旋流煤粉燃烧的一维综合数值模拟

发展了综合考虑气－固两相旋流流动，气相燃烧，颗粒相变与燃烧及两相辐射传热的旋流煤粉燃烧－维数学模型，给出了气－固两相能量方程中颗粒相就源项的计算表达式，应用这一模型对涡旋燃烧炉环形通道内多组工况的旋流气体燃烧和煤粉燃烧进行了数值模拟，计算得到的炉内温度分布和燃烧效率与实验数据基本相符，表明本文建立的模型可用于旋流煤粉燃烧的一维综合数值模拟。     

接枝共聚法制备聚乙二醇(PEG)/聚乙烯醇(PVA)高分子固-固相变材料性能研究

用接枝共聚法将具有相变特征的聚乙二醇(PEG)接枝到具有较高熔点的聚乙烯醇(PVA)主链上,得到了系列性能稳定的PEG/PVA高分子固-固相转变材料,用DSC,WAXD和POM对其相变行为及形态结构进行了研究.结果表明,该材料呈现出可逆的固-固相转变特性;其结晶峰值温度和相变焓比纯PEG低,接枝率对相变温度和归一化相变焓影响不大;接枝率只影响结晶与熔融行为,不影响结晶结构.     

金属Cu液固转变及晶体生长的分子动力学模拟

采用分子动力学模拟研究了液态Ｃｕ在不同冷却速度下的凝固特点,模拟采用ＥＡＭ作用势,计算了不同温度,不同冷却速度下Ｃｕ的偶相关函数,结果表明ＥＡＭ作用势能很好地描述液态Ｃｕ的结构特征,当冷却速度较快时,液Ｃｕ形成非晶;当冷却速度较慢时,液Ｃｕ形成晶体,分析了不同冷却速度下体系的相变热力学及相变动力学过程,最后采用液固两层构型法,描述了Ｃｕ晶体的生长过程。     

KBF4非等温固-固相变热性质的测定

利用DTA-TG和DSC热分析技术研究了无机塑晶材料KBF4固-固相变的热性能,测得转变温度为284.13℃,转变焓为105.73J/g.KBF4固-固相变的机理是随着温度的升高,晶体中离子键部分断裂,晶体逐渐由低对称的正交晶系向高对称立方晶系转变,并在这过程中,同时引入化学键的振动和转动无序,从而吸收大量的相变焓.     

聚乙二醇/二醋酸纤维素相变材料的组成与储能性能间的关系

以刚性的二醋酸纤维素 (CDA)链为骨架 ,接枝上聚乙二醇 (PEG)柔性链段 ,可得到一种具有固固相变性能的网状储能材料 .利用该材料的PEG支链从结晶态到无定形态间的相转变 ,可以实现储能和释能的目的 .具体研究了PEG的百分含量及PEG的分子量对材料储能性能的影响 .研究结果表明 ,通过改变PEG的百分含量与PEG的分子量 ,可以得到不同相变焓和不同相变温度的材料     

四氯合金属(II)酸烷铵在280-500K间的热力学性质和相变:III.四氯合镉(II)酸n-十二烷铵

在280-500K温度范围内用自动绝热量热计测量了(n-C~1~2H~2~5NH~3)~2CdCl~4的热容。在所研究的温度范围内发现一个固-固相转变, 其相变温度, 相变焓和相变熵分别为(332.4±0.1)K,(48.35±0.33)kJ.mol^-^1和(145.5±1.0)J.K^-^1.mol^-^1。结合已发表的(n-C~1~2H~2~5NH~3)~2MCl~4(M=Mn, Zn)的相变参数讨论了此类配合物的中心原子对其相变的影响。[MCl~4]^2^-配位方式的不同被认为是该类配合物的相变热参数产生差异的主要原因。     

四氯合金属(II)酸烷铵在280-500K间的热力学性质和相变:III.四氯合镉(II)酸n-十二烷铵

在280-500K温度范围内用自动绝热量热计测量了(n-C~1~2H~2~5NH~3)~2CdCl~4的热容。在所研究的温度范围内发现一个固-固相转变, 其相变温度, 相变焓和相变熵分别为(332.4±0.1)K,(48.35±0.33)kJ.mol^-^1和(145.5±1.0)J.K^-^1.mol^-^1。结合已发表的(n-C~1~2H~2~5NH~3)~2MCl~4(M=Mn, Zn)的相变参数讨论了此类配合物的中心原子对其相变的影响。[MCl~4]^2^-配位方式的不同被认为是该类配合物的相变热参数产生差异的主要原因。     

芘为荧光探针研究SDS/H2O二元体系的热相变

以芘作为荧光探针, 对十二烷基硫酸钠(SDS)40 g%的水溶液在-20 ℃～30 ℃温区的相变进行了研究。该二元体系的主要相变是凝聚胶-液晶的转变, 测定其相变温度为20 ℃。自由水形成的冰层在0 ℃融化, 由此导致在化冰前后体系呈现出不同的凝聚胶相。在-17 ℃退火处理, 体系出现了新的凝聚胶相。以上出现的各相均可由I_E/I_M值清楚地表征, 从而首次证实了这种探针方法为一种成功的膜模拟体系相变的研究手段。     

变温红外确定硫氰化铵固-固相变机理(英文)

硫氰化铵分子晶体在固 固转变时 ,能可逆地吸收大量的热。作者利用变温红外光谱确定了其固 固相变机理。结果表明 ,随着温度升高 ,固 固转变时分子晶体内相邻的氢键断裂 ,晶型由低对称转变为高对称并引入振动和转动无序 ,吸收大量热。     

界面诱导相分离和特殊相结构的生成

界面诱导相分离是由界面润湿效应所诱发的共混体系非平衡相变现象.本文评述了相分离体系薄膜在界面作用下所表现出来的相形态、相变动力学、润湿层形成机理以及空间维数受限条件下所呈现出来的特殊相结构等.同时着重介绍了针对此现象进行数值模拟的基于Cahn-Hilliard-Cook方程的理论模型以及相应的模拟研究进展.     

The acquirement of desirable dielectric properties of carbon nanofiber composites based on the controlled crystallization

This study focused on uncovering the relationship among nanofiller, crystallization behavior, and dielectric property of polymer composites. The effects of carbon nanofibers (CNFs) and heat treatment on the crystalline structures and dielectric properties of the semi‐crystalline polymers were analyzed by using high density polyethylene (HDPE) as a matrix, which is a representative of non‐polar polymer and contains only one crystal structure. The experimental results showed that the degree of crystallinity, size distribution of crystallity, and relative amount of different crystal planes in the HDPE matrix were changing due to the addition of CNFs. With the increase of CNF loading, the dielectric constant, dielectric loss and AC conductivity of the HDPE composites were increased, presenting a typical percolation characteristic, and the dependence of the dielectric constant on frequency became more obvious. All kinds of electronic transmission, polarization effect, and relaxation behaviors in CNF/HDPE composite system were deeply analyzed. After heat treatment, the degree of crystallinity of HDPE composites was decreased with the enhanced cooling rate. For the CNF/HDPE composites with nanofiller content slightly higher than the percolation threshold, the significant increase of the dielectric constant and the dramatical reduction of the dielectric loss over a wide frequency range were realized simultaneously through rapid cooling treatment. The research indicated that a general commercial polymer material with excellent dielectric properties, which exhibited a high dielectric constant and a low dielectric loss, can be obtained by a simple technical approach different from traditional fabrication method of threshold composites.     

降温速率对高密度聚乙烯在全同立构聚丙烯上附生结晶的影响

用欠焦电子显微术和电子衍射技术研究了降温速率对高密度聚乙烯（ＨＤＰＥ）在全同立构聚丙烯（ｉＰＰ）上附生结晶的影响．ＨＤＰＥ在高取向ｉＰＰ基质膜上的附生生长仅发生在ＨＤＰＥ与ｉＰＰ的直接接触面上，存在一临界附生层厚度，超出这一厚度的ＨＤＰＥ与ｉＰＰ无取向附生关系．降温速率不影响附生层内的ＨＤＰＥ与ｉＰＰ的附生结构关系，但对ｉＰＰ基质膜上附生生长的ＨＤＰＥ的厚度，即ＨＤＰＥ的临界附生层厚度有明显影响．在缓慢降温（０．５℃／ｍｉｎ）条件下，ＨＤＰＥ在ｉＰＰ上的附生层厚度约为１００ｎｍ．而室温空气降温条件下，ＨＤＰＥ在ｉＰＰ上的附生层厚度则为２５０ｎｍ．     

Temperature calibration of an electrical compensation DSC on cooling using thermally stable high purity liquid crystals

Temperature calibration of DSCs is usually carried out on heating. In order to accurately control the temperature during cooling experiments, the calibration has to be carried out on cooling. Therefore, three high-purity, thermally stable liquid crystals were used to perform a temperature calibration of an electrcial compensation DSC on cooling. All three liquid crystals have several liquid crystalline phases, and they all were purified to a 99.9% lovel. Temoperatures of the isotropic to nematic or cholesteric and the mesophase to mesophase transitions were used. It was verified that these liquid crystals have sufficient thermal stability for carrying out the calibration on cooling. The dependence of the real temperature on the indicated temperature has been established for all the combinations of the heating and cooling rates of practical interest. It is also shown that the vant's Hoff equation can only be applied to the crystal to a liquid crystal transition, but not to the liquid crystal to liquid crystal or liquid crystal to isotropic transitions.     

Role of gas cooling time on crystalline morphology and mechanical property of the HDPE parts prepared by gas-assisted injection molding

In this study, the hierarchical crystalline structures of high-density polyethylene (HDPE) samples molded by gas-assisted injection molding (GAIM) with different gas cooling times were characterized via scanning electron microscopy, two-dimensional wide-angle X-ray scattering, tensile testing techniques, and differential scanning calorimetry, respectively. It was found that the shish-kebab, the oriented lamellae, and common spherulite structures orderly distributed from the skin region to gas channel region of samples. More importantly, the wider area with highly oriented structure (shish-kebab) was obtained in the samples with longer gas cooling time, in that the longer gas cooling time tends to increase the cooling rate of polymer melt, and then much more stretched chains are retained. Although lower crystallinity, the higher degree of orientation, and much more shish-kebab structures lead to significant reinforcement from 28 to 785 MPa of the samples with gas cooling time of 0.5 s to 32 and 879 MPa of the samples with gas cooling time of 20 s for tensile strength and modulus, respectively. Finally, combined the HDPE molecular parameter with characteristic of the GAIM temperature field and flow field, the formation and stability of crystalline morphology in different regions of sample were discussed.     

聚丙烯酸酯型高分子侧链液晶的合成及其对聚乙烯成核结晶行为的影响

基于聚烯烃用成核剂的结构特征设计合成了两种极性基团和非极性基团交替排列的乙烯基单体,并利用自由基引发聚合,制备出相应的侧链型液晶聚合物.采用元素分析、红外光谱和核磁共振氢谱对所合成单体和聚合物的结构进行了确认.并采用热失重(TGA)和差示扫描量热仪(DSC)研究了聚合物的热稳定性和相转变温度.结果表明,所合成聚合物的起始热分解温度均在337℃以上,具有优异的热稳定性;液晶相变温度区间可达186 K,具有较宽的液晶态温度范围.热台偏光显微镜(HS-POM)研究结果表明,聚合物均呈现出纹影织构,证明所合成的聚合物均为热致向列型侧链液晶高分子.采用DSC和HS-POM研究了所合成的侧链液晶聚合物对高密度聚乙烯(HDPE)异相成核结晶行为的影响.结果表明,侧链型液晶聚合物在提高HDPE结晶温度、结晶度以及降低HDPE晶粒的尺寸及分布方面均有优异的效果,是一类HDPE有效的成核剂.     

An experimental method for studying nonisothermal crystallization of polymers at very high cooling rates

A new technique based on light depolarizing microscopy was developed for studying non-isothermal crystallization of polymers at average cooling rates up to about 5000°C/min. The polymer is cooled down by a gaseous cooling medium supplied at a constant temperature. The temperature of polymer is measured by a thermocouple imbedded directly in the sample. A heat transfer analysis was used to establish appropriate sample geometry to assure that, under the applied cooling condition, the temperature distribution along the sample thickness can be neglected. A light-scattering effect, which occurs when crystallization is carried out under high cooling rates, was observed. This required the development of a method to correct the depolarized light intensity for the effect of light scattering. An appropriate correction method was developed based on both a theoretical and an experimental analysis of the light intensity measurement. This provided a means to measure the overall crystallization kinetics. Examples of such measurements for iPP, HDPE, and LDPE are presented. In addition to the overall crystallization kinetics, the developed technique includes a video camera and VCR system used for measurements of spherulite growth rates during crystallization under high cooling rates. Constant spherulite growth rates were observed for isotactic polypropylene crystallized under very non-isothermal conditions. © 1996 John Wiley & Sons, Inc.     

Reversible Melting of Semi-Crystalline Polymers 2. Annealing Near to the Melting Point

Annealing experiments have been carried out at a few degrees below the melting point of different polyethylenes (LDPE, LLDPE, HDPE), of polypropylene (PP) and of Nylon-6. The heat capacities decrease during the annealing, within a 2-4 min time scale, to a lower value which corresponds to the extrapolated heat capacity values obtained for the cooling cycle when the polymer is cooled from the melt. Heat capacities in the heating cycle following the cooling cycle of PP, Nylon-6 and HDPE have the same value as during the cooling section. This is not the case for LDPE and LLDPE. Exothermic total heat flow in the cooling section following the annealing indicates that the crystallisation takes place during the cooling rather than during the annealing period. The total melting enthalpy measured before and after the annealing cycle is the same. The reversing heat flow shows an excellent fit to the change of the crystallinity measured by small angle scattering of synchrotron radiation during a heating cycle at temperatures below the melting peak. A coupled thermodynamic interaction of the crystalline and the amorphous phases is concluded from this study. This kind of interaction is possible at the lateral end of polymeric chains incorporated into the crystalline phase. This is an indication of the portion of tie molecules in the system, i.e. the portion of fringed micelle type of crystalline morphology with respect to that of folded chain lamellae. This revised version was published online in July 2006 with corrections to the Cover Date.     

高密度聚乙烯共混调控烯烃嵌段共聚物拉伸性能

通过熔融共混法制备了高密度聚乙烯(HDPE)与烯烃嵌段共聚物(OBC)的共混物,研究了HDPE含量对共混体系结晶和拉伸行为的影响.实验结果表明,共混物熔体存在相分离.结晶时两组分互相影响,出现共结晶现象.共混物具有优异弹性回复与高断裂伸长率,而拉伸模量与断裂强度随着HDPE含量增加而逐渐增大.借助Slip-link橡胶弹性理论对应力应变曲线进行了分析,发现拉伸曲线可以很好的用理论模型进行拟合.将共混物的微观结构变化同模型参数进行了对比,建立了共混物结构和性能的有效关联.     

Mechanical properties and crystallization of high-density polyethylene composites with mesostructured cellular silica foam

In this study, composites of high-density polyethylene (HDPE) with mesostructured cellular foam (MCF) silicas have been prepared by melt mixing and studied for the first time. Two different MCF silica analogues having different pore size were used, i.e., 12 nm (MCF-12) and 50 nm (MCF-50). The MCF content in the mesocomposites was 1, 2.5, 5, and 10 mass%. All HDPE/MCF-50 mesocomposites exhibited improved mechanical properties compared with neat HDPE, indicating that the mesocellular silica foam particles with the large mesopore size can act as efficient reinforcing agents. On the other hand, the MCF-12 silica with the smaller size mesopores induced inferior mechanical properties, mainly due to the poorer dispersion of the silica particles and the formation of large aggregates. The mesocellular silica foam particles also affected the thermal properties and the crystallization characteristics of HDPE. Crystallization of mesocomposites was faster than that of neat HDPE. Crystallization kinetics was analyzed with the Avrami equation for both isothermal and non-isothermal conditions. For isothermal crystallization, the Avrami exponent increased with increasing crystallization temperature from 2 to 3. In non-isothermal crystallization, the values of the Avrami exponent increased from 3 to 6.3 with decreasing cooling rate. Lower activation energy values of non-isothermal crystallization were calculated using the isoconversional method of Friedman, as well as using the Kissinger’s equation. Finally, the nucleation efficiency of the mesocellular silica foam particles was estimated from data associated with non-isothermal crystallization, according to the method of Dobreva.     

电子束辐照交联CB/HDPE凝胶复合物的阻温特性

对电子束辐照交联并经溶剂抽提得到的炭黑/高密度聚乙烯(CB/HDPE)凝胶复合物的阻温特性进行了研究.结果表明,凝胶复合物与未抽提的交联试样和未交联试样相比,其PTC强度显著增大,并伴有明显的NTC现象.经热冷循环后,表现出很好的阻温特性稳定性,并且NTC现象消失.表明阻温特性的稳定性及NTC现象的消除强烈依赖于CB/HDPE导电复合材料凝聚态结构的稳定性