用C++语言从积分法中求反应级数的研究

反应级数的确定在化学反应动力学研究中非常重要,目前很多方法能求反应级数。本文直接从反应级数的积分通项公式出发,采用相对误差的平方和最小进行非线性拟合,突破了不同数量级数据之间难以拟合的界限,是拟合上的一个突破。并用C 语言动态分配内存编程求反应级数,包括整数级和小数级。最后用6个例子说明本方法的正确性。     

Measurement of solubility and diffusion coefficients of ethylene in solid and molten low-density polyethylene with different melt indices

The diffusion behavior of ethylene in polyethylene is of great importance for the polymerization and degassing of polyethylene (PE) industry. Based on the gravimetric sorption and desorption measurement approach, an intelligent gravimetric analyzer is applied to obtain the solubility and diffusion coefficients of ethylene in solid low-density PE (LDPE) with different melt indices at 30°C to 70°C, 0 to 4 atm and in molten LDPE at 160°C to 230°C, 0 to 4 atm, respectively. Results indicate that both the solubility and diffusion coefficients of ethylene in solid LDPE are smaller than those in molten LDPE, while the dissolution enthalpy and diffusion activation energy of ethylene in solid LDPE are higher. In addition, one- and two-dimensional diffusion models are built and the effects of particle size, polymer properties, and operation conditions are systematically investigated on the diffusion behaviors of ethylene in solid and molten LDPE.     

基于制备超细复合含能材料的对置受限式撞击流反应器微观混合性能

由于对置受限式撞击流反应器较高的传热及混合效率,能够制备出粒径小、均匀且分布范围窄的超细颗粒。本文采用碘化物-碘酸盐平行竞争反应体系研究入射速度、结构尺寸对对置受限式撞击流反应器微观混合效果的影响规律,并将混合腔尺寸同等比例放大一倍进行对比研究。结果表明,随着入射速度的增大,离集指数减小,微观混合效果提高。喷嘴间距与喷嘴直径比的增大使得离集指数增大,微观混合效果降低。离集指数随着混合腔高度、混合腔出口尺寸的增大呈现先增大后减小的趋势,且混合腔高度对混合效果的影响较混合腔出口尺寸显著。将对置受限式撞击流反应器混合腔尺寸扩大一倍,离集指数增加到原来的2.4倍,微观混合效果显著下降,但是在较大入射速度下,两种结构的混合效果差距减小。研究结果可为纳米复合含能材料的制备提供高效、安全的技术支持。     

B2O3-K2O-Sb2O3系统玻璃的光学折射率及带隙

高折射率和非线性光学玻璃可以用于高速光开关、光学存储器、新型光纤和光学运算元件等,其研究受到各国科技工作者的高度重视,本文采用熔融淬冷法制备了组成为(85-x)B₂O₃-15K₂O-xSb₂O₃(x=70, 75, 80, 85)的4组玻璃,测试了玻璃样品的密度、折射率、热学性能、拉曼光谱和吸收光谱,利用玻璃样品的吸收光谱计算了其直接允许光学带隙、间接允许光学带隙及Urbach能量。结果表明：随着Sb₂O₃含量的增加,玻璃样品的密度从4.445g/cm³逐渐增加到4.767g/cm³,折射率从1.9438增加到2.0058,玻璃转变温度从291℃降低到260℃,玻璃析晶温度从463℃降低到370℃,直接光学带隙从3.2775eV降低到3.1379eV,间接光学带隙从3.1444eV降低到3.0256eV,Urbach能量从0.137eV逐渐减小到0.107eV。说明Sb₂O₃-K₂O-B₂O₃系统玻璃可以作为新型的非线性光学玻璃候选材料之一。     

Classification and identification of gas–liquid dispersion states in a jet bubbling reactor

Three gas–liquid dispersion states including flooding, loading, and complete dispersion are observed sequentially in a jet bubbling reactor with an increase of the liquid jet velocity at the nozzle outlet (u_j). The gas–liquid dispersion states are identified through the slope (k) of the curve of fluctuation distribution index (FI) versus u_j as follows: (a) under the flooding, k = 0; (b) under the loading, k > 0; (c) under the complete dispersion, k < 0. In particular, the u_j at the transition points from flooding to loading and from loading to complete dispersion are referred to flooding jet velocity (u_jf, the transition point between k = 0 and k > 0) and complete dispersion jet velocity (u_jcd, the transition point from k > 0 to k < 0), respectively. The average relative deviations of the u_j at the transition points obtained through the acoustic emission measurement and visual observation are less than 5%.     

Thermal history and its implications: A case study for ion exchange

Glasses containing monovalent species can be chemically strengthened by the replacement of smaller ions in the glass with larger external ions in the near glass surface. This type of ion exchange puts glass surface under high compressive stress (CS). Glass mainly fails from tension with the presence of surface flaws. Chemical strengthening can change the stress at the flaw tip from tension to compression and further stop the flaw from propagating. Glass damage resistance is therefore significantly improved. For the same glass composition, glass thermal histories can affect the magnitude and depth of the CS generated during ion exchange. In this study, the impact of thermal history on glass physical properties and ion exchange attributes in one alkali-containing glass formed by fusion draw process was investigated. Multiple thermal treatments were done to rewrite the glass thermal histories. Glass density, refractive index, and ion-exchange properties as a function of the thermal treatment were studied. It is concluded that ion exchange-related properties change dramatically with the glass thermal history.     

折光指数快速测定聚丙烯腈溶液固含量

为实时监测聚合反应过程,完善现有检测项目的时效性和准确性,建立了一种快速测定丙烯腈聚合转化率的方法。通过采集不同时间节点聚合样品,分别测量其折光指数和聚丙烯腈溶液固含量,建立两者之间的关系曲线,从而实现各时间节点样品聚丙烯腈固含量的快速测定。结果表明,折光指数与聚丙烯腈溶液固含量呈线性关系,由该线性关系确定的斜率和截距可以作为反映聚合反应批次间差异性的指纹性指标。     

NDQ催化剂在400 kt/a Spheripol聚丙烯工业装置上的应用

以三乙基铝为助催化剂,环已基甲基二甲氧基硅烷为外给电子体,使用NDQ催化剂在400 kt/a的Spheripol聚丙烯工业装置上试生产了注塑专用聚丙烯HA8012和HP-M12。结果表明:试生产期间,装置运行平稳,聚合工艺参数可控可调,聚丙稀细粉含量低;采用NDQ催化剂生产的HA8012和HP-M12具有较宽的相对分子质量分布(6.0~6.5)、较低的二甲苯可溶物含量(质量分数为1.5%~2.0%)、较高的拉伸强度(大于38 MPa)和弯曲模量(1.8~2.2 GPa)。     

催化裂化催化剂形貌分析方法的建立

结合显微镜观察,通过分析毫米级颗粒、微米级Duke粒子及催化裂化催化剂,研究动态数字图像分析仪CamsizerX2分析颗粒形貌的合理准确性。考察分散方式、分散压力和记录颗粒数量因素的影响,建立了催化裂化催化剂球形貌分析方法。     

氮气对复采工作面遗煤复燃的防治效能

为探究不同体积分数N₂对复采工作面遗煤复燃过程的防治效果,采用自主研发的程序升温试验装置,对煤样分别通入体积分数为10%、20%、30%和40%的N₂,以氧化反应过程中耗氧速率V_O2、一氧化碳产生率V_CO和表观活化能E的变化情况来反映煤自燃的发展程度。试验表明:不同体积分数的N₂对煤氧化升温过程均具有抑制作用,相比于煤在纯空气条件下的氧化自燃,通入的N₂体积分数越大,煤初次自燃和二次氧化升温过程的V_O2和V_CO更低、E更高,说明通入的氮气体积分数越大,对煤氧化升温过程的抑制效率越好。其中,在煤初次自燃阶段,当N2体积分数C_N2≥20%时抑制效果更佳;在煤二次氧化复燃阶段,当N₂体积分数C_N2≥40%时抑制效果更佳。