Janus gold nanoparticle with bicompartment polymer brushes templated by polymer single crystals

Janus particles have attracted increasing attention from the communities of materials science, chemistry, physics and biology. While large size Janus particles are readily achieved, synthesizing Janus nanoparticles (JNP) with diameters smaller than ∼20 nm remains a challenging task. In this article, we report a systematic study on growing polymer brushes on polymer-single-crystal-immobilized 6 and 15 nm diameter gold nanoparticles (AuNPs) using atom transfer radical polymerization. JNPs with bicompartment polymer brushes, such as poly(ethylene oxide) (PEO)/poly(methyl methacrylate), PEO/poly(tert-butyl acrylate), and PEO/poly(acrylic acid), were synthesized. The grafting densities can be carefully controlled. The Janus feature of these particles was confirmed using both platinum nanoparticle decoration and UV/Vis spectroscopy analysis. The surface plasmon resonance absorbance of Janus particles exhibited a blue shift compared with that of symmetric AuNPs with either homopolymer or mixed polymer brushes. This work demonstrated that using polymer single crystal as the templates, small size (<20 nm diameter) JNPs having bicompartment polymer brushes can be readily obtained. The ability to tune grafting density and molecular weight of polymer brushes can lead to controlled particle amphiphilicity.     

光折变材料BaTiO3单晶生长及品质鉴定

四方相BaTiO_3单晶是一种新型非线性光学晶体,由于其强的非线性而在光学应用方面具有许多潜在的用途。 本文报道了以两种合成的BaTiO_3为原料,采用顶部籽晶熔盐生长技术进行块状BaTiO_3单晶生长研究。对生长出的晶体进行了结构和成份分析以及结晶学表征,并测量了Curie温度和透光率,从而获得了生长BaTiO_3单晶的较佳工艺条件     

Structural effects in electrocatalysis: oxidation of formaldehyde on gold and platinum single crystal electrodes in alkaline solution

The oxidation of formaldehyde in sodium hydroxide solution has been studied on platinum and gold single crystal electrodes with the (111), (110) and (100) orientations. There is apparently no structural sensitivity of this reaction, since minor differences have been found between the three low index faces. This is valid for both platinum and gold electrodes. The hydrogen adsorption on platinum and the AuOH formation on gold electrodes exhibit structural sensitivity in the same solution. Similar activity of platinum and gold electrodes is noteworthy. A weak adsorption of gem-diol, formed in the interaction of formaldehyde with H₂O or OH^? appears as the origin of the structural insensitivity of this reaction.     

碘化铅单晶体生长工艺分析

在坩埚下降法生长PbI2单晶体的过程中,如何解决晶体中的富碘问题是一个研究关键.本文采用坩埚下降法生长出了三种不同颜色的富碘PbI2单晶体.实验中发现:通过合理的选择坩埚在温场中的生长位置,可最大限度的减轻晶体富碘现象,分析了相关工艺,得出了最优工艺方案.结果表明:在适当的工艺条件下,坩埚下降法设备简单,易于操作,是生长PbI2单晶体的优良方法.     

6.0mol•L－1KOH溶液中锌单晶（002）和（100）晶面的电化学行为

In this article, the electrochemical performance of the electrodes of zinc polycrystal, Zn（002） and Zn（100） single crystals were studied by the Tafel line extrapolation of the potentio-dynamic polarization curves, the cyclic voltammetry and the charge/discharge experiment. The results shows that in 6.0 mol·L^-1 KOH solution the corrosion rate of Zn polycrystal, Zn（100） and Zn（002） single crystals decreases in turn; and the reversibility and the charge/discharge performance of Zn single crystal was superior to Zn polycrystal. The dendrite growth of the surface of Zn polycrvstal was easier than Zn single crystal during the stages of charge/discharge.     

Kinetic study of CO oxidation on step decorated Pt(1 1 1) vicinal single crystal electrodes

In this work, surface modification at atomic level was applied to study the reactivity of step sites on platinum single crystal surfaces. Stepped platinum single crystal electrodes with (1 1 1) terraces separated by monoatomic step sites with different symmetry were decorated with irreversibly adsorbed adatoms, without blocking the terrace sites, and characterized in 0.1 M HClO₄ solution. The kinetics of CO oxidation on the different platinum single crystal planes as well as on the step decorated surfaces has been studied using chronoamperometry. The apparent rate constants, which were determined by fitting the experimental data to a mean-field model, decrease after the steps of platinum single crystal electrodes have been blocked by the adatoms. This behavior indicates that steps are active sites for CO oxidation. Tafel slopes measured from the potential dependence of the apparent rate constants of CO oxidation were similar in all cases. This result demonstrates that the electrochemical oxidation of the CO adlayer on all the surfaces follows the same Langmuir–Hinshelwood model, irrespectively of step modification.     

Phase coexistence and broad depolarization response in (Pb,La)(Zr,Sn,Ti)O3 single crystals

Lead lanthanum zirconate stannate titanate (PLZST) antiferroelectric materials have been intensively studied in the last few decades due to their adjustable phase transition and outstanding performance. Despite the strong interest it has drawn, there is a lack of study of domain structure evolution in antiferroelectric materials with morphotropic phase boundary (MPB) composition, which is of great importance for understanding the phase transition between ferroelectric and antiferroelectric phase. PLZST single crystals with the composition in the MPB region were grown by the flux method in this work. We presented the direct evidence that rhombohedral ferroelectric and tetragonal antiferroelectric phase coexist in the as-grown single crystals. The evolution of phase structure and domain morphology during the temperature-induced phase transition was observed by in situ optical visualization, accompanied by a broadening depolarization response. An enhanced broadening pyroelectric response with a wide temperature window was detected. A modified Ginzburg-Landau-Devonshire theory was employed to elucidate the structural and physical origin of the broadening thermal depolarization. It is anticipated that a further understanding of the phase transition behavior in PLZST single crystals may be helpful in developing novel ferroelectrics and antiferroelectrics with MPB compositions.     

Verneuil growth of TiO2 (rutile) crystals of large size and low dislocation density at low gas flow rate

Large (30 mm in diameter) TiO₂ (rutile) single crystals with low dislocation density were grown by the Verneuil method using a single crystal furnace designed and improved by the authors. The structure of the burner was optimized by numerical simulation analysis so that the crystal could be grown at a low gas flow rate. The investigation of the growth process parameters (i.e., growth rate, outer flow rate of O₂, inner flow rate of O₂, and the increment of H₂ flow rate) shows that the inner flow rate of O₂ and the increment of H₂ flow rate have the strongest influence on the crystal growth process. On this basis, other growth parameters (growth rate, outer flow rate of O₂) were also optimized. Compared with the conventional Verneuil method, the crystal can be grown at a considerably low gas flow rate (40–50% lower) with the method in this work, which reduces the melt turbulence impacted by gas flow, enabling a steady and clear solid-liquid interface and improving the crystal quality. The optimum growth conditions are for the growth rate of 6 mm/h, O₂ outer flow rate of 3.5 L/min, O₂ inner flow rate of 5.5 L/min, and increment of H₂ flow rate of 0.1 L/4 min. The etch pit density of the rutile crystals is 3.29 × 10⁴ cm^?2, an order of magnitude lower than that of the crystals grown by the conventional Verneuil method. The optical properties of the crystal are comparable to those grown by the floating zone method. Especially, it is easier to obtain a larger crystal size with lower production costs. Our results provide a possible route for industrializing the Verneuil production of large, high-quality and low-cost rutile single crystals.     

Conditions for growth of AlN single crystals in Al–Sn flux

In this study, we investigated the Al–Sn flux system and its growth conditions to obtain AlN single crystals. AlN single crystals of a size of 50 μm were successfully grown using an Al–Sn melt under nitrogen gas pressure. The growable region of the AlN crystals was established using a pressure‐temperature diagram. The required nitrogen gas pressure for the growth of the AlN crystals was found to decrease with increasing temperature, and AlN was grown at 0.1 MPa nitrogen pressure above 1300°C. By investigating the AlN yield with various Al concentrations, we confirmed that the Al component in the Al–Sn melt facilitated nitrogen dissolution. Finally, scanning electron microscopy analysis showed that the obtained AlN particles showed good morphology.     

Hydrothermal synthesis of giant single crystals of MFI type zeolite: Modified bulk material dissolution method

In the present study, we aimed at the development of an easy and reproducible synthesis method of giant MFI zeolite crystals. We used a new synthesis method, modified bulk material dissolution (M-BMD) method, in which a piece of quartz glass tube was inserted as a silica source in a small PTFE sleeve together with ZSM-5 powder as seed crystals. We adopted a higher HF concentration (25 mmol/25 ml) of the synthesis solution than that usually used. By using this method, only a few crystal nuclei were formed separately from each other on the surface of the quartz glass tube in the PTFE sleeve and giant zeolite crystals were reproducibly synthesized on it. Giant single crystals of MFI as large as 5.0 mm were successfully synthesized at 453 K for 90 days by using the M-BMD method.     

水热条件下针状羟基磷灰石单晶体的均相合成

用水热法制备出结晶度高、纯净均一的针状羟基磷灰石单晶体。从X-射线衍射谱、红外吸收光谱、透射电镜分析等方面确认了所得晶体为羟基磷灰石单晶体。根据透射电子衍射谱测量计算出的晶面间距d值与羟基磷灰石卡片的d值非常接近,由标定的晶面指数计算出的晶面夹角与实际测量值有很好的吻合,从而确定所得晶体为单晶。     

Comprehensive analysis of Mn:PIN-PMN-PT single crystals for Class IV flextensional transducer

As a crucial part of flextensional transducer (FT), the piezoelectric stack has an essential influence on the transducer. However, up to date, there are no literatures on considering the loss characteristics of the piezoelectric materials in the design of FT. Manganese-modified PIN-PMN-PT (Mn:PIN-PMN-PT) single crystals have greatly improved Q_m values compared with the binary and ternary single crystals. In this paper, Class IV FTs based on Mn:PIN-42%PMN-32%PT and Mn:PIN-47%PMN-29%PT crystals were analyzed comprehensively on the heat losses, as well as transmitting voltage response (TVR), source level (SL), acoustic pressure (AP) and admittance. Compared with PIN-47%PMN-29%PT, PMN-28%PT and PZT4, the Mn:PIN-42%PMN-32%PT FT has a decrease of heat loss by 47.9%, 79.5% and 93.6%, respectively, under the same strain of 5 × 10^?5. The results indicated that the Mn:PIN-PMN-PT FT possesses simultaneously the less heat loss and lower resonant frequency, the higher AP, TVR, SL and effective electromechanical coupling coefficient. This research provides a guide for the design of FT and illuminates the immense potential of Mn:PIN-PMN-PT single crystals in making low heat generation, low frequency and high power FT.     

Li2B4O7单晶生长的研究

用提拉法生长了透明、无芯的四硼酸锂单晶,对该晶体生长过程中产生“芯”的原因进行了详细的讨论,并提出了克服的措施。     

NaBi(WO_4)_2晶体生长与开裂研究

钨酸铋钠 [分子式 :NaBi(WO4) 2 简称NBW ]是一种性能优良的闪烁晶体 .本工作采用提拉法生长出直径为 45mm ,高为 3 5mm的大尺寸NBW晶体 ,对生长的晶体中存在的开裂现象进行了研究 ,从理论上讨论了晶体中的热应力和热应变与晶体尺寸、温度梯度、提拉速度和转速等生长工艺参数之间的关系 .实验研究发现 ,晶体开裂与生长速度过快、转速过大、晶体冷却速率过快所造成的热应力有关 .并给出了制备无开裂优质NBW晶体的最佳生长工艺参数     

The morphology and structure of crystals in Qing Dynasty purple‐gold glaze excavated from the Forbidden City

Ancient Chinese purple‐gold glaze (zijinyou) is popular for its beautiful figuration, unique allure and fine craftsmanship. To understand the crystalline nature in the purple‐gold glaze, the morphology and structure of crystals precipitated in the glaze layer of purple‐gold glaze porcelain fired during the Qing Dynasty were characterized by a variety of methods combining X‐ray and electron‐based techniques. A large quantity of single‐phase twinning ε‐Fe₂O₃ crystals with lengths of 1‐3 μm, widths of less than 1 μm, and thickness of approximately 150 nm are found dispersed across the glaze surface to a depth of approximately tens of micrometers. These crystals show stratification across the cross‐section of the purple glaze consisting of 4 sublayers according to the crystal size. The formation of ε‐Fe₂O₃ crystals primarily contributed to the reddish‐brown tones of the purple‐gold glaze. The presence of anorthite, a strong reducing atmosphere during the firing process and the vitreous nature of the glaze influenced the growth of ε‐Fe₂O₃ crystals. These results suggest the controllability of single‐phase ε‐Fe₂O₃ crystals by identifying and understanding the underlying chemical processes in ancient Chinese crystalline glaze porcelain, and the findings will provide insights for modern material scientists in preparing ε‐Fe₂O₃ crystals with large sizes and high purities.     

Antiferroelectricity of NaNbO3: Single-crystal experimental study and first-principles calculation

Similar to the canonical antiferroelectric (AFE) compound PbZrO₃ in Pb(Zr,Ti)O₃ solid-solutions, the presence of double hysteresis loops and that of electric field–induced phase transitions are important characteristics of NaNbO₃ AFE materials; yet the phase transition behavior in the latter system is typically irreversible with the related mechanisms not fully understood. Here, we explore the phase transition mechanism of ferroelectric and AFE phases in NaNbO₃ based on measurements of single crystals with different directions in conjunction with density-functional theory (DFT) calculations. The tilting and distortion behaviors of the [NbO₆] octahedra are explained by DFT, and the ion displacement in the lattice is traced. The tilting and distortion behaviors of the [NbO₆] octahedra with different orientations are compared. We confirm that the tilt and distortion of the [NbO₆] octahedra along the [1 1 1] direction is the main reason to improve the stability of AFE phase. This conclusion is verified by the experimental characterizations of large-size NaNbO₃ single crystals successfully obtained in this study.     

NaM(WO_4)_2(M:Bi~(3+), Y~(3+), Gd~(3+))晶体生长与结构(英文)

采用提拉法生长出了钨酸铋钠[NaBi(WO4)2,NBW]、钨酸钇钠[NaY(WO4)2,NYW]和钨酸钆钠[NaGd(WO4)2,NGW]晶体.通过热重-差热分析(tbermogravimetry-differential thermal analysis,TG-DTA),X射线衍射(X-ray diffraction,XRD)分析对晶体进行表征.由TG-DTA曲线得到NBW,NYW和NGW晶体的熔点分别为937.7,1210.0℃和1 252.8℃.XRD分析表明:3种晶体都属于四方晶系、白钨矿结构、I41/a空间群.计算了3种晶体的晶胞参数,NBW晶体的晶胞参数要大于NYW和NGW晶体的.测试了晶体的红外光谱及Raman光谱,分析了晶体的振动模式,并将晶体振动光谱进行归属.通过比较认为三者结构基本相同.     

Electrooxidation of ethanol at polycrystalline and platinum stepped single crystals: A study by differential electrochemical mass spectrometry

The electrooxidation of adsorbed and bulk solution of 10⁻² M ethanol and D₆-ethanol at polycrystalline platinum, smooth, roughened and Ru modified Pt(3 3 2), Pt(3 3 1) and Pt(1 1 1) electrodes was studied by on-line differential electrochemical mass spectroscopy (DEMS) using a dual thin layer flow through cell.On polycrystalline Pt, the main (or even single) product is acetaldehyde; due to the flow through conditions the amount of acetaldehyde further oxidized to acetic acid is negligible. At stepped single crystals with (1 1 1) terraces (Pt(s)[n(1 1 1) × (1 1 1)], acetic acid is produced at a lower potential than acetaldehyde. This demonstrates that in addition to the reaction path involving C-C bond splitting leading to CO₂ (via adsorbed CO and CH_x) and the reaction path leading to acetaldehyde there is a third, direct reaction path leading to the formation of acetic acid.Step decoration by Ru does not lead to an increased reactivity. This is different from the strong cocatalytic effect of Ru at step sites on the oxidation of CO. Furthermore, Ru does not influence the relative amount of acetaldehyde formed.     

Solution growth of millimeter-scale Na2SiF6 single crystals for Mn4+-doping as red phosphor

The cation exchange method has been demonstrated to be efficient in doping Mn⁴⁺ ions into various fluorides to synthesize the red-emitting LED phosphors. This paper, however, reports the challenge in using this method to dope Mn⁴⁺ into the Na₂SiF₆ single crystals, to prepare the fluoride phosphor in single-crystal form, a state-of-the-art study in the white LED lighting field. The millimeter-sized Na₂SiF₆ single crystals with a uniform columnar morphology (2–3 mm in length) were successfully grown in solution by a slow cooling process after optimizing the precursors. Then, the crystals were soaked in the HF solution dissolved with K₂MnF₆ to implement Mn⁴⁺-doping via the cation exchange process. Evaluation of the Mn⁴⁺-doping behavior reveals that the Mn⁴⁺ ↔ Si⁴⁺ cation exchange is less efficient in the case of single crystal host compared with the polycrystalline powdery ones and by-reactions also occur which generates new phases. The Na₂SiF₆ single crystals doped with Mn⁴⁺ exhibit a series of discrete sharp peaks with intense zero phonon line emission at 617 nm under 450 nm blue irradiation. This study may trigger the exploration of new single crystal fluoride phosphor.     

Influence of chemical structure on enzymatic degradation of single crystals of PCL-b-PEO amphiphilic block copolymer

Solution-grown lamellar single crystals of PCL homopolymer and amphiphilic block copolymers of PCL-b-PEO-b-PCL and PCL-b-PEO-FG (functional groups FG = NH₂, OCH₃) were prepared by self-seeding procedures. The crystal structure and morphology of these single crystals were mainly studied by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM). The results indicated that the shorter PEO blocks as well as the functional groups bonded to the end of PEO block are in an amorphous state and located in the surface of single crystals. The enzymatic degradation of single crystals prepared from these homopolymer and amphiphilic block copolymers has been well-studied to demonstrate the effects of chemical structure on degradation behavior. The single crystals showed similar morphologies before enzymatic degradation but very different surface character after enzymatic degradation. Such differences resulted from the PEO block and functional end groups. The results of this work indicated the important role of chemical structure in determining biodegradation behavior.