二氧化硅与液体介质的亲和性表征

利用动态核磁脉冲(Dynamic NMR)技术对高浓度的二氧化硅浆料的亲和性进行研究,并建立表征束缚层厚度与亲和性的定量模型。结果表明,在纯丁酮溶剂中,二氧化硅的含量越高,分散时间越长,填料表面束缚层厚度越大;而在树脂溶液体系中,在30%二氧化硅含量附近,填料表面束缚层厚度最大。当处理剂用量约为0.5%(ω/ω)时,颗粒表面与介质的吸附作用最强。使用不同处理剂制备的二氧化硅浆料,其表面吸附效应也有所不同,并且当浆料静置16 h后,其厚度层发生变化,在丁酮体系中,束缚层厚度部分增加,而甲苯体系中,束缚层厚度减小。     

聚乳酸/二氧化硅超疏水材料的制备及其性能研究

本研究采用硅烷偶联剂KH570化学接枝与硬脂酸(SA)物理包覆相结合的方法对纳米二氧化硅(SiO_2)进行有效改性,得到具有一定疏水效果并能在聚合物基体中有效分散的纳米填料,以聚乳酸(PLLA)为聚合物基体,通过非溶剂诱导相分离法制得了超疏水PLLA/SiO_2复合膜,其表观接触角由纯PLLA的120°提高到153°。研究还发现,填料含量不同,基体的结晶性能也不同,随着改性纳米SiO_2填料含量的增加,膜的结晶度从9.8%提高到17.19%,结晶度对材料表面粗糙结构的构建有重要作用,粗糙结构有助于表面疏水性能的提升。     

丝网印刷法制备纳米银线透明导电薄膜

以高纯纳米银线作为导电介质,采用低成本丝网印刷法在普通透明玻璃基底上制备纳米银线薄膜层。经低温退火处理后,采用冷场发射扫描电子显微镜对薄膜的形貌进行表征;分别采用紫外可见分光光度计和四探针测试仪对薄膜的光学透过率和导电性能进行测试。实验系统研究了印刷浆料中纳米银线的含量、印刷层数和退火温度对薄膜的光学透过率和导电性能的影响。当印刷浆料中纳米银线的含量为3%(w/w),印刷层数达到3层,经低温275℃退火后,可制备出光电性能良好的纳米银线薄膜,该薄膜最大可见光透过率为39.4%,表面方块电阻仅为25.6Ω·□~(-1)。     

铝镧共掺杂的氧化锌红外隐身涂料在帐篷织物上的应用

以水性聚氨酯为粘合剂,掺杂Al和La的ZnO为填料,配以其它助剂制成了红外隐身涂料,应用在帐篷织物表面,探究涂层厚度以及填料含量对红外发射率的影响,并研究了导热系数和红外隐身性能之间的关系。 研究发现,涂层厚度和填料含量对涂层织物的红外发射率有着显著的影响。 当填料质量分数为70%时,得到的帐篷涂层织物的红外发射率可降至0.622,调节填料含量和涂层厚度,可以的得到红外发射率在0.622~0.932之间的帐篷涂层织物。 此外,发现导热系数对红外隐身性能也有一定的影响,红外隐身性能随着导热系数的增加而提高。 通过调节填料含量和涂层厚度制作不同红外发射率的涂层帐篷织物,放在不同背景下拍摄红外热成像图,发现涂层在不同的环境中均具有良好的伪装能力。     

W掺杂SiO2介孔材料的制备与表征

以非离子表面活性剂三嵌段共聚物P123为模板剂、正硅酸乙酯(TEOS)为硅源、钨酸钠(Na2WO4·2H2O)为钨源, 通过水热法一步合成了W掺杂的二氧化硅介孔材料W-SiO2, 并通过XRD、HRTEM、EDX、FT-IR、N2吸附-脱附等表征手段, 考察了随着W含量增加, W-SiO2介孔材料结构的变化规律以及钨物种在材料中的存在状态. 结果表明, 当WO3含量w(WO3)约为10%时, W-SiO2中的钨物种是高度分散进入介孔骨架,形成W-O-Si 键; 当w(WO3)=20%时, 样品中开始有未掺入到SiO2骨架中WO3的结晶出现; 当w(WO3)约60%时, W-SiO2 样品能保持很好的介孔孔道结构, 更高含量WO3掺入将破坏二氧化硅介孔结构.     

聚丙烯/硫酸钡复合体系的界面相互作用与流变性质和结晶行为的关系

制备了一系列具有不同界面状态的聚丙烯 (PP) 硫酸钡 (BaSO4)复合体 .PP BaSO4的界面分别用硅烷、硬脂酸、马来酸酐接枝聚丙烯 (PP g MAH)改性 .研究表明 ,填充体系的熔体粘度和熔体弹性均高于基体 .以硅烷和PP g MAH进行界面改性后 ,PP BaSO4的界面相互作用加强 ,导致复合体系中的熔体粘度和熔体弹性进一步提高 ,同时BaSO4对PP的成核活性提高 .填料用硬脂酸处理后 ,硬脂酸能够在填料粒子表面上形成一个包覆层 ,使粒子与PP的亲和性改善 .同时该包覆层具有润滑作用 ,使得复合体系的熔体粘度和熔体弹性下降 ,并使得该体系中BaSO4的成核活性低于硅烷和处理的体系 .本文探讨了由复合体系的熔体粘度定量比较填充复合体系中聚合物 填料界面相互作用的方法 ,讨论了界面改性对复合体系流变性质和结晶行为影响的机理     

二氧化硅纳米颗粒/硅树脂复合超疏水功能涂层的制备和性能研究

将二氧化硅纳米颗粒和硅树脂制成混合液,采用喷涂法(spray-coating)制备出了具备超疏水性的复合涂层.研究了二氧化硅、硅树脂不同含量配比对涂层疏水性能的影响,结果表明复合涂层的接触角随二氧化硅含量的增加而增加.在二氧化硅含量大于3%(质量分数)时,涂层显现超疏水性;当二氧化硅含量为3%(质量分数)、硅树脂含量为7%(质量分数)时,涂层与水的接触角达到151.6°,滚动角接近0°.通过扫描电子显微镜(SEM)观察涂层表面的微观结构,发现超疏水性的涂层具备微-纳复合阶层结构,类球状突起粒径在5μm左右,类球状突起上分布纳米团聚颗粒,直径约为50 nm.这种类似荷叶表面的微(纳复合阶层结构,结合硅树脂的低表面能,使得复合涂层具备了超疏水性能.     

草莓型PMMA/SiO2有机-无机复合微球的合成与表征

在纳米二氧化硅水分散介质中,借助于正离子单体甲基丙烯酰氧乙基三甲基氯化铵(MTC)与未改性纳米二氧化硅颗粒之间的电荷作用,通过MTC与甲基丙烯酸甲酯(MMA)的自由基共聚合,制备了草莓型的PMMA/SiO2复合微球.整个制备反应过程中,纳米二氧化硅无需表面处理,体系中无需另外加入乳化剂或助乳化剂,微球表面吸附的纳米二氧化硅对颗粒起稳定作用.详细讨论了纳米二氧化硅初始添加量、MTC浓度对复合微球的平均粒径、复合微球中二氧化硅含量及微球形态的影响.动态光散射粒度分布仪(DLS)测得复合微球粒径在180~300 nm之间,热重分析(TGA)表明复合微球中二氧化硅含量介于16.4%~40.8%之间.透射电镜(TEM)显示所得复合微球具有草莓型结构,二氧化硅于表面富集.     

草莓型SiO2/PMMA纳米复合微球的制备

在纳米二氧化硅水分散体系中,借助于碱性辅助单体1-乙烯基咪唑(1-VID)与未改性纳米二氧化硅表面羟基之间的酸-碱作用,通过1-VID与甲基丙烯酸甲酯(MMA)的自由基共聚合,制备了草莓型的SiO2/PMMA复合微球.整个反应过程中,纳米二氧化硅无需表面处理,体系中无需另外加入乳化剂或助乳化剂,微球表面吸附的纳米二氧化硅对颗粒起稳定作用.用动态光散射粒度分布仪测得复合微球粒径在120-330nm之间,热重分析结果表明,复合微球中二氧化硅含量介于15%-20%之间.透射电镜和扫描电镜显示所得复合微球具有草莓型结构,二氧化硅富集在表面.     

碳纳米管-聚乙烯复合材料的介电性能

采用熔融共混及模压的方法制备了碳纳米管(CNT)-高密度聚乙烯(HDPE)复合材料,并用介电谱仪研究了逾渗值附近的导电填料对复合材料体系在不同温度、频率条件下的介电常数、介电损耗、交流电阻率的变化规律。结果表明:复合材料的介电常数、介电损耗均随CNT质量分数增加而逐渐增大;在频率为103~106 Hz,温度为40~130℃时,HDPE基体的介电常数随频率和温度的变化较小,而添加CNT填料的复合材料的介电常数随频率和温度的增加而略微降低。当w(CNT)0.5%时,复合材料的交流电阻率表现出对频率的强烈依赖性;而当w(CNT)0.5%时,在低频处表现出直流特性,在高频处显示出交流电阻率的降低。     

Interactions of PEI (polyethylenimine)–silica particles with citric acid in dispersions

Adsorbed polyethylenimine (PEI) of M _w 1,800 and 70,000 on silica (SiO₂) dispersions produced flocculated slurry in the pH range of 5 to 12. Adsorbed citrate widens this flocculated pH regime. It also increases the strength of the interparticle attractive force or the yield stress over the pH range of between 3 and 8. The stronger attractive force is due to particle bridging by the citrate anions bonding with positively charge sites of the adsorbed PEI layer of the interacting particles at the closest point of interaction. The higher M _w PEI being more strongly attached to the silica particle produced a stronger attractive interparticle force with adsorbed citrate anions. Via charge balance calculation using contributions from SiO₂, PEI, and citrate, the pH of zero charge was found to correspond to the pH of zero zeta potential for PEI of M _w 70,000. This suggests 100% adsorption of PEI and citrate on SiO₂. The bridging interaction was confirmed by a linear relationship between yield stress and the square of the limiting citrate charge content. Adsorbed citrate was found for the first time to play the role of a bridging agent, a result of the positive charges being located on a more flexible adsorbed layer rather than being fixed to a rigid surface.     

Electron spin resonance studies of spin-labelled polymers—18: Adsorption of spin-labelled poly(vinyl acetate) on silica surfaces

The adsorption of spin-labelled poly(vinyl acetate) from dilute solutions in ethyl acetate, chloroform and toluene onto three silica adsorbents of different surface silanol contents was studied. The adsorption capacities of the three silica samples, which decreased with decreasing surface silanol content, were dependent on the nature of the solvent, being greatest in the poor solvent toluene and least in the good solvent ethyl acetate. The ESR spectra of the polymer adsorbed on the silica of highest silanol content suggested that the polymer had a relatively flat conformation when toluene or chloroform was solvent and a more looped conformation when ethyl acetate was solvent. With the silica of intermediate silanol content, the polymer adsorbed from chloroform solution also had a loopy conformation. The silica of lowest silanol content was prepared by treating the first silica absorbent with trimethylchlorosilane. The line-shapes in the ESR spectrum of the labelled polymer adsorbed on this modified silica indicated a change in mode of adsorption.     

Fast and Minimal‐Solvent Production of Superinsulating Silica Aerogel Granulate

With their low thermal conductivity (λ ), silica aerogels can reduce carbon emissions from heating and cooling demands, but their widespread adoption is limited by the high production cost. A one‐pot synthesis for silica aerogel granulate is presented that drastically reduces solvent use, production time, and global warming potential. The inclusion of the hydrophobization agent prior to gelation with a post‐gelation activation step, enables a complete production cycle of less than four hours at the lab scale for a solvent use close to the theoretical minimum, and limits the global warming potential. Importantly, the one‐pot aerogel granulate retains the exceptional properties associated with silica aerogel, mostly λ =14.4±1.0 mW m⁻¹⋅K⁻¹ for the pilot scale materials, about half that of standing air (26 mW m⁻¹⋅K⁻¹). The resource‐, time‐, and cost‐effective production will allow silica aerogels to break out of its niche into the mainstream building and industrial insulation markets.     

Effects of surfactants and electrolytes on adsorbed layers and particle stability

Adsorbed polymer and polyelectrolyte layers on colloidal silica nanoparticles have been studied in the presence of various salts and surfactants using photon correlation spectroscopy and solvent relaxation NMR. Poly(ethylene oxide) (PEO; molar mass 103.6 kg mol (-1)) adsorbed with a relatively high affinity and gave a layer thickness of 4.2 +/- 0.2 nm. While the nonionic surfactant used only increased this thickness slightly, anionic surfactants had a much greater effect, mainly due to repulsions between adsorbed aggregates, leading to expansion of the layer. A nonionic/anionic surfactant mixture was also tested and resulted in a larger increase in layer thickness than any of the individual surfactants. The dominant factor on addition of salt was generally the reduced solvency of PEO, which resulted in a further increase in the layer thickness but in some cases caused flocculation. This was not the case when the surfactant was sodium dodecylbenzenesulfonate; instead screening of the intermicellar repulsions possibly combined with surfactant-cation binding resulted in a reduction in the layer thickness. In comparison the affinity between silica and sodium polystyrenesulfonate was very weak. Anionic surfactants and salts did not noticeably increase the strength of adsorption, but instead encouraged flocculation. The situation was different with a nonionic surfactant, which was able to adsorb to silica itself and apparently facilitated a degree of polyelectrolyte adsorption as well.     

Controllable synthesis of silica nanoparticle size and packing efficiency onto PVP-functionalized PMMA via a sol–gel method

This study aimed to investigate synthesis and adsorption behavior of silica nanoparticles onto polyvinylpyrrolidone (PVP)-functionalized poly(methyl methacrylate) under various conditions such as methanol/water ratio, ammonium hydroxide concentration, polymer contents, tetraethylorthosilicate contents, and total volume of solvent via sol–gel method. First, the copolymerization of methyl acrylate as a comonomer and 1-dodecanethiol as a chain transfer agent increased the thermal stability of the product; however, the uniformity of the PMMA particles decreased because of the chain transfer reaction. Second, the adsorption behavior and size of silica nanoparticles could be controlled by adjusting the silica synthesis conditions. The adsorbed silica particle size was greatly influenced by the ammonium hydroxide concentration and the addition of water further enhanced the size increase. However, increasing the water content reduced the packing efficiency of the adsorbed silica particles. Increasing the PVP-functionalized PMMA content at a fixed TEOS content linearly decreased the silica particle size. But TEOS concentration did not significantly affect the silica particle size. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 662–672     

Structure of Protein Layers during Competitive Adsorption

The formation of protein layers during competitive adsorption was studied with ellipsometry. Single, binary, and ternary protein solutions of human serum albumin (HSA), IgG, and fibrinogen (Fgn) were investigated at concentrations corresponding to blood plasma diluted 1/100. As a model surface, hydrophobic hexamethyldisiloxane (HMDSO) plasma polymer modified silica was used. By using multiambient media measurements of the bare substrate prior to protein adsorption the adsorbed amount as well as the thickness and refractive index of the adsorbed protein layer could be followedin situand in real time. Under conditions used in these experiments neither IgG nor fibrinogen could fully displace serum albumin from the interface. The buildup of the protein layer occurred via different mechanisms for the different protein systems. Fgn adsorbed in a rather flat orientation at low adsorbed amounts, while at higher surface coverage the protein reoriented to a more upright orientation in order to accommodate more molecules in the adsorbed layer. IgG adsorption proceeded mainly end-on with little reorientation or conformational change on adsorption. Finally, for HSA an adsorbed layer thickness greater than the molecular dimensions was observed at high concentrations (although not at low), indicating that aggregates or multilayers formed on HMDSO plasma polymer surfaces. For all protein mixtures the adsorbed layer structure and buildup indicated that Fgn was the protein dominating the adsorbed layer, although HSA partially blocked the adsorption of this protein. At high surface concentration, HSA/Fgn mixtures show an abrupt change in both adsorbed layer thickness and refractive index suggesting, e.g., an interfacial phase transition of the mixed protein layer. A similar but less pronounced behavior was observed for HSA/IgG. For IgG/Fgn and HSA/IgG/Fgn a buildup of the adsorbed layer similar to that displayed by Fgn alone was observed.     

Phenol adsorption on active carbon by means of thin-layer chromatography

Summary The effect of the acidity of the media on the adsorption of phenol and creasols was investigated using TLC and using the R_F-values as a measure of the adsorption ability of active carbon. Three types of chromatographic layers were employed: silica gel, silica gel containing 3% of active carbon and silica gel containing 6% of active carbon. Standard solutions of phenol, m-cresol and o-cresol were used as the samples. The acetic acid content of the solvent mixture significantly influences the adsorption of phenol and cresols on the active carbon layer. An increase in the acetic acid content results in a decrease of the adsorption of phenols. However, under specific conditions [81∶5∶7 hexane-diethyl ether-acetic acid, and 48∶2∶8 benzene-acetone-acetic acid developers] the competitive adsorption of phenols and acetic acid may take place, which has been observed by a steep increase in the adsorption of phenol and cresols.     

Kinetics and isotherms of asphaltene adsorption in narrow pores

New data relating to the kinetics and adsorption isotherms of asphaltene in consolidated sandstone core samples are reported. The data were obtained from the measurements of electrokinetics of consolidated sandstone core samples in asphaltene/toluene solutions and petroleum oils. The numerical reduction in the (negative) zeta potential of the sandstone samples were attributed to the adsorption of positively charged molecules of asphaltenes. The hydrodynamics thickness δ of adsorption of asphaltene were followed by monitoring the pressure increase that occurred as the adsorbed layer restricted the rock pores and applying Poiseuille's equation. The flow rates indicated a plateau of asphaltene adsorption at a pore blocking thickness of about δ/r = 0.3, which was also the point at which the streaming current reached a plateau. After increasing to about 30% of the pore radius, the adsorbed layer thickness δ stopped growing either with time or with concentration of asphaltene in the flowing liquid. Alternative hypotheses involving asphaltene adsorption isotherms have been investigated. A theoretical treatment advanced describing particle adsorption in the same terms as molecular adsorption and the Langmuir isotherm, with the free energy of asphaltene adsorption on the rock surface (modeled on silica) calculated on the basis of van der Waals attraction. Acceptable agreement was obtained with the electrokinetic measurements.     

Multilayer adsorption with variable thickness at solid-liquid interfaces

 The multilayer adsorption on the solid/liquid interface in binary mixtures was studied by adsorption space filling with constant and variable layer thickness. Adsorption from benzene/n-heptane mixtures was examined on hydrophilic and hydro-phobic surfaces. The free enthalpy of adsorption, Δ₂₁ G=f (x ₁), was calculated from the adsorption excess isotherm by integration of the Gibbs equation. Supposing that the free enthalpy is mainly due to adsorption in the first layer, the composition of this layer can be calculated from the Δ₂₁ G=f (x ₁) function. It was established that the adsorption layer thickness in benzene/heptane mixtures increases significantly with increasing benzene content. This statement was supported by X-ray diffraction on hydrophobic clay minerals. Received: 2 April 1997 Accepted: 10 June 1997     

Structure of adsorbed polyelectrolyte monolayers investigated by combining optical reflectometry and piezoelectric techniques

Polyelectrolyte monolayers on solid substrates are studied with optical reflectivity and the quartz crystal microbalance (QCM). In particular, we investigate the adsorption of anionic poly(styrene sulfonate) (PSS) on amino-functionalized silica as well as cationic poly(allylamine hydrochloride) (PAH) and poly-L-lysine (PLL) on bare silica. By comparing the dry and wet masses measured on identical substrates with these two techniques, we obtain information on the layer thickness and water content of these layers. Monolayers typically feature an adsorbed dry mass of about 0.1-2 mg/m(2), a layer thickness of 0.5-2 nm, and a water content of 20-50%. One finds that the layer thickness increases with increasing concentrations of monovalent salts and polyelectrolytes.