispersion of inorganic nanocrystals on the 2-D interfaces is to graft them through chemical bonding. The 2-D dispersion would offer a unique opportunity to address one of the primary challenges in the field of nanotechnology: fulfilling excellent chemical and physical properties of the nanocrystals in electronic solid-state devices. In this study, we blended colloidal nanocrystals with graphene oxide in aqueous solution in attempts to bind the nanocrystals on reactive sites of the graphene oxide surface, thereby achieving uniform loading. Interestingly, the nanocrystals undergo significant crystalline transformation even under relatively moderate reaction conditions. The growth of particle size and the drastic crystalline deformation, e.g., from wurtzite CdSe to amorphous Se, appear to take place in the proximity of acidic functional groups on graphene oxide. Photocarriers also play a key role in the reaction: under room light, the transformation yielded dramatic size increase and crystalline transformation, whereas in the dark, the change was suppressed. The experimental results presented in this study provide guidelines for uniform 2-D loading of colloidal nanocrystals on graphene oxide. The findings suggest that the surface acidity be titrated for colloidal nanocrystals to deposit on the graphitic layer and to avoid unwanted changes of nanocrystal size and properties.     

Influence of growth parameters on the fabrication of high-quality colloidal crystals via a controlled evaporation self-assembly method

A controlled evaporation self-assembly method with multiple controllable parameters was used to synthesize high-quality colloidal crystals. The environmental parameters, such as the relative humidity, evaporation temperature and pressure, were studied for the quality controls of colloidal crystals during the formation. In the experimental results, we show how these parameters influence the quality of colloidal crystals significantly. Moreover, it is found that, under the case of the relative humidity of 70%, evaporation temperature of 35 °C and pressure of 6.0 kPa, the fabricating high-quality colloidal crystals is optimal from aqueous solution of monodisperse polystyrene spheres with a diameter of 260 nm in a short time (less than 10 h). Highest possible crystal quality may be obtained after the natural drying in the vacuum chamber.     

Determination of factors affecting kinetics of solid-state transformation of fluconazole polymorph II to polymorph I using diffuse reflectance Fourier transform spectroscopy

Background: It was of interest to investigate the factors affecting kinetics of transformation of fluconazole polymorph II (the metastable form) to fluconazole polymorph I (the stable form) using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Method: Fluconazole polymorphs I and II both were prepared by crystallization in dichloromethane. The two forms were characterized using differential scanning calorimetry, thermogravimetric analysis, powder X-ray diffraction, solubility, and DRIFTS. Transformation of polymorph II to polymorph I was also studied under different isothermal temperatures using DRIFTS. Kinetic analyses of the data were done using model-dependent and model-independent methods. Eighteen solid-state reaction models were used to interpret the experimental results. Results: Based on statistics, the Prout–Tompkins model provided the best fit for the transformation. The activation energy (E_a) value derived from the rate constants of the Prout–Tompkins model was 329 kJ/mol. Model-independent analysis was also applied to the experimental results. The average values calculated using both methods were not significantly different. Factors affecting kinetics of transformation such as mechanical factors, relative humidity, and the effect of seeding were also studied. Mechanical factors, which included trituration and compression, proved to enhance transformation rate significantly. Relative humidity proved to transform both polymorphs to monohydrate form. The presence of seed crystals of polymorph I was proved not to affect the transformation process of polymorph II to polymorph I. Effect of solvent of crystallization (dichloromethane) was studied. A significant change of the rate of transformation was proved in the presence of solvent vapors, and a change on the mechanism was proposed.     

Morphology of hollow crystals of II–VI compounds

Published data on hollow crystals of II–VI compounds are reviewed. The experimental conditions for obtaining hollow crystals are discussed and presented systematically in tables. Some inferences concerning the effect of impurities, supersaturation, type of substrate and other factors on the growth of hollow crystals are made. Particular attention is paid to the structure, form and defects of hollow crystals and it is established that they can be classified in the following groups: hollow hexagonal columns and prisms, hollow pyramids, hollow crystals with spiral-like hexagonal form and hollow crystals with a more complex structure consisting of whisker-pyramid-prism. The mechanism and kinetics of the growth of hollow crystals as presented by different authors are discussed.     

Crystallography of ordered colloids using optical microscopy. 2. Divergent-beam technique

A technique has been developed to extract quantitative crystallographic data from randomly oriented colloidal crystals using a divergent-beam approach. This technique was tested on a series of diverse experimental images of colloidal crystals formed from monodisperse suspensions of sterically stabilized poly-(methyl methacrylate) spheres suspended in organic index-matching solvents. Complete sets of reciprocal lattice basis vectors were extracted in all but one case. When data extraction was successful, results appeared to be accurate to about 1% for lattice parameters and to within approximately 2 degrees for orientation. This approach is easier to implement than a previously developed parallel-beam approach with the drawback that the divergent-beam approach is not as robust in certain situations with random hexagonal close-packed crystals. The two techniques are therefore complimentary to each other, and between them it should be possible to extract quantitative crystallographic data with a conventional optical microscope from any closely index-matched colloidal crystal whose lattice parameters are compatible with visible wavelengths.     

Crystallization of the EGF receptor ectodomain on US space mission STS-47

Although biochemists working in the field of biological signal transduction have characterized cell surface receptors for numerous growth factors within the past ten years, none of the three-dimensional structures could be obtained for these important proteins which represent major components of the cells' growth control system. Now, the extracellular ligand binding domain of the EGF receptor was crystallized in the presence of EGF under microgravity on US Shuttle mission STS-47. In 8 out of 9 experiments prepared under different conditions crystal growth was observed. One of these space-grown crystals showed higher diffraction quality than all crystals previously obtained in the laboratory. It allowed, for the first time, evaluation of the real space group by partial data collection.     

氘代聚苯乙烯胶体晶体的制备及光学性质研究

以水作为介质合成了高度单分散的氘代聚苯乙烯微球,并利用垂直沉积法制备了高质量的氘代聚苯乙烯胶体晶体.傅立叶变换红外光谱清楚地表明氘代苯乙烯单体发生了聚合反应;扫描电镜表面分析展示出胶体微球的高度有序排列,断面分析表明氘代聚苯乙烯胶体晶体为面心立方结构;光学透射谱显示出氘代聚苯乙烯胶体晶体的高次布拉格衍射特征,通过和理论计算的能带结构对比,进一步证实了氘代聚苯乙烯胶体晶体为面心立方结构;变角度光学透射谱测量显示,随着入射角的增大,(111)面的衍射峰蓝移,而(200)和(220)面的衍射峰发生红移.     

Reconfigurable Grating Diffraction Structural Color in Self-Assembled Colloidal Crystals

Self-assembled colloidal crystals display structural colors due to light diffracted from their microscale, ordered structure. This color arises due to Bragg reflection (BR) or grating diffraction (GD); the latter mechanism is much less explored than the former. Here the design space for generating GD structural color is identified and its relative advantages are demonstrated. Electrophoretic deposition is used to self-assemble crystals with fine crystal grains from colloids of diameter 1.0 µm. The structural color in transmission is tunable across the full visible spectrum. The optimum optical response—represented by both color intensity and saturation—is observed at low layer number (≤5 layers). The spectral response is well predicted by Mie scattering of the crystals. Taken together, the experimental and theoretical results demonstrate that vivid grating colors with high color saturation can be produced from thin layers of micron-sized colloids. These colloidal crystals extend the potential of artificial structural color materials.     

Micro-jitter attenuation of spaceborne cooler by using a blade-type hyperelastic shape memory alloy passive isolator

In this study, the primary design objective is to develop a passive isolator that can guarantee structural safety of the cooler assembly in a launch vibration environment without a launch locking mechanism, while effectively isolating the cooler-induced micro-jitter during the on-orbit operation of the cooler. To achieve the design objective, we focused on the utilization of characteristics of the hyperelastic shape memory effects. The major advantage of the isolator is that the micro-jitter isolation performance is much less sensitive to the aligned position of the isolator in comparison with the conventional isolator. Moreover, implementation of an additional 0g compensation device during a satellite level on-ground test, such as a jitter measurement test, is not required. In this study, the basic characteristics of the isolator were measured using the torque test and free vibration test. The micro-jitter attenuation capability and position sensitivity of the proposed isolator design were validated by the micro-jitter measurement test.     

Colloidal Material Box: In-situ Observations of Colloidal Self-Assembly and Liquid Crystal Phase Transitions in Microgravity

To study the self-assembly behavior of colloidal spheres in the solid/liquid interface and elucidate the mechanism of liquid crystal phase transition under microgravity, a Colloidal Material Box (CMB) was designed which consists of three modules: (i) colloidal evaporation experimental module, made up of a sample management unit, an injection management unit and an optical observation unit; (ii) liquid crystal phase transition experimental module, including a sample management unit and an optical observation unit; (iii) electronic control module. The following two experimental plans will be performed inside the CMB aboard the SJ-10 satellite in space. (i) Self-assembly of colloidal spheres (with and without Au shell) induced by droplet evaporation, allowing observation of the dynamic process of the colloidal spheres within the droplet and the change of the droplet outer profile during evaporation; (ii) Phase behavior of Mg₂Al LDHs suspensions in microgravity. The experimental results will be the first experimental observations of depositing ordered colloidal crystals and their self-assembly behavior under microgravity, and will illustrate the influence of gravity on liquid crystal phase transition.     

7075-H18铝合金板材的淬火敏感性与等温转变行为EI北大核心CSCD

以2 mm厚的7075-H18高强度铝合金板材为研究对象,采用微观组织分析、显微硬度测试、动力学建模与计算相结合的方法,对板材的淬火敏感性、等温相变行为及转变动力学进行系统研究,构建"时间-温度-性能"关系图。结果表明:7075-H18板材具有较高的淬火敏感性。"时间-温度-性能"关系图的鼻尖温度约为350℃,孕育期仅为0.23 s,淬火敏感温度区间为271~404℃,转变量为0.5%的曲线对应的临界线性冷却速率为969.7℃/s,超过了冷模淬火所能达到的冷却速率。板材在等温淬火过程中主要形成粗大的η平衡相,等温时间越长,晶内与晶界的η相尺寸越大,晶界η相越趋于连续分布,且无沉淀析出带变宽。基于实验数据构建的等温转变动力学模型,对7075-H18板材的等温相变过程进行准确预测,板材在350℃等温过程中沉淀相的析出速率最大,等温相变类型为"形核-长大"型相变,相变过程为层片状沉淀相的长大、增厚及互相吞并。理论计算结果与透射电子显微镜下观测到的η相特征以及"时间-温度-性能"关系图相一致。     

Large-scale assembly of colloidal nanoparticles and fabrication of periodic subwavelength structures

This paper reports a simple and scalable spin-coating technique for assembling 70?nm silica nanoparticles into non-close-packed colloidal crystals over a large area. The thickness of the shear-aligned colloidal crystals can be controlled from hundreds of layers to a single monolayer by adjusting the spin-coating conditions. We further demonstrate that the spin-coated colloidal monolayers can be used as structural templates to pattern sub-100?nm pillar arrays directly on silicon substrates. The resulting subwavelength-structured pillar arrays exhibit excellent broadband antireflective and superhydrophobic properties, which are promising for developing self-cleaning antireflection coatings for crystalline silicon solar cells. This bottom-up approach enables large-scale production of periodic nanostructures with resolution beyond the optical diffraction limit that have important technological applications ranging from high-density data storage and optoelectronics to biological sensing and subwavelength optics.     

Colloidal hard-sphere crystallization kinetics in microgravity and normal gravity

The hard-sphere disorder-order transition serves as the paradigm for crystallization. We used time-resolved Bragg light scattering from the close-packed planes to measure the kinetics of nucleation and growth of colloidal hard-sphere crystals. The effects of gravity are revealed by comparison of the experiments in microgravity and normal gravity. Crystallites grow faster and larger in microgravity, and the coarsening between crystallites is suppressed by gravity. The face-centered-cubic structure was strongly indicated as being the stable structure for hard-sphere crystals. For a sample with a volume fraction of 0.552, the classic nucleation and growth picture is followed.     

Photolytic Behavior of Silver Iodide

Silver iodide exposed to high intensity radiation in the visible light spectrum was found to yield a powder X-ray diffraction pattern showing marked deviations from ideality. It was found possible to correlate these with a decrease in primary extinction, indicating a constant progress from an ideal to a mosaic type crystallinity. Large single crystals showed pronounced asterism in transmission Laue photographs under similar experimental conditions. Small amounts of colloidal silver were detected. A mechanism for this process in silver iodide is proposed, in general agreement with the theory of the photographic process. The primary difference from the other silver halides appears to be a considerably slower rate, permitting the observation of a two step process in detail.     

Phase II to phase I crystal transformation in polybutene-1 single crystals: a reinvestigation

The spontaneous phase II to phase I crystal-crystal transformation of polybutene-1 was investigated by electron diffraction and bright- and dark-field imaging of solution and thinfilm grown single crystals. Whole single crystals were observed to transform with a single phase II to phase I orientational relationship and, in the case of multiple orientations, the transformed areas were not dependent on growth sectors. These results do not support the views of Holland and Miller of a twinned phase II to I transformation determined by growth sectors but are consistent with a transformation scheme introduced by Fujiwara. Nucleation and growth of the transformation are further discussed.