高分子片状板材热分析测试影响因素的研究

研究了高分子片状板材的取样位置、样品尺寸、升温速率、热历史及气流速率对DSC及(或)TGA测试结果的影响,简要分析了各因素影响测试结果的原因。结果表明,升温速率对测试结果影响很大,热历史对测试结果有一定影响,取样位置及一定范围内的样品尺寸对测试结果影响不大,气流速率对测试结果影响较微。     

样品和方法差异对聚丙烯TMA测试CLTE的影响

从测试角度出发,主要以聚丙烯材料为研究对象,研究样品和方法两大方面各因素对静态热机械试验仪(TMA)测试材料线性热膨胀系数(CLTE)的影响。结果表明:样品方面各因素注塑工艺、样条类型、材料热历史、改性填充及裁样位置对材料的CLTE结果有较大影响,测试方法方面各因素升温速率、施加负荷、放置位置及谱图处理方式对材料的CLTE结果有不同程度的影响。研究结果对深入研究CLTE测试、辅助开发低CLTE材料具有重要指导意义。     

响应面优化光度法测定口罩中环氧乙烷含量

对口罩中环氧乙烷残留量进行监测是确保口罩质量安全的重要手段。本文采用响应面法(Response Surface Methodology, RSM)建立了口罩中环氧乙烷含量定量检测的乙酰丙酮光度法。通过考察超声提取时间、盐酸浓度和显色反应时间优化了实验条件。发现这三个因素对加标样品平均回收率的影响交互作用明显;超声提取时间58.9 min、盐酸浓度0.24 moL·L~(-1)和显色反应时间27.78 min时,加标样品平均回收率可达最佳值(101.09%)。通过单因素法进行验证,所建立的检测方法检出限(limit of detection, LOD)和定量限(limit of quantification, LOQ)分别为0.026μg·g~(-1)和0.087μg·g~(-1)。浓度为0～50.00μg·g~(-1)范围内线性相关系数(R~2)大于0.995,平均加标回收率为98.2%～101.2%,日内精密度为1.5%～4.2%,日间精密度(7天)为1.8%～4.7%。与文献方法相比具有操作简单、检出限低等优点。对8种不同材质和放置时间的实际口罩样品进行检测。发现市售医用外科口罩样品中环氧乙烷的残留量为1.52μg·g~(-1),符合国标要求。使用后的口罩样品中环氧乙烷的残留量随着时间延长残留量下降。本文所建立的方法可用于口罩中环氧乙烷残留量的快速筛查和确证分析。     

测试条件对静态热机械分析仪测试CLTE的影响

利用静态热机械分析仪（TMA）测试了聚丙烯（PP）的线性热膨胀系数（CLTE）,考察了PP在不同的测试条件下的线性热膨胀系数的变化规律,结果表明力值、升温速率、热历史和测试方向对CLTE结果有影响。     

聚丙烯DSC测试影响因素探究

以聚丙烯注塑成型样品为例,分别以不同温度对样品进行状态调节、不同升温速率消除样品热历史和不同降温速率冷却对样品进行DSC实验,分析其对测试结果的影响.结果表明:以不同温度对样品进行状态调节后进行实验,其第一次升温熔融峰温受状态调节温度影响出现先增大后减小,最大偏差2℃,对随后的降温过程和第二次升温过程无影响;以5℃/m...     

密闭式电喷雾离子源中流场的分布特征

利用流体力学模拟软件Fluent构建了电喷雾离子源的二维模型，并基于所构建的模型探讨了离子源构型、辅助气引入方式、气体流速对源内流场分布的影响。结果表明，相比于其它两种结构，矩形结构的离子源能够提供较为稳定的流场。通入同轴辅助气和正交方向辅助气都能够起到聚集样品喷雾的效果，但作用效果却并不相同。提高同轴辅助气流速，能够增大喷口处混返区域，改变气流驻点位置。而增大正交方向辅助气流速，虽然同样能够提高源内各处气体流速，但并不会改变喷口处混返区域的大小。以Turbo V离子源为研究对象，考察了喷针位置、辅助气流速对溶液总离子流的影响，实验趋势与模拟结果基本吻合。     

样品预处理与实时直接分析质谱的联用技术及应用

近年来,与实时直接分析质谱(DART-MS)相结合的样品预处理技术发展迅速,使得对复杂生物、环境、法医学、食品、个体小生物以及单细胞样品中的分析物进行直接分析成为可能。然而固体基质内部分析物检测困难、痕量分析物检测性能不佳已成为限制DART-MS进一步发展的关键问题。针对这些问题,多年来,研究人员在不同领域对样品预处理与质谱联用进行了多种尝试。该文以固相萃取(SPE)、分散固相萃取(DSPE)、搅拌棒吸附萃取(SBSE)、固相微萃取(SPME)、机械化学提取(MCE)和微波提取(MAE)等样品预处理技术为例,对不同研究领域中样品预处理技术与DART-MS联用的研究成果进行了综述,并对未来的发展趋势进行了展望。希望该综述能为开发与DART-MS联用的新型样品处理技术提供参考和帮助。     

吸热型碳氢燃料裂解引发剂筛选及引发机理分析

筛选可溶性添加剂替代多相催化剂, 达到促进吸热型碳氢燃料裂解、提高燃料热沉以及燃烧性能的目的. 采用考察裂解气相产物气体流量的方法进行实验. 测试了10种添加剂在500～650 ℃范围内对正庚烷裂解效果的影响. 研究发现, 三乙胺、2,6-二叔丁基对甲酚(BHT)可促进正庚烷裂解, 其它添加剂均无显著效果. 在550 ℃时, 当三乙胺质量分数达到6%时, 实验总气体收率比计算总气体收率增加80%以上. 机理研究表明, 三乙胺的引发剂基团来源于C—N键的断裂. BHT的结构、性状与前者显著不同, 在550 ℃时, 当BHT质量分数为3.4%时体系的气体收率较之纯正庚烷裂解气体收率增加80%以上, BHT的引发基团主要是连接于叔丁基上的甲基发生脱离的结果     

碰撞池-多接收电感耦合等离子体质谱测定硒同位素的质量偏移效应

通过改变雾化气流量、RF射频发生器功率、矩管位置和碰撞气流量等仪器参数,研究了碰撞池-多接收电感耦合等离子体质谱(Collision Cell-MC-ICP-MS)中的质量偏移效应。实验结果表明,雾化气流量、RF发生器功率和矩管位置等是质量偏移效应的主要来源,而碰撞气流量的影响很小。在此基础上,建立了MC-ICP-MS分析硒同位素丰度的最优化测量条件,同位素比R82/76的测量精度达到0.0043%。采用化学计量方法配制了两个系列硒同位素丰度校正样品,通过不同的同位素丰度比的质量偏移校正因子β和与其对应的同位素对的质量平均值成线性的关系,分析了样品GBW(E)080215和SRM3149中硒的同位素丰度组成。与样品SRM3149中82Se/76Se的比值相比,样品GBW(E)080215中的硒同位素分馏系数δ82/76为-4.78‰。     

微波消解-电感耦合等离子体发射光谱(ICP-OES)法测生物质中的碱金属和碱土金属

为研究并解决测试生物质样品中碱金属和碱土金属含量的干扰,采用微波消解-电感耦合等离子体发射光谱(ICP-OES)法对生物质中的碱金属和碱土金属钾、钙、钠、镁元素进行测定,考察了样品消解后不同的酸体系,共存元素干扰对钾、钠、钙、镁含量测定的干扰研究。经过研究表明,接近分析标准曲线酸浓度的样品干扰小,铅、铟、钛、锰元素对钠元素测定造成干扰,砷、铜、镉对钙元素测定干扰,铝对钾元素测定有干扰,镁测定不受共存元素干扰影响,运用干扰系数法可以减少共存元素对测定元素的误差。各待测元素标准曲线相关系数大于0.9996,检出限为0.0014~0.023 mg/L,玉米芯各元素的相对标准偏差为0.98%~1.9%,加标回收率为80.2%~106%;西瓜皮的各元素相对标准偏差为0.91%~2.3%,加标回收率为85.3%~106%。方法用于测定国家标准物质GBW07603,各元素结果均在标准值参考范围内。方法用于测定生物质中碱金属和碱土金属的结果,用t检验法与离子色谱测定值进行比对,结果无显著性差异。     

中学化学实验室气体环境的实测研究

对中学化学学生实验活动中产生的气体污染物进行测试,得到不同通风条件下化学实验室内部空气污染物的数据。结果表明,中学化学学生分组实验产生的主要气体污染物有苯、甲苯、甲醛、氨气等,实验过程中如不采取任何通风措施,实验室气体污染物的浓度短时间内会急剧升高,所以采取有效措施对实验室内部空气污染物进行消除是非常必要的。目前中学化学实验室配备的通风设备以桌面排风设备为主,相比于自然通风的环境,学生实验时开启桌面排风设备,能够有效降低实验产生的气体污染物浓度。     

CO2预处理操作条件对Ni-Co双金属催化剂性能与结构的影响

The performance of the Ni-Co bimetallic catalyst was significantly improved by a novel H₂ and CO₂ (HCD) pretreatment in the dry reforming of methane compared with traditional H₂ pretreatment. The effects of the HCD pretreatment operating conditions, such as pretreatment time, temperature, gas feeding ratio, and gas flow rate, on the catalytic performance of Ni-Co bimetallic catalyst were investigated. The optimal pretreatment time, temperature, gas feeding ratio (CH₄/CO₂), and gas flow rate were 0.5-1 h, 780-800 ℃, 0:10, and 175-200 mL·min^-1, respectively. Biogas was simulated with CH₄ and CO₂ in a volume ratio of 1 and without any other diluted gas. The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry (TG) coupled to differential scanning calorimetry (DSC). In a 511 h stability test under the optimized operating conditions, the catalyst pretreated with both H₂ and CO₂ exhibited excellent stability. The average conversions of CH₄ and CO₂, selectivities for H₂ and CO, and volume ratio of H₂/CO were 96%, 97%, 98%, 99%, and 0.98, respectively. The average carbon deposition rate over the Ni-Co bimetallic catalyst was only about 0.2 mg·g^-1·h^-1. The characterization results revealed that the sintering speed of the metal greatly decreased with testing time, and the metal particle will not greatly sinter with further testing time. The amount of deposited carbon on the catalyst gradually decreased and growth of filamentous carbon over the surface of the catalyst could be inhibited. The performance of the Ni-Co bimetallic catalyst was significantly improved by a novel H₂ and CO₂ (HCD) pretreatment in the dry reforming of methane compared with traditional H₂ pretreatment. The effects of the HCD pretreatment operating conditions, such as pretreatment time, temperature, gas feeding ratio, and gas flow rate, on the catalytic performance of Ni-Co bimetallic catalyst were investigated. The optimal pretreatment time, temperature, gas feeding ratio (CH₄/CO₂), and gas flow rate were 0.5-1 h, 780-800 ℃, 0:10, and 175-200 mL·min^-1, respectively. Biogas was simulated with CH₄ and CO₂ in a volume ratio of 1 and without any other diluted gas. The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry (TG) coupled to differential scanning calorimetry (DSC). In a 511 h stability test under the optimized operating conditions, the catalyst pretreated with both H₂ and CO₂ exhibited excellent stability. The average conversions of CH₄ and CO₂, selectivities for H₂ and CO, and volume ratio of H₂/CO were 96%, 97%, 98%, 99%, and 0.98, respectively. The average carbon deposition rate over the Ni-Co bimetallic catalyst was only about 0.2 mg·g^-1·h^-1. The characterization results revealed that the sintering speed of the metal greatly decreased with testing time, and the metal particle will not greatly sinter with further testing time. The amount of deposited carbon on the catalyst gradually decreased and growth of filamentous carbon over the surface of the catalyst could be inhibited. Thereby, great catalytic activity and stability could be obtained during the dry reforming of methane reaction.     

Fluctuation-enhanced gas sensing

The sensitivity of gas sensors was earlier measured by classical method-comparison the resistance of sensors in gas media and air. Here we reported results of the study of low-frequency noise characteristics of sensors. We compare data for different Figaro TGS sensors as well as our sol-gel H₂ tin dioxide and porous silicon sensors. The study was performed in dry air and in a mix of dry air with carbon monoxide, hydrogen and alcohol of different concentrations. Higher sensitivity of spectral dependence of noise (SDN) to gas concentration in comparison with classical method of the measurements of gas sensing by a change in the Ohmic resistance part of current-voltage characteristics of samples allows using such SND powerful method for determination of gas concentration in the air or environment.     

Stability of reactive low boiling hydrocarbons on carbon based adsorbents typically used for adsorptive enrichment and thermal desorption

In the context of evaluating air sampling methods, laboratory experiments were performed to investigate the stability of eleven selected low boiling hydrocarbons (e.g. 1,3-butadiene, isoprene) adsorbed on four different carbon based adsorbents. The carbon molecular sieves Carboxen 569, Carboxen 1003, Carbosieve SIII and the graphitized carbon black Carbotrap X were tested. The influence of storage duration on the recovery of the analytes was examined by loading the adsorbent tubes with the test compounds via a sample loop under inert gas. Furthermore, the influence of sampling the hydrocarbons continuously from air on the recovery of the analytes was investigated using a simple experimental set-up providing a flow of synthetic air spiked with the hydrocarbons. Analysis of the loaded adsorbent tubes was performed by thermal desorption and capillary gas chromatography. Losses up to 80% of 1,3-butadiene and isoprene were observed for the carbon molecular sieves, occurring even immediately after the sampling step. In contrast, no significant losses of these reactive constituents were detected for Carbotrap X over a storage time of seven days. The laboratory investigations were confirmed in a field experiment.     

不同前处理制样方法对钢中氧、氮测定结果的影响

讨论了不同物理和化学制样方法对钢中氧、氮测定结果的影响。试验结果表明,物理制样采用锉刀打磨样品表面后剪切,再用乙醚清洗除去油污;化学制样先用20%盐酸溶液溶解样品表面氧化层,再用滴加了4滴30%过氧化氢的10%草酸溶液浸泡,取出后依次用水、无水乙醇浸洗,风干。用以上两种方法制样,钢标准样品中氧、氮含量测定值与标示值一致。在测定钢中氮含量时,可用乙醚清洗后直接测定,以缩短检测周期和减轻劳动强度。该研究结果可用于指导钢样品中氧、氮含量测定时样品的处理。     

Modeling on the Momentum and Heat/Mass Transfer Characteristics of an Argon Plasma Jet Issuing into Air Surroundings and Interacting with a Counter-Injected Argon Jet

Modeling study is performed to reveal the momentum and heat/mass transfer characteristics of a turbulent or laminar plasma reactor consisting of an argon plasma jet issuing into ambient air and interacting with a co-axially counter-injected argon jet. The combined-diffusion-coefficient method and the turbulence-enhanced combined-diffusion-coefficient method are employed to treat the diffusion of argon in the argon–air mixture for the laminar and the turbulent regimes, respectively. Modeling results presented include the streamline, isotherm and argon mass fraction distributions for the cases with different jet-inlet parameters and different distances between the counter-injected jet exit and the plasma torch exit. It is shown that there exists a quench layer with steep temperature gradients inside the reactor; a great amount of ambient air is always entrained into the plasma reactor; and the flow direction of the entrained air, the location and shape of the quench layer are dependent on the momentum flux ratio of the plasma jet to the counter-injected cold gas. Two quite different flow patterns are obtained at higher and lower momentum flux ratios, and thus there exists a critical momentum flux ratio to separate the different flow patterns and to obtain the widest quench layer. There exists a high argon concentration or even ‘air-free’ channel along the reactor axis. No appreciable difference is found between the turbulent and laminar plasma reactors in their overall plasma parameter distributions and the quench layer locations, but the values of the critical momentum flux ratio are somewhat different.     

Stability of reactive low boiling hydrocarbons on carbon based adsorbents typically used for adsorptive enrichment and thermal desorption

In the context of evaluating air sampling methods, laboratory experiments were performed to investigate the stability of eleven selected low boiling hydrocarbons (e.g. 1,3-butadiene, isoprene) adsorbed on four different carbon based adsorbents. The carbon molecular sieves Carboxen 569, Carboxen 1003, Carbosieve SIII and the graphitized carbon black Carbotrap X were tested. The influence of storage duration on the recovery of the analytes was examined by loading the adsorbent tubes with the test compounds via a sample loop under inert gas. Furthermore, the influence of sampling the hydrocarbons continuously from air on the recovery of the analytes was investigated using a simple experimental set-up providing a flow of synthetic air spiked with the hydrocarbons. Analysis of the loaded adsorbent tubes was performed by thermal desorption and capillary gas chromatography. Losses up to 80% of 1,3-butadiene and isoprene were observed for the carbon molecular sieves, occurring even immediately after the sampling step. In contrast, no significant losses of these reactive constituents were detected for Carbotrap X over a storage time of seven days. The laboratory investigations were confirmed in a field experiment. Received: 28 June 1999 / Revised: 18 August 1999 / Accepted: 23 August 1999     

太原东山煤地下气化模型试验研究

通过地下气化模型试验，获得了东山煤地下气化过程的一般规律。进行了东山煤空气气化及纯氧-水蒸气气化试验，研究了鼓风量及气氧比对煤气组成的影响、气化过程的稳定性以及试验条件下的煤层气化速率变化，进行了纯氧-水蒸气地下气化的物料衡算。试验结果表明，东山煤空气气化可以生产低热值空气煤气，鼓风量会影响空气煤气的组成；纯氧-水蒸气地下气化可以获得合格的二甲醚合成原料气，但需根据气化工作面的移动及煤气组成变化，采用移动点供风气化维持气化过程连续稳定进行。气化过程的物料衡算可以用来预测气化煤气的基本组成。气氧比影响煤气组成变化，试验条件下适宜的气氧比范围为1.8～2.2。气化工作面扩展速率在供风点附近出现最大值，变化平稳，瘦煤地下气化具有较高的稳定性。     

CO2预处理操作条件对Ni-Co双金属催化剂性能与结构的影响

与传统H₂预处理方法相比,新型H₂+CO₂预处理方法（HCD）能显著提升Ni-Co双金属催化剂的沼气重整活性及抗积碳性能. 考察了HCD预处理操作条件对催化剂性能与结构的影响. 较好的HCD预处理操作条件是在催化剂经H₂处理之后,再用175-200 mL·min^-1的原料气CH₄/CO₂（比例为0：10）在780-800 ℃下还原0.5-1h. 在优化预处理操作条件下对催化剂进行了511 h的耐久性考察,并运用X射线衍射（XRD）、热重-差示扫描量热（TG-DSC）、透射电子显微镜（TEM）等手段对耐久性测试后的催化剂进行了表征. 在511 h 的稳定性实验内,CH₄、CO₂转化率,H₂、CO选择性及H₂/CO体积比分别高达96%、97%,98%、99%及0.98. 催化剂在测试期间的平均积碳速率仅为0.2 mg·g^-1·h^-1. 在该预处理操作参数下,催化剂拥有最好的综合性能和良好的耐久性.     

炭化过程对铁基费托合成催化剂强度和结构的影响

以模型费托合成Fe基催化剂为研究对象,在纯CO气氛中对催化剂进行不同时间的预处理,采用多种手段对预处理后催化剂的物理化学性质和抗磨损能力进行了表征。结果表明,在预处理初期,随着预处理时间的延长,催化剂的炭化程度显著提高,伴随着催化剂比表面积的降低和颗粒粒径的减小,而催化剂的抗磨损能力逐渐提高。当预处理时间超过72 h后,继续延长预处理时间,催化剂的炭化程度不再增加,而积炭程度逐渐增加,伴随着催化剂比表面积和颗粒粒径的增加,催化剂的质量也同时增加,并导致催化剂的抗磨损能力逐渐降低。