石英晶体微天平的研究进展综述

石英晶体微天平(QCM)能够感知到纳克级的质量变化,在分析化学、电化学、有机化学、生物医学等方面得到了广泛的应用。根据与QCM电极表面相接触的研究介质即应用对象的不同,分别阐述了刚性薄层、牛顿流体、粘弹性膜层的基础方程、分析方法及应用,并探讨了其存在的问题与发展趋势。     

Carbon dioxide sorption in conventional and plasma polymerized methyl methacrylate thin films

CO₂ sorption isotherms are reported for plasma polymerized methyl methacrylate (ppMMA) and the conventionally polymerized analog, poly(methyl methacrylate) (PMMA). The isotherms are measured at temperatures ranging from 20 to 95 °C and analyzed using the Dual-Mode sorption model. In the lower temperature range, the magnitude of the Henry's law (k_D) and the coupled Langmuir component parameters (C′_Hb) for both materials are similar. The expected collapse of the Langmuir sorption mode in conventional PMMA near the glass transition temperature is clearly observed. However, the Langmuir component in the plasma polymerized material does not diminish in the same manner as that for the conventional polymer analog. In contrast with the ppMMA, the PMMA materials are shown to exhibit significant dilation for extended conditioning times at high CO₂ pressures. The response of the isotherms for the two materials to ‘quench’ and ‘slow cool’ thermal conditioning protocols are similar, but small.     

Quantitative determination of corrosion products and adsorbed water on copper in humid air containing SO2 by IR-RAS measurements

The time dependency of the amounts of corrosion products and co-existing adsorbed water on copper in humid air containing SO₂ was estimated from a series of in situ time-resolved IR-RAS spectra on the basis of the relations between the band intensities and the mass changes of the corrosion products, which were determined by simultaneous measurement of IR-RAS and QCM. The amounts of both corrosion products increased slowly at the initial stage and later increased rapidly. Although the relative humidity was kept constant, the amount of adsorbed water increased nearly the same behavior as that of corrosion products in the stage of relatively small amounts of corrosion products and later increased rapidly when the amounts of corrosion products increased. In humid air without SO₂, sulfite gradually decomposed and some of it changed into sulfate.     

DESIGN OF TEMPERATURE CONTROLLED QUARTZ CRYSTAL MICROBALANCE SYSTEM

In this study, the dual modulated quartz crystal microbalance (QCM) with heating and cooling control has been developed for the quantitative determination of biological molecules, as a biosensor. On the other hand, since, the Sauerbrey formula is misprinted in some publications, the correct form of formula is also discussed. The proposed QCM biosensor has three main parts, which are the oscillator circuit, temperature control circuit, and the differential frequency measurement unit. Colpitts oscillators with the buffer amplifier, microcontroller (PIC16F877) for the temperature control circuit and a peltier element were used for heating and cooling inside the developed system. Differential frequency measurement is a known technique to compensate environmental effects causing instability of crystals. For this reason, one of the crystals is implemented with oscillatory circuits, i.e., the detector; the other one is used as the reference. The designed system was tested between 8°C and 50°C and frequency shift versus temperature is observed at 0.5 ppm/°C over a given temperature range.     

基于ARM的嵌入式高精度频率计的设计

利用石英晶体微天平测量微量元素时,设计一种高分辨率的频率计至关重要。通过改进硬件电路,解决了多周期同步测频方法在实际应用中并未完全消除＋1误差的问题,彻底消除了被测信号的±1量化误差。采用高精度有源晶振作为基准频率,利用ARM7微控制器LPC2220实现频率的计算、校准、闸门智能切换等,提高了频率计精度,频率测量分辨率达到0．1Hz以上,尤其适用于实时、高速、高精度测量等场合。在QCM微量元素分析仪中的应用表明,此方案稳定可靠,测量快速,结果精确。     

石英晶体微天平原位研究铝的大气腐蚀

目的研究NaCl,（NH4）：SO4,Na2SO4和NH4Cl的潮解性能及其沉积铝的大气腐蚀行为,揭示盐的潮解性对铝腐蚀的影响规律．方法在温度25℃±1℃,相对湿度80％±2％的净化空气中,采用石英晶体微天平（QCM）在镀金的石英晶片上研究了NaCl,（NH4）2SO4,Na2SO4和NH4Cl的潮解性．在温度25±2±1℃,相对湿度80％±2％的净化空气和含SO2的气氛中,用石英晶体微天平（QCM）研究了盐沉积后铝的腐蚀行为,通过扫描电子显微镜、X射线能谱仪、傅立叶红外光谱手段进行表征．结果发现NH4Cl的潮解性能最强,其后依次为（NH4）2SO4,NaCl,Na2SO4．铝在含SO2的气氛中的腐蚀比在净化空气中严重,并且经NH4Cl沉积的铝腐蚀最为严重,接着依次为（NH4）2SO4,NaCl,Na2SO4．盐沉积后,铝在盐沉积区开始腐蚀,然后扩展到其他区域．结论经盐沉积后铝腐蚀的程度与盐的潮解性能有关,潮解性能越大,腐蚀越严重．对腐蚀产物结构的测定,在含SO2的气氛中铝的腐蚀产物主要是由硫酸盐组成。因而其腐蚀较为严重．     

Designing of MIP-based QCM sensor for the determination of Cu(II) ions in solution

A novel quartz crystal microbalance (QCM) sensor with a high selectivity and sensitivity has been developed for the determination of Cu(II) ions, based on the modification of Cu(II) ion-imprinted polymer (Cu(II)-IIP) film onto a quartz crystal. The performance of the developed MIP-QCM sensor was evaluated and the results indicated that a sensitive MIP-QCM sensor could be fabricated. The obtained MIP-QCM sensor presents high-selectivity monitoring of Cu(II) ions, better reproducibility, shorter response time (6 min), wider linear range (0.001–50 μM) and lower detection limit (8 × 10⁻⁴ μM). The practical analysis of the MIP-QCM sensor confirms the feasibility of Cu(II) determination in wastewater.     

Self-assembly of polyelectrolytic multilayer thin films of polyelectrolytes on quartz crystal microbalance for detecting low humidity

Low-humidity sensors were made by layer-by-layer (LBL) self-assembly of poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA) or poly(styrenesulfonic acid) sodium salt (PSS) and poly(allylamine hydrochloride) (PAH) into multilayer thin films on a gold electrode of quartz crystal microbalance (QCM). The thin films were characterized by QCM and atomic force microscopy (AFM). The effects of maleic acid (MA) in PSSMA, the number of layers and the ionic strength on the low-humidity sensing properties (sensitivity) were compared with those of PSS. The sensitivity of the PSSMA/PAH multilayer thin film exceeded that of the PSS/PAH multilayer thin film when the multilayered thin films of polyelectrolytes were prepared from solutions without NaCl. The sensitivity of both PSSMA/PAH and PSS/PAH multilayered thin films was increased by increasing the number of layers and by adding salt to the deposition solution. The PSS/PAH multilayered thin film that was prepared from the solutions with NaCl had the highest sensitivity (1.923 −ΔHz/Δppm_v at 27.5 ppm_v) and a short response time. Spin-coating was also adopted to fabricate PSS-based low-humidity sensors for comparison.     

基于QCM的水果中金属离子检测方法研究

以压电石英晶体的波动方程作为理论基础,首先推导了气相条件下石英晶体微天平(QCM)传感器的相位 质量关系式。然后以猕猴桃中Cu2+检测为例,分别测量出QCM传感器对应的频率偏移量及相位偏移量,应用Sauerbrey方程和新推导的相位——质量方程,计算出猕猴桃中Cu2+的含量;最后,将这两种方法的实验结果进行分析比较并进行了相关讨论。结果表明,基于压电QCM相位检测原理的金属离子检测也是一种有效的金属离子检测方法。     

ADSORPTION OF ETHOXYLATED NONIONIC SURFACTANTS FROM SILOXANE-BASED SOLVENT AND AQUEOUS SYSTEMS: USE OF QCM AND MODEL POLYMERIC SURFACES

Adsorption behavior was quantified with pure ethoxylated nonionic surfactants onto different polymeric surfaces (hydrophilic cotton and hydrophobic polyester) and model hydrophilic gold surface. The polymer materials used for the study were characterized using SEM. The role of ethylene oxide group variation in surfactant-polymer interaction was established using pure surfactant with the same alkyl chain length but varying ethoxylate chain lengths. It was observed that surfactant with more ethylene oxide groups per molecule, being more hydrophilic, interacts favorably with cotton in the hydrophobic siloxane solvent environment. The adsorption of the pure surfactants on model gold surface from hydrophobic solvent and water was also established using the quartz crystal microbalance with dissipation monitoring (QCM-D) system. Effect of ethylene oxide chain length and surfactant concentration on the extent of adsorption was quantified. At the gold-water interface, the plateau adsorption for C₁₂ E₃ (15.9 × 10^?6 mole/m²) is about four times higher than for C₁₂E₈. An opposite trend was observed for adsorption of the surfactants on gold in the hydrophobic D5 environment. Information about thickness, adsorption and desorption kinetics, and structure of adsorbed layer was obtained from the QCM-D frequency-dissipation data. The study is an important contribution towards fundamental understanding of applications involving the use of ethoxylated nonionic surfactants.