茂金属支化及线性聚乙烯结晶行为的软物质特征

本论文以茂金属支化及线性聚乙烯为研究对象，系统的研究了共聚物体系结晶序列长度的多分散性以及动力学效应控制的聚合物结晶有序化过程：以茂金属支化聚乙烯为研究对象，提出了结晶序列长度多分散性的概念，并建立了一整套以热分级技术为基础的定量表征结晶序列长度多分散性的方法。从这一概念出发成功的解释了支化聚乙烯等温结晶后的双重熔融峰现象，不同长度的结晶序列在等温结晶过程中形成折叠链和捆束状晶体，它们具有不同的热力学稳定性，升温过程中形成熔融双峰。不仅如此，结晶序列长度多分散性的概念被成功的应用到聚丙烯体系，为监测和表征双向拉伸聚丙烯（BOPP）微观结构提供了新的研究方法和指标。对两个极端序列长度体系结晶行为的研究表明，聚合物结晶是能量效应、墒效应和动力学效应共同作用的结果。对短结晶序列在受限环境下的结晶熔融行为的研究证明除结晶完善过程外还存在非晶区嫡减的过程；线性聚乙烯在超薄膜条件下，结晶初始成核受到抑制，结晶从较厚的部分开始，超薄膜中的分子通过扩散过程在已经结晶的表面成核结晶，分子扩散过程成为结晶速率控制步骤，得到典型的支化晶体；分子在结晶前沿的吸附与解吸附过程是能量效应的体现，决定支化结晶的特征宽度，结晶温度越高，解吸附概率越大，结晶越宽，反之亦然；分子链在晶体中沿b轴倾斜约350，使得在生长面与基板成锐角的一侧分子的构象受到限制，导致结晶速率降低，结晶生长速度的不对称导致结晶形态的不对称。

对称取代烷基聚硅烷的软物质特性

本论文以聚二己基硅烷和聚二丁基硅烷两种对称取代烷基聚硅烷为研究对象，深入系统地研究了它们的软物质特性，调控了超薄膜中分子链的取向，考察了与之相应的光电各向异性，探索了聚硅烷这种非碳主链高分子功能材料使用的可能性。聚硅烷分子的化学环境的微弱变化对它们的链构象、相结构和相形态产生了巨大影响。在结晶相中，聚二己基硅烷的分子链为全反式构象，而聚二丁基硅烷则为7／3螺旋构象；聚二己基硅烷在室温下形成结晶相和液晶相周期性排列的片层结构，在相变过程中可以观察到明显的纳米结构和形态变化，而聚二丁基硅烷的结晶相则形成非周期结构，在相变过程中保持不变。通过改变两种样品的物理环境，实现了超薄膜的软有序化，既可以使分子链在基板上呈面外垂直取向，也可呈面内取向。利用软物质的墒效应，调控了聚二己基硅烷超薄膜中分子链的面外垂直取向和面内取向，分别获得了flat-on和edge-on片晶。通过控制高分子自组织的动力学过程，调节了聚二丁基硅烷的分子链构象，使之从7／3螺旋构象转变为全反式构象，同时得到了高有序的超薄膜及具有正交和六方晶体结构的单晶。利用紫外一可见吸收光谱，验证了分子链的有序排列导致的各向异性。

Ring-shaped morphology in H-shaped block copolymer thin films

The formation of ring-shaped structures in an H-shaped block copolymer [a poly(ethylene glycol) backbone with polystyrene branches, i.e., (PS)(2)PEG(PS)(2)] thin film was investigated when it was annealed in saturated PEG-selective acetonitrile vapor. Our results clearly indicate that ring formation is determined by the initial morphology of the spin-coated film, the solvent vapor selectivity and the environmental temperature of the solvent-annealing process. Only the films with the initial core-shell cylindrical structure in strongly PEG-selective acetonitrile vapor could form the ring-shaped structures.

Investigation of the dewetting inhibition mechanism of thin polymer films

The mechanism of inhibition of polymer film dewetting is investigated by adding a star comb-like polymer, four-arm P(S-ran-VB-g-PMMA), to PS film and PMMA film on different substrates. It is found that the mechanism of inhibition of polymer film dewetting is kinetic in nature, and is related to the miscibility between the additional compound and the polymer film. On addition to the miscible system [four-arm P(S-ran-VB-g-PMMA) and PMMA], the star comb-like polymers can increase the resistant force of dewetting with hole growth and inhibit the dewetting process of the thin polymer film by enrichment in the rim.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).

Counterion exchange at the surface of polyelectrolyte multilayer film for wettability modulation

Counterions present at the surface of polyelectrolyte multilayers (PEMs) were utilized for modulation of surface wettability via ion exchange. The PEM film was dipped in aqueous solutions of different anions, respectively, and the water contact angle of the surface varied from about 10 degrees to 120 degrees, depending on the hydration characteristics of the anion. The ion exchange mechanism was verified by X-ray photoelectron spectroscopy. The process was rapid and reversible. Ionic strength of the polyelectrolyte solution used for preparing the PEMs was found to be crucial to the surface wetting properties and the reversibility and kinetics of the process, and the effects were correlated to the surface density of the excess charge and counterion. This work provides a general, facile and rapid approach of surface property modulation.

A stable PEO-tethered PDMS surface having controllable wetting property by a swelling-deswelling process

A PEO-tethered layer on a PDMS (polydimethylsiloxane) cross-linked network has been prepared by a swelling-deswelling process. During swelling, the PDMS block of a PDMS-b-PEO diblock copolymer penetrates into the PDMS substrate and interacts with PDMS chains because of the van der Waals force and hydrophobic interaction between them. Upon deswelling, the PDMS block is trapped in the PDMS matrix while the PEO, as a hydrophilic block, is tethered to the surface. The PEO-tethered layer showed stability when treated in water for 16 h. The surface fraction of PEO and the wetting property of the PEO-tethered PDMS surface can be controlled by the cross linking density of the PDMS matrix. A patterned PEO-tethered layer on a PDMS network was also created by microcontact printing and water condensation figures (CFs) were used to study the patterned surface with different wetting properties.

Nanometer scale mechanical study on well defined nanostructured chain aggregation of polyethylene

Two kinds of polyethylene chain aggregation with chain axis perpendicular and parallel to the supported substrate were designed and successfully obtained from melt under an electric field and by melt-drawn method

Effects of animal-plant protein ratio in extruded and expanded diets on nitrogen and energy budgets of juvenile Chinese soft-shelled turtle (Pelodiscus sinensis Wiegmann)

In this study, we investigated the effects of animal-plant protein ratio in extruded and expanded diets on nutrient digestibility, nitrogen and energy budgets of juvenile soft-shelled turtle (Pelodiscus sinensis). Four extruded and expanded feeds (diets 1-4) were formulated with different animal-plant protein ratios (diet 1, 1.50:1; diet 2, 2.95:1; diet 3, 4.92:1; diet 4, 7.29:1). The apparent digestibility coefficients (ADCs) of dry matter and crude lipid for diet 1 were significantly lower than those for diets 2-4. There was no significant difference in crude protein digestibility among diets 1-4. The ADC of carbohydrate was significantly increased with the increase in animal-plant protein. Although nitrogen intake rate, faecal nitrogen loss rate and excretory nitrogen loss rate of turtles fed diet 1 were significantly higher than those fed diets 2-4, nitrogen retention rate, net protein utilization and biological value of protein in these turtles were significantly lower than those fed diets 2-4. In addition, energy intake rate, excretory energy loss rate and heat production rate of turtles fed diet 1 were also significantly higher than those fed diets 2-4. Faecal energy loss was significantly reduced with the increase in the animal-plant protein ratio. The ADC of energy and assimilation efficiency of energy significantly increased with a higher animal-plant protein ratio. The growth efficiency of energy in the group fed diet 1 was significantly lower than those in the groups fed diets 2-4. Together, our results suggest that the optimum animal-plant protein ratio in extruded and expanded diets is around 3:1.

Evidence of ultrafast energy exchange-induced soft'mode of phonons and lattice instability: a nanotime effect

With a series of supportive experimental phenomena as induced by ion beam bombardment, energetic beaminduced athermal activation process in Si is demonstrated. This is correlated with phenomena induced by ultrafast energy exchange in condensed matter in general. A critical modelling is presented on the above process and a universal concept: the ultrafast energy exchange-induced soft mode of phonons and the lattice instability in condensed matter are proposed.

Circumstantial Evidence for a Soft Nuclear Symmetry Energy at Suprasaturation Densities

Within an isospin- and momentum-dependent hadronic transport model, it is shown that the recent FOPI data on the pi(-)/pi(+) ratio in central heavy-ion collisions at SIS/GSI energies [Willy Reisdorf , Nucl. Phys. A 781, 459 (2007)] provide circumstantial evidence suggesting a rather soft nuclear symmetry energy E-sym(rho) at rho >= 2 rho(0) compared to the Akmal-Pandharipande-Ravenhall prediction. Some astrophysical implications and the need for further experimental confirmations are discussed.

Nuclear matter at a HIRFL-CSR energy regime

We report some recent progress in constraining the symmetry energy E-sym(rho) at high densities using high-energy heavy-ion collisions. Circumstantial evidence of a soft E-sym(rho) at supra-saturation density is obtained by comparing the pion ratio pi(-)/pi(+) measured recently with FOPI at GSI and the IBUU04 model calculations. Detailed studies indicate that the power of determining the E-sym(rho)from pi(-)/pi(+) is enhanced with decreasing the beam energy to near the pion production threshold, showing a correlation to the increasing nuclear stopping. Among several heavy-ion reaction facilities in the world, the cooling storage ring (HIRFL-CSR), newly commissioned at Lanzhou, delivering heavy-ion beams up to 1 A GeV, to be coupled with advanced detectors will contribute significantly to further studies of the equation of state of asymmetric nuclear matter.

Recent Progress in Constraining the Equation of State of Dense Neutron-Rich Nuclear Matter with Heavy-Ion Reactions

The nuclear symmetry energy E-sym(rho) is the most uncertain part of the Equation of State (EOS) of dense neutron-rich nuclear matter. In this talk, we discuss the underlying physics responsible for the uncertain E-sym(rho) especially at supra-saturation densities, the circumstantial evidence for a super-soft E-sym(rho) from analyzing pi(-)/pi(+) ratio in relativistic heavy-ion collisions and its impacts on astrophysics and cosmology.

Preparation, patterning and luminescent properties of oxyapatite La-9.33(SiO6)(4)O-2 : A (A = Eu3+, Tb3+, Ce3+) phosphor films by sol-gel soft lithography

Silicate oxyapatite La-9.33 (SiO6)(4)O-2:A (A = Eu3+, Tb3+ and/or Ce3+) phosphor films and their patterning were fabricated by a sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, atomic force microscopy, optical microscopy and photoluminescence spectra, as well as lifetimes, were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800degreesC and the crystallinity increased with the increase in annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of rodlike grains with a size between 150 and 210 nm. Patterned thin films with different bandwidths (20, 50 mum) were obtained by the micromoulding in capillaries technique. The doped rare earth ions (Eu3+, Tb3+ and Ce3+) showed their characteristic emission in crystalline La-9.33(SiO6)(4)O-2 phosphor films, i.e. Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4), Tb3+ D-5(3,4)-F-7(J) (J = 3, 4, 5, 6) and Ce3+ 5d (D-2)-4f (F-2(2/5), F-2(2/7)) emissions, respectively. Both the lifetimes and PL intensity of the Eu3+, Tb3+ ions increased with increasing annealing temperature from 800 to 1100 degreesC, and the optimum concentrations for Eu3+, Tb3+ were determined to be 9 and 7 mol% of La3+ in La-9.33(SiO6)(4)O-2 films, respectively. An energy transfer from Ce3+ to Tb3+ was observed in the La-9.33(SiO6)(4)O-2:Ce, Tb phosphor films, and the energy transfer efficiency was estimated as a function of Tb3+ concentration.