氧化石墨烯对VS55冻融过程结晶行为的影响

借助差示扫描量热仪(DSC)和低温显微系统,研究了升降温速率(5、10、25、50和100℃/min)和氧化石墨烯(GO)浓度(0.01、0.1、1和5 mg/ml)对VS55溶液降温过程结晶和升温过程冰晶再生长的影响。结果表明:(1)随着升降温速率的增加,VS55溶液体系在降温过程中的结晶焓Hf以及升温过程中的再结晶焓HTd都会减小;(2)对浓度为2.1 mol/L的VS55溶液进行降温时,GO浓度越大,其结晶焓Hf越大,且初始冻结温度显著提高;但对4.2 mol/L VS55降温时,其结晶焓Hf会随着GO浓度增加呈现出先减小后增大的特点;8.4 mol/L VS55已完全玻璃化,GO对其没有影响;(3)在升温过程中,GO浓度越高,VS55浓度越低,其溶液体系内冰晶再生长抑制程度越大,如GO浓度为5 mg/ml时,2.1 mol/L VS55溶液添加GO前后再结晶焓的差值ΔHTd为14.55 J/g,而4.2 mol/L VS55就显著降低到7.95 J/g,接近8.4 mol/L VS55的6.91 J/g。总体来看,GO对VS55溶液降温过程冰晶生长特点的影响主要取决于VS55浓度和GO浓度,但对复温过程反玻璃化或冰晶再生长特点的影响主要取决于VS55浓度、GO浓度以及升降温速率。     

聚乙二醇/纤维素相变材料的制备及性能表征

以微晶纤维素（MCC）为原料，制备纤维素海绵（Cell），并以其作为基体，通过物理共混的方法与聚乙二醇（PEG）PEG-6000进行复合，制备聚乙二醇/纤维素相变材料（PCMs），研究了PCMs的结构与相变储能性能。实验结果表明：PCMs中PEG的质量分数可以达到90.77%，且相变过程中不会发生液体泄漏的问题。FT-IR分析表明纤维素基体和PEG之间存在明显的氢键作用，无新化合物产生。XRD分析结果表明：与纯PEG-6000相比，纤维素基体的加入不会改变PEG的结晶形态，但会降低PEG的结晶度。DSC结果表明，PCMs的熔融焓（ΔH_f）随着PCMs中PEG质量分数的增加而增大，ΔH_f最高可达146.88J/g（PCM₅），但均小于纯的PEG（179.09J/g）；PCMs的结晶焓（ΔH_c）随着PCMs中PEG质量分数的增加而降低，ΔH_c的绝对值最高可达137.81J/g。TG分析表明，当环境温度小于250℃时，PCMs的热稳定性较好。     

测试速率对PEG/GO定型相变材料熔融和结晶性能的影响

以聚乙二醇/氧化石墨烯(PEG/GO)定型相变材料为测试样品,采用差示扫描量热法(DSC)对其熔融、结晶性能进行了表征,研究了测试速率(即升/降温速率)对该相变材料熔融、结晶温度和热焓的影响。结果表明:随着降温速率的增加,PEG/GO相变材料的结晶温度逐渐降低;随着升温速率的增加,材料的熔融温度逐渐提升;测试速率越高,焓值越小;随着GO加入量的增加,升降温时的焓值均呈现降低的趋势;相同GO含量的PEG/GO定型相变材料,其熔融焓总是大于同等测试速率下得到的结晶焓,而且测试速率越快,差值越大;在相同测试速率下,GO的添加量基本不会对PEG/GO相变材料的熔融、结晶温度产生影响。     

磁纳米粒子对Vs55溶液反玻璃化等温结晶行为的影响

借助差示扫描量热仪（DSC）和低温显微系统,研究了磁纳米粒子对典型玻璃化溶液Vs55在反玻璃化过程中等温结晶行为的影响。结果表明：（1）磁纳米粒子经过羧酸（CA）和聚乙二醇（PEG）表面修饰后,对Vs55溶液的玻璃化转变温度（T_g）几乎没有影响,但对其反玻璃化转变温度（T_d）和反玻璃化结晶焓（H_Td）影响较大;（2）在Vs55的反玻璃化温区范围内（-85~-60℃）,随着等温温度的升高和降温速率的增大,经CA修饰的磁纳米粒子均会显著促进Vs55的反玻璃化现象,在-85℃等温时的冰晶生长速率为0.37 μm·s^-1,75℃等温时则为2.19 μm·s^-1,而当降温速率从2℃·min^-1增大到100℃·min^-1时（在-75℃等温结晶）,其反玻璃化冰晶生长的速率由1.72 μm·s^-1增大到3.54 μm·s^-1;（3）与Vs55相比,两种修饰均明显促进了其反玻璃化,在-80℃等温结晶时,Vs55溶液的生长速率为0,而CA和PEG修饰分别达到了1.04 μm·s^-1和2.31 μm·s^-1;与CA修饰相比,PEG修饰后的磁纳米粒子更加促进了Vs55溶液的反玻璃化现象,在-85℃等温时的冰晶生长速率为0.62 μm·s^-1,而-75℃等温时则达到了6.25 μm·s^-1,这个结果也充分说明了磁纳米粒子表面修饰物质的不同必定会显著影响Vs55的反玻璃化结晶生长。     

聚丁二酸丁二醇酯/聚乙二醇硬脂酸酯共混物非等温结晶行为

以聚丁二酸丁二醇酯（PBS）和聚乙二醇硬脂酸酯（PEOST）为原料,采用溶液共混法制备了PEOST质量分数分别为10%（POS-10）和30%（POS-30）的两种合金材料。通过差示扫描量热法（DSC）研究了合金材料的非等温结晶行为,用莫志深（Mo）法分析了PBS的非等温结晶动力学,采用Kissinger法和Friedman法计算PBS的结晶活化能,并用红外（FTIR）和偏光显微镜（POM）进行表征。研究结果表明：PBS先结晶形成结晶微区不利于PEOST结晶,而较高含量的PEOST有利于PBS的结晶。受PBS先结晶的影响,POS-10降温DSC曲线没有出现PEOST的结晶峰,而POS-30在低的降温速率情况下出现了PEOST双结晶峰;升温DSC曲线中两试样均出现了PEOST的熔融峰。在相同的冷却速率下,POS-30的PEOST熔融温度（T_m）和熔融焓（△H_m）大于POS-10;POS-30的PBS结晶峰温度（T_p）、结晶焓（△H_c）大于POS-10,而结晶半峰宽（D）值更小;但两者的T_m和△H_m相当。随冷却速率的增加,PBS的D值增大,而PEOST的D值却降低;冷却速率的增加对PBS的T_m值影响不大,但使PEOST的T_m略有减小。Mo法适合用于共混物中PBS的非等温结晶动力学分析。POS-30的PBS绝对值结晶活化能要大于POS-10。POS-30在红外光谱谱图中出现了PEOST结晶的红外响应峰（1109cm^-1和841cm^-1）而POS-10没有。     

聚L-乳酸的热性能研究

为了了解聚L-乳酸(PLLA)自身结构特点,更好地控制其成型加工过程,研究了PLLA的非等温结晶行为、熔融行为和热失重过程。结果表明:降温速率对PLLA的非等温结晶过程具有显著影响,在1℃/min的降温速率下,PLLA的结晶起始温度为121℃,结晶焓为3.363 J/g;PLLA的熔融双峰遵循熔融-再结晶的机理;PLLA热分解温度在300℃左右,且随升温速率的增加而增大。     

半芳香族耐高温PA10T/1010的非等温结晶动力学研究

利用对苯二甲酸、癸二胺、癸二酸合成了聚对苯二甲酰癸二胺(PA10T)和聚酰胺(PA)1010的共聚物PA10T/1010,通过差示扫描量热法研究了PA10T/1010的非等温结晶动力学,结果表明随着降温速率的增加,结晶温度和熔点不断降低,同时结晶温度的范围变宽,结晶所需时间减少。用Jeziorny法描述了PA10T/1010的非等温结晶过程,发现其结晶过程分为两段,晶体生长方式在前期为二维盘状生长,后期为多维生长。通过Mo法描述了PA10T/1010的非等温结晶动力学,发现降温速率越大,在单位时间内PA10T/1010所能达到的相对结晶度越高。最后通过Kissinger方法计算得到PA10T/1010非等温结晶活化能为–171.47 k J/mol。     

用Avrami-Ozawa模型研究6-叔丁基间甲酚非等温结晶动力学

主要研究了6-叔丁基间甲酚（3M6TB）的静态熔融结晶动力学。通过差示扫描量热仪（DSC）在不同的降温速率下测定降温结晶过程中的放热曲线,然后对数据进行分析得到相对转化度随温度变化的关系。用Avrami-Ozawa模型处理试验数据得到3M6TB静态熔融结晶过程的力学参数F_T（达到给定结晶度所需要的冷却速率的值）以及θ（Avrami常数对Ozawa常数的比值）,F_T和θ均随着降温速率的增大而增大,导致在本研究试验条件下一定结晶时间内3M6TB的相对结晶度随降温速率的增加而提高。     

小型动态制冰机工作过程的结晶特性

利用所搭建的小型动态制冰装置制取冰浆,实验探讨了结晶时间、载冷剂温度、添加剂种类与浓度、刮削速度等因素对冰浆动态制备过程的影响,研究中基于热平衡方法测得结晶过程不同时刻的含冰率,对所制取的冰浆进行显微拍照,并基于图像处理获取冰晶尺寸的当量直径。实验结果表明,在动态结晶过程的测试时间内,制冰溶液的降温速率受外界条件影响较小,但添加剂种类与浓度对制冰溶液的相变结晶温度以及过冷度影响较大;制冰溶液的含冰率与冰晶尺寸均随时间的增加而增大,其中载冷剂温度、添加剂种类与浓度对溶液含冰率影响较大,而对冰晶尺寸影响最大的因素是刮削速度与添加剂浓度;当结晶过程进行到30 min时溶液的含冰率均达到25%,冰晶尺寸均能达到0.12 mm左右。     

POM与POM/碳酸钙复合材料非等温结晶动力学研究

采用差示扫描量热仪研究了聚甲醛（POM）和POM /碳酸钙复合材料在不同降温速率下的非等温结晶行为,并用Jeziorny法和莫志深法计算了POM及其复合材料的非等温结晶动力学参数。结果表明：提高降温速率,POM与POM/碳酸钙复合材料的结晶峰均向低温方向移动,且结晶放热峰逐渐变宽;降温速率为5、10、15和20 ℃/min时对应POM/碳酸钙复合材料的结晶峰峰值和结晶放热焓分别为144.6、142.4、141.2、140.2 ℃和177.4、152.2、148.0、137.2 J/g;加入碳酸钙的使POM的结晶温度提高,结晶速率加快,其在体系中起到了异相成核的作用。     

Thermal behavior of transparent poly(etheretherketone)(PEEK) film

The thermal behavior of poly(etheretherketone)(PEEK) film heated in an open differential scanning calorimetry (DSC) pan at 20°C/min is distorted by relaxation of the strained film. PEEK film in a closed pan or quenched PEEK in open or closed pans shows a glass-transition temperature (T_g) around 144°C, cold crystallization (～22 J/g) at 177°C, melt-temperature (T_m) peaking at 335–340°C, with an enthalpy of fusion of 32–34 J/g, and recrystallization on cooling at 285°C, with a crystallization exotherm of about 40 J/g. The enthalpy of fusion decreases with increasing heating rate from 2–100°C/min and approaches the enthalpy of cold crystallization. With increasing heating rate, further crystallization of PEEK during the DSC scan is suppressed. With increasing cooling rate, PEEK melt crystallizes at larger supercoolings to a lesser extent. Crystallization on cooling the melt was more complete than cold crystallization and annealing on heating.     

Energy Crossovers in Nanocrystalline Zirconia

The synthesis of nanocrystalline powders of zirconia often produces the tetragonal phase, which for coarse-grained powders is stable only at high temperatures and transforms into the monoclinic form on cooling. This stability reversal has been suggested to be due to differences in the surface energies of the monoclinic and tetragonal polymorphs. In the present study, we have used high-temperature oxide melt solution calorimetry to test this hypothesis directly. We measured the excess enthalpies of nanocrystalline tetragonal, monoclinic, and amorphous zirconia. Monoclinic ZrO₂ was found to have the largest surface enthalpy and amorphous zirconia the smallest. Stability crossovers with increasing surface area between monoclinic, tetragonal, and amorphous zirconia were confirmed. The surface enthalpy of amorphous zirconia was estimated to be 0.5 J/m². The linear fit of excess enthalpies for nanocrystalline zirconia, as a function of area from nitrogen adsorption (BET) gave apparent surface enthalpies of 6.4 and 2.1 J/m², for the monoclinic and tetragonal polymorphs, respectively. Due to aggregation, the surface areas calculated from crystallite size are larger than those measured by BET. The fit of enthalpy versus calculated total interface/surface area gave surface enthalpies of 4.2 J/m² for the monoclinic form and 0.9 J/m² for the tetragonal polymorph. From solution calorimetry, the enthalpy of the monoclinic to tetragonal phase transition for ZrO₂ was estimated to be 10±1 kJ/mol and amorphization enthalpy to be 34±2 kJ/mol.     

Layer double hydroxides for enhanced poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) crystallization

Enabling the widespread utilization of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV) is strongly associated with enhancing its crystallization kinetics. In this article, we utilize a highly surface active (one reactive group per nanometer square) anion exchanged layered‐double hydroxide (LDH) functionalized by stearic acid to probe the crystallization kinetics of PHBV. Our prior work has shown that the addition of LDH decreases the cold crystallization and induces a melt recrystallization peak in PHBV. Since the melt‐recrystallization temperature shifted to higher temperature and its corresponding enthalpy increased with increasing LDH loading, this article is focused on understanding the effect of LDH on kinetics and energetics of PHBV crystallization. Both Avrami and Lauritzen–Hoffman modeling are utilized to develop a comprehensive understanding of thermal history effects through differential scanning calorimetry and polarized optical microscopy measurements. Five concentrations by weight of LDH are used: 1, 3, 5, and 7%. The results show that the addition of LDH promoted both primary and secondary nucleation at low concentrations but additional LDH resulted in primary nucleation alone. The crystallization rate and activation energy show a significant increase, which is accompanied by a decrease in the nucleation constant, the surface energy and the work of chain folding for PHBV crystallization. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2013     

左旋海松酸的分离及其理化数据测试

采用胺化法从松脂中分离左旋海松酸,然后利用超声波辅助左旋海松酸粗品重结晶进行纯化,通过单因素和正交试验优化左旋海松酸分离的工艺条件,得到的最佳工艺条件为：无水乙醇用量20 mL(1 g左旋海松酸),结晶温度0 ℃,超声波频率为53 kHz,重结晶次数为2次,此条件下得到的左旋海松酸纯度达97%。超声波辅助左旋海松酸重结晶,大幅度缩短了晶体成核时间,5~6 h可得到晶型细小均匀分散的长方型片状透明晶体。通过红外光谱(FT-IR)、核磁共振(¹H NMR, ¹³C NMR)、气相色谱-质谱联用(GC-MS)表征了纯化后左旋海松酸的分子结构,依据氧弹量热法、TG-DSC法和基团贡献法分析得到左旋海松酸的标准摩尔生成焓(Δ_fH_m^?)-700.23 kJ/mol和熔化焓94.99 kJ/mol。     

Comparison of crystallization behaviors of poly(ε‐caprolactone) in confined environment with that in bulk

The spatial confinement of poly(ε‐caprolactone) (PCL) in the matrix of PMMA was synthesized by insitu polymerization and characterized by WAXD and SEM. The nonisothermal crystallization behavior and the kinetics of PCL in PMMA/PCL (85/15) blend and pure PCL were investigated by means of DSC. Jeziorny and Ozawa's theoretical prediction methods were used to analyze the crystallization kinetics. The melting behavior after cooling was also studied. There was an additional interesting phenomenon of double‐melting peak for pure PCL. Peaks at lower temperature shifted to lower temperature, and peaks at higher temperature did not shift with the increasing cooling rate. This behavior can be due to recrystallization. For the high‐crystallization activity energy and low‐crystallization rate, PCL in bulk would recrystallize during the melting process, and displayed a double‐melting behavior. Under spatial confinement of the rigid PMMA, PCL had much lower crystallization activity energy and had only one melting peak. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of L‐phenylalanine as a nucleation agent on the nonisothermal crystallization,melting behavior,and mechanical properties of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHHx) is a thermoplastic biopolyester with a slow crystallization rate. L ‐Phenylalanine (L ‐PH) was used to improve the crystallization rate of PHBHHx. The nonisothermal crystallization kinetics and melting behaviors of PHBHHx and PHBHHx/L ‐PH samples were characterized and compared with differential scanning calorimetry. At cooling rates of 2, 5, 10, and 20°C/min, PHBHHx/L ‐PH could crystallize at higher temperatures than pure PHBHHx. A modified Avrami equation based analysis showed that the addition of L ‐PH shortened the half‐time of crystallization of PHBHHx from 9.6 to 8.0 min and increased the composite rate constant of PHBHHx from 0.201 to 0.283 during the nonisothermal crystallization process at a cooling rate of 10°C/min. For other cooling rates, similar trends of changes were observed. These indicated a faster crystallization rate of PHBHHx in the presence of L ‐PH. PHBHHx/L ‐PH samples showed a higher melting temperature and a sharper melting peak than those of the pure PHBHHx, which suggested that L ‐PH as a nucleation agent improved the perfection of the PHBHHx crystals. Stress–strain measurements showed that both PHBHHx and PHBHHx/L ‐PH maintained their ductile and elastic properties during the 60 days of the aging study. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Interaction of ciprofloxacin hydrochloride with sodium dodecyl sulfate in aqueous/electrolytes solution at different temperatures and compositions

Interactions of ciprofloxacin hydrochloride(CPFH) with sodium dodecyl sulfate(SDS) were investigated by conductivity measurement in H_2O/electrolyte solutions(NaCl, Na_2SO_4 Na_3PO_4) over 298.15–318.15 K temperature range(with 5 K interval) considering the human body temperature. In all cases, two critical micelle concentrations(c~*) were observed which are increased in the presence of drug and decreased in the presence of salts enunciating the presence of interaction amongst the studied components. For(CPFH + SDS) system in the presence of salt, the c~*values at 303.15 K and I = 0.50 mmol·kg~(-1) followed the order: C_(NaCl)C_(Na_2SO_4)C_(Na_3PO_4). The ΔG_(1,m)~0 and Δ G_(2,m)~0values are found to be negative for all systems that show that the micellization process is thermodynamically spontaneous. For(CPFH + SDS) system in water, the Δ H_m~0 Δ S_m~0 values reveal that the micellization processes is both entropy dominated in almost all cases. In the occurrence of electrolytes, Δ H_m~0 and Δ S_m~0 values indicate that micellization processes are both entropy enthalpy restricted at upper temperature but it becomes totally entropy dependent at higher temperature. The higher positive Δ S_m~0 values indicate the enhanced hydrophobic interaction in presence of salts. The enthalpy-entropy compensation was determined from the linear relationship betweenΔ H_m~0 and Δ S_m~0 values in every state. Different transfer energies as well as compensation temperature and intrinsic enthalpy were also evaluated and the behaviors were comparable to other biological system.