聚-α-甲基苯乙烯热降解动力学研究

利用热分析技术(TG/DTG)对聚--甲基苯乙烯(PAMS)在氮气气氛下以不同升温速率为条件进行热降解动力学研究。研究结果表明:PAMS的热降解步骤为一步反应,在升温速率为10 ℃/min时,主要失重温度区间为302～343 ℃,热失重速率最大时温度为325 ℃。在同一温度下,随着升温速率的不断提高,主要降解温度向高温区移动。采用了Kissinger,Flynn-Wall-Ozawa及Coats-Redfern方法研究其动力学参数,确定了PAMS的降解活化能在160～220 kJ/mol之间、反应级数为一级。     

高温超导涂层导体CeO2缓冲层的化学溶液法制备及其热反应过程研究

本文通过化学溶液法在双轴织构的金属Ni-W衬底上外延生长了CeO2超导涂层导体缓冲层薄膜.X衍射极图表明其面内外织构良好.扫描电子显微镜和原子力显微镜观察薄膜表面光滑、平整且粗糙度低.采用差热分析研究了升温速率及样品质量对前驱溶液热反应过程的影响,结果表明其热反应主要经历了三个过程,其中吸附水的脱去和醋酸组的解离分别发生在110～140℃与230～240℃两个温度范围内,且受升温速率的影响很小,表明这两个反应都在较短的时间内完成.而发生在250～500℃温度段的氧化合成反应则需要较长的时间,其反应结束温度与升温速率近似成线性增加.X衍射分析进一步证实了上述三个热反应过程,当温度达到700℃时CeO2可以得到完好的结晶.     

高CO2浓度下钙基吸收剂脱硫的实验研究

本文进行了高CO2浓度下钙基吸收剂脱硫的实验研究.结果表明,高浓度CO2下钙基吸收剂的脱硫效率随脱硫时间的变化与空气条件下显著不同.孔隙结构分析及热重分析等手段表明高CO2浓度主要影响了钙基吸收剂的煅烧分解过程,形成了有利于脱硫反应的孔隙结构.实验结果还表明提高温度有利于改善高浓度CO2气氛下钙基吸收剂煅烧后孔隙结构,在适当的脱硫时间内,高温下高浓度CO2气氛比空气气氛更有利于炉内喷钙脱硫.     

基于养护龄期的煅烧煤矸石细集料砂浆X射线衍射及扫描电镜分析

采用X射线衍射法(XRD)和环境扫描电镜(SEM)分析方法,研究了不同煅烧温度下煤矸石细集料的活性,针对活性最高的700 ℃高温煅烧煤矸石细集料砂浆的水化产物、微观结构和强度进行了探讨,并分析了砂浆强度随养护龄期(3,7,14,28,60和90 d)增长的变化规律。试验研究表明：煤矸石细集料随着煅烧温度的升高,其活性逐步增加,当煅烧温度达到700 ℃左右时,煤矸石细集料的活性达到最高,当煅烧温度继续升高时,活性呈下降趋势。经过700 ℃高温煅烧的煤矸石细集料具有明显的火山灰活性,其活性组分SiO₂和Al₂O₃能与水泥水化产物发生一定程度的二次水化反应,通过对不同养护龄期的活性最高的700 ℃高温煅烧煤矸石细集料砂浆XRD和SEM分析可知,随着养护龄期的增长,二次水化反应将更加充分,而且水化产物的数量也逐步增多,与早龄期的水泥砂浆相比,生成物相更为稳定的水化产物填充在砂浆的微观孔隙中,能够进一步改善砂浆的微观结构,增强砂浆的界面性能,使砂浆内部结构更加均匀,煅烧的煤矸石细集料和水泥砂浆更趋为一个坚固连续的整体,水泥硬化砂浆的后期强度有较大增幅,活性最高的700 ℃高温煅烧煤矸石细集料火山灰效应明显。     

新型气化装置中生物质传热特性研究

基于生物质部分氧化气化动力学参数难于采用热重分析仪进行研究,本文设计了一个移动床实验方案,样品槽携带生物质样品进入具有线性温度分布的炉膛中加热,并配合一定流量的空气与逐步升温的生物质反应,以达到连续稳定的部分氧化气化。求解动力学参数,需要为生物质提供稳定的升温速率,因此,本文着重研究生物质样品在线性温度分布的炉膛中的升温特性,研究了样品厚度、样品槽运动速度对样品升温特性的影响。在生物质进样速率一定的情况下,改变样品槽运动速度,得到生物质有稳定的升温特性,并且升温速率可控,能达到生物质部分氧化气化动力学实验研究的要求。     

炭黑非催化还原NO的实验研究

在石英管式炉固定床反应器上研究了程序升温条件下炭黑与NO反应的规律。实验表明:天然气炭黑比其它炭黑具有更高的脱除率、最低的起始反应温度;炭黑的起始反应温度随着NO反应气浓度增大而升高;升温速率越大,NO 的脱除率越大,起始反应温度越低;炭黑质量浓度越大,NO的脱除率越大,起始反应温度越低;反应气中氧存在可以降低炭黑-NO起始反应温度。     

氯化钾异相硫化机理的试验研究

生物质燃烧释放的碱金属氯化物蒸气会在受热面上冷凝,并在烟气中SO_2/O_2/水蒸汽等共同作用下发生异相硫化反应,从而影响碱金属对受热面的腐蚀。本文利用固定床反应器研究了反应温度、停留时间、氯化物及SO_2/O_2/H_2O等浓度等对固相KCl硫化的影响,实验结果表明:KCl非均相硫化的主要产物是K_2SO_4,在O_2和H_2O较低是KCl异相硫化较慢,KCl异相硫化速率随SO_2/O_2和H_2O浓度增大而提高,随停留时间的延长呈线性递增,并随反应温度的升高呈指数关系升高。     

煅烧温度对Cu/HMOR催化剂结构及其催化二甲醚羰基化反应性能影响

采用离子交换法在不同煅烧温度下制备HMOR负载Cu(Cu/HMOR)催化剂,用于催化二甲醚(DME)羰基化合成乙酸甲酯(MA)反应. 活性测试结果表明430 oC煅烧制得Cu/HMOR具有较好催化活性,在210 oC、1.5 MPa、空速4883 h^-1下DME转化率为97.2%,MA选择性为97.9%. 对催化剂进行X射线衍射、N₂物理吸附、NH₃程序升温脱附、CO程序升温脱附及拉曼方法表征. 催化剂经一定的煅烧温度有利于Cu离子迁移及扩散和硝酸铜完全分解,从而使HMOR载体具有较多的酸性活性位、大比表面、适宜的微孔结构以及更多的CO吸附位.     

热重分析技术研究聚-α-甲基苯乙烯降解温度

采用热重分析技术研究了4种聚-α-甲基苯乙烯原料和其它微球壳层材料的热降解温度。研究表明,聚-α-甲基苯乙烯原料主要失重温度范围为220～340℃,等离子体辉光放电涂层材料的降解温度为350～450℃。升温速率在20℃/min和30℃/min时,降解温度基本相同,升温速率不影响降解的温度范围,低于20℃/min时,随着升温速率升高,降解温度升高。     

煤的热天平燃烧反应动力学特性的研究

采用热天平获得同一种煤在不同升温速率下的TG、DTG曲线,可求出燃烧速率、燃烧温度随燃烬度的变化曲线,根据两个不同升温速率下的数据,可计算出化学动力学参数活化能和指前因子随燃烬度的变化曲线。根据实验数据计算得到四个煤种的反应动力学参数随燃烬度变化的曲线,并预测其中一种煤在第三个升温速率下的燃烧速率随燃烬度的变化曲线,计算结果与实验结果符合较好。用此模型预测了在不同的恒定温度下试验煤种的煤粉燃烧速率随燃烬度的变化趋势。     

Effect of heat treatment on pore structure in nanocrystalline NiO: A small angle neutron scattering study

Nanocrystalline nickel oxide powders were calcined at 300, 600 and 900°C and pore structure evolution was followed by small angle neutron scattering (SANS). Pore size distributions at two widely separated size ranges have been revealed. Shrinkage of larger-sized pore with reduction in polydispersity has been observed with increasing heat treatment temperature. The pore structures at various heat treatment temperatures do not scale. This has been attributed to the grain boundary diffusion leading to an asymmetric shrinkage of the pores.      

~(32)S离子辐照PET薄膜制备亚微米孔径核孔膜研究

使用中国原子能科学研究院HI-13串列加速器产生的32S离子轰击BOPET薄膜,薄膜在空气中陈化3个月后在专用装置中使用Na OH溶液蚀刻制备核孔膜,研究Na OH溶液浓度、蚀刻温度对微孔孔形的影响。在不同温度和蚀刻液浓度条件下,蚀刻出微孔孔径为0.2至0.93μm的亚微米核孔膜,计算其微孔锥角,得出微孔锥角随着蚀刻温度、蚀刻液浓度和微孔孔径的变化趋势。研究表明,采用低浓度、高温度的Na OH溶液蚀刻有利于减小微孔锥角,有利于制备较小孔径的核孔膜。如选用0.5mol/L的Na OH溶液浓度,在蚀刻温度为90℃的条件下蚀刻,此时蚀刻时间小于2 h,既可以得到高质量微孔膜也有利于提高生产效率。     

α-Al_2O_3介孔材料导热特性的模拟

本文针对α-Al2O3有序介孔材料的导热特性开展分子动力学模拟分析.提出了一种保证电中性的孔道结构构造方法;采用逆非平衡分子动力学方法(muller-plathe法),选取Matsui势为作用势,模拟计算了Al2O3介孔晶体材料在不同环境温度下沿孔道轴向方向的热导率;并借助全面实验分析法,设计了模拟条件,以考察孔径和孔隙率对热导率的影响.模拟结果显示:介孔Al2O3热导率先随温度的升高呈上升趋势,并在200—400 K之间取得极值;而后在400—1400 K范围内,热导率随温度的升高几乎呈线性下降.孔隙率一定时,随孔径增大,介孔Al2O3材料比表面积降低,界面散射的抑制作用减弱,使材料热导率略有上升;孔径一定时,随孔隙率上升,孔道壁面声子数减少,材料热导率下降明显;相对于孔径因素,材料孔隙率对声子导热影响更大.     

气孔对透明陶瓷激光输出性能的影响

定量分析气孔大小和气孔率对陶瓷激光输出性能的影响,建立了气孔分布模型并结合Mie散射和固体激光技术相关理论,讨论气孔散射对陶瓷激光透过率和输出性能的影响。结果表明,气孔率对激光陶瓷的透过率和斜率效率有着决定性的影响。在给定的气孔尺寸分布下,气孔率越高,陶瓷透过率和激光斜率效率越低;在给定的气孔率下,气孔中心尺寸越大,陶瓷样品的透过率和激光斜率效率越低。减小气孔尺寸至0.3 m以下能有效提高激光斜率效率。气孔越大,激光阈值随气孔率增大而上升越快,越不利于实现激光输出。在实际工作中,改进和控制工艺减小气孔尺寸对提高陶瓷的输出性能同样有着重要意义。     

Deposition conditions in tailoring the morphology of highly porous reticular films prepared by electrostatic spray deposition (ESD) technique

Spongy-like reticular structure is a unique morphology fabricated by electrostatic spray deposition (ESD) technique. The effects of solvent, substrate temperature, precursor feeding rate, static electric field strength, and deposition time on tailoring the reticular structure were investigated. Scanning electron microscopy was used to observe the film morphology. MnO_x or LiMn₂O₄ were selected as the model materials. It is found that in addition to the conventional solvent butyl carbitol, other kinds of solvents such as ethylene glycol and propylene glycol can also be used to obtain reticular films at a suitable substrate temperature. Porous films with a low cross-linking degree pore structure can be prepared by increasing precursor feeding rate or decreasing substrate temperature. Increasing the deposition time or the electric field strength helps to obtain reticular films with more homogeneous pore size distribution. In addition, the addition of a high boiling-point solvent in mixed alcohol solvent results in the increase of proper substrate temperature. It is concluded that the fluidity of the spray droplets on the surface of a hot substrate is an important factor to form a reticular film.     

Crystallization of carboxylic acids as studied by NMR Spectrometry

The temperature dependences of the narrow ¹H NMR signals, in the temperature range below phase transition point from the plastic to brittle crystal for pivalic acid (PA) confined in the controlled pore size glasses with mean diameters of 7.9 and 23.9 nm have been investigated in order to determine the depression of the crystallization temperature and the pore size distribution parameters. The obtained parameters and the temperature dependences of the narrow ¹H NMR signals in the solid phases of PA and other carboxylic acids (hexadecanoic (C₁₆), heptadecanoic (C₁₇), octadecanoic (C₁₈), nonadecanoic (C₁₉)) have been used for studying the pore size distributions appeared during the natural crystallization. It was found that the pore size distribution for the even-numbered acids (C₁₆ and C₁₈) is spread over much wider range of the sizes comparing with those for odd-numbered acids (C₁₇ and C₁₉). The maximal value of the pore radius R?=?40.4 nm has been found at the temperature just below the melting point of C₁₈, which is about eight times bigger than that found for C₁₇.     

去合金化工艺对纳米多孔铜纯度的影响

采用腐蚀去合金化方法制备纳米多孔铜材料。研究了固溶时间、腐蚀时间及腐蚀温度对纳米多孔铜表面形貌及残余Mn含量的影响。研究表明:由于固溶时间的延长，合金成分越来越均匀化，去合金化后所得纳米多孔铜的残余Mn原子分数降低。固溶95 h的前驱体合金，随着腐蚀时间的延长，其残余Mn含量降低不明显；随着温度的升高，其残余Mn原子分数由25 ℃的3.54%降至60℃的1.14%，但是60 ℃腐蚀后的孔隙与丝径尺寸明显粗化，样品易碎。通过调整去合金化参数，实验所制备的纳米多孔铜呈现均匀的海绵状纳米多孔结构，残余Mn原子分数1.23%, 平均丝径尺寸40 nm。     

Characterizing the Evolution of Porosity during Controlled Drug Release

Nuclear magnetic resonance (NMR) techniques have been successfully used to characterize the evolving pore structure of partially soluble pharmaceutical pellets as they absorb water and release soluble components. The restricted diffusivity of water trapped within pellets, which have been immersed in water for differing times, has been measured by pulsed field gradient NMR. These measurements have been used to calculate the surface-to-volume ratio and tortuosity of the pore structure. A one-shot Carr–Purcell–Meiboom–Gill sequence has been used to measure the spin–spin (T ₂) relaxation time of water trapped within the pellets. These data have been regularized and then analyzed by the Brownstein–Tarr model to provide a pore size distribution for the pellets as a function of increasing immersion time. It has been found that pore structure changes significantly as water enters the pellet matrix. Two pellet formulations (herein referred to as placebo and drug-loaded) were studied and showed the same trends of a decreasing surface-to-volume ratio and tortuosity with increasing immersion time. At an immersion time of 10 min, both of these parameters decreased to approximately 70% of their values compared to an immersion time of 2 min. The placebo material tested consistently had both a higher tortuosity and surface-to-volume ratio than the drug-loaded material. At an immersion time of 2 min, the tortuosity for the placebo and drug-loaded materials were about 18 and about 10, respectively, and surface-to-volume ratios of about 6 μm⁻¹ and about 5 μm⁻¹, respectively. The materials tested also show changes in their pore size distribution with immersion time. In both formulations the mean and modal pore sizes increase with immersion time. The placebo material maintains an approximately similar mean and modal pore size, about 2 μm over the timescales studied, suggesting a more symmetric pore size distribution. In the drug-loaded pellets the mean pore size is much higher than the modal pore size, their values being 6.5 and 2.1 μm after 10 min immersion time, respectively. Authors' address: Michael D. Mantle, Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK     

氢化多孔石墨烯反渗透特性及机理分析

单层石墨烯凭借超薄的厚度和优异的力学化学防污性能,成为新一代纳滤膜材料的最佳选择之一.本文采用经典分子动力学方法,研究了氢化多孔石墨烯反渗透膜对盐水的反渗透特性.结果表明,水渗透量会随着驱动力、孔径和温度的增加而增加;而孔径大于水合半径的条件下,盐离子截留率会随驱动力和温度的增加而降低.当反渗透膜和盐水存在切向运动时,随着切向速度的增加可以有效提高盐离子截留率和减弱浓差极化现象,但也在一定程度上牺牲了水通量.通过分析水流沿渗透方向的能障分布、水分子的氢键分布和离子水合状态,解释了各参数变化对盐水在氢化多孔石墨烯中反渗透特性的影响机理.研究结果将提供基于单层多孔石墨烯反渗透特性的理论认识,并将为纳米级反渗透膜的设计提供帮助.     

超临界CO_2在岩石孔隙内流动状态的分子模拟

本文采用分子模拟的方法研究了地质封存条件下超临界CO_2在镁橄榄石孔隙内的流动,分析了孔隙尺寸、温度、压强对超临界CO_2的密度分布和流动速度的影响.研究结果表明,只有当孔隙尺寸大于5.0 nm时,超临界CO_2分子在岩石孔隙内的流动才符合Poiseuille流动;同时,超临界CO_2分子在岩石近壁面存在1.5 nm的密度震荡,当孔隙尺寸小于15 nm时,密度振荡现象会影响CO_2分子在岩石孔隙内的平均密度;升高温度、降低压强的方法可以减小密度震荡的第一峰值,减弱岩石壁面与CO_2的相互作用,使得CO_2的流动速度增加.