高温煤焦/CO2气化反应的动力学研究

对煤气化随机孔模型的动力学控制区的假设进行了改进,建立了高温煤焦/CO2气化反应碳转化率(X)与反应时间(t)的修正随机孔模型:X=1-exp[-kt(a+bkt+k2t2)],并在950℃～1 400℃气化温度范围内,用修正随机孔模型模拟淮南慢速热解煤焦和淮南快速热解煤焦/CO2气化反应,所得表观活化能范围分别为121.99kJ/mol～153.75kJ/mol和88.57kJ/mol～121.39kJ/mol.结果表明,修正随机孔模型的拟合效果优于随机孔模型和收缩未反应芯模型的拟合效果,能很好地体现煤焦气化反应的动力学特征,且该模型适用于不同煤焦的气化反应模拟.     

矾土基β-sialon结合刚玉/碳化硅复合材料的高温弯曲蠕变性能

研究了矾土基β-sialon(15%～25%,质量分数)结合刚玉/碳化硅复合材料在1 250～1 400℃,2～3.5MPa应力下弯曲蠕变性能.结果表明:1 250～1 400℃间,材料的弯曲蠕变过程可以分为两个阶段:30 min以前为减速蠕变阶段,减速指数m在0.5～0.9之间;30 min～3 h为稳态蠕变阶段,应力指数约为1.稳态蠕变时,蠕变活化能在280～335 kJ/mol之间,且减速指数和蠕变活化能均随β-sialon含量的增加而增加,说明β-sialon含量的增加有助于提高复合材料的弯曲蠕变性能.     

脉冲FCVI制备炭/炭复合材料的氧化行为

采用脉冲强制流动热梯度化学气相渗透工艺(IFCVI)制备了炭/炭复合材料(C/C复合材料),利用等温氧化实验对C/C复合材料在不同温度(673～1173 K)条件下的氧化行为进行了研究,并借助于扫描电子显微镜观察了C/C复合材料的氧化形貌.实验结果表明:C/C复合材料的基体在氧化反应中优先氧化,氧化反应速率随温度的升高而增大;在高于或低于临界温度973 K时,C/C复合材料的氧化反应分别受2种不同机制控制,其反应活化能分别为1.29×105 J/mol和2.94× 104 J/mol.     

生物玻璃的烧结与析晶

利用玻璃的烧结收缩,结合差热分析和X射线衍射分析,研究了CaO-SjO_2-P_2O_5系统生物玻璃的烧结和析晶动力学。确定它的烧结机制主要是粘性流动烧结。A玻璃和Ⅰ-2玻璃的烧结活化能分别为540kJ/mol和476kJ/mol。析晶相是磷灰石和硅灰石。A玻璃和Ⅰ-2玻璃的析晶表观活化能分别约为480kJ/mol和390kJ/mol。通过分析烧结温度、Na_2O含量对烧结和析晶的影响,选择了合适的烧结条件,控制烧结和析晶程度,获得了既有足够的自身强度,又有一定的结合强度的多孔玻璃陶瓷。     

热塑性木薯淀粉/SiO_2复合材料的热降解动力学

通过熔融共混法制备热塑性木薯淀粉(TPS)/二氧化硅(SiO_2)复合材料,利用热失重分析(TG)方法研究TPS/SiO_2复合材料的热降解温度及热降解动力学。结果表明,随着升温速率增加或加入SiO_2后,TPS/SiO_2复合材料的热降解温度增加。利用Kissinger方法对TPS/SiO_2复合材料热降解动力学进行研究,发现未添加SiO_2时TPS热降解活化能为206.90 kJ/mol;当添加2份SiO_2时,TPS/SiO_2复合材料热降解活化能提高到223.41kJ/mol;添加亲水SiO_2后TPS/SiO_2复合材料的热降解活化能高于添加疏水SiO_2的。采用Flynn-Wall-Ozawa方法发现,随着SiO_2的加入,TPS/SiO_2复合材料的热降解活化能增加。     

丁腈橡胶/AG-80/E-44环氧树脂复合材料的固化行为研究

采用示差扫描量热法(DSC)对丁腈橡胶/AG-80/E-44环氧树脂复合材料的固化行为进行了研究。研究了反应温度对环氧树脂复合材料黏度的影响、凝胶时间随温度变化曲线,热失重法(TGA)测试了环氧树脂复合材料的耐热性能,计算了环氧树脂固化反应的反应焓、表观活化能,最后推导出固化反应条件。结果表明,随着温度升高,丁腈橡胶/AG-80/E-44环氧树脂复合材料的黏度降低,确定40℃为最佳操作温度,环氧树脂复合材料的耐热性良好。通过凝胶时间随温度变化曲线测试,确定了2步固化步骤,先低温抽真空,再高温固化。环氧树脂复合材料固化反应的表观活化能E_a为45.52kJ/mol,频率因子A为2.16×10~5/s,反应级数n为0.9,固化工艺为:80℃/2h+120℃/2h+200℃/2h。     

氢化双酚A环氧/甲基六氢苯酐体系固化动力学

运用Kissinger和Ozawa法采用非等温DSC对氢化双酚A型环氧树脂/甲基六氢苯酐体系的固化反动力学进行了研究,得到其固化反应活化能分别为41.28 kJ/mol和44.80 kJ/mol,起始固化温度T i,峰顶固化温度T p和终了固化温度T f分别为44.55℃,63.4℃和108.14℃。结果表明:2种方法计算得到活化能大小一致。随着升温速率的提高,T i,T p和T f都有提高。     

低密度聚乙烯/超细煤粉复合材料的热反应性研究

选用神府主焦煤(SFC)作为原煤,通过行星球磨机制备超细煤粉,用氯化铁(FeCl3.6H2O)过渡金属盐对超细样品进行机械力化学固相改性,制备出活性煤粉,以不同配比与低密度聚乙烯(PE-LD)共混制备复合材料。利用差示扫描量热仪等分析测试手段,探讨了SFC、PE-LD以及PE-LD/SFC复合材料的热解反应性和热解动力学。结果表明,Kissiger法和Flynn-Wall-Ozawa法在热分析动力学允许的范围内,计算结果具有一致性;SFC在340～380℃时活化能为113kJ/mol,520～550℃时热解活化能为149kJ/mol;添加10%(质量分数,下同)和20%铁改性SFC的PE-LD/SFC复合材料,在低温区(120～135℃)的热解活化能分别为182.87、250.62kJ/mol;铁改性SFC含量为10%时,煤与PE-LD的反应性较好,两组分之间存在一定协同作用。     

酚酞聚芳醚砜/灌流硅胶微球复合材料的耐热性能研究

利用热重分析仪对PES-C/PSM复合材料的耐热性能进行分析,并以Kissinger法研究其热分解动力学,计算热分解表观活化能Ea。结果表明,在空气氛下复合材料的热分解温度随PSM含量的增大而升高,且当PSM的含量提高至1.0%,复合材料的热分解结束温度提高了41.29℃。复合材料的表观热降解活化能随PSM含量的增加而增大,与纯PES-C(Ea_(PES-C)=241 kJ/mol)相比,当PSM含量为1.0%时,PES-C/PSM复合材料的活化能为264.76 kJ/mol,较纯PES-C提高了9.86%。     

环氧树脂/胺基酰亚胺潜伏性固化体系非等温固化动力学研究

分别采用Kissinger模型和Flnn-Wall-Ozawa(FWO)模型研究了E-51型环氧树脂/胺基酰亚胺潜伏性固化体系的非等温固化动力学,得到了该体系在这2种模型下的固化反应活化能.分析了不同动力学模型对该体系固化反应动力学研究的影响.结果表明,由2种模型得到的固化动力学参数基本相近.E-51/胺基酰亚胺体系的固化反应具有变活化能特征,固化反应起始阶段的活化能较高,约为103～112 kJ/mol;当固化度为0.9时,活化能约为63～82 kJ/mol.     

Compact Swelling in Bi1.4Pb0.6Sr2Ca2Cu3.6Oy During the Formation of High-Tc Superconducting Phase

Compact swelling in Pb-doped Bi-Sr-Ca-Cu-O superconductor has been studied by observing the effects of the size of calcined powders, volatilization of materials, and sintering of high- T _c (2223) powders. The bulk density increases at the early stage of sintering, for about 20 h, and then decreases. Densification occurs when the low- T _c (2212) phase and a liquid phase exist, whereas dedensification occurs with the formation of the 2223 phase regardless of the presence of the liquid. Gas evolution from specimens does not appear to be responsible for compact swelling. Compact swelling is explained by anisotropic growth of thin, platelike 2223 grains in random orientation. When 2223 grains grow in a preferred direction, compact swelling is suppressed.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

(Bi1/2Na1/2)TiO3–Ba(Cu1/2W1/2)O3 Lead-Free Piezoelectric Ceramics

(Bi_1/2Na_1/2)TiO₃ with 0–6 mol% Ba(Cu_1/2W_1/2)O₃ (BNT-BCW), a new member of the BNT-based group, has been prepared following the conventional mixed oxide route. The compacted bodies were sintered at 1130°C for 2 h to get dense ceramics. The addition of BCW into BNT ceramics facilitated the poling process because of a reduction in leakage current. 0.995BNT·0.005BCW ceramics exhibit a relatively high piezoelectric constant ( d ₃₃= 80 × 10⁻¹² C/N) and a relatively low dielectric loss (tan δ= 1.5%). Increased amount of BCW was found to increase the dielectric constant and loss of BNT-BCW ceramics and to suppress the grain growth. During sintering, some BCW diffuses into the lattice of BNT to form a solid solution and some remains on the grain boundaries.     

Synthetic routes to nanoscale BxCyNz architectures

B_xC_yN_z nanoscale materials, hybrids of h-BN and graphite, have been recently synthesised using various techniques. Here, we present the latest advances in the synthesis and characterisation of B-C-N nanotubes and nanofibres. In particular, we focus on layered BC₂N, BN, BC and CN_x systems, reviewing their production methods as well as their structural and electronic properties. These materials may find important applications in the fabrication of nanotransistors, robust nanocomposites, conducting polymers, storage components and field emission sources.     

炭黑/煤矸石/碳纳米管复合填料体系对天然橡胶性能的影响研究*

利用硝酸氧化法对碳纳米管(CNTs)进行纯化,并用环氧天然橡胶(ENR)进行改性处理。结合胶质量分数测定结果表明, ENR用量15%(质量)时效果最佳。采用胶乳凝聚法制备CNTs/天然橡胶(NR)母料。煤矸石粉(CG)经高温煅烧和表面改性处理。 将CNTs/天然橡胶(NR)母料、CG和炭黑(CB)通过机械混炼法与天然橡胶及配合剂混合,制备CB/CG/CNTs/NR复合材料,并对复合材料进行硫化特性及物理机械性能。结果表明： CNTs延迟硫化效应明显;相比炭黑,CG对硫化具有促进作用。硫化特性和甲苯溶胀法测定结果表明,在填料份数相同的条件下,单独由CB填充的NR有最大的交联密度,CNTs对交联密度影响不明显。物理机械性能测试结果表明,当CG：CB：CNTs=17.5:16.5:1(Phr)时,NR硫化胶的300%定伸应力和扯断伸长率明显高于单独由CB填充NR,而拉伸强度与之接近,复合填料样填充NR具有较好的综合性能。扫描电镜测试结果表明,复合填料在NR基体中分布均匀。     

Structure Evolution from Pb(Mg1/3Nb2/3)O3 to La(Mg2/3Nb1/3)O3

The crystal structure of lanthanum-modified lead magnesium niobates having composition (Pb_{1− x} La _x ) (Mg_{(1+ x )/3}-Nb_{(2− x )/3})O₃ with X = 0 to 1 was investigated by X-ray powder diffraction. It was found that the fundamental reflections from perovskite structure remain in the whole range of composition. The superlattice reflections from the A(B'_1/2-B"_1/2)O₃ ordered structure are also well preserved for La content greater than 50 at.%; however, a series of extra peaks of mixing indices appears, with intensities gradually enhanced with the increase of La content. For the complete substitution of Pb by La, a splitting of some reflections can be observed in the diffraction pattern. The results indicate that the crystal structure evolves continuously with the La content, from disordered cubic perovskite of space group Pm 3 m for X = 0, to ordered cubic perovskite of space group Fm 3 m for X = 0.5, distorted cubic perovskite of space group Pa 3 for 0.5 < X < 0.9, and finally to a rhombohedral perovskite, possibly belonging to the space group R 3 , for X ≥ 0.9. In the evolution of structure, a linear reduction of the lattice constant of the perovskite cell from 4.048 to 3.964 Å was observed.