反相微乳液法制备陶瓷彩喷墨水(Ⅱ)

通过红外光谱仪测定两种墨水的微乳液结构。结果表明,醚氧键中的羟基与H2O分子作用后因形成氢键,而且有强烈的相互作用;正己醇分子在该反相微乳液中水分子作用很弱,而且推断它位于反相微乳液的栅状层;随着微乳液中含水量的增大,水分子O-H伸缩振动峰的强度和频率均发生变化,其吸收强度变大,峰面积增加,频率也向低频方向位移;体系中存在三种水:结合水、捕获水和自由水。并探讨了其反应机理。     

聚乙烯吡咯烷酮/壳聚糖共混水凝胶的制备与水的状态

以戊二醛作为交联剂,制备了聚乙烯吡咯烷酮（PVP）/壳聚糖（CHI）共混水凝胶,共混物的玻璃化转变温度T_g随CHI含量的升高而升高,SEM图谱观察到PVP/CHI凝胶表面呈现随CHI∶PVP比而变化的微相分离.凝胶溶胀率随着PVP含量升高、PVP分子量降低、CHI脱乙酰度增大而升高.DSC分析表明,非冷冻状态下,CHI∶PVP为1∶2时,游离水、可冻结结合水、非冻结结合水含量分别为42.7%、43.3 %、14.0 %;CHI∶PVP为1∶8时,凝胶中含非冻结结合水少,DSC曲线上只有一个明显的失水吸热峰,由游离水与可冻结结合水叠加而成.-123℃冷冻条件下凝胶的DSC升温曲线在0、38、53℃观察到一组明显的焓化峰,这是由于低温时冻结为结晶相的游离水、可冻结结合水,随温度升高吸热又转化为游离水、可冻结结合水所致.     

铝硅酸盐矿物的Raman振动特征解析

分别测定了蓝晶石、红柱石和夕线石3种铝硅酸盐天然矿物晶体的Raman光谱,并利用Materials Studio3.0软件计算3种矿物的Raman振动频率,分析其简正振动模式,确定了三种矿物特征谱峰的归属,解析了铝对铝硅酸盐Raman光谱振动特征的影响.结果表明:随着四配位铝的增加(从蓝晶石、红柱石到夕线石),800～1 200 cm-1波数区间内谱峰频率降低,该区间的谱峰归属于Si-Onb间非桥氧对称伸缩振动;700～800 cm-1区间内出现的谱峰归属于Al-Onb间非桥氧的对称伸缩振动.当铝全部为六配位时,会引起800～1 200 cm-1区间内的谱峰向高频方向迁移.这为进一步利用Raman光谱来研究硅酸盐玻璃和熔体结构中铝的作用提供了重要依据.     

C_(12)-2-C_(12)·2Br/正己醇/正庚烷/水微乳体系中水结构的FTIR研究

用Peakfit(Version4．12 Seasolve)曲线拟合软件解析了C12-2-C12·2Br／正己醇／正庚烷／水微乳体系的傅里叶变换红外光谱(FTIR)。根据微乳体系中水分子O-H伸缩振动峰的二阶导数谱,对3100-3700 cm-1的吸收峰进行分峰拟合,得到位于(3 240±10)cm-1、(3 380±15)cm-1、(3 470±30)cm-1、(3 570±30)cm-1的4个子峰,分别对应于表面活性剂阳离子头基结合水、本体水、阴离子结合水和束缚水。随着体系中加水量的增加,本体水和阴离子结合水的质量分数减小,阳离子结合水的质量分数增加,而束缚水的质量分数变化很小。     

透闪石结构的Raman光谱

将硅氧"四面体应力指数(stress index of tetrahedron,SIT)"值的计算和透闪石矿物Raman光谱的实际测定与量子化学自洽场分子轨道"从头计算"的方法相结合,用以探讨透闪石的Raman光谱在800～1200 cm-1高频区间内特征Raman谱峰的位移和结构含义,为深入理解链状硅酸盐矿物的结构特征提供理论依据.研究表明:实际测定的透闪石Raman光谱高频区的特征峰值1 030 cm-1和1 061 cm-1与用SIT计算和用量子化学"从头计算"方法对透闪石晶体模拟结构Si6O17Na10计算所获得的结果基本一致,证明了链状硅酸盐矿物透闪石的晶体结构中Q2和Q3两种结构单元所对应的特征Raman谱峰应分别位于1 033 cm-1和1 059 cm-1处,代表了Q2和Q3两种结构单元中非桥氧的对称伸缩振动.实际测定的透闪石Raman光谱中930 cm-1附近的谱峰,可能为Si-Onb间伸缩振动的反映.在SIT的计算和量子化学"从头计算"结果中都缺乏这个谱峰,初步的解释是与透闪石晶体中Q2的2个非桥氧与金属阳离子的配位互不等价,导致Q2非桥氧的伸缩振动发生分裂有关.     

水在凝胶中的存在状态及其对凝胶力学性能的影响

以偶氮二异丁腈为引发剂,通过化学引发聚合合成甲基丙烯酸β-羟乙酯（HEMA）/N-乙烯基吡咯烷酮（NVP）二元共聚物和HEMA /NVP /甲基丙烯酸甲酯（或甲基丙烯酸丁酯）三元共聚物水凝胶,通过示差扫描量热法（DSC）结合热重法（TG）研究了不同单体配比的共聚物水凝胶中水的状态,证明了凝胶中存在3种不同状态的水：非冻结结合水、可冻结结合水和可冻结自由水.结果发现可冻结水的含量主要由NVP含量所决定,NVP单元基本不能键合水,而非冻结水的含量主要受HEMA含量和疏水性单体甲基丙烯酸酯含量影响.疏水性单体的引入使材料的力学强度提高,对凝胶体系具有增塑作用的是非冻结水而不是可冻结的结合水和自由水.     

天然纤维素/PVA复合水凝胶的形成机理及力学性能研究

为提高聚乙烯醇(PVA)水凝胶的力学性能,利用Na OH/尿素溶剂,通过物理交联循环冷冻-解冻法,制备了α-纤维素(α-CE)/PVA复合水凝胶。红外光谱,扫描电镜结果表明α-CE与PVA水凝胶基体形成互穿交联网状结构。研究发现α-CE与PVA分子链上的羟基间所形成的氢键使两者牢固结合。力学性能测试表明,复合水凝胶的力学性能得到了大幅度提高,当α-CE含量为4%(wt)时,复合水凝胶的拉伸强度以及在压缩型变量60%下的压缩应力分别由0.09和0.07 MPa提高到0.64和0.52 MPa,比纯PVA水凝胶提高了611%和643%。此外发现,α-CE能明显增强PVA水凝胶的弹性及压缩后的形变回复能力。     

负热膨胀材料钨酸钇的快速合成及其Raman光谱(英文)

用二氧化碳激光快速凝同技术合成了负热膨胀材料钨酸钇.场发射扫描电子显微镜和X射线衍射分析表明:二氧化碳激光快速凝固技术合成的钨酸钇(Y2W3O12)为正变相的层状致密块体.Y2W3O12由于在大气中存放后会形成Y2W3O12·xH2O,Raman光谱研究表明:其中的水分子不仅能阻碍其共亭项角多面体的摇摆,而且将阻碍每一种振动.低于388 K,所释放的水分子对[WO4]四面体内振动的影响较小,在该温度以上能够释放的水分子对Y2W3O12框架结构中的多面体的摇摆运动、伸缩振动、弯曲振动、天平动和平动均有较大的阻碍作用.变温Raman光谱揭示:不仅低频卢子模,而且高频光学卢子模对负热膨胀也有贡献.     

盐离子对蒙脱石水化膨胀特性的影响

采用热失重法与经离心法、直接烘干法、冷冻干燥法结合对蒙脱石样品水含量进行测量,分析了NaCl浓度对蒙脱石中结合水与自由水含量的影响,探讨了蒙脱石中总含水量及结合水含量随NaCl溶液浓度变化的规律,研究了NaCl溶液中蒙脱石的水化膨胀特性及盐离子的抑制作用。结果表明,蒙脱石的水化膨胀受盐离子的抑制,盐离子的存在减小了渗透水化力,影响了水分子间的范德华力及水分子和蒙脱石表面间的氢键力和静电引力,总含水量随盐离子浓度增加而降低,盐离子浓度为0.2 mol/L时趋近最低值,样品膨胀程度由6.6缩小至1.6,盐离子对蒙脱石水化膨胀的抑制作用达峰值。盐离子浓度大于0.2 mol/L时,随盐离子浓度增加,自由水与结合水含量变化不明显。     

微波电场对甘油水溶液体系中氢键的影响

通过分子动力学模拟考察微波电场对不同水含量甘油溶液中氢键的影响。研究发现：甘油含量高时,甘油分子在溶液中以较大的团簇结构存在,水分子以较小的团簇结构或游离状态存在,电场作用下,大的甘油分子团簇变成较小的团簇并且变得更加有序;随着电场强度继续增加,甘油分子整体结构变化不大,但是团簇结构边缘甘油分子氢键断裂,变成游离状态。对于水分子而言,其较小的团簇结构在电场作用下被打开,团簇结构消失,水分子在电场方向上整齐排布,且电场强度继续增大,其结构变化不大,同样个别水分子氢键断裂变成游离状态。因此,甘油浓度高时,水分子间氢键数减少,甘油分子氢键数先增大后略微减少;甘油浓度低时,水分子氢键数先增大后略有减少,甘油分子间氢键减少。     

PVA水凝胶中水的状态研究

用环氧氯丙烷作交联剂,制备了聚乙烯醇（PVA）亲水水凝胶。并用示差扫描量热法（DSC）对不同含水量的此种亲水水凝胶进行了测试,获得了各种状态水进入水凝胶聚合物网络体系的先后顺序情况,并研究了PVA水凝胶中三种状态水的含量随水凝胶含水量的变化而变化的规律。     

Enhancing mechanical properties of poly(vinyl alcohol) blown films by drawing and surface crosslinking

Thermal blowing of poly(vinyl alcohol) (PVA) film was successfully realized based on molecular complexation. Ways to enhance the performance of the PVA blown films (drawing and surface crosslinking) were studied. The experimental results showed that water exists in PVA films in different states through hydrogen bonds with PVA and other modifiers and influences the drawability of PVA films, as well as the structure and properties of the stretched films. When the initial water content of the film was higher than 35.0%, the draw ratio of the PVA film was quite large because of the effects of the bound water with PVA, as well as the plasticization of free water. With the increase of the initial water content in PVA, the free water content and draw ratio of the films increased but the strength of the films decreased because of the higher residual water in the films. Surface crosslinking can improve the stretchability of PVA films because more water remains in the films and disrupts the hydrogen bonding of PVA. In addition, crosslinking enhances the mechanical properties of stretched PVA films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 774–779, 2005     

Water states and thermal processability of boric acid modified poly(vinyl alcohol)

To further improve the processability of water plasticized poly(vinyl alcohol) (PVA), boric acid (BA), which can rapidly form reversible crosslinked structure with the hydroxyl groups of PVA, was adopted as a modifier, and the water states, thermal performance, and rheological properties of modified PVA were investigated. The results showed that ascribing to the formation of the crosslinked structure between PVA and BA, the content of nonfreezing water in system increased, indicating that the bondage of PVA matrix on water enhanced, thus retarding the tempestuous evaporation of water in system during melt process and making more water remained in system to play the role of plasticizer. Meanwhile, this crosslinked structure shielded part hydroxyl groups in PVA chains, leading to the further weakening of the self‐hydrogen bonding of PVA, and guaranteeing a lower melting point and higher decomposition temperature, thus obtaining a quite wide thermal processing window, i.e., ≥179°C. The melt viscosity of BA modified PVA slightly increased, but still satisfied the requirements for thermal processing, thus reinforcing the flow stability of the melt at high shearing rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43246.     

Modeling water states in polyvinyl alcohol-fumed silica nano-composites

We proposed a mathematical model to account for water contents in different states as a function of filler concentration in polymer-filler composites. The water states were characterized in polyvinyl alcohol (PVA) and PVA-fumed silica (FS) composites using low temperature differential scanning calorimetry. This model takes into consideration the inert filler dilution effect, the equilibrium of bound water to free and freezable water states associated with FS nano-particles, and the suppressed hydrogen-bonding ability of hydroxyl groups in polymer chains caused by FS shielding. Predicted results were in excellent agreement with experimental data. This model can yield a great understanding of the distribution of water states into bound and free (and freezable) water states for homogeneous, heterogeneous or micro-phase separated polymers, and especially perfluorosulfonic acid membranes and water-retaining hydrogels.     

Water stability of high‐molecular‐weight (HMW) syndiotacticity‐rich poly(vinyl alcohol) (PVA)/HMW atactic PVA/iodine complex blend films

To precisely identify the effect of blend ratios of syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA)/atactic PVA (a‐PVA) on the water stability of s‐PVA/a‐PVA/iodine complex blend films, we prepared two PVAs with similar number‐averaged degrees of polymerization of 4000 and degrees of saponification of 99.9% and with different syndiotactic diad contents of 58.5 and 53.5%, respectively. The desorption behavior of iodine in s‐PVA/a‐PVA/iodine complex films in water was investigated in terms of the solubility of s‐PVA/a‐PVA blend films in water. The degree of solubility of s‐PVA/a‐PVA blend films with s‐PVA content over 50% in water at 70°C was limited to about 10–20%, whereas that of s‐PVA/a‐PVA blend films with s‐PVA content of 10% was 85% under the same conditions. The degree of iodine desorption of complex blend films decreased with increasing s‐PVA content. The degree of iodine desorption of s‐PVA/a‐PVA drawn film with s‐PVA content of 90% was limited to 7%, regardless of the soaking temperature from 30 to 70°C. The desorption of iodine in water was strongly affected by the dissolution of blends. Moreover, the stability of iodine in the drawn s‐PVA/a‐PVA/iodine blend films in hot water was far superior to that of the undrawn film. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1435–1439, 2004     

Controlled release of riboflavin and insulin through crosslinked poly(vinyl alcohol)/chitosan blend membrane

The permeation of riboflavin and insulin through poly(vinyl alcohol) (PVA) and chitosan blend membrane was conducted. The permeability coefficients of both solutes through the crosslinked PVA and chitosan blend membrane were in the order of 10^?6?10^?7 cm³ cm/cm²s and showed a pH dependence. The pH-dependent permeation behavior was discussed in terms of water content and water structure inside of the swollen membrane. Riboflavin and insulin were presumed to permeate through the free water region in the swollen blend membrane. The DSC thermograms of these membranes indicated that the content of free water and the amount of freezing bound water increased with the water content in the membrane. The greater permeation rate of solutes in acidic solution rather than in neutral solution was due to an increase in both water content and the amount of free water and freezing bound water.     

Water sorption and water‐resistance properties of poly(vinyl alcohol)/clay nanocomposite films: Effects of chemical structure and morphology

A series of poly(vinyl alcohol)/sodium montmorillonite (PVA/NaMMT) nanocomposite films were prepared via a solution method, and their water sorption and water‐resistant properties were investigated as a function of clay content. The water sorption and water resistance properties were strongly dependent on the chemical structure and film morphology originating from the NaMMT content. The water diffusion coefficient and water uptake of the PVA/NaMMT nanocomposite films were obtained by best fits to a Fickian diffusion model. The diffusion coefficient and water uptake in the PVA/NaMMT nanocomposite films varied between 8.16 × 10⁻¹⁰ and 3.60 × 10⁻¹⁰ cm² s⁻¹ and 35.6 and 29.9 wt%, respectively. Both the diffusion coefficient and water uptake decreased as the content of NaMMT in pure PVA was increased. Additionally, the water resistance pressure (mm) of the PVA/NaMMT nanocomposite films increased with increasing NaMMT content. Contact angle analyses showed that the chemical affinity to water and the surface energy of the nanocomposite films decreased with increasing NaMMT content. Furthermore, the well‐dispersed and exfoliated structure in the nanocomposite films not only induced an increased tortuous path for water molecules to pass through, but also increased the molecular order. However, to enhance the water sorption properties and water resistance of hydrophilic PVA, further studies to increase the dispersion of clay particles and ensure desired morphological qualities such as crystallinity and molecular packing order in the PVA/clay nanocomposite films are required. POLYM. COMPOS., 36:660–667, 2015. © 2014 Society of Plastics Engineers     

Preparation of poly (vinyl alcohol)/gelatin composites via in-situ thermal/mechanochemical degradation of collagen fibers during melt extrusion: effect of extrusion temperature

By in-situ degradation of collagen fibers into gelatin under the thermal/mechanochemical effects of the extruder, PVA/gelatin composites were successfully prepared using PVA and collagen fibers derived from cattle hide limed split wastes as raw materials. The effect of extrusion temperature on the degradation of collagen fibers and the thermal processability and mechanical properties of the composites were studied. The results showed that the controllable degradation of collagen fibers in extruder could be realized by adjusting the extrusion temperature. Particularly, high extrusion temperature promoted the generation of low-molecular-weight gelatin and the esterification between the hydroxyl of PVA and the carboxyl of gelatin, as well as the hydrogen bonding between O-H, C = O, N-H in gelatin and water or O-H in PVA, thus endowing gelatin with the good compatibility with PVA, and significantly increasing the content of non-freezable bound water in system. Ascribing to the plasticization of the gelatin with lower molecular weight and more non-freezable bound water, PVA/gelatin composites exhibited the improved thermal processability and the decreased mechanical properties with the increase of extrusion temperature. Even so, the tensile strength and Young’s modulus of the composite obtained at 175 °C still above 40 MPa and 1.0 GPa respectively, satisfying some practical applications.     

Preparation and characterization of polysaccaride interpolymer complexes: I‐PVA/ι‐carrageenan

Thermal and spectroscopic charaterization of PVA, iota carrageenan (IC), and their interpolymer complexes were studied in terms of stability, complex formation, and species determination by XRF, FTIR, Raman, DSC, and TGA. Thermogravimetry analysis showed that initial thermal degradation temperature of PVA/IC decreased from 276 to 256°C with an increase of IC content. The complexation of IC to PVA significantly increased, the thermal stability of IC, where as the thermal stability of PVA increased rather insignificantly. Fourier Transform Infrared (FTIR) and Raman spectroscopic results showed that PVA interacted with IC through ? OH groups of PVA and IC as shown by the frequency and scattering shift at ? OH band of FTIR and Raman spectra of each complex. The involvements of ester sulfate and ether groups of IC in interaction were not significant. In the results of the thermal and spectroscopic analysis, 17% content of PVA/IC is the most miscible and intercomplexable weight fraction of PVA/IC. The natural source of IC, which was unknown was characterized by XRF and found to be as potassium salt and Euchema specie of marine red algee of the class Rhodophceae. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of Bound Water on the Fractal Geometry of Nanosized Cracks in Glasses Prepared by Vacuum Pressure-Assisted Sintering

The vibrational properties of fractal nanocracks in vitreous SiO₂samples prepared by vacuum pressure-assisted sintering are investigated by low-frequency Raman scattering spectroscopy. In the Raman spectrum, nanosized discontinuities with a fractal geometry manifest themselves in a specific frequency dependence of the scattering intensity: a monotonic decrease in the intensity according to the law of light scattering by acoustic vibrations localized on fractals is observed instead of the boson peak. The frequency dependence of the low-frequency Raman scattering intensity is analyzed for samples of different origins. A smoothing of the nanocrack profile with a decrease in the amount of bound water in the material is revealed.