Diffractive microlens with a cascade focal plane fabricated by single mask UV-photolithography and common KOH:H2O etching

A diffractive microlens with a cascade focal plane along the main optical axis of the device is fabricated using a low-cost technique mainly including single mask ultraviolet (UV) photolithography and dual-step KOH:H2O etching. Based on the evolutionary behavior of converse pyramid-shaped microholes (CPSMs) preshaped over a {100}-oriented silicon wafer in KOH etchant, the first-step KOH etching is performed to transfer initial square micro-openings in a SiO2 film grown by plasma enhanced chemical vapor deposition (PECVD) and patterned by single mask UV-photolithography, into CPSMs with needed dimension. After completely removing a thinned SiO2 mask, basic annular phase steps with a relatively steep sidewall and scheduled height can be shaped in the overlapped etching region between the neighboring silicon concave-arc microstructures evolved from CPSMs through the second-step KOH etching. Morphological measurements demonstrate a desirable surface of the silicon microlens with a roughness in nanometer scale and the feature height of the phase steps formed in the submicrometer range. Conventional optics measurements of the plastic diffractive microlens obtained by further hot embossing the fine microrelief phase map over the nickel mask made through a common electrochemical method indicate a highly efficient cascaded focusing performance.

青藏高原东缘川西云杉林皆伐后灌木生长、繁殖与更新的研究

植物群落及其环境在干扰后的演替格局和过程的研究，是群落和生态系统动态研究的一个热点。选取青藏高原东缘山原区川西云杉林皆伐后，从草地过渡到灌丛的关键阶段的4 个皆伐迹地（恢复时间为8 a、10 a、16 a 和21 a），研究皆伐及自然恢复过程对林下典型灌木银露梅（Potentilla glabra）和唐古特忍冬（Lonicera tangutica）的生长与繁殖能力的影响以及灌木植物在迹地上的更新情况，分析灌木在不同生境中的适应对策和适应能力的差异,为揭示青藏高原东缘山原区迹地植被从草甸到灌丛演替的过程和特点及促进迹地演替与植被恢复进程提供理论依据和技术支撑。研究主要结论如下：1）皆伐后银露梅生长和繁殖能力显著提高，但对唐古特忍冬的影响不明显。皆伐后银露梅丛基径、高度和各部分生物量都显著增加（P < 0.05），但唐古特忍冬只有叶生物量和地下生物量增加，总生物量和其余构件生物量无显著变化。皆伐后，银露梅的结实数量、结实株数、不结实株数和结实株/不结实株比例显著增加（P < 0.05）。自然恢复过程中，银露梅和唐古特忍冬生长能力以及银露梅的结实量都表现出降低的趋势。随着迹地自然恢复时间的增加，银露梅和唐古特忍冬的基径、高度、丛叶片数和各部分生物量有减少的趋势。银露梅的结实株数增加, 但结实数量减少。2）皆伐对银露梅和唐古特忍冬生物量分配模式影响不一致。原始林和迹地中（除CT85）银露梅的生物量大小关系皆为：地下>茎>侧枝>叶。唐古特忍冬在原始林中的生物量大小关系为：茎＞地下部分＞侧枝＞叶,而皆伐后生物量的分配情况改变，生物量大小关系变为：地下部分＞茎＞侧枝＞叶。随着自然恢复时间的增加，银露梅减少了地下生物量的分配，而唐古特忍冬增加了地下生物量的分配。3）皆伐和恢复时间的增加改变了迹地物种组成，促使阳性乔、灌木在迹地上定居。4 个迹地上共出现了灌木15 种，乔木3 种，没有出现天然云杉和冷杉幼苗。随着恢复时间的增加，迹地上的灌木物种由原始林下的耐阴物种逐步发展为以针刺悬钩子（Rubus pungens）为主的阳性灌木。4）影响灌木幼苗密度和幼树密度的因子不一致。灌木幼苗密度与灌木层盖度显著负相关，与苔藓层盖度显著正相关。幼树密度与草本层盖度正相关，与苔藓层盖度、灌木层盖度和高度负相关。5）研究发现在青藏高原东缘山原区皆伐15～20 a 后，迹地仍以草本植物为主，推测皆伐后至少20 a 以上迹地才可能向灌丛阶段过渡，比高山峡谷地区的演替进程至少推迟了20 a。银露梅和唐古特忍冬在皆伐后自然恢复过程中表现出不同的生长与繁殖策略是由两个物种的生物学特性的差异引起的。银露梅比唐古特忍冬更适应迹地退化环境。促进青藏高原东缘山原林区迹地森林恢复一方面是尽量减少人为活动的破坏，另一方面，可以通过在迹地中播种适当的乡土乔、灌木种子（如白桦、银露梅）等人工措施，以加快演替进程。The succession pattern and process of plant community and their environments is a hot spotin community and ecosystem dynamic study. Four clearcuts were chosen in Rangtang(recovery time of 8 a、10 a、16 a and 21 a), which represented the key stage of thecommunity evolved from grass stage to shrub stage in the eastern margin of theQinghai-Tibetan Plateau. The growth and reproduction of the Potentilla glabra andLonicera tangutica and the natural regeneration of shrub plants in the primary Piceabalfouriana forest and 4 clearcuts were studied to explore how clear cutting andnatural recovery process affected the understory shrub species during the 21 years inthe eastern margin of the Qinghai-Tibetan Plateau. The main results were below.1) The growth and reproduction of P. glabra significantly increased after forestclear cutting.. But it was not so significant as to the L. tangutica. The organismbiomass and total biomass of P. glabra were increased obviously after clear cutting（P< 0.05）. But only leaves and underground biomass of L. tangutica increasedsignificantly after clear cutting（P < 0.05）. The number of fruit and growth of P. glabraincreased significantly after clear cutting too（P < 0.05）. The ramet height, basaldiameter , organism biomass and friut number of P. glabra and L. tangutica reducedas the increase of recovery time.2) The biomass allocation patterns varied between P. glabra and L. tangutica inthe primary forest and clearcuts. The biomass allocation of P. glabra both in primary forest and clearcuts was followed as: underground part > stem > branch > leaves.However, the biomass allocation of L. tangutica had changed after the clear cutting.The biomass allocation of L. tangutica in the primary forest was followed as: stem >underground part > branch > leaves and it was underground part > stem > branch >leave in clearcuts. The biomass allocation of P. glabra and L. tangutica varied amongclearcuts. Aboveground biomass was increased while underground biomass decreasedfor P. glabra with the increase of recovery period. However, the L. tangutica showedthe reverse changing pattern.3) Clear cutting and recovery time had changed the species composition of theclearcuts. There were 15.shruby species and 3 tree species in the four clearcuts. Nospruce and fir seedlings were found. In the early stage after clear cutting, there wereonly understory shrub species from the primary Picea balfouriana forest. The sunnyspecies, especieally Rubus pungens invaded intensly as the increase of recovery time.4) There was a significant negative relationship between density of seedlingswith shrub layer coverage and positive correlation with moss coverage. The saplingshad significantly positive correlation with herb layer coverage and negativecorrelation with moss coverage, shrub layer coverage and height.5）Comparing to studies in Miyalou, a nearby high mountain and canyon area,the secondary sucession in this subalpine plateau areas lagged at least 20 years.P. glabra and L. tangutica showed different growth and reproduction strategies toclear cutting and natural recovery , which may associated with the difference of theirbiological characters. P. glabra was more adaptive to the clear cutting than the L.tangutica. Two suggestions were probably recommended to promote the recoveryprogress in the subalpine plateau areas based on the results of this study. Limitanthropogenic disturbance, and meanwhile sow native tree and shrub seeds inclearcuts.

若尔盖自然保护区高原林蛙(Rana kukunoris)扩散模型与景观连接分析

揭示水体中繁殖的两栖动物在异质性景观中的空间扩散特点，探讨景观面积丧失和破碎化对于两栖动物的影响，为两栖动物的保护提供理论依据。本文以四川西北部若尔盖湿地自然保护区的高原林蛙(Rana kukunoris)为研究对象，通过运用地理信息系统及建立景观模型等方法，在分析若尔盖湿地自然保护区范围内现有景观格局的基础上，建立了高原林蛙的景观扩散模型，并模拟了“沼泽→草甸”的湿地逆演化过程下高原林蛙的空间分布与景观连接的变化特点。主要结果是： 1．若尔盖湿地自然保护区呈典型的沼泽—草甸式斑块—基质景观格局。草甸面积占整个景观面积的79.42%，景观蔓延度指数（CONTAG）为79.00远离最小值0而更趋向于最大值100，面积和景观蔓延度指数表明草甸是整个景观中面积占绝对优势且景观连接好的类型，构成了景观的基质，对景观的动态格局演变起主导作用。沼泽面积仅占整个景观面积的18.08%，但却是整个景观中斑块数目最多的单元，占所有斑块数的82.9%。因此沼泽斑块与草甸基质之间的动态结构对高原林蛙的扩散起着决定性的作用。 2．空间扩散模型表明，其它类型的景观不但扩展了高原林蛙的活动范围，而且也为高原林蛙在不同沼泽斑块间的连接提供了通道。高原林蛙的空间扩散区域使得彼此间成斑块化隔离状分布的沼泽形成了潜在景观功能连接，促进了不同斑块间物种的交流。小型沼泽作为垫脚石（stepping-stone），使得整个景观中的相隔距离较远的大型斑块联结为一个功能整体，促进了高原林蛙在整个景观中的相互动态联系。 3．模拟“沼泽→草甸”的湿地逆演化过程表明，大量小型沼泽湿地的消失将会 对在沼泽中繁殖并扩散到其它景观类型中去的高原林蛙造成潜在影响。逆演化过程不仅使沼泽斑块的分布范围，沼泽源斑块的面积和空间扩散面积减少，而且对景观连接也有很大影响。小型沼泽的消失，将使得景观斑块的功能连接变小，使得依靠小型沼泽作为跳板的动物在沼泽斑块之间的移动将变得更加困难。 本文是对生境丧失与破碎化影响下两栖动物的行为反应的一种尝试。影响模型的因素很多，包括动物对各种类型景观的偏好程度，地理数据的精度，及模型的可靠程度都是制约模型准确度的因素。 The spatial diffusion of water—breeding amphibian through heterogeneous landscape and the effects of landscape losing and fragmentation to amphibian were the core theory of the landscape ecology of amphibian. Geographical information system (GIS) and landscape model were used to model the diffused area of Rana kukunoris in Zoige Wetland Natural Reserve. Model was also used to analysis the spatial distribution variation of R. kukunoris and the change of landscape connectivity when simulated the retrogressive succession of landscape. The main results are below: 1. There was peatland—meadow pattern which was typical patch—matrix landscape pattern in Zoige Natural Reserve. The meadow area occupied 79.42% of the entire landscape area, contagion index (CONTAG) was 79.00 which was far away the minimum value (0) but tend to the maximum value (100). Both of these showed that meadow was the largest part and the most continue units. It was shown that meadow was matrix of the landscape, which evolved the leading role to the landscape dynamic pattern. Though their area only occupies 18.08% of entire landscape area, peatlands were according to 82.9% of the total patches. Dynamic of the pattern between peatlands and meadows decided the spatial diffusion of R. kukunoris. 2．The model indicated that the other types of landscape not only expanded diffusion of R. kukunoris, but also have provided the potential channels for frog's connections among different peatlands. The spatial diffusion zone of R. kukunoris forced isolated patch peatlands to be potential landscape functional connectivity. The small peatlands, as stepping-stone, made the large peatlands connect as a functional one and promoted the integrated and dynamic connectivity of R. kukunoris in the whole landscape. 3. The simulation of “peatlands→meadows”retrogressive succession process indicated that the decrease of small peatlands will have potential effect to R. kukunoris because they must bred in peatlands and diffuse to other type of the landscape. Retrogressive succession process not only made the decrease of distribution of peatlands, patches number of peatlands and diffused area of R. kukunoris, but also reduced the connectivity among source patches. As stepping-stone, the disappearance of small peatlands will made the migration of R. kukunoris among patches more difficult. The model was an experiment of the amphibian behavior reaction to habitat losing and fragmentation. There were many factors that could influence the accuracy of model, such as the preference of animals to each type of landscape, the geographical data precision, reliable degree of model.

香港地区湍蛙遗传多样性研究

依据线粒体上ND2和CO1两个变异较大的基因序列分析了香港地区香港湍蛙7种群、华南湍蛙1种群，以及大陆其他地区华南湍蛙7种群，戴云湍蛙1种群，武夷湍蛙1种群的系统发育关系，进而探讨香港湍蛙的遗传多样性、香港湍蛙特有性、如何确定香港湍蛙最佳保护单元以及这四种湍蛙的物种分类地位。 1． 香港湍蛙保护遗传学研究 香港湍蛙核苷酸传多样性较低，从其遗传多样性信息、单倍型网络分析、中性检验值以及岐点分布结果一致显示香港湍蛙很可能经历了瓶颈后的扩张，种群正在由一个较小的有效种群大小迅速增长, 有足够的时间通过变异用于积累单倍型的多态性, 而对于提高核苷酸多样化而言, 时间尚短（Nei M et al，1975，Avise J C，2000；李明等，2003）。 分子变异分析结果显示香港湍蛙种群间存在较多的基因交流，且系统发育树上各种群间交叉在一起，没有形成与地理单元相关的分支，而从其单倍型网络看，他们源于共同的祖先，是一个单系群，与地理单元间没有形成显著的遗传分化。因此应作为一个进化显著单元（ESU）。结合其与其他湍蛙发育关系及遗传距离以及野外采集信息认为香港湍蛙只在香港地区有分布，属于香港特有种。该物种内遗传多样性较低，又属于世界自然保护联盟红皮书中的近危种，同时也是《野生动物保护条例》中的受保护野生动物，且由于香港城市建设等使得其栖息环境受到威胁，因此在香港特别行政区应该受到重点保护。 从单倍型分布和核苷酸多样性可以看出大榄涌种群和城门种群具有较高的单倍型多样性和核苷酸多样性，应该作为保护的重点区域。 2. 华南湍蛙东、南沿海种群间系统关系 华南湍蛙分布广，各种群存在着丰富的遗传多样性信息且中部种群广西龙胜和湖南张家界种群核苷酸多样性明显高于其他边缘种群华南湍蛙。种群间几乎没有基因交流，且各种群间无共享单倍型，可见已形成了显著的遗传分化。各种群间遗传距离都较远，其中广东南昆山种群以及福建三港种群与其他种群距离最远，因此可以推测其他种群（广东深圳、香港大屿山、广西龙胜和防城以及湖南张家界种群）可能为独立进化的种群。但是否是一新种或一隐存种，还需要结合形态学进行更深入的研究。 本研究中无论从系统关系看还是从遗传距离看，大屿山种群与深圳种群最近，支持陈坚峰等将其定为华南湍蛙，即华南湍蛙新增一个分布点：香港大屿山。 系统树上广西防城种群（支B）与龙胜和湖南种群（支A）形成姐妹群。香港大屿山种群与深圳种群先形成姐妹群（支C），但却没有与其距离很近的广东南岭及南昆山种群（支D）形成姐妹群，可能粤北和粤中的环境及气候较复杂因此与粤南其他种群形成了明显的隔离。同时可以看出华南湍蛙种群遗传分化与地理距离没有显著的相关性。 3. 四种湍蛙间的系统关系 根据线粒体CO1基因建立四种湍蛙间的系统关系及其遗传距离，很清楚地看到，香港湍蛙与戴云湍蛙关系很近，而华南湍蛙则与武夷湍蛙较近。然而，戴云湍蛙同一个种群内部共有两个单倍型DY1和DY2，且两个单倍型间遗传距离大于DY1与香港湍蛙间遗传距离，更远远大于香港湍蛙种群内部的距离，即戴云湍蛙内部两个单倍型间遗传距离达到了种级水平，同样在系统发育树上这两个单倍型与香港湍蛙形成并系。但是，戴云湍蛙种内在形态上差异不显著。因此，其是否属于萌芽物种分化形成（budding speciation）或已经完全分化为两个不同的种值得进一步研究？ 与戴云湍蛙香港湍蛙关系类似，从系统树上看华南湍蛙不形成单系，而是分成两个大支，与武夷湍蛙形成并系，且福建和南昆山的华南湍蛙与武夷湍蛙遗传距离远大于武夷湍蛙种内福建种群与浙江种群的遗传距离，达到了种级分化水平。由此，可以推断武夷湍蛙是有效种。系统树上广东深圳、香港大屿山、广西防城和龙胜以及湖南张家界种群与华南湍蛙福建及南昆山各种群间遗传距离已超出了种内各种群间的遗传距离，但是至于这一支是否应为另外一个种，有必要扩大采样，并结合核基因及形态信息进行进一步研究。 MtDNA of ND2 and CO1 gene were used to investigate genetic diversity of Amolops in Hongkong .We collected seven populations of A. hongkongensis,，one population of A.ricketti from Hong Kong and other seven populations of A.ricketti from East and South of Chinese mainland. As well as one population of A. daiyunensis and one population of A.wuyiensis Phylogenetic relationship were analyzed of four species. Discussed whether A.hongkongensis is an endemic species and how can we make the conservation and management decisions. 1. Conservation Genetics of A. hongkongensis A. hongkongensis has a low nucleotide diversity, the results of genetic diversity, haplotype network, neutrality test and the mismatch distributions indicate that A. hongkongensis experienced a recent expansion after a bottle neck. They had enough time to accumulated haplotype diversity, but it’s too short to have a high nucleotide diversity（Nei M et al，1975，Avise J C，2000；Li et al，2003）. The result of AMOVA reveals that it has much gene exchange among the populations of A. hongkongensis. The clades of the phylogenetic tree were mixed together, no significant genetic differentiation among 8 populations and they share the same ancestor from the network analysis, these indicate that they are monophyly and should be protected as one ESU. Combined with the information of relationships of interspecies, genetic distance and distribution investigate, We conclude that A. hongkongensis is an endemic species of Hong Kong. Considering on the status of low genetic diversity in A.hongkongensis, and this species was listed in the IUCN red list as near threatened, as well as listed in the . Furthermore, it’s habitat loss and degradation more rapidly as the human activity got higher and higher. So it’s urgent to protect them in Hong Kong. Our results suggest that Tai Lam Wu and TAI MO Shan -Shing Mun populations have the higher priority to be protected because their higher genetic diversity. 2．Phylogenetic relationships among populations of Amolops ricketti from the Southern and eastern China A. ricketti has the considerable genetic diversity of mitochondrial haplotypes within and among populations, and Mitochondrial DNA diversity was higher in populations at the central area of the present distribution range of the frog，i. e. the Longsheng population and Zhangjiajie population, than at the edges of their distribution range. They have no share haplotype among populations, and have a significant genetic differentiation. Genetic distance is high among the populations, especially the distance of Nankun and Sangang group with others, which suggested that they evolved independently. May be there is a cryptic species or a new species, a further study is needed. The results of gene tree and the genetic distance clearly demonstrate that the population from LanTau island is A. ricketti, so we agree with Chen et al(2005) . That means A.ricketti have a new distribution site: LanTau island, HongKong. Phylogenetic relationships were analyzed through NJ and Mrbayes methods and got a consistent topological structure, the structure indicated that the ingroup were comprised four groups. Populations Longsheng and Zhangjiajie were first clustered as clade A; Populations Fangcheng was clustered together (clade B) as a sister group to clade A；Populations Shenzhen and Lantau island were sister groups and clustered as clade C；Then the clade D included populations Nankunshan and Nanling in Guangdong province and Sangang in Fujian province. 3. Phylogenetic Relationships among these four specises Phylogenetic relationships based on 1503bp CO1 gene and the genetic distance show that A. hongkongensis close to A. daiyunensis whereas A.ricketti near to A.wuyiensis. Nevertheless, there are two haplotypes in A.daiyunensis and the genetic distance between them higher than the distance between DY1 with A. hongkongensis. A. hongkongensis is nested in the paraphyletic ancestral species A. daiyunensis. Without significant difference in the morphological characters, So, we considered both A.daiyunensis and A.hongkongensis are valid species, may be this represents a case of ‘budding speciation’ like Batrachuperus pinchonii(Fu and Zeng,2008) in the population of A. daiyunensis. Just like two species above A. wuyiensis and A. ricketti are not monophyly, instead, A.wuyiensis is nested in the paraphyletic ancestral species A.ricketti. We need do more research to make sure whether they are new species.

Study of He-induced nano-cavities as sinks of oxygen for forming silicon-on-insulator

In the present work, a Cz-Silicon wafer is implanted with helium ions to produce a buried porous layer, and then thermally annealed in a dry oxygen atmosphere to make oxygen transport into the cavities. The formation of the buried oxide layer in the case of internal oxidation (ITOX) of the buried porous layer of cavities in the silicon sample is studied by positron beam annihilation (PBA). The cavities are formed by 15 keV He implantation at a fluence of 2 x 10(16) cm(-2) and followed by thermal annealing at 673 K for 30 min in vacuum. The internal oxidation is carried out at temperatures ranging from 1073 to 1473 K for 2 h in a dry oxygen atmosphere. The layered structures evolved in the silicon are detected by using the PBA and the thicknesses of their layers and nature are also investigated. It is found that rather high temperatures must be chosen to establish a sufficient flux of oxygen into the cavity layer. On the other hand high temperatures lead to coarsening the cavities and removing the cavity layer finally.

Studies on advantages of heavy ions in radiotherapy compared with gamma-rays

Hepatoma and melanoma cells were exposed to C-12(6+) beams generated by HIRFL facility and gamma-rays and the cell response was studied by colony assays as well as the analysis of RBE of carbon ions was evolved. The survival curves of cells irradiated by heavy ions were different from those of cells irradiated by gamma-rays. And two kinds of cell showed the obvious discrepancy in response to the photon and ion irradiation. The results showed that heavy ions have special physical properties and mighty potency to kill cell in both single and fractional irradiation meanwhile it can kill tumor cells with high radioresistance more efficiently. When involved in clinical therapy, heavy ions will enhance the therapy efficiency and decrease the suffering of patients because it can impair the repair for sublethal damage of cells which can lead to fewer irradiation fractions.

The application of spline wavelet transform to the determination of electroosmotic mobility in capillary electrophoresis

The rule of current change was studied during capillary electrophoresis (CE) separation process while the conductivity of the sample solution was different from that of the buffer. Using a quadratic spline wavelet of compact support, the wavelet transforms (WTs) of capillary electrophoretic currents were performed. The time corresponding to the maximum of WT coefficients was chosen as the time of current inflection to calculate electroosmotic mobility. The proposed method was suitable for different CE modes, including capillary zone electrophoresis, nonaqueous CE and micellar electrokinctic chromatography. Compared with the neutral marker method, the relative errors of the developed method for the determination of electroosmotic mobility were all below 2.5%. (C) 2002 Elsevier Science B.V. All rights reserved.

The integration of coastal zone management into national development planning

The broad acceptance and collective commitment of countries to the tasks involved in the implementation of Agenda 21, Chapter 17, have profound implications vis-à-vis the interplay between coastal zone management (CZM) and national development planning (NDP). It appears that in many countries, CZM has evolved in isolation from the mainstream of national development processes. The paper examines various forms and elements for the effective integration of CZM into NDP.

基于非均匀DCT的量化索引调制隐写

基于量化索引调制(QIM)的隐写技术正日益受到隐写分析的威胁。该文将通常在DCT域隐写的做法改为在非均匀DCT域进行,将参数作为密钥,提出了一种NDCT-QIM图像隐写方法。由于在攻击者猜测的域中,嵌入信号具有扩散性,NDCT-QIM方法不利于隐写分析对隐写特征的检测,分析和实验表明,它能够更好地抵御基于梯度能量、直方图及小波统计特征等常用统计量的隐写分析,增强了隐写的隐蔽性。

33轮SHACAL-2的差分非线性攻击

利用SHACAL-2的一个17轮差分非线性区分器,结合被猜测子密钥空间分割的方法和快速傅立叶变换,提出了一种攻击33轮SHACAL-2的新方法.该方法攻击33轮SHACAL-2需要244的选择明文、2496.6的33轮SHACAL-2加密和2502次算术运算,攻击成功概率为99%.与已有的结果相比较,新攻击有效地提高了单密钥下SHACAL-2的攻击轮数.

Crystallization of mechanically alloyed amorphous W-Mg alloy under high pressure

Pure metal powder mixtures of W and Mg at the desired composition were milled in conventional high-energy ball mill, and amorphous alloy W50Mg50 was obtained after milling for 20 h. The structure evolution of elemental powder mixtures was studied following milling and subsequent high pressure and high temperature treatment. The amorphous alloy transform into a nanocrystalline material below 1050 degreesC at 4.0 GPa. On increasing the temperature, it transforms into a mixture of several new crystal phases under high-pressure condition. It also found that both mechanical alloying and high pressure treatment are the two necessary processes to form the nanocrystalline and the new phases.

Inverted to normal phase transition in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films

We have investigated the inverted phase formation and the transition from inverted to normal phase for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer in solution-cast films with thickness about 300 nm during the process of the solution concentrating by slow solvent evaporation. The cast solvent is 1, 1,2,2-tetrachloroethane (Tetra-CE), a good solvent for both blocks but having preferential affinity for the minority PMMA block. During such solution concentrating process, the phase behavior was examined by freeze-drying the samples at different evaporation time, corresponding to at different block copolymer concentrations, phi. As phi increases from similar to 0.1 % (nu/nu), the phase structure evolved from the disordered sphere phase (DS), consisting of random arranged spheres with the majority PS block as I core and the minority PMMA block as a corona, to ordered inverted phases including inverted spheres (IS), inverted cylinders (IC), and inverted hexagonally perforated lamellae (IHPL) with the minority PMMA block comprising the continuum phase, and then to the lamellar (LAM) phase with alternate layers of the two blocks, and finally to the normal cylinder (NC) phase with the majority PS block comprising the continuum phase. The solvent nature and the copolymer solution concentration are shown to be mainly responsible for the inverted phase formation and the phase transition process.

Discrete wavelets transform for signal denoising in capillary electrophoresis with electrochemiluminescence detection

Discrete wavelets transform (DWT). was applied to noise on removal capillary electrophoresis-electrochemiluminescence (CE-ECL) electropherograms. Several typical wavelet transforms, including Haar, Daublets, Coiflets, and Symmlets, were evaluated. Four types of determining threshold methods, fixed form threshold, rigorous Stein's unbiased estimate of risk (rigorous SURE), heuristic SURE and minimax, combined with hard and soft thresholding methods were compared. The denoising study on synthetic signals showed that wave Symmlet 4 with a level decomposition of 5 and the thresholding method of heuristic SURE-hard provide the optimum denoising strategy. Using this strategy, the noise on CE-ECL electropherograms could be removed adequately. Compared with the Savitzky-Golay and Fourier transform denoising methods, DWT is an efficient method for noise removal with a better preservation of the shape of peaks.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

Phase transition and transition kinetics of a thermotropic poly(amide-imide) derived from 70% pyromellitic dianhydride, 30% terephthaloyl chloride, and 1,3-bis[4-(4 '-aminophenoxy)cumyl]benzene

The phase transition and transition kinetics of a liquid crystalline copoly(amide-imide) (PAI37), which was synthesized from 70 mol% pyromellitic dianhydride, 30 mol% terephthaloyl chloride, and 1,3-bis[4-(4'-aminophenoxy)cumyl]benzene, was characterized by differential scanning calorimetry, polarized light microscopy, X-ray diffraction, and rheology. PAI37 exhibits a glass transition temperature at 182 degreesC followed by multiple phase transitions. The crystalline phase starts to melt at similar to 220 degreesC and forms smectic C (S-C) phase. The Sc phase transforms into smectic A (S-A) phase when the temperature is above 237 degreesC. The S-C to S-A transition spans a broad temperature range in which the S-A phase vanishes and forms isotropic melt. The WARD fiber pattern of PAI37 pulled from the anisotropic melt revealed an anomalous chain orientation, which was characterized by its layer normal perpendicular to the fiber direction. The transition kinetics for the mesophase and crystalline phase formation was also studied.