磁响应性贵金属核/壳纳米复合粒子制备研究进展

磁响应的贵金属核/壳结构复合纳米粒子具有不同于单组分纳米粒子更优越的多重功能,在催化剂、光学材料、生物传感器及生物医学领域具有重要前景。从核/壳结构类型出发,综述了具有磁响应的贵金属核/壳结构纳米复合粒子的化学制备与结构特征,并简要对其应用研究进展做了讨论。     

Gelatin/BaTiO3核壳复合粒子的制备及电场响应性能研究

以平均粒径为0.7~0.9 mm的明胶(Gelatin)微球为基核, 通过定向沉积自组装法成功制备了以Gelatin为核、BaTiO₃为壳的Gelatin/BaTiO₃核壳复合粒子。利用TEM、XRD、FT-IR、TG和光学接触角测量等技术对复合粒子的形貌、结构、组成及表面亲水性能进行了研究。结果表明, 复合粒子为球形微粒, 具有良好的表面亲水性和分散稳定性, BaTiO₃壳层约占粒子总质量的18.8%, 具有立方相晶相结构。将粒子分散到水凝胶弹性体中, 测量在有/无电场作用下得到的弹性体的储能模量, 借以考察复合粒子在弹性体中的电场响应性能, 发现Gelatin/BaTiO₃复合粒子的电场响应性能明显强于纯BaTiO₃粒子。说明将BaTiO₃包覆在聚合物上能显著提高BaTiO₃粒子的电场响应性能。     

BaTiO3/gelatin核壳复合粒子的制备及电场响应性能研究

为了提高BaTiO3颗粒在含水弹性体中的电场响应能力,以粒径约为500nm的单分散球型Ba-TiO3颗粒为基础,采用微乳液法成功制备了BaTiO3为核、明胶(gelatin)为壳的BaTiO3/gelatin核壳复合粒子。利用TEM、XRD、FT-IR、TG和光学接触角测量等手段对粒子的组成、结构及表面亲水性能进行了表征和测量。结果表明,在立方相BaTiO3核的表面均匀包覆了1层约40～50nm的gelatin,Gelatin壳层约占粒子总重的4.0%,且粒子表面保持良好的亲水性。将粒子分散到含水胶体体系中,通过测量在无/有电场作用下胶凝得到的含水弹性体的储能模量考察了粒子在此体系中的电场响应性能,发现BaTiO3/gelat-in复合粒子在明胶(或壳聚糖)水凝胶弹性体中的电场响应性能均明显强于纯BaTiO3粒子,而且在明胶水凝胶中的响应性能更强。结果说明,聚合物包覆能够明显提高BaTiO3粒子的电场响应性能,而且粒子表面与分散体系相容性越高,粒子的响应性能越好。     

原位聚合法制备炭黑/聚甲基丙烯酸酯导电复合材料

通过原位聚合法制备了炭黑/聚甲基丙烯酸甲酯(CB/PMMA)、炭黑/聚甲基丙烯酸丁酯(CB/PB-MA)和炭黑/聚甲基丙烯酸2-乙基己酯(CB/PEHMA)三种导电复合材料,研究了这三种聚合物基体对复合材料的导电性影响。结果表明:由于炭黑的阻聚作用,当复合材料的炭黑含量增加时,均聚物的数均分子量呈下降趋势,多分散性系数PDI变大。而且炭黑粒子表面发生了接枝聚合反应,这有利于炭黑粒子在聚合物基体中的分散。当聚合物基体的玻璃化温度Tg较高时,复合材料逾渗阈值较低。     

HDPE/EVA/CB复合导电材料的研究

研究了HDPE/EVA/CB(炭黑)复合材料的导电性及正温度系数(PTC)特性,包括电阻-温度特性和电流-时间特性.发现在HDPE/CB复合材料中加入少量的EVA能降低室温电阻率、改善炭黑粒子的分散、增强PTC效应以及缩短材料的响应时间,并从基体的结晶性及炭黑在共混基体中分布的角度探讨了EVA组分对复合材料电性能影响的作用机理.     

低压缩永久变形导电炭黑/硅橡胶复合材料的制备与性能

为获得一种低压缩、永久变形及高回弹的导电屏蔽硅橡胶密封材料,以经偶联剂表面处理的炭黑作补强剂及导电填料,乙烯基硅橡胶生胶作基料,制备出一种导电炭黑/硅橡胶复合材料。研究了不同炭黑含量的导电炭黑/硅橡胶复合材料的力学性能、弹性、分散性以及电性能,采用SEM观察了炭黑在硅橡胶基体中的分布形貌,分析了导电炭黑/硅橡胶复合材料的导电机制及屏蔽机制。结果表明:随着炭黑含量的增加,导电炭黑/硅橡胶复合材料的Shore A硬度由31增至70;拉伸强度先由3.31 MPa增至5.28 MPa,而后趋于稳定;拉断伸长率先由198%增至297%,然后再减小至210%;恒定压缩永久变形量先减小后增大,瞬间回弹率逐渐减小;由于"炭黑簇"的形成及导电通路的完善,导电炭黑/硅橡胶复合材料的导电性能及屏蔽效能增强。     

炭黑粒子表面改性及其电磁特性研究

采用溶胶-凝胶法制备钛酸钡改性炭黑的复合粒子,并观察和分析了改性后粒子的颗粒结构、体电阻率和介电性能.经XRD分析可知复合粒子中存在钛酸钡和炭黑;TEM和SEM研究表明,通过溶胶-凝胶法在炭黑表面包覆了钛酸钡绝缘层,从而使得改性后的炭黑粒子之间不能建立发达的导电网络,复合粒子导电性能降低.研究表明钛酸钡改性对复合粒子的电导率和介电性能有着重要影响.     

还原剂用量对HGM/Ni-P核/壳复合粒子微波吸收性能的影响

以NaH2PO2为还原剂,采用化学镀方法,在空心玻璃微球表面沉积Ni-P层,获得了轻质空心玻璃微球/Ni-P核/壳复合粒子(简称为HGM/Ni-P核/壳粒子)。采用扫描电子显微镜(SEM)、能谱仪(EDX)、X射线衍射仪(XRD)以及网络矢量分析仪(VNA)研究了化学镀过程中不同还原剂用量对复合粒子形貌、结构、成分及其微波吸收性能的影响规律。结果表明,随着还原剂NaH2PO2用量的增大,HGM/Ni-P核/壳粒子的表面形貌变化不大,壳层中P含量随之升高,非晶成分增多。HGM在镀覆后介电性质与磁导率较镀覆前显著提高。随着NaH2PO2由20g/L增加到30g/L时ε′和ε″的响应峰向高频移动,增加到40g/L时其响应峰消失,且介电常数下降。同时,HGM/Ni-P核/壳粒子的μ′和μ″曲线中6～8GHz处代表自然共振的峰随着NaH2PO2浓度的增加而消失。     

钛酸钡化学原位改性炭黑粒子的电磁性能

采用溶胶-凝胶法制备出了钛酸钡改性炭黑的复合粒子,并观察和分析了改性粒子的颗粒成分、结构、微波介电特性及其对电磁波的吸收性能.XRD分析可知复合粒子中含有钛酸钡晶体和炭黑.TEM研究表明,溶胶-凝胶法很好地在炭黑表面包覆了一层钛酸钡绝缘层,从而使得基体中的炭黑粒子形成导电孤岛.结果表明钛酸钡改性对不同炭黑含量有着不同的影响:当炭黑体积含量较低时(＜20%),钛酸钡的包覆降低了复合材料的吸波效能;当体积百分含量超过20%时,钛酸钡的包覆提高了复合材料的吸波效能.这主要是因为钛酸钡包覆炭黑粒子形成的"导电孤岛"对复合材料的电性能影响的缘故.     

聚合物接枝改性炭黑粒子表面性质研究

研究了由聚合物表面接枝改性炭黑和氯化钾水溶液组成的分散体系中炭黑粒子表面的ｚｅｔａ电位的变化，探讨了阴离子表面活性剂十二烷基苯磺酸钠和阳离子表面活性剂十二烷基苄基二甲基氯化胺在普通炭黑和聚合物接枝改性炭黑表面的吸附行为。研究表明，聚丙烯酸接枝改性炭黑粒子表面的ｚｅｔａ电位远低于未接枝改性的炭黑子粒，但由聚丙烯酰胺接枝改性炭黑粒子的表面ｚｅｔａ电位值不发生明显的变化。     

膜空分所产氮气湿度的影响因素

就空分（Ｎ２／Ｏ２分离）膜的进气压力、进气波量、进气温度和湿度及氮气纯度这些可能影响膜所产氮湿度的因素进行了试验研究,发现除进气湿度外,其它因素对之没有直接的影响;当进气湿度一定时,所产氮气的湿度只跟氮气的纯度有关,而且成确定的对应关系。试验表明了水气对该膜具有较强的渗透能力,这为膜组件的空气预处理方案设计提供重要的试验依据。     

A New Strategy for Humidity Independent Oxide Chemiresistors: Dynamic Self‐Refreshing of In2O3 Sensing Surface Assisted by Layer‐by‐Layer Coated CeO2 Nanoclusters

The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self‐refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In₂O₃ hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO₂ nanoclusters is uniformly loaded onto In₂O₃ hollow spheres via layer‐by‐layer (LBL) assembly. Moreover, In₂O₃ sensors LBL‐coated with CeO₂ nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In₂O₃ sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO₂ and the chemical interaction among CeO₂, In₂O₃, and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring.     

Effect of Structure on Environmentally Assisted Subcritical Crack Growth in Brittle Materials

Subcritical crack growth in brittle materials is considered when it is thermally activated and water vapor affected. Effects of material structure on the crack growth were investigated. Special case of subcritical crack growth is examined when the crack growth is decided by water vapor enhanced rupture of some particulate strength controlling elements of material structure. The water vapor is assumed to be transported to these elements through the material by diffusion in a gas filling a system of interconnected open pore channels in the material volume. Calculated crack velocity plots versus the stress intensity factor, temperature and humidity are presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

压缩空气脱湿和乙醇气相脱水的集成膜过程研究

采用聚酰亚胺中空纤维膜以气流吹扫操作方式进行乙醇气相脱水研究 ,干燥的吹扫气流由压缩空气膜法脱湿组件提供 ,此两过程构成了集成膜过程 ;讨论了膜材料改性、吹扫气流的湿度和流速、操作温度等条件对乙醇脱水效率的影响 .     

碳湿敏元件非线性感湿特性的影响因素

研究了不同配比导电炭黑和羟乙基纤维素(HEC)感湿胶制备的碳湿敏元件的感湿特性,探讨了山梨醇增湿剂对感湿非线性特性的影响。对碳湿敏元件的体积电阻率、湿敏特性和复阻抗谱的测试结果表明,炭黑含量和山梨醇含量对非线性感湿特性有很大影响,2%炭黑试样在80%湿度附近开始出现电阻的非线性增大;适量山梨醇使试样的非线性湿度响应移向较低湿度区。试样的复阻抗谱在54%湿度时为1个带拖尾的半圆弧,80%湿度时变为带拖尾的2个半圆弧,更高湿度时是拖尾拉长变形明显的2个半圆弧,表明其等效电路是由包括体电阻、炭黑粒界电阻和电极接触电阻三个阻容并联体的串联组成。半圆弧数目随湿度增加的现象,与感湿膜中水分子增加使不同极化机制的作用变得更加明显有关。     

The power source effect on SiOx coating deposition by plasma enhanced chemical vapor deposition

SiOx coatings were prepared by capacitively coupled plasma enhanced chemical vapor deposition on polyethyleneterephtalate substrates in 23 kHz middle-frequency and radio frequency power supplies, respectively, where hexamethyldisiloxane was used as gas source. The influences of discharge conditions on gas phase intermediate species and active radicals for SiOx formation was investigated by mass spectrometry as real-time in-situ diagnosis. The deposited SiOx coating chemical structures were also analyzed by Fourier transform infrared spectroscopy. Meanwhile, the film barrier property, oxygen transmission rate, was measured at 23 °C and 50% humidity circumstance. The better barrier property was obtained in the MF power source depositing SiOx coated PET.     

A new polysiloxane coating on QCM sensor for DMMP vapor detection

A new material-poly{methyl [3-(2-hydroxyl, 4,6-bistrifluoromethyl)phenyl]propylsiloxane} (PMTFMPS), which was sensitive to toxic organophosphate vapor, was synthesized via O-alkylation, claisen rearrange reaction and hydrosilylation reaction. The polymer was coated on quartz crystal microbalance (QCM) to investigate its gas sensitive properties to nerve agents’ simulant dimethyl methylphosphonate (DMMP) vapor, as well as other interfering vapors. It was found that QCM sensor responded linearly to DMMP vapor with a slope of 27 Hz/ppm in the 10–50 ppm range. The material was much more sensitive to DMMP than to other interfering vapors, thus high selectivity to DMMP was demonstrated. The influence of humidity on the sensor response was also examined. The results showed that the frequency shifts were about 60% when tested in 77% RH wet air than in dry N₂. When compared with our previously studied unfluorinated phenol-modified siloxane PMPS, PMTFMPS exhibited sensitivity enhancement of 2.3 times and an increased resistance to humidity variations.     

FATIGUE CRACK CLOSURE AND RESIDUAL DISPLACEMENT MEASUREMENTS ON ALUMINUM ALLOYS

Abstract —Ultrasonic bulk measurement technique was used to measure crack closure and a clip-on gage surface measurement technique was used to measure residual displacement at the crack tip of a propagating fatigue crack in 2219 and 7075 aluminum alloys. Experiments were carried out in vacuum, humid air, dry O₂ gas, N₂ gas, and deuteriated water vapor environments to evaluate effects of environments on residual strain and crack closure loads. It was observed that the closure load detected by ultrasonics decreased with introduction of humidity while the residual strain parameter dincreased with the humidity. The results are modeled as a build-up of oxide layer in addition to strengthening of asperities on the fracture surface. In the light of these observations, the effectiveness of surface and bulk measurements is evaluated. The results demonstrate that surface measurements are not always representative of the bulk behavior and use of such measurements in predictive analysis for fatigue can be misleading.     

一种基于碳黑/聚四乙烯吡啶纳米复合物的新型湿度传感器

以4-羟-2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)为引发剂,通过本体聚合方法制备聚四乙烯吡啶(P4VP)接枝纳米碳黑(CB)复合材料,以溴丁烷和1,4-二溴丁烷分别与之进行季胺化和交联季胺化反应,制得了新型电阻型湿敏材料.测试了该类纳米复合湿敏材料的温度响应特性,发现其在低湿环境下也具有较好的导电性,而且材料的导电行为同时存在离子导电和电子导电两种机理.通过改变碳黑与聚合物的相对比例,使聚合物产生季胺化以及交联季胺化反应等,可以调控两种导电机理的复合材料在电响应中所起的作用,从而改变其湿敏响应特性,制备可以全程响应的电阻型湿度传感器.     

Selective real-time measurement of styrene vapor using a surface-acoustic-wave sensor with a regenerable organoplatinum coating

The performance of a coated surface-acoustic-wave (SAW) sensor for monitoring styrene vapor is investigated. The effects of several organic co-contaminants and atmospheric humidity are described, and regeneration of the sensor coating is demonstrated. The dual-SAW delay-line oscillator employs a reagent coating of trans-PtCl2(ethylene)(pyridine) to trap styrene via ethylene substitution. The rate of change of the sensor frequency is used to provide real-time measurement of styrene vapor concentrations. No effect on the response to styrene is observed upon simultaneous exposure to each of several olefin and non-olefin solvent vapors used with styrene in industrial processes. Butadiene, however, presents a reversible negative interference by successfully competing with styrene for reaction with the trapping agent. The response to styrene exhibits a moderate positive humidity dependence. Following prolonged exposure, the original complex can be regenerated in situ by exposure to ethylene gas, permitting repeated use of the sensor. An emphasis is placed on the application of the sensor to workplace air monitoring.