金掺杂PMP泡沫的制备与表征

以聚-4-甲基-1-戊烯(PMP)为泡沫骨架材料,金颗粒为掺杂材料,均四甲苯与萘为混合溶剂体系,通过热诱导倒相技术制备出金掺杂低密度聚合物泡沫。实验结果表明:在金含量不变的情况下,掺杂泡沫的实际密度与理论密度呈线性关系;在理论密度不变的情况下,掺杂泡沫的实际密度随掺杂质量分数的增加趋近于理论值;金实际掺杂质量分数低于理论掺杂质量分数;掺杂泡沫与纯PMP泡沫具有类似的孔洞结构,随掺杂质量分数的增加泡沫的孔洞直径分布变宽且网络骨架尺寸有变大的趋势。     

铁掺杂PMP泡沫制备工艺研究

 以聚-4-甲基-1-戊烯为泡沫骨架，二茂铁为掺杂材料，通过热诱导倒相技术制备出铁掺杂聚合物泡沫。掺杂泡沫的实际密度均高于理论密度，且沿轴向从上至下逐渐增大。在理论密度不变的情况下，掺杂泡沫实际密度随掺杂元素原子百分含量的升高而呈降低趋势。与PMP泡沫相比，掺杂泡沫的孔洞直径分布变宽且网络骨架尺寸有变大的趋势。     

采用高分辨电镜分析Cu掺杂聚-4-甲基-1-戊烯泡沫材料采用高分辨电镜分析Cu掺杂聚-4-甲基-1-戊烯泡沫材料

利用物理掺杂的方法,制备了铜掺杂聚-4-甲基-1-戊烯(PMP)低密度泡沫材料,采用高分辨扫描电子显微镜和透射电子显微镜,分析了泡沫材料的微观结构、成分及微区成分分布。结果表明:与PMP泡沫相比,铜掺杂PMP泡沫的孔洞直径和网络骨架尺寸变大;铜颗粒镶嵌在PMP泡沫的有机骨架上且有团聚现象;泡沫材料中除碳、铜外,还残留有杂质元素氧;铜颗粒被PMP泡沫包裹,与碳网络骨架之间接触紧密。     

μm量级钨掺杂PMP泡沫制备

以聚-4-甲基-1-戊烯（PMP）为泡沫骨架,m量级钨为掺杂材料,超高分子量聚乙烯（UHWPE）为溶液粘度控制剂,通过热诱导倒相技术实现了低密度钨掺杂聚合物泡沫的制备。实验结果表明:当UHWPE质量分数为25%时,能够实现粒径10 m的钨在泡沫体内的均匀掺杂;泡沫密度为20 mg/cm3时,钨掺杂质量分数最高可达60%。     

溴掺杂低密度PMP泡沫的制备技术研究

 详细论述了掺溴聚-4-甲基-1-戊烯(PMP)低密度泡沫的制备方法与性质测量。以PMP为泡沫骨架材料,均四甲苯/萘为溶剂,六溴苯为掺杂单体,利用热诱导倒相法制备出密度20～60 mg/cm³的掺溴低密度泡沫。在理论密度为50 mg/cm³时掺杂溴原子最大质量分数可达58.91%。利用扫描电镜观测泡沫结构表明：聚合物泡沫均是一种“叶片”状开放的结构,“叶片”的大小依赖于聚合物掺杂量的多少。随着掺杂量的增大,可供形核-长大的晶核也逐渐增多,最终得到的聚合物“叶片”较小。整个体系中密度分布是较为均匀的,掺杂单体在整个聚合物体系中基本不存在沉降的趋势。整个泡沫体系在低温区未出现较大的失重,溶剂的脱出较为完全线。     

ICF靶所用掺杂聚合物及泡沫的研制

针对ICF靶所用掺杂聚合物及其泡沫的研制，制备出铜掺杂聚-4-甲基-1-戊烯(PMP)泡沫和掺溴聚合物材料。在掺杂聚合物泡沫过程中采用了超声波振荡的方式，提高了纳米铜粉在PMP泡沫骨架中的分布均匀性。掺杂纳米铜粉CH泡沫已用于今年“神光”Ⅱ试验中，并取得了较好的物理实验结果。利用溴(Br2)和PMP在光照条件下发生的自由基取代反应，制备了部分溴代聚4-甲基-1-戊烯样品。通过控制加入溴的量来控制最终产物中溴的掺杂量。利用红外光谱与元素分析确证样品中溴原子的存在。样品在150℃以前比较稳定，但在150℃以后就会失去溴化氢(HBr)。这对制造靶材料要求的泡沫材料提出了较高的要求。本课题还进行了低密度泡沫铜制备技术和无氰化学镀铁工艺研究。制备得到体积密度约3％的泡沫铜以及化学镀铁样品。     

低密度微孔聚合物泡沫的制备

 介绍了一种利用聚合物和溶剂的相分离，经过冷冻干燥来制备聚合物泡沫（特别是聚苯乙烯类泡沫）的通用技术。采用该技术制备的具有开放状孔洞结构的聚苯乙烯泡沫的密度为0.02~0.1g/cm3，平均孔径为1～20μm，而且泡沫具有各向同性，孔径非常均匀。通过对聚合物泡沫的表征，对影响泡沫形貌和密度的因素，如聚合物/溶剂体系，冷却速率等进行了研究，结果表明：所用溶剂对于该聚合物的Θ温度（溶剂与聚合物作用力为零的温度）必须高于该溶剂的熔点；采用单轴冷却方式可以减小由于溶液中心处和外围处的温差而引起的热应力对泡沫形貌的影响，冷却速率为100℃/min。     

卤素掺杂PMP低密度泡沫材料的研制

在ICF实验研究中，聚4-甲基-1-戊烯（PMP）因只包含C、H两种元素，且泡沫容易加工成型，因而在ICF物理实验中得到了广泛的应用。近年来随着强激光技术的发展，在实验室中利用激光与黑腔靶耦合产生的辐射场开展辐射输运实验研究已成为可能。在辐射输运过程中，输运介质的性质影响着辐射传输的过程。若在腔内泡沫材料中掺入一定量的中、高原子序数亿l介质可以在输运介质热容量变化不大的同时大为降低泡沫中的Rosseland平均自由程，从而提高其辐射传输光学厚度。因此，进行掺杂聚合物低密度泡沫材料的研制具有重要的意义。本年度主要开展了卤素掺杂PMP低密度泡沫材料的研制工作，六氯苯和六溴苯具备溶剂（均四甲苯／萘）的良好相溶性及较高的卤素原子含量，以六氯苯和六溴苯为掺杂单体，PMP为泡沫骨架材料，利用热诱导倒相法制备出最大质量分数为58．91％的卤素掺杂低密度泡沫材料。     

PMP/Cu泡沫材料中Cu颗粒的三维分布

为观测和分析铜掺杂聚-4-甲基-1-戊烯(PMP/Cu)低密度泡沫材料中铜颗粒的三维空间分布,采用高分辨X射线断层扫描技术,扫描PMP/Cu泡沫材料样品,对铜颗粒在聚合物泡沫中的分布进行了成像分析。经过图像处理和三维重构,获得铜颗粒在PMP聚合物泡沫中的三维立体分布图。结果分析显示:铜纳米粒子在PMP泡沫中存在团聚现象;不同尺寸的团聚物形态呈现出明显的多样化特征,小颗粒团聚物趋于球形,大颗粒团聚物趋于不规则的短木棒状,与在电子显微镜下直接观测到的结果一致。研究表明,该技术可以在不破坏样品的前提下,实现对有机聚合物泡沫材料中掺杂金属颗粒空间分布情况的直接观测。     

掺杂丙烯酸酯单体合成及泡沫制备技术

 通过丙烯酸、2-甲基丙烯酸、巴豆酸与五氯苯酚的酯化反应实现了3种丙烯酸酯单体的掺杂改性合成,采用核磁共振和质谱测试技术对掺杂丙烯酸酯单体进行了表征。利用掺杂改性后的丙烯酸单体与季戊四醇四丙烯酸酯之间的共聚反应,结合超临界萃取技术,制备出理论密度为50 mg·cm^-3、掺杂氯元素质量百分数平均值最高约为15%的掺杂丙烯酸酯聚合物泡沫。通过测定聚合物凝胶速率,初步探讨了掺杂丙烯酸酯单体与多元丙烯酸酯单体的共聚合反应机理。     

Hydrogen loading for fiber grating writing with a femtosecond laser and a phase mask

The threshold for the fabrication of fiber Bragg gratings with ultrafast 800-nm radiation and a phase mask was studied in SMF-28 and all-silica core fiber by use of 125-fs pulses. High-pressure molecular hydrogen loading (H2 loading) was observed to significantly lower the grating writing threshold in standard Ge-doped telecommunication fiber. No reduction was observed with all-silica core fiber. The index change appeared to be confined to the Ge-doped core region of the fiber. Gratings in H2-loaded SMF-28 had thermal annealing behavior similar to UV-induced gratings. Unlike UV-induced H2-loaded gratings, no absorption associated with Ge-OH defect formation was observed.     

Comparison of thermoluminescence energy response of optical fiber subject to photon irradiation between Monte Carlo simulation and experiments

This study is focused on energy response of Ge-doped silicon dioxide optical fiber subjected to photon irradiation. The TL responses for photon energies, ranging from 20 keV to 20MeV, were investigated as energy absorbed in the TL materials of Ge-doped silicon dioxide optical fiber. The simulation was performed using Monte Carlo N-particle transport code version 5 (MCNP5). The input parameters included in this study are source information, geometry specification, material information and tallies F6. Comparisons of energy response were done between simulation and previous results of experiments. A flat response can only be seen in the energy range of 200 keV to 10 MeV.     

Density functional investigation of structural, electronic and optical properties of Ge-doped ZnO

Recent experiments reported fascinating phenomenon of photoluminescence (PL) blueshift in Ge-doped ZnO. To understand it, we examined the structural, electronic and optical properties of Ge-doped ZnO (ZnO:Ge) systematically by means of density functional theory calculations. Our results show that Ge atoms tend to cluster in heavily doped ZnO. Ge clusters can limit the conductivity of doped ZnO but reinforce the near-band-edge emission. The substitutional Ge for Zn leads to Fermi level pinning in the conduction band, which indicates Ge-doped ZnO is of n-type conductivity character. It is found that the delocalized Ge 4s states hybridize with conduction band bottom, and is dominant in the region near the Fermi level, suggesting that Ge-4s states provides major free carriers in ZnO:Ge crystal. The observed blueshift of PL in Ge-doped ZnO originates from the electron transition energy from the valence band to the empty levels above Fermi level larger than the gap of undoped ZnO. The electron transition between the gap states induced by oxygen vacancy and conduction band minimum may be the origin of the new PL peak at 590 nm.     

掺Ge锐钛矿相TiO_2光学性质的计算

合理的掺杂是改善TiO_2活性,使其光催化性能在可见光照射下发挥作用的最有效途径之一,本文利用基于密度泛函理论的第一原理全电势线性缀加平面波方法计算掺Ge锐钛矿相TiO_2介电函数的实部、虚部和光学吸收系数.计算结果显示掺Ge锐钛矿相TiO_2介电函数虚部谱发生蓝移,与实验趋势相符;通过不用剪刀算符和固定晶格常数两方案研究掺Ge前后光谱的平移,得到蓝移是由于Ge原子替代Ti原子后晶胞体积减小造成.     

Morphology and Pore Size Distribution of Biocompatible Interconnected Porous Poly(L-lactic acid) Foams with Nanofibrous Structure Prepared by Thermally Induced Liquid–Liquid Phase Separation

Biocompatible, highly interconnected microporous poly(L-lactic acid) (PLLA) foams with nanofibrous structure, containing pores with average diameter below 1 μm and fibers with diameters of 10² nm scale, were prepared through the thermally induced liquid–liquid phase separation (TIPS) method consisting of quenching of the PLLA solution, freeze extraction with ethanol, and vacuum drying. Diverse foam morphologies were obtained by systematically changing parameters involved in the TIPS process, such as polymer concentration, solvent composition, and quenching temperatures. The morphology of different foams was examined by scanning electron microscopy to characterize the pore size and the pore size distribution. The results showed that most porous foams had a nanofibrous structure with interconnected open pores. In the case of using tetrahydrofuran (THF) as solvent, the higher the PLLA concentration, the smaller the average pore diameter and the narrower the pore size distribution. In the case of using the mixed solvents of THF/DOX (1,4-dioxane) with higher than 6/4 volume ratio, there appeared a maximum value of average pore diameter and a widest pore size distribution at 0.09 g/mL PLLA concentration. The average pore diameter of the foams increased with increasing DOX content in the mixed solvent and ranged from 0.2 to 0.9 μm depending on the process parameters. When the DOX content reached 60% by volume, the morphology of the foams contained some large closed pores with diameter ranging from 1 to 10 μm. By decreasing the quenching temperature, the average pore diameter of foams decreased and the pore size distribution became narrower. All the pore size distribution fit F-distribution equations.     

Effects of Ge doping on the properties of Sb2Te3 phase-change thin films

Ge-doped Sb₂Te₃ films were prepared by magnetron sputtering of Ge and Sb₂Te₃ targets on SiO₂/Si (1 0 0) substrates. The effect of Ge doping on the structure was studied in details by X-ray diffraction, differential scanning calorimetry, and X-ray photoelectron spectroscopy measurements. It is indicated that Ge atoms substitute for Sb/Te in lattice sites and form Ge-Te bonds, moreover, a metastable phase was observed in Ge-doped specimens. Both crystallization temperature and resistivity of amorphous Sb₂Te₃ increase after Ge doping, which are beneficial for improving room temperature stability of the amorphous state and reducing the SET current of chalcogenide random access memory.     

Ultraviolet photosensitive response in an antimony-doped optical fiber

A silica optical fiber doped with Sb is fabricated with a refractive-index profile that is comparable with standard single-mode fiber. In D(2)-loaded samples, we observe UV photosensitivity with an initial refractive-index-modulation growth rate six times higher than that of the equivalent Ge-doped standard fibers. Enhanced temperature stability of the Bragg grating strength up to 200 degrees C is also observed. Grating growth kinetics in the Sb-doped fiber is compared with those of other Ge-doped photosensitive fibers.     

A DFT study of 5-fluorouracil adsorption on the pure and doped BN nanotubes

The electronic and adsorption properties of the pristine, Al-, Ga-, and Ge-doped BN nanotubes interacted with 5-fluorouracil molecule (5-FU) were theoretically investigated in the gas phase using the B3LYP density functional theory (DFT) calculations. It was found that the adsorption behavior of 5FU molecule on the pristine (8, 0) and (5, 5) BNNTs are electrostatic in nature. In contrast, the 5FU molecule (O-side) implies strong adsorption on the metal-doped BNNTs. Our results indicate that the Ga-doped presents high sensitivity and strong adsorption with the 5-FU molecule than the Al- and Ge-doped BNNTs. Therefore, it can be introduced as a carrier for drug delivery applications.     

The Origin of Phase Transition and the Usual Evolutions of the Unit-Cell Constants of the NASICON Structures of the Solid Solution LiTi2 – xGex(PO4)3

Physics of the Solid State - Ge-doped LiTi2(PO4)3 has been synthesized by a conventional solid-state reaction. Compounds LiM$$_{2}^{{{\text{IV}}}}$$(PO4)3 with LTP-type structure present a...     

Search for new transparent conductors: Effect of Ge doping on the conductivity of Ga2O3, In2O3 and Ga1.4In0.6O3

Only a small amount (≤3.5 mol%) of Ge can be doped in Ga₂O₃, Ga_1.4In_0.6O₃ and In₂O₃ by means of solid state reactions at 1400 °C. All these samples are optically transparent in the visible range, but Ge-doped Ga₂O₃ and Ga_1.4In_0.6O₃ are insulating. Only Ge-doped In₂O₃ exhibits a significant decrease in resistivity, the resistivity decreasing further on thermal quenching and H₂ reduction. The resistivity of 2.7% Ge-doped In₂O₃ after H₂ reduction shows a metallic behavior, and a resistivity of ～1 mΩ cm at room temperature, comparable to that of Sn-doped In₂O₃.