丙烯酰胺类共聚物水凝胶的合成及性能研究

用自由基聚合法合成了不同摩尔配比的HEMA／AM共聚物水凝胶材料。研究了单体组成、温度、pH值、离子强度等因素对凝胶溶胀性能的影响。结果表明：水凝胶的溶胀速度较快;水凝胶在pH值小于4及pH值大于9的酸、碱溶液中发生水解,导致水凝胶的饱和含水量大幅增加,而在弱酸性溶液中几乎没有变化;水凝胶的饱和含水量对离子强度的变化不够敏感;随着温度的升高水凝胶的饱和含水量略有减少,说明此类水凝胶对温度的敏感性也较弱。     

NVP-HEMA-AM三元共聚物水凝胶对氯霉素的缓释作用

采用本体共聚法制备了丙烯酰胺(AM)与甲基丙烯酸-2羟-基乙酯(HEMA)以及N-乙烯基吡咯烷酮(NVP)共聚物水凝胶,研究了AM-HEMA-NVP共聚物水凝胶对广谱抗菌药物氯霉素的缓释作用。结果表明,随氯霉素溶液浓度增大、NaC l浓度降低、温度升高以及NVP或者AM组分的含量增大,AM-HE-MA-NVP三元共聚物水凝胶对氯霉素的吸收量增大;随AM-HEMA-NVP三元共聚物水凝胶中NVP或者AM组分含量的增大,氯霉素的释放速度明显增大;氯霉素从水凝胶中缓释的动力学可采用Fick扩散动力学描述,其释放过程受水凝胶溶胀过程以及氯霉素扩散过程控制。     

甲基丙烯酸β-羟乙酯共聚水凝胶的合成及性能研究

以HEMA、AAM为共聚单体,采用溶液聚合法合成了HEMA/AAM共聚水凝胶,并对其溶胀动力学、离子强度、温度、pH值等性能进行了测定。实验表明:合成的水凝胶初始溶胀迅速,达到平衡溶胀比平衡约6h;在不同离子强度的水溶液中,随着离子强度I的增大,凝胶的ESR不断降低;在pH<7时,其EKR随pH值的增加而减少,在pH>7时,其ESR随pH值的增加而猛增,因为发生了水解反应;凝胶的ESR随温度的升高而降低。     

聚甲基丙烯酸/丙烯酰胺pH敏感凝胶的合成与溶胀行为研究

以单体丙烯酰胺(AM)、甲基丙烯酸(MAA),交联剂N-N'亚甲基双丙酰胺(BIS)为原料,通过自由基共聚合成了聚甲基丙烯酸/丙烯酰胺[P(MAA-co-AM)]水凝胶.研究了干凝胶在不同pH溶液中的溶胀动力学,结果表明不同AM、MAA单体配比的凝胶溶胀性具有很大差异,其溶胀率都随着溶液的pH增加而增大,在pH=12和pH=2溶液反复变换时显示可逆溶胀-退溶胀和快速响应特性,溶胀-退溶胀过程中搅拌作用对凝胶响应速率有显著影响.吸水平衡P(MAA-co-AM)水凝胶在酸性及碱性条件下均出现收缩,在pH=2下10 min之内凝胶收缩90%以上,随着pH增大逐渐减慢.通过不同浓度的NaCl与CaCl2溶液研究了溶液离子强度以及反离子的电荷数对凝胶溶胀性影响,在NaCl溶液和水中,呈现反复溶胀-退溶胀响应特性.     

水凝胶-水凝胶复合材料的制备与表征

将聚乙二醇400(PEG400)溶胀的交联N-乙烯吡咯烷酮(NVP)水凝胶微粒浸渍在含有引发剂过氧化苯甲酰(BPO)的甲基丙烯酸-2-羟基乙酯(HEMA)单体中并加热引发聚合反应,制备水凝胶-水凝胶复合材料,研究了产物的溶胀行为,并采用SEM、DSC对产物进行了表征。结果表明,水凝胶-水凝胶复合材料的饱和含水量随交联NVP水凝胶颗粒的含量及饱和含水量增大而增大,两种水凝胶之间的界面结构可分为包埋、部分互穿网络以及完全部分互穿网络等三种,其原因在于HEMA单体部分进入交联NVP水凝胶微粒并进行原位聚合的程度不同;处于分散相的水凝胶与处于连续相的水凝胶的吸水倍率不同,导致水凝胶-水凝胶复合材料吸水溶胀时不同相结构之间互相制约,处于分散相的水凝胶的大分子链不能充分伸展,非冻结水的熔融峰被自由水的熔融峰掩盖,表现为DSC谱图上非冻结水的熔融峰被自由水的熔融峰掩盖。     

温度、pH及离子强度敏感性聚氨酯水凝胶的合成与性能研究

以甲苯二异氰酸酯(TDI)、聚乙二醇(PEG-6000)、二羟甲基丙酸(DMPA)及三乙撑四胺(TEFA)等为原料,合成了温度、pH、及离子强度敏感性聚氨酯水凝胶(PUHG)。研究了PUHG溶胀率(SR)受温度(T)、pH、离子强度(I)、交联剂用量等因素的影响。结果表明PUHG的溶胀率在20~45℃的范围内随温度的升高而减小,45℃后不再变化;在酸性(pH4)溶液中收缩,在碱性(pH9)溶液中溶胀,表现出良好的pH值敏感性;在一定温度和pH下,随着离子强度的增加PUHG的溶胀率减小。水凝胶溶胀动力学研究表明,PUHG具有良好的溶胀-退胀可逆性。     

P（MA—AA）／PEG水凝胶的制备与性能研究

合成了马来酸酐-丙烯酸共聚物,并与长链分子聚乙二醇交联反应制备了马来酸酐-丙烯酸共聚物／聚乙二醇水凝胶。通过红外光谱对聚合物、水凝胶结构进行了表征,测试了不同pH值下水凝胶的溶胀度以及水凝胶在酸碱条件发生变化时的溶胀速率。研究结果表明,马来酸酐-丙烯酸共聚物／聚乙二醇水凝胶具有较强的吸水溶胀能力,并且对pH值极为敏感：交联剂含量7％的凝胶在pH=10时SR=62657％、pH=2时SR=825％,酸碱条件下具有近百倍的溶胀度变化;并且在pH发生变化时P（MA-AA）／PEG凝胶具有快速的响应速率：由pH=2溶液中转移至pH=10溶液中20min即可溶胀完全,而由pH=10溶液中转移至pH=2溶液中10min即可完全收缩。     

新型pH敏感性壳聚糖/明胶水凝胶的制备及其性能

用天然多糖壳聚糖和明胶制备了具有pH敏感性的壳聚糖/明胶水凝胶,研究了pH值对于该凝胶溶胀度的影响,采用红外光谱和电镜扫描对其结构进行了表征。结果表明,水凝胶在碱性和酸性环境中均具有pH敏感性,在酸性溶液中凝胶的溶胀比远大于碱性溶液中的溶胀比,其在pH值3.0时的溶胀度最大,在pH值9.0时的溶胀度最小,且其在不同pH 溶液中重复可逆溶胀收缩。同时,随着交联剂用量的增大,水凝胶的溶胀度减小。     

NVP-HEMA-KH570共聚水凝胶的合成及其溶胀性能研究

以N,N’-亚甲基双丙烯酰胺为交联剂,偶氮二异丁氰（AIBN）为引发剂,合成不溶于水的乙烯吡咯烷酮（NVP）／甲基丙烯酸β-羟乙酯（HEMA）／γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（KH-570）共聚水凝胶,研究了PVP水凝胶的平衡溶胀度及脱水性能。结果表明,随着NVP在水凝胶中含量的增大,水凝胶的平衡溶胀度逐渐增大;环境温度升高,KH570、BIS的含量及浸泡溶液的离子浓度增大,水凝胶的平衡溶胀度逐渐减少;在相同的时间内,环境温度越高,水凝胶的脱水率也越大;在同一温度下,HE-MA含量越大,凝胶脱水的速度就越慢,而浸泡的溶液离子浓度越高,脱水率就越大。     

温度和pH双重刺激响应型水凝胶的溶胀性能研究

以丙烯酰胺、丙烯酸和双丙酮丙烯酰胺为原料,以N,N'-亚甲基双丙烯酰胺为交联剂,2-酮戊二酸为引发剂,采用光引发聚合方法制备出系列新型温度和pH响应型水凝胶。考察了交联剂用量、水凝胶组成、温度和pH值对凝胶溶胀性能的影响。结果表明,随交联剂用量的增加,凝胶的溶胀率减小,随凝胶组成中AA含量的增加,凝胶的溶胀率增加。凝胶的溶胀率随温度的升高而减小,随pH值的增大而增加,表现出显著的温敏和pH敏感性。     

Interactions between shrinkage reducing admixtures (SRA) and cement paste's pore solution

Shrinkage reducing admixtures (SRA) have been developed to combat shrinkage cracking in concrete elements. While SRA has been shown to have significant benefits in reducing the magnitude of drying and autogenous shrinkage, it has been reported that SRA may cause a negative side effect as it reduces the rate of cement hydration and strength development in concrete. To examine the influence of SRA on cement hydration, this study explores the interactions between SRA and cement paste's pore solution. It is described that SRA is mainly composed of amphiphilic (i.e., surfactant) molecules that when added to an aqueous solution, accumulate at the solution-air interface and can significantly reduce the interfacial tension. However, these surfactants can also self-aggregate in the bulk solution (i.e., micellation) and this may limit the surface tension reduction capacity of SRA. In synthetic pore solutions, SRA is observed to form an oil-water-surfactant emulsion that may or may not be stable. Specifically, at concentrations above a critical threshold, the mixture of SRA and pore fluid is unstable and can separate into two distinct phases (an SRA-rich phase and an SRA-dilute phase). Further, chemical analysis of extracted pore solutions shows that addition of SRA to the mixing water depresses the dissolution of alkalis in the pore fluid. This results in a pore fluid with lower alkalinity which causes a reduction in the rate of cement hydration. This may explain why concrete containing SRA shows a delayed setting and a slower strength development.     

Influence of bleed water reabsorption on cement paste autogenous deformation

The effects of bleed water reabsorption and subsequent early age expansion on observed autogenous deformation are investigated in this research. Bleeding was induced by varying superplasticizer and shrinkage-reducing admixture dosages and by increasing the water-to-cement ratio. This research revealed that significant early age expansion occurs with increasing chemical admixture dosages and higher water-to-cement ratios, as expected, due to increasing bleeding of those samples. When samples were rotated, negligible early age expansion was observed. Thus, bleed water reabsorption is shown to be the primary mechanism causing initial expansion in sealed autogenous deformation samples. Thermal dilation and ettringite growth appear to have a minimal influence on the observed expansion. Rotating the samples during setting eliminates the potential for bleed water reabsorption and is recommended for all autogenous deformation testing.     

Chemical model for cement-based materials: Thermodynamic data assessment for phases other than C-S-H

In the context of waste confinement, concrete may be used both as a confinement and as a building material. Concerning radwaste, the heat released during radioactive decay will modify the equilibrium constants of the minerals forming the concrete. The present work aims to elucidate the temperature dependency of the thermodynamic functions related to minerals from the concrete or associated with some of its degradation products. A large set of experimental data has been collected, for the chemical systems SO₃-Al₂O₃-CaO-CO₂-Cl-H₂O and SiO₂-Al₂O₃-CaO-H₂O, including iron and magnesium bearing phases. Most of the data collected concern experiments in aqueous media but results from calorimetric studies were also included, when available. Based on selected thermodynamic properties for each phase, predominance diagrams were drawn for the chemical elements listed above. Phase relations reported into predominance diagram appear rather consistent with most of the literature results. The case of katoite has been especially discussed, because it shows inconsistencies with respect to a hydrogarnet-grossular solid solution and with respect to phase relations reported into already published works. Finally, we underline the chemical compatibility of Portland cement pastes with carbonate aggregates, compared to silicates, for long-term storage applications.     

An investigation of microstructure evolution in cement paste through setting using ultrasonic and rheological measurements

The response of hydrating cement paste through setting are monitored using rheological measurements and ultrasonic reflection measurements. Increases in the elastic modulus and yield stress of cement paste with time are obtained from the rheological measurements. Ultrasonic measurements are performed using horizontally polarized shear waves (SH) reflected off of the hydrating cement paste. Changes in the ultrasonic signal through setting are related with changes in the porosity and stiffness of an equivalent water-filled poroelastic material, which provides identical acoustic impedance. The measured changes in the shear modulus obtained from ultrasonic measurement are shown to correlate well with increase in elastic modulus obtained from rheological measurements. The increase in the shear modulus of the porous material obtained from the ultrasonic measurements is shown to correspond well with the observed increase in the yield stress of the cement paste. By combining the information from rheological and ultrasonic measurements, it is found that even in the fluid stage there is sufficient structural integrity in the arrangement of cement grains to support low-amplitude shear stress and the evolution of a continuously connected network of cement particles within the paste is coincident with a rapid increase in the shear modulus of the porous skeleton.     

Nonlinear ultrasonic evaluation of load effects on discontinuities in concrete

The presence of discontinuity surfaces in concrete structures, i.e. two or more layers in contact, may be an existing situation with evident relapses on damage formation and progression. Differences occur depending on the type of discontinuity, which could be a thin weaker layer or a pre-existing crack. The behavior of pre-existing interfaces is here studied by means of the Scaling Subtraction Method, a Nonlinear Ultrasonic Non-Destructive Technique, that revealed to be effective in describing the mechanical evolution of concrete samples with discontinuity surfaces under the effects of compressive loads.     

Assessment of the long-term stability of cementitious barriers of radioactive waste repositories by using digital-image-based microstructure generation and reactive transport modelling

Cement-based grout plays a significant role in the design and performance of nuclear waste repositories: used correctly, it can enhance their safety. However, the high water-to-binder ratios, which are required to meet the desired workability and injection ability at early age, lead to high porosity that may affect the durability of this material and undermine its long-term geochemical performance.In this paper, a new methodology is presented in order to help the process of mix design which best meets the compromise between these two conflicting requirements. It involves the combined use of the computer programs CEMHYD3D for the generation of digital-image-based microstructures and CrunchFlow, for the reactive transport calculations affecting the materials so simulated. This approach is exemplified with two grout types, namely, the so-called Standard mix 5/5, used in the upper parts of the structure, and the “low-pH” P308B, to be injected at higher depths.The results of the digital reconstruction of the mineralogical composition of the hardened paste are entirely logical, as the microstructures display high degrees of hydration, large porosities and low or nil contents of aluminium compounds.Diffusion of solutes in the pore solution was considered to be the dominant transport process. A single scenario was studied for both mix designs and their performances were compared. The reactive transport model adequately reproduces the process of decalcification of the C-S-H and the precipitation of calcite, which is corroborated by empirical observations. It was found that the evolution of the deterioration process is sensitive to the chemical composition of groundwater, its effects being more severe when grout is set under continuous exposure to poorly mineralized groundwater. Results obtained appear to indicate that a correct conceptualization of the problem was accomplished and support the assumption that, in absence of more reliable empirical data, it might constitute a useful tool to estimate the durability of cement-based structures.     

Wavelet-based analysis of ultrasonic longitudinal and transverse pulses in cement-based materials

Ultrasonic pulse velocity has been used for decades to detect localized damage and to estimate concrete properties. More recent applications aim at diffuse damage characterization, such as environmental and mechanical damage. In most applications the methodology to calculate pulse speed is a very important issue. This work, applying continuous wavelet transform (CWT) to construct time-frequency signal representations, calculates frequency-dependent velocity of longitudinal and transverse ultrasonic pulses using wavelet scales. The method is applied to a total of 14 specimens of 5 different mixes and frequency-dependent velocities are calculated using four wavelet families. The CWT capability to decompose the inquiring pulse spectrum and analyze phase velocities is discussed with regard to wavelet, pulse type, and mixture. Frequency-dependent velocity of longitudinal pulses at lower frequencies (from 100 kHz up to 250 kHz) was proven to be much more sensitive to mix proportions than transverse pulses.     

Effects of adhesive type and polystyrene concentration on the shear strength of bonded polystyrene/high-density polyethylene blends

The lap-shear strengths of adhesively bonded polystyrene (PS), high-density polyethylene (HDPE), and their blends, were studied as a function of adhesive type and blend composition. The performance of virgin and recycled polymer systems was examined. The lap-shear strength depended strongly on the amount of PS in the blend and the type of adhesive, and the acrylic adhesives demonstrated the best performance for all compositions. Bonded strengths of HDPE increased by approximately 50% when HDPE was blended with 34% PS, the co-continuous composition. The results indicate that structural elements made from PS/HDPE immiscible blends may be effectively bonded with adhesives without expensive surface treatments.     

Monitoring evolution of compressive damage in concrete with linear and nonlinear ultrasonic methods

An experimental study was conducted on different concrete cylinders damaged in compression. The evolution of damage was followed by means of linear and nonlinear ultrasonic methods, with the purpose to provide a better understanding of mechanical degradation processes in concrete and highlight the potentialities and limitations of the Non-Destructive Techniques used.